Thin Solid Films 518 (2009) 15901594

Contents lists available at ScienceDirect

Thin Solid Films

journal homepage: www. elsevier.com/locate/ts f

Glancing angle deposited titania lms for dye-sensitized solar cells

a

Hsiao-Yun Yang , Ming-Fu Lee , Chia-Hua Huang , Yu-Shi Lo , Yi-Jia Chen

a
b
c
d

a,d

, Ming-Show Wong

a,d,

Inst. of Electronics Engineering, National Dong Hwa University, Hualien, Taiwan

Dept. of Electrical Engineering, National Dong Hwa University, Hualien, Taiwan
Dept. of Chemistry, National Dong Hwa University, Hualien, Taiwan
Dept. of Materials Science and Engineering, National Dong Hwa University, Hualien, Taiwan

a r t i c l e

i n f o

a b s t r a c t

Available online 19 September 2009

A series of sculptured porous nano-columnar titanium oxide lms were prepared by glancing angle

Keywords:

deposition

Dye-sensitized solar cell (DSSC)

TiO2
Anatase
Porous lm
Sculptured lm
Glancing angle deposition (GLAD)

(GLAD) method using an electron-beam evaporation system. The lms were deposited on ITO glasses at
various
incident angles from 53 to 86and used as photoanode in a dye-sensitized solar cell (DSSC). The asdeposited
TiO2 lms are comprised of helical nano-columns and assembled in an orderly manner with gaps or

1. Introduction

pores in
between. The porous nanostructured lms provide a synergetic effect of high surface area, effective rou
te for
electron transfer, tight interfaces, and enhanced light trapping, which are all benecial for higher cell efc
iency.
The DSSCs incorporated with the GLAD lms of 4 m thick exhibited a high ll factor (FF) up to 0.77. The
TiO2 lm
deposited at an incident angle of 73 provides the largest internal surface area and the largest amount
of dye
absorption and results in the highest light conversion efciency of 2.78%.
2009 Elsevier B.V. All rights reserved.

region, and limited access to the entire internal surface [4 6]. Thus, it
is of
interest to DSSC technology to develop new and improved porous Ti
O2
Dye-sensitized solar cell (DSSC) has become a popular and
promising photovoltaic cell since its introduction by M. Grtzel in
1991,
because it is made of low-cost materials and is relatively easy to
prepare
[1,2]. A lot of progress has been made to increase the solar conv
ersion
ef ciency, reliability and fabrication cost of the cells through impr
ovement on photoanode, dye, electrolyte and counter electrode [1
6]. The
photoanode made of a high-bandgap semiconductor is used mainl
y for
absorption of dye and charge separation and transport, a
nd the
photoelectrons are provided by the photosensitive dye. C
harge
separation occurs at the surfaces between the dye, the semicon
ductor
and the electrolyte.

The photoanode is usually a ~10 20 m thick layer of sint

ered
titanium dioxide (TiO2 ) nanoparticles (NP) forming a highly por
ous
structure with an extremely high surface area, and serving as a scaff
old to
hold a large number of the light-absorbing dye molecules in a 3-D
matrix.
The photoanode is usually prepared with anatase TiO2 nanoparti
cles
about 20 nm in size by the doctor-blade method [7] following with
lowtemperature calcinations at about 450 C [1]. Light conversion ef ci
encies
up to 11.2% were reported with DSSCs incorporating TiO2 NP lm [
3].
Nevertheless, there are still rooms for improvement in the rando
mly
porous nanostructured TiO2 layer, including low porosity, lack of mat
erial

generality, tedious particle synthesis, low conductivity, low space nanostructures to further enhance the cell ef ciency.
charge
Recently, physical vapor deposition technique has been used t
o
deposit porous TiO2 thin lms with large surface area for use in DSS
Corresponding author. Department of Materials Science and Engineering, Nat C
and achieved decent conversion ef ciency [8 11]. The new met
ional
hDong Hwa University, Hualien, 974 Taiwan, ROC. Tel.: +886 3 8634206; fax: +
odology applied a so-called glancing angle deposition techniqu
886 3
e
8634200.
E-mail address: mswong@mail.ndhu.edu.tw (M.-S. Wong).
(GLAD) to prepare three-dimensional nanostructures of nanostructured columnar lms with controlled porosity and geometry [12
0040-6090/$ see front matter 2009 Elsevier B.V. All rights reserved.
17].
doi:10.1016/j.tsf.2009.09.026
By placing a substrate above a material vapor source at an obliq
ue
angle and rotating the substrate, various nanostructures can
be
prepared, such as porous nano-columnar lm, nanorod arrays
with
diff erent shapes, nanospring arrays, and even multilay
er
nanostructures.
In this study we used an electron-beam evaporation system
and
applied the GLAD method to prepare a series of highlyordered,
sculptured porous nano-columnar titanium oxide lms on ITO glasse
s
and used them as photoanode in the dye-sensitized solar c
ells
(DSSCs). We varied the glancing angle and lm thickness, and focus
ed
on the structure, crystallinity, dye absorption, and light-absorption
of
the lms, and their effects on the performance of DSSCs.
The
preparation, characterization, and implementation of porous titaniu
m
oxide layer in DSSCs are reported.
2. Experimental
The TiO2 thin lms were prepared in the electron-beam evaporation system assembled by Branchy Vacuum Technology Co.,
Ltd
(Toayuan, Taiwan) [18]. The distance between the regular horizont
al
H.-Y. Yang et al. / Thin Solid Films 518 (2009) 15901594

1591

rotation holder and the electron-beam evaporation source was

550 mm. An additional variable glancing angle substrate holder was
installed from the chamber sidewall and the distance between the
GLAD substrate holder and the normal of e-beam source is 260 mm.
The deposition ux is incident onto a substrate with a large angle ( )
with respect to the surface normal and the substrate is rotating. GLAD
produces columnar structures through the effect of shadowing during
lm growth, while the substrate rotation controls the shape of the
columns. In this technique, there are three parameters that determine
the morphology of the columns: the incident angle, the deposition
rate and the substrate rotation rate. The angle and rotation rate of the
GLAD holder can be adjusted in the ranges of 45 to 90 and of 0.05 to
8.6 rpm, respectively.
The chamber was evacuated by a mechanical pump (ALCATEL2033SD) and a cryo-pump (CTI-Cryo-Torr8) to a base pressure below
5
2
5.310 Pa. The substrates used were 1815 mm indium-tin oxide
(ITO) oxide coated, 0.5 mm thick soda lime glass with an as-delivered
resistivity of 7.0 /square. The TiO2 lms were deposited at
rutile TiO2 (99.99%) as a source material. The lm deposition r
350C
ate was
3
2.0 nm/s and controlled by a quartz crystal monitor. A dense TiO
maintained by quartz lamps in oxygen atmosphere(4.010 Pa)
using
2 lm of

200 nm thick as barrier layer was rst deposited using the

regular
substrate holder. Then, the samples were transferred to the GLAD
holder
rotating at a constant rate of 1 rpm for deposition of a porous TiO2
layer
of 4 m thick without subsequent calcination. A series of titanium
oxide
lms were deposited at four different oblique angles to the subs
trate
normal: 53, 65, 73, and 86, and they were assigned as Films
A, B, C
and D, respectively.
The lm structure and crystallinity were investigated by a Ri
gaku
D/MAX-2500 V 18 kW low angle X-ray diffractometer (XRD)
operating with Cu-K radiation at 40 kV and 150 mA. The lm morphol
ogies
were investigated using a eld emission scanning electron micro
scope
(SEM) of JEOL JSM-7000F. The optical absorption spectra o
f the
samples were measured by UV visible spectrometer of Jasco
V650 in a
wavelength region of 200~900 nm.
DSSC comprises a dye-coated TiO2 lm on a transparent
conducting glass substrate, a Pt-coated counter electrode, and a
redox
electrolyte. Before dye sensitization, the TiO2 lms were heated
on a
hot plate at 100 C for 10 min to get rid of water vapor. The lms
were
4
then immersed in a dye solution of 5 10 M of N719
(cis-bis
(isothiocyanato)bis(2,2 -bipyridyl-4,4 -dicarboxylato)ruthenium
(II)bis-tetrabutylammonium) (Ru 620-1H3TBA, Solaronix SA,
Switzerland) in ethanol and kept at 70 C for 24 h. The excess dye
of the
sample was removed by rinsing with ethanol and the sampl
e was
dried inside a vent hood. The dye-coated TiO2 lm was then
bonded
to a counter electrode prepared by sputtering a ~100 nm of plati
num
lm on a glass plate. A redox electrolyte of 0.1 M I 2 , 1.0 M
LiI and
0.5 M 4-ter-butylpyridine in acetonitrile was introduced into
the
inter-electrode space by capillary action. A clip was used to hold
the
sandwiched electrodes together. The DSSCs incorporated with Fi
lms
A, B, C and D as photoanode are designated as Cells A, B, C
and D,
respectively. The cells were illuminated with a class A xenon ar
c solar
simulator, which contains a 1000 W Xenon arc lamp. The curr
ent
voltage characteristics of devices were measured under the sta
ndard
conditions at 25 C with air mass 1.5 and power density of 100
0 W/
2
m . The solar simulator was calibrated with a referen
ce cell
calibrated by National Renewable Energy Laboratory [19]
. The

overall energy conversion ef ciency, , of a solar cell determi

nes its
performance. Three parameters are used to characterize s
olar cell
outputs including short circuit current, Isc, open circuit voltag
e, Voc,
and ll factor (FF). The FF is calculated from the ratio of the m
aximum
power point (de ned by the square of the I V curve) divided
by the
product of Isc and Voc . The maximum cell power output, Pm , i
s given
by Pm = FF Isc Voc. The energy conversion ef ciency is t
hen given
by Pm /Pin , where Pin is the total power input by the light incid
ent on
the cell [20].

densely-packed helical columnar structure. For the lms

deposited at
=65 and above, pores are clearly seen on the top surfac
6.
e and
empty spaces or gaps between the helical columns are obvious f
rom
3. Results and discussion
side view. The diameters of the helical columns and the separ
ation
Fig. 1 shows the XRD patterns of the GLAD TiO2 lms of Films A,
(gap) between them increase with increasing incident ang
le of
B,
deposition. It is evident from Fig. 2 that as the deposition an
C and D deposited at various incident angles. Most of the peaks in t gle is
he
increased from 65, 73 to 86 the diameter of the helical col
patterns could be assigned to the anatase phase of TiO2 in addition umns
to
increases and the gaps between the columns increases from ~15
the peaks from the ITO substrate. The intensities and positions of t nm,
he
~16 nm to ~56 nm, respectively. Thus, the effective surface area
peaks remain about the same except the width of the peaks. also
The
changes with deposition angle. The surface area of the lm contin
widths of the peaks become broader as gauged from the full width ues
at
to increase with deposition angle until all the columns be
half maximum (FWHM) of the (101) peak. The FWHMs of the (10 come
1)
isolated. Thereafter, the surface area decreases since the density
peaks increase from 0.64 to 0.81, when the incident angle is increas of the
ed
number of columns decreases due to increases in column size and
from 53 to 86, indicating a reduction of overall anatase crystallini gap.
ty.
It was reported that the effective surface area becomes maximu
Fig. 2 shows the FESEM micrographs of the top and crossm at
sectional
=~70 as a result of the competition due to the columnar forma
view of the GLAD TiO2 lms. The micrographs reveal a signi c
tion
ant
and due to the columnar spacing or gap [21,22].
difference between lms deposited at different incident angles fro
Fig. 3 shows the UV Visible absorption spectra of the asm
deposited
53 to 86. Under normal lm growth by vapor deposition method
TiO2 lms (solid line) and of the lms after dye absorption (do
s,
tted
the substrate surface is usually normal to the ux of source mater
line) as well as of the absorbed dye alone (inset). The spectra s
ial
how
( =0) and the typical resultant lm is of dense columnar structu two important characteristics. As the incident angle is increas
re
ed to
and with a packing factor over 90% [17]. With the increasing incide 86, the absorption edges of TiO2 lms red-shift to 450 nm, and at
nt
the
angle, the lm morphology changes and the lm porosity increas
same time, the absorption tails in visible region (400 700
1
es
cm )
due to the self-shadowing effect. Film A deposited at =53is st
becomes more intense. This phenomenon can be attributed to
ill
the
relatively dense from top view, but cross-sectional view reveal increasing lm porosity, crystallinity and defects. After the lms w
s a
ere
Fig. 1. XRD patterns of TiO2 lms deposited at various incident angles from 53to 8

1592

H.-Y. Yang et al. / Thin Solid Films 518 (2009) 15901594

Fig. 2. FESEM micrographs of the top and cross-sectional view of the TiO2 lms deposited at different incident angles of (a) 53, (b) 65, (c) 73 and (d) 86 from
53 to 86.

impregnated with the N713 dye, the absorption edges of a impregnation and from the difference of the two spectra we obtaine
ll the
d
spectra red-shifted further with higher levels of absorption tail. the net absorption by the absorbed dye alone (inset in Fig. 3).
This is
The
clearly due to the absorption of dye on the internal surface integrated light absorption by the as-deposited lms, by the
of the
lms
porous sculptured TiO2 lm. The dye which is present in the form absorbed with dye and by the dye alone as well as the normali
zed
of a
highly dispersed covering or as a shell on the surface of titania g light absorption by dye alone are tabulated in Table 1. Film D has th
e
rains,
is re ected in the UV Vis spectra as an intense, broad
largest light absorption of all, but Film C has the largest net li
ght
absorption in
the visible region. We have integrated the absorption be absorption by the absorbed dye. Film A has the lowest porosity an
d
tween
400 nm and 700 nm of the spectra of each lm before and afte absorbed the smallest amount of dye.
r dye
H.-Y. Yang et al. / Thin Solid Films 518 (2009) 15901594

1593

Fig. 3. UVVisible absorption spectra of the as-deposited TiO2 lms (solid

line) and of
the lms after dye absorption (dotted line). The inset is the net absorpt
ion by the
absorbed dye.

Table 2 provides the summarized results from cell character

ization

of DSSCs incorporating the GLAD TiO2 lms, and Fig. 4 sho

ws the
photovoltaic measurements used to generate the values in Ta
ble 2.
The cell performance of the DSSCs made of the GLAD TiO2 lms
varied
quite a lot with the incident angle of deposition. Cell C perf
ormed
signi cantly better than the rest of the cells in terms of short c
ircuit
current density Jsc and the overall solar conversion ef ciency
of the
cells. The open circuit voltage (Voc) is about 0.6 V and the ll fa
ctor is
above 71% for all the DSSCs. The maximum photovoltage obtai
nable
from this type of solar cell is dependent on the relative position
of the
conduction band edge (VCB) of TiO2 electrode and the redox pot
ential
of the electrolyte. All the lms were deposited at a relativel
y high
substrate temperature at 350 C, resulting in lms of com
parable
crystallinity and thus similar Voc. The same electrolyte was use
d in all
the DSSCs and should possess similar redox potential. Therefor
e, the
values of Voc for all the DSSCs are about the same.
The short circuit current densities (Jsc ) are quite different a
mong
the DSSCs. Cell C has the highest Jsc and followed by Cells D, B
and A.
The Jsc is directly linked to the amount of light absorb
ed and
converted by the cell, so it is in uenced mainly by the am
ount of
dye absorbed. However, the amount of light trapped and the qua
lity of
TiO2 photoanode that determines the electron diffusion ef cienc
y can
also affect Jsc . Photoanode of TiO2 in the anatase phase
of high
crystallinity will improve the transport of injected electrons, re
duce
recombination with the electrolyte and result in higher qu
antum
ef ciencies. The maximum Jsc of Cell C may be explained with r
egard
to the largest amount of adsorbed dye, since the amount
of dye
adsorbed will be proportional to the accessible surface area and
Film C
of the GLAD TiO2 layer provides the most accessible internal su
rface
area. The GLAD lms with connected open pores likely improv
e the
accessibility of the entire lm internal surface to the dye and t
o the
Table 1
The crystallinity of the GLAD titania lm and the integrated light absorption (ILA
) by the
lms, the lms absorbed with dye and the dye alone.
Film ID

Incident Angle

53

65

73

86

FWHM, An(101)
ILA of Film alone
ILA of Film+Dye

0.65
36.4
56.0

0.81
44
177

0.80
68
242.9

0. 81
196.5
308.3

ILA of Dye alone

Normalized dye absorption

19.6
0.11

133
0.76

174.9
1

111.8
0.64

Table 2
Photovoltaic characteristics of the DSSCs incorporating the GLAD TiO2 lms.

The overall ef ciencies of the DSSCs incorporated with the GL

AD
Film/Cell
A
B
C
D
TiO2 photoanode in this study were decided largely by their Js
c . As
Incident Angle
53
65
73
86
such, the cells with TiO2 layer annealed at higher temperatur
Voc (V)
0.59 (0.02)
0.64 (0.02)
0.62(0.01)
0.58(0
es to
.03)
enhance crystallinity and with thicker TiO2 layer to increas
2
Jsc (mA/cm )
2.2 (0.1)
3.9 (0.2)
6.0 (0.1)
5.4(
e the
0.3)
amount of dye absorption will likely increase Jsc values and the ov
FF%
71 (2)
72 (4)
74 (2)
77 ( 3)
erall
%
0.92(0.09)
1.81 (0.15)
2.78(0.08)
2.40(ef ciency. Indeed, we have prepared another series of GLAD TiO2
0.1)
lms
with various thicknesses from 4 10 m at incident angle of 86.
The
electrolyte, leading to a more direct path for the injected electro
lms were deposited at ambient temperature and subsequ
ently
ns.
Furthermore, the columnar nature of the GLAD lms provides a mor annealed at 350 C to optimize their crystallinity. The cell ef cien
cies
e
increase monotonically with TiO2 lm thickness up to 5.23% for
direct and shorter path for electron transfer. This result is consiste
the
nt
with the report by Taga et al. The results of their simulation and act 10 m thick lm and the results will be reported in another p
aper.
ual
preparation of GLAD TiO2 lms indicated that the effective surf Further improvement in cell ef ciency should be possibl
e by
ace
optimization of crystallinity, nanostructures, porosity and
area is enhanced by oblique deposition owing to columnar formatio
lm
n
and becomes maximum at a deposition angle of 70. The thickness of the GLAD TiO2 photoanode.
lms
deposited at 70 possess the maximum effective surface area and t
he
best photocatalytic performance [21,22].
The ll factors of the DSSCs are 71 77%, much higher than most
of
the reported values in literature [5,6]. As the ll factor is in uenced
by
the interfaces of the major components in DSSCs. Two of the interfac
es
are from the contacts between the TiO2 photoanode and
the
conducting electrodes of ITO and Pt. Since GLAD produces a w
elladhered and well-organized sculptured structure on the ITO layer
and
the top surfaces of porous TiO2 layer are relatively at which ensur
es
good contact with the other conducting electrode of Pt-coated
glass.
The tight interfaces between the TiO2 photoanode layer and the tw
o
Fig. 4. IV photovoltaic measurements of the DSSCs used to generate the values in
conducting electrodes contribute positively to a high ll factor.
Table 2.

1594

H.-Y. Yang et al. / Thin Solid Films 518 (2009) 15901594

4. Conclusions

nanostructures of semiconducting oxides created by GLAD can

be
Photoanode of sculptured porous nano-columnar titanium o further optimized systematically for DSSCs to achieve even hi
xide
gher
lms were successfully prepared by glancing angle deposition (G power ef ciencies.
LAD)
method and integrated into DSSCs. The photoanode of ordered po Acknowledgements
rous
nano-columnar TiO2 layer provides large surface area fo
Financial grant by Taiwan National Science Council under No. 96
r dye
absorption, fast electron transfer path, enhanced light trapping, 2221-E-259-010-MY3 and the use of core-facility of
Nanotechnology
and
tight interfaces to conducting electrodes and contributes to a hig Center in East Taiwan are acknowledged.
h ll
factor and an overall cell ef ciency. A wide variety of
porous

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[1] O'Regan, M. Grtzel, A low-cost, high-efciency solar cell based on dye-