Materials Letters 64 (2010) 1701–1703

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Preparation of fluorine-doped tin oxide (SnO2:F) film on polyethylene terephthalate

(PET) substrate
Xiaoming Huang, Zhexun Yu, Shuqing Huang, Quanxin Zhang, Dongmei Li, Yanhong Luo, Qingbo Meng ⁎
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, PO Box 603, Beijing 100190, China

a r t i c l e i n f o a b s t r a c t

Article history: Fluorine-doped tin oxide (FTO), one of the most popular transparent conductive oxide (TCO) materials,
Received 5 February 2010 coated on glass has been used in various applications including many new-generation solar cells. However,
Accepted 5 May 2010 there is a lack of reporting when it comes to FTO coated on flexible transparent substrate. For this paper,
Available online 11 May 2010
spray pyrolysis technique was used to have FTO firstly coated on to a brass substrate, which was then
dissolved away after cementing an upper flexible transparent polyethylene terephthalate (PET) substrate,
Keywords:
finally leaving high quality FTO film on PET substrate. Their structural, electrical, optical and flexible
Fluorine-doped tin oxide
Thin films
properties were investigated. The lowest resistivity was 7.6 × 10− 4 Ω cm, which is as good as conventional
Flexible substrate FTO deposited on glass. Their fold ability could be significantly improved to transcend commercial ITO/PET
Deposition only by increasing the pretreating time of the brass substrate.
Fold ability © 2010 Elsevier B.V. All rights reserved.

1. Introduction
Flexible transparent conductive oxides (TCO) substrates are
expected to be widely used as flexible electrodes in various
applications such as flexible solar cells [1], plastic liquid crystal
displays [2] and flexible organic light-emitting devices [3]. At present,
TCO materials mainly include tin-doped indium oxide (ITO) [4],
fluorine-doped tin oxide (FTO) [5] and aluminum-doped zinc oxide
(AZO) [6]. Among these TCO materials, ITO deposited on flexible
polymer substrates have been widely researched and industrialized
[1–4], and AZO coated on organic substrates also have increasingly
been the subject of report in recent years [6]. To our knowledge,
however, FTO film prepared on flexible transparent substrate has
never been reported on. FTO has advantages over others such as
superior chemical stability and high resistance to physical abrasion
[7], which are highly attractive for applications that require caustic
chemical treatments during preparation [8]. Additionally, due to its
abundant material elements, FTO is a good candidate since ITO
includes rare element indium. High temperature (above 400 °C) is the
crucial factor for depositing high quality FTO thin film, but flexible
transparent substrate, such as polyethylene terephthalate (PET),
normally can only stand temperatures below 150 °C. It is this
temperature conflict that makes it almost impossible to prepare FTO
film on flexible transparent substrate in the past. In this paper, we
⁎ Corresponding author. Tel./fax.: + 86 10 8264 9242.
E-mail address: qbmeng@aphy.iphy.ac.cn (Q. Meng).
develop a new method to avoid this conflict, firstly reporting on the
preparation and properties of FTO film on flexible PET substrate.
2. Experimental procedure
Brass substrate (Cu0.62Zn0.38, 60 mm* 25 mm* 0.3 mm) was pre-
treated in 30 mL of 5 M nitric acid for 4 min, and cleaned using distilled
water. The FTO film was then deposited on the pretreated brass
substrate via spray pyrolysis technique (SPT) [9] at a temperature of
400 °C. The solution for spraying was prepared as follows: after 15.75 g
of SnCl4 5H2O was fully dissolved in 600 mL of ethanol, 10 mL of 7.5 M
NH4F solution was admixed to it and stirred until completely dissolved.
The schematic diagram of deposition setup was published elsewhere
[10]. The spraying time was varied from 10 min to 60 min in order to
obtain FTO film with different thicknesses. After FTO film was coated on
brass substrate, transparent substrate (TS) such as PET or glass was
conglutinated on the FTO film with α-cyanaloc acrylic adhesive resin.
The brass substrate can be completely dissolved away in 4.5 M nitric
acid after the resin was solidified, leaving FTO film adhered on TS, which
was then completely cleaned using distilled water. Eventually, FTO film
was successfully transferred onto TS as the structure of TS/resin/FTO.
Herein, as an example, we only take PET and glass as TS, even though TS
basically could be any flexible or rigid transparent substrate. The
thickness of the resin was about 25 μm to 30 μm. The structural
properties of FTO films adhered on PET were analyzed by X-ray
diffractometer (XRD, Mac Science, M18X-AHF) using Cu Kα radiation
and scanning electron microscopy (SEM, FEI, NovaNano 430). The
optical transmissions were characterized by UV–VIS spectroscopy
(SHIMADZU, UV2550). The electrical properties were measured by
four-point probes resistivity measurement system (Four Probes Tech,

0167-577X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2010.05.001
1702 X. Huang et al. / Materials Letters 64 (2010) 1701–1703

Fig. 1. XRD patterns of (a) FTO film on PET, (b) bare PET substrate with resin, (c) FTO Fig. 3. Transmittance spectrum of PET substrate with resin and FTO films deposited with
film on glass, (d) bare glass substrate with resin. different spraying time.

RTS-9). The flexible properties were investigated using home-made

equipment. Table 1
The electrical properties of FTO films on PET with different spraying time.

3. Results and discussions Spraying time Sheet resistance(Rs) Thickness(d) Resistivity(ρ)

(min) (Ω/□) (nm) (Ω cm)
3.1. Structural properties 10 48.3 220 1.1 × 10− 3
20 18.6 410 7.6 × 10− 4
Fig. 1(a) and (c) shows an XRD pattern of an FTO thin film on PET 35 17.2 720 1.2 × 10− 3
45 15.4 945 1.5 × 10− 3
substrate and glass substrate, respectively. Fig. 1(b) and (d) shows an
60 15.1 1140 1.7 × 10− 3
XRD pattern of a bare PET substrate with resin and bare glass substrate
with resin, respectively.
This FTO thin film was first deposited by spraying for 20 min to
obtain an average thickness of 410 nm before being transferred. Fig. 1 3.2. Optical properties
(c) shows the cassiterite crystal structure and the diffraction peaks
can be clearly indexed to SnO2 phase with tetragonal structure [11,12]. Fig. 3 shows the optical transmission spectrum of bare PET
No phases corresponding to fluorine were observed, which is in substrate with resin and several bare FTO films. These FTO films
accordance with other groups' work [11,13]. The mean crystallite size were deposited with spraying time of 10 min, 20 min, 35 min, 45 min
calculated using Scherrer equation [14] was around 30 nm. Fig. 1(a) and 60 min, which corresponded to the average transmittance of
shows the same diffraction peaks as Fig. 1(c), except peaks (110) and 81.3%, 72.5%, 64.6%, 60.9% and 57.2% respectively in the range of
(220) were covered by the strong diffraction peaks of PET substrate 400 nm to 800 nm. This result directly indicates that the average
that could be observed from Fig. 1(b). The XRD patterns indicate that transmittance of bare FTO films declined with longer spraying time,
the same crystal structure of FTO film could be obtained no matter the which caused increasing thickness of FTO films shown in Table 1.
film was transferred onto PET or glass substrate. Therefore, the decreasing transmittance was mainly due to the
Fig. 2 displays SEM micrographs of this FTO film on PET substrate. increasing thickness of FTO films. The average transmittance of bare
Fig. 2a shows the surface morphology of the FTO film, which seems PET substrate with resin was as high as 89.1%.
quite rough under lower magnification. Because the FTO film was first
deposited on the pretreated brass substrate, the roughness morphol- 3.3. Electrical properties
ogy was thereby copied from the surface morphology of the
pretreated brass substrate. Fig. 2b is the magnified image of the Table 1 shows the sheet resistances Rs of several different FTO films
central part of Fig. 2a. As Fig. 2b shows, the film was comprised of on PET substrate with different spraying time. The thicknesses d of the
many small grains with grain size between 20 nm and 50 nm, which is films were measured by cross-section images of SEM. The resistivity of
in accordance with the result from XRD. the corresponding film was calculated according to the formula:

Fig. 2. SEM micrographs of FTO film prepared on PET substrate with low and high magnification.
 X. Huang et al. / Materials Letters 64 (2010) 1701–1703
Fig. 4. (a) The movement of two ends of PET substrate in one folding cycle. (b) The sheet resistance increment ratio of FTO film with different pretreating time and ITO/PET after
different folding cycles.
ρ = Rs × d. It is seen that the resistivity firstly decreased and
then increased with longer spraying time. The lowest resistivity of
7.6 × 10− 4 Ω cm, which is comparable to literature values of conven-
tional FTO films deposited directly on glass substrate [15,16], could be
obtained when the spraying time was 20 min.
3.4. Flexible properties
Fold ability is a particular property for TCO on flexible transparent
substrate [17]. Therefore, it is necessary to evaluate the fold ability of
our FTO films on flexible PET substrates by measuring their sheet
resistance with respect to folding cycles. One folding cycle can be
described as follows: the distance between the two ends of PET
substrate varies from 6 cm (unfolding) to 2 cm (folding) and recovers
back to 6 cm (See Fig. 4a).
The preparation of these samples has been described in the
experimental procedure, except one difference: The pretreating time
of brass substrate in nitric acid was set as 0 min, 2 min, 4 min and 6 min,
respectively. The spraying time was fixed as 20 min according to the
above result. Before folding, the sheet resistance of these samples with
pretreating time of 0 min, 2 min, 4 min, and 6 min were 798 Ω/□,
39.7 Ω/□, 18.6 Ω/□ and 12.3 Ω/□, respectively, which indicates that the
sheet resistance would decrease significantly with rising pretreating
time of brass substrate. After the folding cycles, the sheet resistance
increased across the board. To better express the increment degree of
the sheet resistance after folding, here we define k(t) = Rs(t)/Rs(0),
where Rs(t) represents the sheet resistance after t times folding cycles.
Fig. 4b shows the result of how k(t) increased with folding cycles for
these four samples, as well as a commercial ITO coated PET (Tobi Co.,
OTEC, 113B-N125N, 13.5 Ω/□) for comparison. The result indicates that,
with rising pretreating time of brass substrate, the increment range of k
(t) becomes narrower, which results in better fold ability. When the
pretreating time was longer than 4 min, our samples achieve superior
fold ability than commercial ITO/PET. Especially, when the pretreating
time was 6 min, the sheet resistance of our sample only increased 10.5
times after 1000 folding cycles, while it only took 10 folding cycles to
increase 10.9 times for the sheet resistance of commercial ITO/PET.
4. Conclusions
High transparent and low sheet resistance FTO films were
successfully prepared on flexible PET substrate by combining spray
1703
pyrolysis and transferring techniques. Their structural, electrical,
optical and flexible properties were characterized, and these
reproducible results were discussed. The transmittance and sheet
resistance decreased due to the increasing thickness of FTO films
caused by rising spraying time. Resistivity as low as 7.6 × 10− 4 Ω cm
with a film thickness of 410 nm and an average transmission in visible
wavelength of 72.5% could be obtained when the spraying time was
20 min. The fold ability was improved significantly as the pretreating
time of brass substrate increased. When pretreating time was longer
than 4 min, our samples achieved superior fold ability compared to
commercial ITO/PET.
Acknowledgements
This work was supported by NSFC (Nos. 20725311, 20673141,
20703063, 20873178 and 20721140647) and the Ministry of Science
and Technology of China (973 Project, no. 2006CB202606 and 863
Project, no. 2006AA03Z341).
References
[1] Al-Ibrahim M, Roth HK, Zhokhavets U, Gobsch G, Sensfuss S. Sol Energy Mater Sol
Cells 2005;85:13–20.
[2] Fujikake H, Sato H, Murashige T. Displays 2004;25:3–8.
[3] Zhou LS, Wanga A, Wu SC, Sun J, Park S, Jackson TN. Appl Phys Lett 2008;88:
083502.
[4] Wong FL, Fung MK, Tong SW, Lee CS, Lee ST. Thin Solid Films 2004;466:225–30.
[5] Rakhshani AE, Makdisi Y, Ramazaniyan HA. J Appl Phys 1998;83:1049–57.
[6] Yang TL, Zhang DH, Ma J, Ma HL, Chen Y. Thin Solid Films 1998;326:60–2.
[7] Morris GC, McElnea AE. Appl Surf Sci 1996;92:167–70.
[8] Wang ZS, Yamaguchi T, Sugihara H, Arakawa H. Langmuir 2005;21:4272–6.
[9] Patil PS. Mater Chem Phys 1999;59:185–98.
[10] Huang XM, Zhang YD, Sun HC, Li DM, Luo YH, Meng QB. J Renew Sust Energ
2009;1:063107.
[11] Zhi X, Zhao GY, Zhu T, Li Y. Surf Interface Anal 2008;40:67–70.
[12] Rozati SM. Mater Charact 2006;57:150–3.
[13] Russo B, Cao GZ. Appl Phys A 2008;90:311–5.
[14] Cullity BD, Stock SR. 3rd Ed. Prentice-Hall Inc; 2001. p. 167–71.
[15] Moholkar AV, Pawar SM, Rajpure KY, Bhosale CH. Mater lett 2007;61:3030–6.
[16] Purushothaman KK, Dhanashankar M, Muralidharan G. Curr Appl Phys 2009;9:
67–72.
[17] Cairns DR, Witte RP, Sparacin DK, Sachsman SM, Paine DC, Crawford GP, et al. Appl
Phys Lett 2000;76:1425–7.