NANO: Brief Reports and Reviews

Vol. 9, No. 6 (2014) 1450061 (8 pages)

© World Scienti¯c Publishing Company
DOI: 10.1142/S1793292014500611

SYNTHESIS, CHARACTERISTICS AND

APPLICATIONS OF ZnO NANOWIRES IN
DYE-SENSITIZED SOLAR CELLS VIA
WATER BATH METHOD

MUHAMMAD SALEEM*,†,‡, L. FANG†, M. ASHFAQ AHMAD*, RIZWAN RAZA*,

F. WU†, W. J. LI†, C. L. XU†, L. HU† and S. J. XUE†
*Department of Physics, COMSATS Institute of Information Technology
Lahore 54000, Pakistan
†StateKey Laboratory of Power Transmission and
System Security and New Technology
College of Physics, Chongqing University
Chongqing 400044, P. R. China
‡[email protected]

Received 19 March 2014

Accepted 9 April 2014
Published 5 June 2014

Zinc oxide (ZnO) nanowire (NW) ¯lms were synthesized at low temperature (95
C) through
amine-assisted solution process and used as photoanode for the fabrication of dye-sensitized solar
cells (DSSCs). It was found that with the addition of polyethyleneimine (PEI) and ammonium
hydroxide (NH4OH) in growth solution, the NWs were smaller in diameter and longer in length
by prolonging the growth time without refreshing the growth solution. A reasonable overall
conversion e±ciency of 1.25% was achieved with photoanode based on ZnO NWs containing PEI
and NH4OH. However, DSSC fabricated with ZnO NWs not containing PEI and NH4OH showed
low conversion e±ciency of 0.58%. All the DSSCs exhibited almost similar values of open circuit
voltage (VOC ) and ¯ll factor (FF). Interestingly, DSSC based on ZnO NWs with PEI and NH4OH
obtained two times higher short circuit current density (JSC ) compared to ZnO NWs photoanode
without PEI and NH4OH. The increase in e±ciency and JSC with the length of NWs is attributed
to the increase in internal surface area for su±cient dye loading and light harvesting.

Keywords: ZnO nanowire; polyethyleneimine; photovoltaic performance; dye-sensitized solar cell.

1. Introduction semiconductor solar cell e.g., p-n junction diode.1–7

During the past several years, harnessing solar en- Among the alternative approaches such as nano-
ergy on a large-scale with cheap materials and particles, nanotubes, nanobelts8–15 and nanowires
manufacturing methods has become an important (NWs),11,16,17 ZnO NWs are promising candidates for
challenge. For a decade, several new concepts for potential application in photodetectors, gas/chemi-
solar-to-electric energy conversion have been cal sensors, room-temperature ultraviolet lasing
reported to challenge conventional solid-state cavities and dye-sensitized solar cells (DSSCs).18–26

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M. Saleem et al.

Generally speaking, ZnO is an alternative material while allowing the growth of ZnO NWs at pre-
to TiO2 for improving the e±ciency in DSSCs due existing nuclei on seeded substrates.
to (1) the bandgap 3.2 eV2 at 298 K and conduc- In this study, ZnO NW arrays ¯lms were grown
tion band edge of ZnO is similar to that of TiO2 on °uorine-doped tin oxide (FTO) substrates by the
(anatase), (2) ZnO has a higher electron mobility simple, cost e®ective, low temperature solution-
 115–155 cm2/Vs27 than that for TiO2 which has based water bath method (liquid-phase chemical
been reported to be  10 5 cm2/Vs,28 which should process). The e®ect of growth time and the addition
favor electron transport. of PEI and NH4OH in growth solution on the
Although, PCEs 0.4–5.8% obtained for ZnO are structure, micro-morphology and energy conversion
much lower than the maximum reported 11.2% for properties in DSSC were discussed.
TiO2 in 2005.29 In order to achieve high power
conversion e±ciency, recently, the researchers have
tried to apply e®ective approaches to control the 2. Experimental Section
morphology (orientation, aspect ratio and density)
2.1. Preparation and characterization
of ZnO nanostructures which can signi¯cantly in-
crease dye loading and light harvesting30,31 and to of ZnO nanonwire arrays
modify the surface of ZnO nanostructure ¯lms that First, prior to the deposition, the F:SnO2 (FTO)
can suppress carrier recombination.26 One-dimen- substrates were ultrasonically cleaned in boiled soap
sional ZnO nanowires/nanorods have been synthe- solution, ethanol and then in acetone for 30 min,
sized by a wide range of techniques such as wet respectively. For the oriented seeds, 0.005 M zinc
chemical methods (liquid-phase deposition) gas- acetate dehydrate (Zn(CH3COO)2  2H2O) was
phase reactions and form-in-place processes. Com- dissolved in 60 mL of ethanol. The resultant solution
paratively speaking, wet chemical methods are was stirred magnetically at room temperature for
attractive for several reasons: simple, cost-e®ective, 30 min to ensure full and uniform mixing. The pre-
low temperature and thus capable of easy scaling cursor solution was spin-coated onto FTO sub-
up. However, major drawbacks in solution-based strates at 2000 rpm for 20 s. After each coating the
approaches are (1) ZnO forms, both on the seeded substrates were heated in a furnace at 100
C for
substrates through heterogeneous NWs growth and 10 min, then removed out from the furnace and
homogeneous nucleation of zinc oxide crystals in cooled down to room temperature for coating the
the bulk solution simultaneously. The formation of next layer. The procedure was repeated four times
homogeneous nucleation consumes zinc oxide pre- for uniform and dense seeding, after the ¯nal layer of
cursors rapidly and causes early termination on the the substrates were annealed at 350
C for 1 h to
seeded substrate. Therefore, reduction of the pre- convert zinc acetate to ZnO nanocrystals on the
cursor is inevitable and growth rate of wires surface of the substrates and these ZnO nanocrys-
decreases as reaction time increases. (2) The sub- tals were prerequisite for the growth of wires. Next,
strates are easily contaminated by the ZnO precipi- the growth solution consists of 0.025 M zinc nitrate
tate out of the bulk solution degrading the cell hexahydrate (ZNH), 0.025 M hexamethylenetetra-
performance. In order to obtain long and high den- mine (HMTA), 0.005 mM PEI (molecular weight
sity wires, the substrates must be repeatedly refre- 70 000 Aladin) and 0.4 M ammonium hydroxide
shed with new solution for several hours, which (NH4OH). ZnO NW arrays were grown by im-
makes it time consuming.24,25,32 (3) Moreover, the mersing vertically the seeded substrate with the
introduction of fresh solution not only increases the help of a clip in 60 mL of the growth solution. The
fabrication cost, but also decreases the reproduc- beaker was covered and then placed in a water bath
ibility, because ZnO seeds are easily destroyed by at 95
C for 4–12 h as shown in Fig. 1. For a com-
fresh growth solution involving hydrogen ions (H þ ) parison, we also prepared a sample without PEI and
in the initial growth stage due to low chemical sta- NH4OH, but with the same concentration of ZNH,
bility.33 In this situation, we have introduced a HMTA and growth temperature for 12 h. Finally,
coupled use of polyethyleneimine (PEI) and ammo- after the deposition, ZnO NWs grown on the sub-
nium hydroxide which prevents homogeneous nu- strates were thoroughly washed with distilled water
cleation, formation of ZnO particles in the bulk and annealed at 450
C for 30 min to remove any
solution and hence contamination of the substrates, residual polymer.

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 Synthesis, Characteristics and Applications of ZnO NWs in DSSCs

blade. The ¯lms were sensitized by immersing in dry

ethanol containing 0.3 mM of commonly used N-719
dye for 1 h to complete the dye adsorption and
sandwiched together and bonded with Pt-coated
FTO counter electrodes separated by 30 m hot-
melt surlyn ¯lm. Then the ¯lms were rinsed with
ethanol and acetonitrile to remove the additional
dye. The electrolyte solution consisting of (0.1 M LiI,
0.05 M I2, 0.06 M I, 2-dimethyl-3-n-propylimidazo-
lium iodide and 0.4 M 4-tert-butylpyridine in ace-
tonitrile) was introduced into internal space between
the two electrodes through one of the two predrilled
holes in the counter electrode by capillary force.
Fig. 1. Pictogram of water bath growth of ZnO NWs.
Afterward, these holes were covered and sealed with
a small square glass sealing sheet to prevent leakage
2.2. Material characterization of the °uid-type electrolyte.
The crystal structure of the ¯lms was characterized
by X-ray di®raction (XRD-Single Scan with Cu K

radiation,  ¼ 1:5406

A, 20 mA, 36 KV) from 20
to 3. Results and Discussion
80
at a scanning speed of 4
/min. The surface and 3.1. Structural characterization
cross section morphology of the ¯lms were observed of ZnO NWs
on scanning electron microscopy (FEG-SEM, Nova-
400). The thickness of the as-prepared ¯lms was Figure 2(a) shows the XRD patterns of the ¯lms
measured by a step pro¯ler (Dektak 150). Photo- grown on FTO substrate for deposition time of 4–
current–voltage (J–V) characteristics of the DSSC 12 h in the scan range of 2 ¼ 20
–80
. The XRD
was tested with a Keithley 2400 Source Meter using pattern displays only the strong (002) di®raction
simulated AM 1.5 G sunlight with intensity of peak, indicates that the NWs were oriented along
100 mWcm 2 . The UV-Vis absorbance spectrosco- the (001) crystallographic face (about c-axis),
py of the ¯lms was recorded by UV-3600 spectro- showing that PEI and ammonium hydroxide in
photometer. growth solution has no obvious e®ects on the struc-
ture of ZnO ¯lms because their structure is similar to
the sample 4 prepared without PEI and NH4OH for
2.3. DSSCs fabrication comparison. Besides, the intensities of the sample 2
To fabricate DSSCs, the resulting NW ¯lms were and sample 3 have increased to be comparable with
limited to 0.25 cm2 by removing extra NWs with a that of samples 1 and 4, once the samples were grown

(a) (b)
Fig. 2. (a), (b). XRD patterns of the ZnO Films 1–4 on FTO substrate.

1450061-3
M. Saleem et al.

Fig. 3. SEM images of the top views and cross section views for samples 1–4.

for a long period of time. In the studies by Lupan 5.2 m, 6.5 m, 3.2 m, respectively. To avoid pos-
et al.34 and Fujimura et al.,35 it is suggested that at sible variations at the top of zinc oxide NWs, the
ZnO (002) orientation, the surface energy reaches its diameters of NWs were measured below their top.
minimum value and the growth orientation develops Almost all ZnO NWs are vertically aligned with the
into one crystallographic direction of the lowest substrates and have uniform length. The densities of
surface energy. The (002) texture of the ZnO NWs ZnO NWs for samples 1–4 were 1.2 wires cm 2 ,
must form in an e®ective equilibrium state where 1.9 wires cm 2 , 2.1 wires cm 2 and 0:8  10 9 wires
enough surface mobility is given to impinging atoms cm 2 , respectively. From the resulting observations,
under a certain deposition condition.34,36 The we can conclude that the high density of the NWs
resulting observation can be inferred from SEM ob- achieved is attributed to the concentration of the
servation in Fig. 3. Figure 2(b) also shows the XRD reactants, such as HMTA and Zn(NO3)2.37 The
spectra of the ZnO NW arrays ¯lm around (002) density of NWs increased with Zn 2þ at low con-
planes. By comparing with standard powder value centrations and decreased with Zn 2þ at high con-
data (2 ¼ 34:43
) of the (002) peak, the (002) dif- centration levels. It was found that with the addition
fraction peak of the NW array ¯lms prepared with of PEI and NH4OH in growth solution, the NWs
and without PEI and NH4OH shifts to lower angle were smaller in diameter and longer in length by
34:12
as the growth time increased from 4–12 h, prolonging the growth time without refreshing the
indicating that there is a residual (uniform) strain in growth solution as compared with sample 4 prepared
the ¯lms. This residual strain is mainly attributed by without PEI and NH4OH, because the depleted
conventional Ostwald ripening mechanism, espe- Zn 2þ ions during the growth would be replenished
cially for the well-oriented seeds, since the seeds through the decomposition of PEI-Zn 2þ complexes38
share small lattice mismatch between the ¯lm and or under the mediation of NH4OH. However, Zn 2þ
the substrate (in-of-plane) because of the hexagonal could be stabilized through the reversible reaction
shape.37 given in Eq. (4). It was also found that the average
diameter ( 99 nm) of the NW arrays derived from
the solution with PEI and NH4OH was smaller than
3.2. Morphological characterization of
that ( 150 nm) of the sample 4 prepared in the
ZnO nanorods solution without PEI and NH4OH for 12 h. This may
Figure 3 displays the top view and the cross section be attributed that, when no PEI and NH4OH were
SEM images of samples 1–4. The mean value of di- added, large size NWs are formed by the direct
ameter is 134 nm, 116 nm, 99 nm, 150 nm and length combination of the neighbored crystals. Further-
of these ¯lms obtained by the step pro¯ler is 3.3 m, more, the length of the NWs produced from the

1450061-4
 Synthesis, Characteristics and Applications of ZnO NWs in DSSCs

solution without PEI and NH4OH was smaller than coupling between the excited dye and the surface of
that of the solution with PEI and NH4OH, because ZnO ¯lms. It can also be seen from Fig. 4 that the
more precipitate was formed during the NW growth samples with PEI and NH4OH show signi¯cant
when no PEI and NH4OH was added in growth so- improvement in dye loading as compared to that of
lution. Meanwhile, the spaces between the NW the sample without PEI and NH4OH (sample 4). It
arrays were enlarged by adding PEI and NH4OH. In indicates that the length of ZnO NWs with PEI and
other words, the surface area increased which is more NH4OH (sample 3) is larger than that of sample 4
bene¯cial for su±cient dye loading and light har- (without PEI and NH4OH), that is, a structure with
vesting. large density and spacing is obtained. Therefore, we
conclude that as the length and spacing of ZnO
NWs with PEI and NH4OH increases, more surface
3.3. UV-Vis absorption spectra of N719 area is available for the dye molecules anchoring and
dye adsorbed on ZnO NWs hence Jsc and e±ciency increase.
Figure 4 illustrates the UV-Vis absorption spectra
of four ZnO NW arrays ¯lms with dye sensitization.
They re°ect the di®erences in light harvesting ca- 3.4. Synthesis schemes for ZnO NWs
pabilities of the ¯lms. From the UV-Vis absorption In the typical solution-based water bath grown
spectra, it is clear that all the ZnO four samples process, following reactions are involved in the
exhibit an intrinsic absorption with similar absorp- growth of ZnO NWs.39
tion intensity around 390 nm which may be attrib-
uted to the electron transfer from the valance band ðCH2 Þ6 N4 þ 6H2 O ! 6HCHO þ 4NH3 ð1Þ
to the conduction band of ZnO semiconductor. NH3 þ H2 O $ NH þ
4 þ OH

ð2Þ
However, absorption in visible wavelength range of 
2OH þ Zn 2þ
! ZnO þ H2 O ð3Þ
400–800 nm varies signi¯cantly. Such absorption
originates from the dye molecules adsorbed on the Zn 2þ
þ 4NH3 $ ZnðNH3 Þ 2þ
4 ð4Þ
surface of ZnO and is related to the ¯lm structure. It
has the highest intensity for sample 3, less intensity Or
for samples 1 and 2, and the lowest intensity for Zn 2þ þ nNH3 $ ZnðNH3 Þ 2þ
n
sample 4. Their metal-to-ligand charge transfer
(MLCT) peak position centered around 521 nm in ðwhere n ¼ 1; 2; 3 or 4Þ
N719 dye, but a slight blue shifted due to electron
In the present study, ZNH was the precursor,
HMTA/NH4OH was used as the hydroxide source
and PEI was the surfactant. Generally, the solution-
based method uses a closed system that contains
limited amount of precursor solution. Additionally,
to the heterogeneous NWs growth on the ZnO seed
layer, there is also homogeneous nucleation of ZnO
crystals in the bulk solution. As the reaction pro-
ceeded, the formation of homogeneous nucleation
consumes ZnO precursors rapidly and causes early
termination of growth on the seeded substrate.
Therefore, reduction of the precursor is inevitable
and growth rate decreases as the reaction time in-
creases. In this situation, we have introduced a
coupled use of ammonium hydroxide and PEI to the
growth system in order to obtain long and dense
ZnO NWs. The complexes given in Eq. (4) formed by
ammonium hydroxide serve as bu®er layer for Zn 2þ
Fig. 4. UV-Vis absorption spectra of N719 dye adsorbed on ions. These complexes incessantly supplies Zn 2þ ions
ZnO NWs of samples 1–4. while lowering the degree of supersaturation of the

1450061-5
M. Saleem et al.

(a) (b) (c) (d)

Fig. 5. Schematic illustration for the fabrication of ZnO NW arrays (a) sample 1, (b) sample 2, (c) sample 3 and (d) sample 4.

reaction system. In other words, the zinc–ammonia 3.5. Solar cell performance
complexes gradually decomposed, thus, maintaining
Figure 6 illustrates photocurrent density (Jsc )–
a stable level of Zn 2þ in the solution. The use of
voltage (V) characteristics for DSSCs using ZnO
NH4OH and PEI substantially suppresses ZnO ho- NWs ¯lms deposited for di®erent time duration 4–
mogeneous nucleation process. Moreover, we ob- 12 h. Solar cell made from ZnO NWs containing PEI
served that in the presence of both PEI and NH4OH, and NH4OH in growth solution (growth time for
bulk phase nucleation can be e®ectively prevented 12 h) generates short-circuit current density ðJsc Þ ¼
while heterogeneous nucleation of ZnO wires still 2:88 mAcm 2 , open-circuit voltage ðVoc Þ ¼ 0:72 V,
grow on the seeded substrate more energetically. ¯ll factor ðFFÞ ¼ 0:59, and solar-to-electricity con-
The explanation is given by Law et al.25 and Greene version e±ciency ðÞ ¼ 1:25% which is very close to
et al.32 enlighten that the additive PEI preferentially that of 1.2% and 1.31% reported in Refs. 25 and 33.
adsorbs to certain crystal faces of clusters and pro- These results are remarkably improved to those
hibits further crystal growth along these faces. In the resulted from NWs cell not containing PEI and
case of homogeneous nucleation, at the initial NH4OH in growth solution (Jsc ¼ 1:46 mA/cm2,
growth stage ZnO clusters formed due to thermal Voc ¼ 0:69 V, FF ¼ 0:56 and  ¼ 0:58%). The pho-
°uctuation is so small that the polymer chain of PEI tovoltaic performance of this device is much lower
adsorbed to certain crystal faces is long enough to
cover other faces. As a result, the PEI chain which
acts as steric hinder prohibits the crystal growth
along all faces. Accordingly, the clusters have a little
chance to grow to the critical size that thermody-
namically favors the growth of crystals. However,
the pre-existing seed layers on the seeded substrates
are large enough in spite of PEI adsorption to certain
crystal faces.40 So the growth of ZnO NWs can
normally occur on the seeded substrates. Therefore,
the entire reaction nutrient only contributed to the
heterogeneous growth of ZnO NWs on the seeded
substrate, so that the growth could last for a long
time without replenishing the solution. From the
above discussion, we conclude that the coupled use
of PEI and NH4OH, the high density and long ZnO
NWs now may grow on the seeded substrates with-
out precipitation in the bulk solution, as shown in
Fig. 5. Fig. 6. Current density–voltage characteristics for samples 1–4.

1450061-6
 Synthesis, Characteristics and Applications of ZnO NWs in DSSCs

due to the lower NW density and insu±cient NW Acknowledgments

length. The PCEs for samples 1 and 2 have reached
This work was sponsored by the Fundamental
0.9% (Voc ¼ 0:74 V, Jsc ¼ 2:21 mA/cm2, FF ¼ 59%)
Research Fund for the Central Universities No.
and 1.07% (Voc ¼ 0:71 V, Jsc ¼ 2:47 mA/cm2, FF ¼
CDJXS10102207, the National Natural Science
60%), respectively. The improvement in PCE of
Foundationof China (Grant Nos. 11075314 and
NW cell with PEI and NH4OH comes from the in-
50942021) and Natural Science Foundation of
creased Jsc , however the Voc does not change much
Chongqing City under Grant CSTC, 2011BA4031.
with the length of NWs which may be attributed to
the presence of mid-gap states on the surface of
ZnO, or high electron mobility within the NW/NR
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