Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Improvement of ZnO nanorod-based dye-sensitized solar cell efficiency

by Al-doping
Sining Yun a,b, Juneyoung Lee a, Jooyoung Chung a, Sangwoo Lim a,n
a
Department of Chemical and Biomolecular Engineering, Yonsei University, 134 Shinchon-dong, Seodaemoon-gu, Seoul 120-749, Republic of Korea
b
School of Material Science and Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China

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

Article history: The current study investigates the performance of dye-sensitized solar cells (DSSCs) based on Al-doped
Received 17 March 2010 and undoped ZnO nanorod arrays synthesized by a simple hydrothermal method. Current density–
Received in revised form voltage (J–V) characterizations indicate that Al-doping in ZnO crystal structure can significantly
11 August 2010
improve current densities and the energy conversion efficiency (Z) of ZnO nanorod-based DSSCs. The
Accepted 29 August 2010
maximum Z, 1.34%, was achieved in DSSC when Al-doped ZnO nanorod arrays were grown in 0.04 M
zinc acetate dihydrate solution with 5 mM aluminum nitrate nonahydrate. This result represents a large
Keywords: increase of Z in Al-doped ZnO nanorod-based DSSCs as compared to undoped (0.05%). The improved
A. Nanostructures DSSC photovoltaic performance can be attributed to two main factors: (1) increased light harvesting
A. Semiconductors
efficiency due to a large amount of N719 adsorbed on the large surface area of Al-doped ZnO nanorod
B. Chemical synthesis
arrays, and (2) increased electrical conductivity due to A13 + ion doped into the ZnO lattice at the
D. Electrical conductivity
D. electrical properties divalent Zn2 + site, allowing electrons to move easily into the Al-doped ZnO conduction band.
& 2010 Elsevier Ltd. All rights reserved.

1. Introduction photoexcited electrons into the conduction band easier [4,10,11].

Dye-sensitized solar cells (DSSCs) have been reported to
challenge conventional solid-state photovoltaic devices based on
the p–n junction diode [1–6]. A typical DSSC consists of a
transparent conducting oxide (TCO) substrate, a dye-sensitized
semiconductor oxide layer, a liquid redox electrolyte, and a
Pt-coated counterelectrode [2–4,6]. DSSCs based on TiO2 nano-
particles have been widely investigated due to its high energy
conversion efficiency (Z) [6–9]. However, some disadvantages are
found in this case: (i) decreased TiO2 nanoparticle film thickness
decreases not only electron transport resistance but also the
surface area, and (ii) anisotropical growth of TiO2 with a very high
nanorod aspect ratio is difficult [9]. A key to the DSSC design is a
well-aligned and densely packed nanorod/nanowire arrays of
semiconductor oxide, which can provide both an effective path for
electron transport and a higher surface area for dye absorption
[3]. Therefore, the choice of the optimum semiconductor oxide to
obtain efficient light harvest has been a critical issue in fabricating
DSSCs.
Compared to TiO2, a ZnO semiconductor has a similar band gap
and electron affinity, making it a possible candidate for an
effective nanorod-based DSSC semiconductor. In particular, ZnO
has a higher electronic mobility than TiO2, making injection of
n
Corresponding author. Tel.: + 82 2 21235754; fax: + 82 2 3126401.
E-mail address: swlim@yonsei.ac.kr (S. Lim).
As a consequence, the Z for ZnO-based DSSCs is second to TiO2
[12–14]. DSSCs based on ZnO nanorods have been demonstrated
[1–4,10–15], and the different technologies, such as metal–
organic chemical vapor deposition (MOCVD) [2,3], hydrothermal
synthesis [1,4,14,15], vapor deposition [10,15], and other synth-
esis methods [12,13], have been employed to grow ZnO nanorod
arrays. Compared to hydrothermal growth with vapor deposition,
DSSCs based on ZnO nanorod arrays prepared using hydrothermal
growth exhibited a higher Z, which can be attributed to the higher
dye adsorption [15]. Moreover, low-temperature hydrothermal
synthesis requires a simple facility, no catalyst, and low cost
[1,4,14–17], which make the hydrothermally grown ZnO nanorod
arrays promising for the high-bendable and flexible DSSCs [18].
Especially, in order to enhance electrical and optical proper-
ties, group II, III, IV, V, and VI elements have been selected to dope
into the ZnO structure [19–32]. Al, a group III element, has been
regarded as one of the most representative dopants for forming
n-type ZnO with good optical quality, low resistivity, high
conductance, and high crystal quality [23–28]. While several
Al-doped ZnO nanostructures, such as nanodisks [25], nano-
spheres [26], and nanoparticles [28], have been synthesized by a
hydrothermal method, only a few investigations have been
carried out on the hydrothermally grown Al-doped ZnO nanorod
arrays. Furthermore, extended investigations on the effects of the
hydrothermally grown Al-doped ZnO nanorod arrays on the
photo-to-electric performance of DSSCs have not been conducted.
Based on the above mentioned some particulars such as the

0022-3697/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2010.08.020
 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731
preponderance of ZnO semiconductor for fabricating DSSC, the
advantage of low-temperature hydrothermal synthesis, and the
unique properties of ZnO nanorods by Al-doping, the aim of
this study is to improve the Z of ZnO nanorod-based DSSCs by
Al-doping and discuss a possible mechanism by which improved
photovoltaic performance is achievable.
2. Experimental section
2.1. Deposition of ZnO seed layer and pre-annealing
Al-doped ZnO nanorod arrays were synthesized using a
hydrothermal method at low temperatures to fabricate inexpen-
sive solar-to-electric conversion systems on TCO substrates. The
TCO substrates, including indium tin oxide (ITO) and fluorine-
doped tin oxide (FTO), are now the most widely used in DSSC
design. TCO substrates as an optical window determine the
amount of light that enters the device and as the electrode
extracts photocurrent. Because of increase in concerns about the
large-scale use in solar cells, the scarcity and high cost of indium,
and toxicity of tin oxide [2], FTO substrates were used in the
present study.
To grow well-aligned ZnO nanorod arrays by an aqueous
solution method, a ZnO seed layer was first deposited on FTO
glass substrates by 13.56 MHz radio frequency (RF) magnetron
sputtering at room temperature in ambient Ar using a ZnO target
with 99.99% purity. The sputtered zinc oxide seed layer has
several advantages, including easy thickness control, unfirom
morphology, and process repeatability. It has been found that pre-
annealing the seed layer significantly influences the properties
and growth of nanorod arrays [33,34]. Our previous research has
indicated that pretreating the seed layer at 300 1C for 1 h in a
reductive ambient (90% N2 +10% H2) at a pressure of 1 Torr gives a
high Z for DSSCs [35]. Therefore, after deposition, FTO substrates
were annealed using this pretreatment protocol. Then, the
substrates were rinsed with deionized water before they were
used to grow ZnO nanorod arrays.
2.2. Preparation of Al-doped ZnO nanorod arrays
So far, different counter-ions (NO3  ,SO24 þ ,CH3 COO , etc.) have
been used to prepare ZnO nanorod arrays using hydrothermal
method [20,25,26,32]. To establish the influences of the alumi-
num precursor and its concentration on the microstructural and
optical characteristics of the Al-doped ZnO nanorod arrays
synthesized in an aqueous solution, different combinations of
precursors (zinc and aluminum) were employed in our previous
research [32]. Based on the improved optical properties and the
increased densities of ZnO nanorod arrays by Al-doping, different
combinations of precursors are used in the present research to
investigate the effect of Al-doping on the cell performance.
Vertically aligned Al-doped ZnO nanorods were grown on an
FTO substrate using a hydrothermal aqueous solution process in a
synthesis solution with different Zn and Al precursors. The
hydrothermal solutions were synthesized as follows:
(i) 0.04 M zinc acetate dihydrate (Zn(CH3COO)2  2H2O, 99.0%,
Aldrich) was dissolved in 80 ml deionized water prepared
in a three-stage Millipore Milli-Q Plus purification system
with a resistivity higher than 18.2 M O cm. Ammonium
hydroxide (28 wt% NH3 in water, 99.99%, Showa) was
added to bring the pH to 10.3. To prepare Al-doped ZnO
nanorod arrays, either 5 mM aluminum nitrate nonahydrate
(Al(NO3)3  9H2O, 99.997%, Aldrich) or aluminum sulfate
1725
hydrate (Al2(SO4)3  xH2O, 99.998%, Aldrich) was dissolved in a
zinc acetate solution.
(ii) 0.03 M zinc nitrate hexahydrate (Zn(NO3)2  6H2O, 98%,
Aldrich) was dissolved in 80 ml deionized water and brought
to pH 10.3 with ammonium hydroxide (28 wt% NH3 in water,
99.99%, Showa). To prepare the Al-doped ZnO nanorod arrays,
either 5 mM aluminum nitrate nonahydrate or aluminum
sulfate hydrate was dissolved in a zinc nitrate solution.
Next, FTO substrates with a ZnO seed layer were immersed in
two different synthesis solutions heated to 60 1C for 6 h. The FTO
substrates in a Teflon holder were suspended with the surface
faced down in the solution. The FTO substrate was then removed
from the vessel and rinsed several times in deionized water. The
FTO substrate was finally dried at room temperature. Zinc nitrate
hexahydrate and zinc acetate dehydrate were the zinc precursors
for growing Al-doped ZnO nanorods, and are hereafter designated
as Zn:N and Zn:A, respectively. Aluminum nitrate nonahydrate
and aluminum sulfate hydrate were the Al sources, designated as
Al:N and Al:S, respectively. Al-doped ZnO nanorods grown in a
solution with different Zn and Al precursors are denoted in
shortened form, e.g., Zn:N +Al:S stands for the Al-doped ZnO
nanorods grown in a 0.03 M of Zn:N solution with 5 mM of Al:S.
In order to further investigate the effect of Al concentration on
the efficiency of DSSCs based on ZnO nanorod arrays, different
Al:N concentrations (2.5, 5.0, and 7.5 mM) were added to the Zn:A
solution. They are designated as Zn:A+Al:N (2.5 mM), Zn:A+Al:N
(5.0 mM), and Zn:A+ Al:N (7.5 mM). To characterize the electrical
properties of Al-doped ZnO nanorod arrays, nanorods were grown
on p-type Si wafers (r ¼0.05 O cm) in the presence of a ZnO seed
layer, and gold electrodes were deposited on the top surface of the
nanorods by thermal evaporation using a shadow mask. Part of
the ZnO seed layer was etched in a 5 wt% NH4Cl solution, so that
Si substrate was used as the bottom electrode.
2.3. DSSC fabrication
To fabricate DSSCs, Al-doped ZnO nanorod arrays were
immersed in 0.5 mM ethanolic solution of cis-bis (iso-
thiocyanato)bis(2,20 -bipyridyl-4, 40 -dicarboxylato)-ruthenium(II)
bis-tetrabutylammonium dye (N719) purchased from Solaronix
at room temperature for 1 h. A platinized conductive oxide glass
was prepared as a counterelectrode by sputtering, using a Pt
(99.99% purity) target in ambient Ar (99.999% purity) with RF
power of 100 W at room temperature at 5 mTorr. The substrate
with ZnO nanorod arrays and dye was bonded with a sputtered Pt
counterelectrode using a 50 mm-thick hot-melt spacer (grade
1702, Dupont). Sealing was accomplished by pressing the two
electrodes together at about 200 1C a few seconds. The redox
electrolyte, consisting of 0.5 M LiI, 50 mM I2, and 0.5 M
4-tertbutylpyridine in 3-methoxypropionitrile (Fluka), was then
introduced into the cell by capillary forces through a hole drilled
in the counterelectrode. Finally, the hole was covered and sealed
with a quickly solidifying epoxy polymer to prevent fluid-type
electrolyte leakage. The resulting active electrode area was
approximately 1 cm2. A schematic diagram of the ZnO nanorod-
based dye-sensitized solar cell is shown in Fig. 1.
2.4. Characterizations
The structures and morphologies of undoped and Al-doped
ZnO nanorods were studied using X-ray diffraction (XRD, X’pert
PRO, Philips) and a field-emission scanning electron microscope
(FESEM, S-4200, Hitachi). The binding energy level and chemical
structure of ZnO nanorod arrays were measured by X-ray
1726 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731

ABET-Technologies) under white light illumination (Xe arc lamp,

Al-doped ZnOnanorodswith absorbed dye- 1.5AM, 1000 W m  2). Two-point current–voltage (I–V) measure-
Sealed hole ments for the Al-doped ZnO nanorod arrays were conducted using a
probe station and an HP 4145B semiconductor parameter analyzer.
Liquid electrolyte All the measurements were performed at room temperature.

3. Results and discussion

3.1. Al-doped nanorod array growth and characterization

Load FESEM images, shown in Fig. 2, exhibit the morphologies of

ZnO nanorod arrays. All of the arrays were composed of oriented
nanorods approximately 1.5 mm in length (cross-section of the
oriented rod arrays not shown). The ZnO nanorod diameters are
not homogeneous (inset of top-view FESEM images) and are more
Light visible for the undoped ZnO sample (Fig. 2a and d). Most rods are
about 100 nm in diameter, but some are only 20–50 nm. Most
nanorods in Fig. 2a grow directly from the substrate surface. Fig. 2
also demonstrates that the nanorod arrays become better aligned
and densely packed after Al-doping. For Al-doped ZnO samples
shown in the insets of Fig. 2b, c, e, and f, the nanorods are about
50 nm in diameter. Individual nanorods with reduced diameters
nm mm

and identical lengths suggest an enlarged surface area after

Al-doping. Here, different morphologies are formed on the FTO
22

Glass substrate substrate. Some nanorods grow sideways and form flower-like
0
25

FTO(F:SnO2) bundles (Fig. 2a), belt-like bundles (Fig. 2b), and grass-like
clusters (Fig. 2c, e, and f). Therefore, it is difficult to quantitate
m m
m 0 n 50 0 µ

Pt-electrode the average diameter of nanorods from the number of nanorods

22 25 ~6 ~5

Electrolyte
m m n

Nanorods Spacer per mm2. FESEM images allow comparison of the number of
Dye (N719) ZnO seed layer nanorods per mm2 in Al-doped and undoped ZnO nanorod arrays.
Al-doped ZnO nanorod arrays are denser than undoped, again
ire

indicating a higher surface area of Al-doped ZnO nanorod arrays.

tw

FTO(F:SnO2)
ac

The increased surface area allows more dye to be loaded, thereby

nt

Glass substrate enhancing Z for the DCCSs. Dye loading was confirmed from the
Co

absorption spectra of dye N719, attached to Al-doped ZnO

(I) (II)
Al-ZnOnanorods
ZnO seed layer
FTO substrate
Fig. 1. The Al-doped ZnO nanorod-based dye-sensitized solar cell: (a) schematic
diagram of a DSSC, (b) device structure of an optimized tandem cell used in the
experiment, and (c) typical FESEM of a nanorod array on FTO. (I) Top–down FESEM
image of the oriented nanorod arrays. Scale bar: 300 nm, (II) cross-sectional FESEM
image of the oriented nanorod arrays. Scale bar: 1.5 mm. In this array, rod length
and seed layer thickness are approximately 1.5 mm and 650 nm, respectively.
photoelectron spectroscopy (XPS, Multilab 2000, Thermo VG
Scientific) with a monochromatic Al Ka radiation source at room
temperature. The influence of Al-doping on the optical properties
of the ZnO nanorods was studied using photoluminescence
spectroscopy (PL, IK3203R-D, Kimmon) with a 325 nm He–Cd
laser at 25 mW. The amount of adsorbed dye was determined
immersing 1 cm2 of Al-doped ZnO nanorod arrays into 1 mM KOH
(pH 11.30) for 30 min to desorb and fully deprotonate the
dye. The absorbance of the resulting solution was measured using
a UV–vis spectrophotometer (UV–vis, Optizen 2120, Mecasys
Corporation). The device photovoltaic characteristics were
measured by Sun 2000 Series Solar Simulators (Model 11000,
nanorod arrays.
Fig. 3 shows the XRD pattern of Al-doped and undoped ZnO
nanorods. Al-doped and undoped ZnO samples exhibited the
hexagonal wurtzite structure in correspondence with the JCPDS
database of card number 36-1451. The patterns are dominated
mainly by the (0 0 2) peak of wurtzite ZnO, implying that the
preferred orientation of Al-doped ZnO nanorods is along the
(0 0 2) direction. It should be noted that no additional diffraction
peaks, such as double oxide gahnite, were detected. It is clear that
the (0 0 2) peaks are located at 34.411 and 34.431 for undoped and
Al-doped ZnO nanorods on FTO substrates, respectively. That is,
Al-doping shifts the diffraction peak to a higher two-theta value
by 0.021, indicating that the lattice constant of the ZnO crystal
decreases when Zn2 + is partly substituted with Al3 + , consistent
with the radius of Al3 + (0.054 nm), as compared to Zn2 +
(0.074 nm). The full width at half maximum (FWHM), calculated
from Al-doped ZnO nanorod XRD patterns, was also slightly
smaller than that of undoped ZnO nanorods, which could be due
to the strain in the lattice by Al incorporation.
In previous research on Al-doped ZnO nanorod arrays grown
on a Si substrate [32], Al elements have been successfully doped
into the ZnO lattice. A logical assumption would be that Al
elements should be doped into the lattice of ZnO nanorods grown
on an FTO substrate when using the synthesis conditions
presented here (substituting Si substrate for FTO glass substrate).
XPS analysis confirmed this assumption, as seen in Fig. 4,
representatively for Al-doped ZnO nanorod arrays grown in
aqueous solutions with combination of Zn:A and Al:N precursors.
Al doped ZnO nanorod arrays were composed of Al, Zn, and O.
Peaks were observed at 1021.40 eV for Zn 2p3/2, 1044.60 eV for
 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731 1727

Fig. 2. Top–down FESEM images of Al-doped and undoped ZnO nanorod arrays grown in aqueous solution with different precursor combinations: (a) Zn:N, (b) Zn:N+ Al:S,
(c) Zn:N + Al:N, (d) Zn:A, (e) Zn:A +Al:S, and (f) Zn:A+ Al:N. Scale bars: 2 mm. The inset is the magnified top–down FESEM image. Scale bars: 500 nm.

Zn 2p1/2, and 74.50 eV for Al 2p. There is no significant difference

(002)

in the chemical shift and signal for Zn 2p3/2, Zn 2p1/2, and Al 2p

for all samples. The concentration of chemical element can be
calculated from the ratio of peak area to the atomic sensitivity
34.43° factor (A/S.F.) from XPS spectrum, and the atomic concentration of
aluminum is observed to be 3.04 at% in the present work.
Intensity (a.u.)

The O 1s peaks of the ZnO structure can be consistently fitted

from a high binding energy to a low binding energy by three
Gaussian components, centered at 532.40 70.15, 531.2570.20,
(103)

and 530.1570.15 eV, respectively [20,32,36,37]. Generally, the

Al-ZnO
(102)

(Zn:A+Al:N) component on the highest binding energy side of the O 1s spectra

can be ascribed to the presence of specific chemisorbed oxygen
ZnO (Zn:A) [37–39], which cannot easily be removed, even by annealing at a
34.41°
high temperature. The component with medium binding energy is
FTO
related to the O2  ions in the oxygen-deficient regions within the
matrix of ZnO [40], whose intensity partly represents the
variation in the concentration of oxygen vacancies. The compo-
20 25 30 35 40 45 50 55 60 65 70
nent on the lower binding energy side of the O 1s spectra is
2θ (degree)
attributed to the O2  ions on wurtzite structure of hexagonal
Fig. 3. XRD patterns of Al-doped and undoped ZnO nanorod arrays. The XRD Zn2 + ion arrays, surrounded by Zn (or substitutional Al) atoms
pattern of FTO substrate is also shown. with their full complement of nearest-neighbor O2  ions [36,41].
1728 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731

Zn 2p3/2
1021.40 eV

Intensity (a.u.)
Zn 2p1/2
1044.60 eV
Zn:N+Al:N

Zn:N+Al:S

Zn:N

Zn:A+Al:S

Zn:A+Al:N

Zn:A

1010 1020 1030 1040 1050 1060 300 400 500 600 700 800
Wavelength (nm)

Fig. 5. PL spectra of Al-doped ZnO nanorod arrays grown in aqueous solutions

Al 3.04 at.%
with different precursor combinations.
Intensity (a.u.)

Al 2p
74.50 eV The optical properties of the Al-doped ZnO nanorod arrays
were characterized by the room temperature PL measurements.
As shown in Fig. 5, a band edge emission at 376 nm and a deep
level defect emission at  557 nm, which are typical character-
istics of ZnO, are observed. Both Al-doped and undoped ZnO
nanorods showed PL emission characteristics similar to those of
broad visible emission. The broad emission at 557 nm has been
attributed to singly ionized oxygen vacancies (green emission) or
the interstitial oxygen ions (yellow emission) [42–44]. Emission
closer to 600 nm has been reported for the solution-grown
nanorods, associated with excess oxygen [45,46]. The actual
64 66 68 70 72 74 76 78 80 82 84 location and magnitude of these emissions depend sensitively
Measured on the synthesis conditions, pre-/post-annealing temperature,
O 1s
Fitted and pre-/post-annealing atmosphere. In the present research,
Zn-O (529.99 eV)
Al-O (530.47 eV) Al-doped ZnO nanorods with diameters about 50 nm showed a
green emission, possibly suggesting that ionized oxygen vacancies
are primarily at the ZnO nanorod array surface.

3.2. Nanorod-based DSSCs

Fig. 6 shows the current density–voltage (J–V) curves of the

529 530 531 532
Binding Energy (eV)
Fig. 4. XPS spectra of Al-doped ZnO nanorod arrays grown in aqueous solution
with combinations of Zn:A and Al:N precursors: (a) Zn 2p 3/2 and Zn 2p 1/2,
(b) Al 2p, and (c) O 1s spectra.
It can be found from Fig. 4(c) that the O 1s peak has been fitted by
four nearly Gaussian distributions. Each resolved component has
a full width at half maximum (FWHM) lower than 2.00 eV. From
the deconvoluted O 1s peak, one can determine a mixture of two
components on the lower binding energy side of the O 1s spectra
corresponding to Al–O (530.47 eV) and Zn–O (529.99 eV) bonds.
More detailed information on XPS spectrum of the undoped and
doped ZnO nanorod arrays can be also seen from our previous
researches [20,32].
ZnO nanorod-based DSSCs under AM 1.5G light illumination.
There is a spike at 0 V in the J–V characteristics of the DSSC, this
being due to the sensitivity of the measurement apparatus
because all samples show a spike at 0 V. The photoelectrochem-
ical properties of these electrodes are listed in Table 1; FF, Voc, and
533 Jsc are fill factor, open circuit photovoltage, and short-circuit
photocurrent, respectively. For the undoped ZnO nanorod-based
DSSC, Jsc, Voc, FF, and Z were 0.657 mA cm  2, 0.3208 V, 0.2590, and
0.05%, respectively. After Al-doping, the performance of DSSCs
based on ZnO nanorod arrays is improved greatly. As illustrated in
Fig. 6 and Table 1, Jsc, Voc, FF, and Z increase drastically after
Al-doping, and result in the maximum Jsc (8.857 mA cm  2) and Z
(1.34%). A large improvement in Z was obtained, as compared to
the undoped ZnO nanorod-based DSSC (0.05%). The Al-doped ZnO
nanorod-based DSSC has a higher FF than the undoped DSSC,
indicating that the Al-doped ZnO nanorod array exhibits more
efficient electron transport. And Al-doping increased Jsc signifi-
cantly more than FF.
It has been well known that the improved optical properties of
ZnO materials can be characterized by the ratio of the peak of the
UV emission to Vis emission (IUV/IVis). The relative intensity of UV
emission peak (IUV) and Vis emission peak (IVis) can be calculated
 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731 1729

11 0.35
Zn:N+Al:N (η=0.67 %)
10 Zn:N+Al:S (η=0.43 %)
Zn:N (η=0.03 %) 0.30
9
Current density (mA cm-2)

Zn:A+Al:N (η=1.34%)
8 Zn:A+Al:S (η=0.16 %) 0.25
Zn:A (η=0.05 %)
7

IUV / I Vis
0.20
6
5 0.15

4
0.10
3
2 0.05

1 0
Zn:N Zn:N+Al:S Zn:N+Al:N Zn:A Zn:A+Al:S Zn:A+Al:N
0
0 0.1 0.2 0.3 0.4 0.5 Combination of Al and Zn Precursors
Voltage ( V )
Fig. 7. The ratio of UV emission to visible emission for Al-doped ZnO nanorod
Fig. 6. Current density–voltage (J–V) characteristics for solar cells constructed arrays.
using Al-doped and undoped ZnO nanorod arrays.

0.24
Al-ZnO (Zn:A+Al:N)
Table 1
. Parameters of Al-doped ZnO nanorod array-based DSSCs (light intensity:
ZnO (Zn:A)
0.20
1000 W m  2).

Samples Jsc (mA cm  2) Voc (V) FF g (%) 0.16

Absorbance

Zn:N 0.607 0.1982 0.2561 0.03

Zn:N + Al:S 2.231 0.4971 0.3862 0.43 0.12
Zn:N + Al:N 5.064 0.4832 0.2723 0.67
Zn:A 0.657 0.3208 0.2590 0.05
Zn:A + Al:S 1.317 0.4575 0.2595 0.16 0.08
Zn:A + Al:N 8.857 0.4776 0.3172 1.34

0.04

from PL spectrum in Fig. 5. IUV is equal to the difference between

Imax and Io, where Imax and Io are the maximum (or Vis emission)
and the baseline of the intensity of UV emission (or Vis emission)
peak in Fig. 5, respectively. Fig. 7 shows UV–vis emission ratios
(IUV/IVis) of nanorods grown using the hydrothermal method. The
IUV/IVis of ZnO nanorod arrays prepared using different combina-
tions of Zn and Al precursors have been greatly increased after
Al-doping, indicating that the optical properties of ZnO nanorod
arrays have been improved by Al-doping. The best optical
properties were achieved in the case of Zn:A+ Al:N, as shown in
Fig. 7, which can be attributed to the better crystallized and
preferentially c-axis orientation of Al-doped ZnO nanorods grown
in a 0.04 M of Zn:A solution with 5 mM of Al:N [32], as shown in
the XRD patterns (Fig. 3). Al-doped ZnO nanorod arrays with the
best optical properties had the highest Z in the solar cells.
However, the Al-doped ZnO nanorods synthesized in aqueous
solution (Zn:A+ Al:S) with higher UV–vis emission ratios exhib-
ited lower Z, as compared to those synthesized in other aqueous
solutions (Zn:N+Al:S, Zn:N+ Al:N) (see Fig. 7 and Table 1). There-
fore, there is no simple correlation between the UV–vis emission
ratio and photovoltaic performance for Al-doped ZnO nanorod
samples. It is also further suggested that the relationship between
the properties of these nanorod properties and their photovoltaic
performance is comparatively complex.
Fig. 8 shows the absorption spectra of dye N719 attached to
Al-doped and undoped ZnO nanorod arrays. Upon adsorption onto
ZnO arrays, the dye N719 spectra have the same maximum values
around 505 nm. The absorption peak intensity of N719 from
Al-doped ZnO nanorod arrays is higher than undoped ones,
suggesting that more dye has adsorbed onto the Al-doped ZnO
nanorod arrays. Therefore, a higher Jsc and Z for Al-doped ZnO
0
400 450 500 550 600 650 700 750
Wavelength ( nm )
Fig. 8. Absorbance of the dye (N719) desorbed for Al-doped and undoped ZnO
nanorod arrays.
nanorod-based DSSC, as compared to the undoped, can be partly
ascribed to increased light harvesting efficiency as a result of a
large amount of N719 adsorbed on the Al-doped ZnO nanorod
surface area.
Two-point current–voltage (I–V) measurements substantiated
the effect of Al-doping on electrical conductivity in Al-doped ZnO
nanorod arrays. One simple relation pertaining to electrical
conductivity is discussed here:
1 A
¼r¼R ð1Þ
s L
where s is the electrical conductivity (O  1 m  1), r is the
electrical resistivity (r, O m), R is the electrical resistance (O), A
is the area of round gold electrodes 1 mm in diameter (m2), and L
is the length of the nanorod arrays (mm). Fig. 9 shows the I–V
curves through Al-doped ZnO nanorod arrays grown on p-type Si
substrate. All curves show an almost linear I–V relationship at a
certain voltage region, indicating barrier-free contacts between
nanorods and substrates. The electrical resistance (R) of the
nanorod arrays (the reciprocal of the slope) can be calculated from
the linear part of the experimental data by linear fitting. Table 2
shows that the calculated electrical resistance of Al-doped ZnO
nanorod arrays decreases as the Al:N concentration increases.
L can be calculated from cross-sectional FESEM images of the
1730 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731

Al-doped ZnO nanorod arrays grown on a p-type Si substrate. The
corresponding electrical resistivity (r) and electrical conductivity
(s) of the nanorod arrays, presented in Table 2, can be calculated
using Eq. (1).
Compared to pure ZnO nanorod arrays with an electrical
conductivity of 4.9225  10  5 O  1 m  1, the Al-doped ZnO na-
norod arrays show a significant increase to 3.2275  10  4 O  1
m  1 when the Al:N concentration increases to 7.5 mM. The
trivalent A13 + ion, acting as a donor dopant in the ZnO lattice
(testified by XPS spectrum in Fig. 4) will occupy the divalent Zn2 +

ion site (AlZn ), allowing electrons to easily move to the conduction
band of Al-doped ZnO nanorod arrays. The corresponding defect
equation is described as follows:
ZnO 
Al2 O3 !2AlZn þ 6OO þ V 00 Zn
This doping can increase the net electron concentration and
thus increase the electrical conductivity. Table 2 shows that the
electrical conductivity of Al-doped ZnO nanorod arrays increases
with increase in Al:N concentration. The increased electrical
conductivity of ZnO nanorod arrays after Al-doping helps the
Zn:A+Al:N (7.5 mM)
0.02
Zn:A+Al:N (5.0 mM)
Zn:A+Al:N (2.5 mM)
Zn:A
Linear Fitting
0.01
Current (mA)
electrons to move to the conduction band, resulting in improved
DSSC performance.
For the improved performance of DSSC based ZnO nanorod
arrays by Al-doping, two reasons should be addressed here: first,
as discussed previously, the increased Z in ZnO nanorod-based
DSSCs after Al-doping can be ascribed to increased light harvest-
ing efficiency due to a large amount of N719 adsorbed on the
nanorod array surface. And second, the increased Z of Al-doped
ZnO nanorod-based DSSCs may result from increased electrical
conductivity, which allows electrons to move to the conduction
band of Al-doped ZnO nanorod arrays more easily.
As mentioned in the introduction, there are many methods to
fabricate ZnO nanostructure-based DSSCs [1–4,10–15,47–51], but
the performance strongly depends on the fabrication method, the
ð2Þ aspect ratio of component nanorods, and their array structures
[1,2,12,14,48,49]. The DSSC using Al-doped ZnO nanorod arrays
synthesized in a 0.04 M Zn:A solution with 5 mM Al:N as the
photoelectrode showed the best Z (1.34%) as compared to
Al-doped ZnO nanorod arrays synthesized in other solutions
such as Zn:N +Al:S, Zn:N+Al:N, and Zn:A+ Al:S. An Z of about
0.03–0.05% (see also Table 1) is still lower than those reported in
Table 3 for ZnO nanorod-based DSSCs. Moreover, FF is also rather
low compared to other DSSCs listed in Table 3. Low Z is partially
attributable to low surface area. The aspect ratio (about 100 nm in
diameter and 1.5 mm in length) of undoped ZnO nanorod arrays
synthesized at 60 1C for 6 h for one growth cycle in the present
research is much lower than those listed in Table 3 (more growth
cycles are used in other reports resulting in the length of an
individual nanorod up to 25 mm). Compared with Table 1, increase

in the length while decrease in the diameter of an individual

0.00 nanorod (diameter: lager than 100 nm, length: much high than
Au 1.5 mm) will enlarge the electrode surface area, which may
Electrode increase the dye loading and enhance Z and FF in Table 3.
Although Z cannot be directly compared among DSSCs due to
-0.01
Nanorod differences in the active layer thicknesses and morphologies, some
arrays
useful information can be obtained from comparing Tables 1 and 3:
Seed layer
(i) Al-doping remarkably improves the Z of DSSC ZnO-based
-0.02 Si substrate
nanorods, (ii) the Z of the dye-sensitized ZnO nanorod array
electrode is much higher when nanorod aspect ratio (length and
-0.6 -0.3 0.0 0.3 0.6
diameter of nanorod) is controlled by the synthesis conditions, such
Voltage (V)
as by increasing synthesis temperature, extending the soak time,
Fig. 9. The measured current–voltage (I–V) curves of Al-doped ZnO nanorod and increasing the number of hydrothermal synthesis cycles.
arrays grown on a p-type Si substrate. Increasing the aspect ratio, that is, increasing the length while

Table 2
Electrical properties of Al-doped ZnO nanorod arrays grown on a p-type Si substrate.

Samples Length (L, lm) Resistance (R, X) Electrical conductivity (r, X  1 m  1) Electrical resistivity (q, X m)

Zn:A 1.6 4.1303  104 4.9225  10  5 2.0315  104

Zn:A + Al:N (2.5 mM) 3.7 2.1979  104 2.1735  10  4 4.6009  103
Zn:A + Al:N (5.0 mM) 4.4 1.8162  104 3.0995  10  4 3.2263  103
Zn:A + Al:N (7.5 mM) 2.9 1.1458  104 3.2275  10  4 3.0983  103

Table 3
Comparison of DSSC characteristics based on ZnO nanorod arrays synthesized using the hydrothermal method. N719 dye was used for all references here.

Substrate Diameter (nm) Length (lm) Voc (V) Jsc (mA cm  2) FF g (%) Area (cm2) Light intensity (W m  2) Refs.

ZnO/FTO 200 25 0.71 5.85 0.38 1.5 0.8 100 [4]

ZnO/FTO n.a. 3.5 0.76 1.17 0.25 0.22 0.385 1000 [15]
ZnO/FTO 155 8.0 0.67 1.30 0.32 0.3 0.5 1000 [42]
TiO2/FTO  200 4 0.66 6.17 0.36 1.46 0.2 1000 [47]
ZnO/PET/ITO  190 7 n.a. n.a. n.a. 0.9 0.3 100 [18]
ZnO/FTO n.a. 8 0.652 1.02 0.287 0.2 900 1000 [48]
ZnO/FTO  200  11 0.63 4.5 0.36 1.0 0.4 1000 [36]

*n.a.: not available. PET: plastic polyethylene terephtalate.

 S. Yun et al. / Journal of Physics and Chemistry of Solids 71 (2010) 1724–1731
decreasing (or not changing) the diameter of an individual nanorod
suggests enlarging the electrode surface area, which could increase
the dye loading and enhance Z. Actually, it has been shown that a
higher Z can be obtained by regulating the nanorod aspect ratio
[1,14,47], modifying the array structures (like the branched
nanowire [48] or hybrid nanowire-nanoparticle [49,50]), adopting
other dyes (like C217 [55] and N3 [14]), or fabricating a ZnO–TiO2
composite photoanode [51,52]. Al-doped ZnO nanorod arrays in the
present research possess the potential to significantly improve Z by
taking the measures mentioned above. On the other hand, the dye
and electrolyte employed both in the present research and in ZnO-
based DSSC studies reported previously are directly adopted from
TiO2-based DSSC research, which may be not appropriate for ZnO
material. For many realistic applications, to fabricate large-area,
well-aligned, single-crystalline ZnO nanorod arrays with optimum
aspect ratio, good uniformity, and narrow size distribution by a
simple low-cost and low-temperature hydrothermal synthesis still
remains a great challenge.
4. Conclusions
The photovoltaic performance of DSSCs prepared with Al-doped
ZnO nanorod arrays grown on FTO glass by a simple hydrothermal
method was investigated. Al-doping and the resulting optical and
electronic properties of the nanorod arrays play a significant role in
the photovoltaic performance. Al-doping significantly improved the
energy conversion efficiency of ZnO nanorod-based DSSC in ZnO
structure. There is no single correlation between the UV–vis
emission ratio and photovoltaic performance. The trivalent A13 +
ions doping into the ZnO lattice occupied the divalent Zn2 + ions
sites, causing a net increase in the electron concentration, and thus
increase in the electrical conductivity of ZnO nanorod arrays. The
improved cell efficiency in ZnO nanorod-based DSSC after Al-doping
can be generally ascribed to two main factors: (1) increased light
harvesting efficiency due to a large amount of N719 adsorbed on the
Al-doped ZnO nanorod surface area arrays, and (2) increased
electrical conductivity due to A13 + occupying the divalent Zn2 +
site, which allows electrons to move easily into the Al-doped ZnO
conduction band.
Acknowledgments
The authors acknowledge the financial support through the
second-stage Brain Korea 21 Program by the Ministry of
Education, Science and Technology. This work was also supported
by Priority Research Centers Program through the National
Research Foundation of Korea (NRF) funded by the Ministry of
Education, Science and Technology (2009-0093823).
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