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Synthesis of nanocrystalline ZnO powder via

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Article in Solar Energy Materials and Solar Cells December 2008
Impact Factor: 5.34 DOI: 10.1016/j.solmat.2008.07.015

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ARTICLE IN PRESS
Solar Energy Materials & Solar Cells 92 (2008) 16391645

Contents lists available at ScienceDirect

Solar Energy Materials & Solar Cells

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

Synthesis of nanocrystalline ZnO powder via solgel route for dye-sensitized

solar cells
Seema Rani a, Poonam Suri b, P.K. Shishodia c, R.M. Mehra a,
a
b
c

Department of Electronic Science, University of Delhi South Campus, New Delhi 110 021, India
Deen Dayal Upadhayaya College, University of Delhi, New Delhi 110 015, India
Department of Physics & Electronics, Zakir Husain College, University of Delhi, New Delhi 110 002, India

a r t i c l e in fo

abstract

Article history:
Received 31 March 2008
Received in revised form
17 July 2008
Accepted 28 July 2008
Available online 6 September 2008

This paper reports the growth mechanism of solgel-derived nanocrystalline ZnO powder. The inuence
of pH value of the sol on the crystallite size, morphology and structure of ZnO powder was investigated
by using X-ray diffraction, transmission and scanning electron microscopy. Maximum size nanocrystallite (14 nm) of ZnO powder was obtained for pH value of 9. An increase in the band gap (blue shift)
was observed with decrease in the size of the ZnO nanocrystallites. The variation in band gap was found
to be in agreement with theoretical calculations using effective mass model. The growth mechanism of
ZnO particles from zinc acetate dihydrate precursor by the solgel process has been discussed in terms
of solvation, hydrolysis and polymerization. The synthesized ZnO powders were successfully used as the
electrode material for dye-sensitized solar cells.
& 2008 Elsevier B.V. All rights reserved.

Keywords:
Solgel
pH
ZnO nanocrystallites
Dye-sensitized solar cell

1. Introduction
ZnO, a wide band gap semiconductor with a large exciton
binding energy of 60 meV at room temperature, has high
transmittance and good electrical conductivity [1]. ZnO, in thin
lm form, is extensively used for various applications such as gas
sensors [2], transparent electrode for solar cell window [3,4]. It is
one of the potential semi-conducting materials in solar energy
conversion due to its stability against photocorrosion and photochemical properties [5,6]. Recently, ZnO (in powder form) is being
used in the fabrication of third-generation solar cells namely; the
dye-sensitized solar cells (DSSCs). ZnO is expected to be an
alternating material for TiO2 [7]. Rensmo et al. [8] obtained high
overall solar energy conversion efciency of 2% for Ru (II) complex
sensitized photo-electrochemical DSSC having electrode of nanostructured ZnO powder. One of the factors which control the
efciency of a DSSC is the nature and size of the ZnO powder [9].
A number of investigations on the synthesis of ZnO nanoparticles have been reported in the literature [1015]. There have
been several reports of solution-phase synthesis of ZnO nanoparticles at low temperature. The synthesis of these particles is
mainly based on the alcoholic hydrolysis of zinc precursors
[16,17], hydrothermal methods [18] and electrochemical routes
[19]. Among these techniques, the hydrolysis route is very

 Corresponding author. Tel.: +9111 24115849; fax: +9111 24110876.

E-mail address: rammehra2003@yahoo.com (R.M. Mehra).

0927-0248/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2008.07.015

attractive because it is relatively easy to perform and allows us

to tailor the morphology of the particles by controlling the rate of
hydrolysis and condensation reactions [20].
Spanhel and Anderson [17] have explained the synthesis of
nanocrystals of ZnO using distillation set-up starting with product
of zinc acetate and ethanol. They have obtained highly concentrated colloidal nanocrystals of ZnO of size varying from 3.5 to
5.5 nm. Hossain et al. [21] have further modied this technique to
obtain nanobelts of ZnO of length 700 mm using reuxing
technique. Several workers have used capping agent such as vinyl
pyridine (PVP), polyethylene glycol (PEG), etc. to stop particle
agglomeration and obtained nanoparticles of size less than 5 nm
[22,23].
Much research has been focused on the preparation and the
properties of ZnO nanocrystals; however, little of it dealt with the
pH effect of the sol on the crystallite size of ZnO powder. For
instance, Li et al. [24] concluded that the solution conditions have
a certain effect on the particle size of ZnO powders under
hydrothermal conditions. Zhang et al. [25] found that the pH value
can change the quantity of ZnO nuclei and of growth units. Lu and
Yeh [26] found that the characteristics of ZnO powder profoundly
depend on the pH of the starting solutions. In addition the
crystallinity and particle size of ZnO powder increase with a rise
in the pH of solution.
In this work ZnO powder was synthesized using solgel route.
Zinc acetate dihydrate was used as a precursor due to easier
control of hydrolysis. The pH value of sol was varied from 6
(acidic) to 11 (basic). The size and crystallinity of the powder was

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S. Rani et al. / Solar Energy Materials & Solar Cells 92 (2008) 16391645

found to depend strongly on the pH value of sol. The absorbance

of the powder in the visible region was measured and compared
with the theoretical results using effective mass model [27].
Typical currentvoltage characteristics of DSSCs made using the
above-synthesized powder were reported.

energy-dispersive X-ray (EDX) measurements. The absorbance of

the powder in the visible region was measured using Shimadzu
UVVISNIR spectrophotometer (SolidSpec-3700).

2.2. Preparation of ZnO electrodes and measurement of IV

characteristics
2. Experimental

Intensity (a.u.)

(102)

(101)

1000
500
0

(002)

(100)

The ZnO sols were prepared by dissolving zinc acetate

dihydrate (99.5% (CH3COO)2Zn  2H2O, Merck) in methanol at
room temperature. A clear solution of 0.2 M was obtained by
ultrasonic magnetic stirrer at 25 1C for 120 min. The sol prepared
was found to be stable and transparent with no precipitate or
turbidity. ZnO powders were prepared by varying the pH value of
sol from 6 to 11. The pH value of the sols was adjusted to the
desired value using sodium hydroxide (0.1 N NaOH, Merck)
solution. The modied sols were stirred ultrasonically for 60 min
at room temperature. The clear solution was ltered through
micron lter paper. The resulting transparent lterate was kept for
48 h to complete the gelation and hydrolysis process. During this
period of time, white ZnO precipitates were slowly crystallized
and settled down in the bottom of the ask. The white precipitate
was ltered and washed with excess methanol to remove the
starting materials and dried at 120 1C for 2 h. The acidic nature of
the sol (p6) prevents the easy precipitation of ZnO powder at
room temperature [28].
A detailed elucidation of the structure and composition was
carried out by various characterization techniques. X-ray diffraction (XRD) of the samples was obtained using a (Philips analytical
Model no. -PW1830) having CuKa incident beam (l 1.54 A). The
crystallite size was determined by XRD peak broadening. The
crystallite size calculated from the broadening of diffraction peak
was conrmed by transmission electron microscope (TEM)
(Morgagni-268D, 80 kV). The surface morphology and size of
ZnO particles were also analyzed by using the scanning electron
microscope (SEM) (LEO 435 Vp, variable pressure SEM, Cambridge
UK). Quantitative analysis of constituents was carried out by

DSSCs were fabricated using the synthesized ZnO powder. The

porous ZnO lms were deposited on indium-tin-oxide (ITO)coated glass substrates by doctor blade technique. The substrates
were cleaned using acetone, methanol and distilled water in
sequence in an ultrasonic bath. ZnO powder (1.2 g) was ground by
a mortar and pestle with 4 ml deionized water, and polyethylene
glycol (PEG20,000, 0.5 g) to break up the aggregated particles into a
dispersed paste. The paste was spread on the surface of
conducting substrate with a glass rod, using an adhesive tape as
spacers. After drying in air, the lms were sintered for 30 min at
400 1C in air. The resulting lms were immersed in a 3.0  104 M
solution of Eosin-Y dye in ethanol for 24 h. To minimize
adsorption of impurities from moisture in the ambient air, the
electrodes were dipped in the dye solution while they were still
warm (80 1C). The dye-covered electrodes were then rinsed with
ethanol to remove excess dye on the surface and dried at room
temperature. A sandwich-type DSSC was fabricated with the dyesensitized ZnO electrode, a thin platinum sheet as counter
electrode, a spacer and an electrolyte.
The gel electrolyte was prepared as follows: 4 ml of tetraethyl
orthosilicate (TEOS), 0.4 ml of glacial acetic acid and 0.5 ml of
water were mixed together and sonicated for 15 min 0.3 ml of
PEG6000 was then added and sonication continued for more
10 min. In the resulting mixture, 7 ml of redox electrolyte
containing 0.03 g NaI, 0.003 g I2, 0.15 g ethylene carbonate:propylene carbonate 1:1 in 25 ml acetone, was added. Low-molecularweight PEG was used for both good mechanical strength and good
ion transfer. This gel electrolyte turned viscous on 15 min
sonication. The above-prepared dye-coated ZnO lm electrode
was immersed in the gel electrolyte for 10 min prior to dip
coating, the back of the ITO was masked with insulating tape in
order to prevent contact with the gel electrolyte. The dip-coated

(110)

2.1. Preparation and characterization of powder

11 pH

1000
500
0

10 pH

1000
500
0

9 pH

1000
500
0

8 pH

1000
500
0

7 pH

1000
500
0

6 pH
20

30

40
2 (deg.)

50

60

Fig. 1. XRD pattern of the nanosized ZnO powder synthesized using sol having different pH value.

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electrode was kept in a clean dish in slanting position and excess

solvents were removed from sides. The ZnO electrode coated with
gel electrolyte was then sandwiched by simple hand pressure onto

1641

a Pt-sheet as counter electrode. IV characteristics of the cell were

recorded using a Keithley source meter (Model 2400) with a
100 mW W lamp as the light source. The active electrode area was
typically 1 cm2.

15
3. Results and discussion

14

crystallite size (nm)

13

The XRD patterns of all samples of ZnO powder obtained at

different pH value are shown in Fig. 1. The powders showed the
crystalline nature with peaks corresponding to (1 0 0), (0 0 2) and
(1 0 1) planes. The preferred orientation corresponding to the
(1 0 1) plane is observed for ZnO powders. The spacing values and
relative intensities of the peak coincide with the JCPDS Card no.
36-1451 for ZnO powder. Crystallite size D was obtained by
measurements of the broadening of diffraction lines and applying
the DebyeScherrer formula [29]

12
11
10
9

6
6

10

11

pH
Fig. 2. Variation of crystallite size of ZnO powder synthesized using sol having
different pH value.

0:94l
b cos y

(1)

where l is the wavelength of CuKa radiations (1.54 A), b the fullwidth at half-maximum of the peak corresponding to the plane
/1 0 1S and y the angle obtained from 2y value corresponding to
maximum intensity peak in XRD pattern. The diameter of
crystallite size of obtained ZnO particles was varying from 6 to

110
102
100
002
101

Fig. 3. TEM images of ZnO powder prepared at: (a) 7 pH, (b) 8 pH, (c) 9 pH, (d) 10 pH and (e) 11 pH.

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Eg Ebulk

g
Ebulk
g

_2 p2
2er 2

1
1

me mh




1:8e2
4p0 r

(2)

is the bulk energy gap, r is the crystallite radius, me is

where
the effective mass of the electrons, mh is the effective mass of
holes, e is the relative permittivity, e0 is the permittivity of free
space, _ is Plancks constant divided by 2p, and e is the charge of
the electron. For ZnO, Ebulk
3.35 eV, me 0.24mo, mh 0.45mo,
g
where mo is the free electron mass and e 8.656.
Fig. 5 shows a plot of the band gap variation with the size of
nanocrystallites. The solid curve shows the theoretical results of
Eq. (2) and the points (*) represent the band gap values as
determined from absorption measurements. For theoretical
calculations, the values of r have been taken from the XRD data.
It is noticed that the band gap measured from absorption spectra
closely coincides with the theoretical results.
Fig. 6(af) shows SEM images of ZnO powder at different pH
value. The SEM images clearly show microstructural homogeneities and remarkably different morphology for ZnO powder
prepared with different pH value of sol. The diameter of ZnO
particles as seen in Fig. 6(df) is 1 mm which is much larger than
crystallite size determined by XRD and TEM analysis. It is
envisaged that the micron size particles as seen by SEM are
consisting of large number of primary nanocrystallites which are
detected by TEM and XRD. The overall mechanism for the
formation of ZnO particles is discussed below.
The growth of ZnO from zinc acetate dihydrate precursor using
solgel process generally undergoes four stages, such as solvation,
hydrolysis, polymerization and transformation into ZnO. The zinc
acetate dihydrate precursor was rst solvated in methanol, and
then hydrolyzed, regarded as removal of the intercalated acetate
ions and results in a colloidalgel of zinc hydroxide (Eq. (3)). The
size and activity of solvent have obvious inuence on the reacting
progress and product. Methanol has smaller size and a more
active OH and OCH3 groups. Methanol can react more easily to
form a polymer precursor with a higher polymerization degree,
which is required to convert sol into gel [31]. These zinc hydroxide

4.5

3.507 eV
8 pH

Absorption (a.u.)

4.0

3.51 eV
7 pH

3.5
3.0
2.5
2.0
1.5

3.57 eV
6 pH

1.0
4.0

3.5

3.0
Energy (eV)

2.5

2.0

4.5
3.41 eV
9 pH

4.0

Absorption (a.u.)

14 nm. The crystallite size of the ZnO powder as a function of pH

value of sol is plotted in Fig. 2, showing that the largest crystallite
size of 14 nm was found at 9 pH. The absence of any sharp peak
in the XRD pattern of the powder obtained at 6 pH sol indicates its
amorphous nature. As the pH increases from 6 to 9, the intensity
of the reections peaks increases as seen from Fig. 1. The ZnO
powder at 9 pH has the most intense peaks, is thus the most
crystalline sample and has maximum crystallite size of 14 nm. The
intensity of the reection peak was found to decrease for 10 and
11 pH. The poor crystal quality for pH value greater than 9 can be
attributed to higher reaction rate, when precipitates start to
dissolve [26].
Fig. 3(ae) shows the TEM images of the ZnO powder grown
with different pH value ranging from 7 to 11. A hexagonal shape of
ZnO particles having diameter in the range 1416 nm are observed
at 9 pH (Fig. 3(c)). The selected area diffraction (SAED) pattern of
this powder is also shown as inset in Fig. 3(c). From the SAED
pattern, it is clear that the ZnO particles are highly crystalline in
nature. The results from TEM are consistent with the observation
from XRD.
Fig. 4(a and b) shows the optical absorption spectra of the ZnO
powder synthesized at 6, 7, 8, 9, 10 and 11 pH versus the energy. It
is seen from these gures that the absorption exhibits a
progressive blue shift from 3.41 to 3.57 eV as the size of ZnO
nanocrystallites decreases from 14 to 6 nm. This is attributed to
the quantum size effect [16,30]. The variation in the band gap of
nanoparticles can also be evaluated from the effective mass model
expression [27] as

3.43 eV
11 pH

3.5

3.0

3.42 eV
10 pH

2.5

2.0
1.5
4.0

3.5

3.0

2.5

Energy (eV)
Fig. 4. (a and b) Absorbance as a function of energy of the nanosized ZnO powder
of different crystallite size.

3.58
Theoretical
* UV Absorption

3.56
3.54
3.52
Eg (eV)

1642

3.50
3.48
3.46
3.44
3.42
3.40
3.38
6

9
10
11
12
Crystallite Size (nm)

13

14

Fig. 5. Variation of band gap with crystallite size of ZnO powder.

15

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S. Rani et al. / Solar Energy Materials & Solar Cells 92 (2008) 16391645

1643

Fig. 6. SEM micrographs of ZnO powder synthesized using sol having different pH value: (a) 6 pH, (b) 7 pH, (c) 8 pH, (d) 9 pH, (e) 10 pH and (f) 11 pH.

splits into Zn2+ cation and OH anion according to reactions (Eq.
(4)) and followed by polymerization of hydroxyl complex to form
ZnOZn bridges and nally transformed into ZnO (Eq. (5)) [13]
ZnCH3 COO2  2H2 O 2NaOH ! ZnOH2 2CH3 COONa 2H2 O
(3)
ZnOH2 2H2 O ! ZnOH4 2 2H2

(4)

ZnOH4 2 2ZnO H2 O 2OH

(5)

When the concentration of OH, i.e. pH is low, the growth of

ZnO particle does not proceed because of the lack of Zn(OH)2
formation in the solution. Therefore, in solgel technique there is

a threshold pH level above which the nanostructure may be

formed.
In this study, the growth of ZnO nanoparticles in zinc acetate
solution was observed from a solution having pH of 7. A solution
with a pHo7 would have insufcient OH concentration to
synthesize ZnO which is also clear from XRD pattern (Fig. 1). Since
pH controls the rate of ZnO formation, it affects the size and their
way of combination to get stable state. As the freshly formed
nuclei in the solution are unstable, it has a tendency to grow into
larger particles. The largest crystallite size was observed when the
pH of the solution was 9. Further increase in the concentration of
OH from this point, reduced the crystallite size of ZnO. This is
presumed to be because of the dissolution of ZnO (back reaction of

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S. Rani et al. / Solar Energy Materials & Solar Cells 92 (2008) 16391645

4.0

Zn

Elmt
O K
Zn K
Total

Counts

20000

Spect.
Type
ED
ED

Element
%
27.18
72.82
100.00

10000

Zn

Zn

3.5

Atomic
%
60.40
39.60
100.00

CurrentDensity (mA/cm2)

30000

3.0
2.5

2.0

1.5
1.0

Zn

0
2

4
6
Energy (keV)

0.5

10

0.0
0.0

Fig. 7. EDX spectrum of nanosized ZnO powder at 9 pH value.

Eq. (5)). When ZnO reacts with OH, the dissolution of ZnO occurs
[28]. The continuous decrease in crystallite size above 9 pH level
as seen from Fig. 2 is the evidence of the acceleration of ZnO
dissolution during competitive ZnO formation.
The secondary ZnO (1 mm) particles as observed by SEM
images consist of primary ZnO nanocrystallites (10 nm). The
primary nanocrystallites can combined to form a larger particle
(secondary) by the following two routes [9]:
(1) Fusion of one primary crystallite (10 nm) into another.
(2) Aggregation of the primary crystallites (10 nm).
The rst mechanism will yield a large particle giving crystallite
size of micrometer scale (mm). The second route will result a
bigger particle consisting of primary (10 nm) subunits with
porosity. In the present work it appears that the aggregation is the
dominant mechanism which occurred during the crystallization of
gel network leading to macroscopic ZnO particles.
The chemical composition of the synthesized ZnO powder
obtained from 9 pH sol was examined by EDX measurements and
is shown in Fig. 7. The EDX analysis shows that the weight
percentage of zinc and oxygen (Zn/O) is close to the stoichiometric
composition.
The ZnO powder so developed has been used in the fabrication
of DSSC. Fig. 8 shows the photovoltaic performance of quasi-solidstate DSSCs A, B and C fabricated using the ZnO powder
synthesized from 8, 9 and 10 pH sol, respectively. The various
solar cell parameters are given in Table 1. It can be seen from the
table that open circuit voltage is same for all the devices, whereas
the short-circuit current, ll factor and power conversion
efciency for the cell B is higher than for A and C. The better
solar cell parameters, as observed for cell B, can be attributed to
the high-quality nanocrystalline ZnO powder obtained from the
9 pH sol. As discussed in the growth mechanism, the synthesized
powder consists of aggregated ZnO nanocrystallites with porosity
which helps in adsorption of dye and hence capturing larger
number of photons. The nanocrystalline nature and stoichiometric
composition of ZnO powder (obtained from 9 pH sol) further
enhance the performance of the DSSC.

4. Conclusions
The effect of pH on the crystallite size of ZnO powder grown by
solgel technique at room temperature has been studied. Largest
crystallite size of 14 nm with stoichiometric composition has

0.1

0.2

0.3
0.4
Voltage (V)

0.5

0.6

0.7

Fig. 8. IV characteristics of dye-sensitized solar cells using ZnO powder

synthesized at: (A) 8 pH, (B) 9 pH and (C) 10 pH.

Table 1
Cell parameters of the dye-sensitized solar cells
ZnO powder (pH)

Solar cell

Voc (V)

Jsc (mA/cm2)

FF

Z (%)

8
9
10

A
B
C

0.53
0.539
0.535

1.8
3.63
2.36

0.47
0.57
0.53

0.45
1.11
0.67

been obtained at 9 pH value. Aggregation has been found to be

dominant growth mechanism of microscopic ZnO particles. The
inuence of nanocrystallinity of the ZnO powder has been seen in
the band gap enhancement. DSSC made with stoichiometric ZnO
powder grown at 9 pH shows the best photovoltaic performance.

Acknowledgments
This work has been nancially supported under the MNRE
project No. 31/7/200405/PVR&D, Govt. of India. One of the
authors, Seema Rani, gratefully acknowledges the nancial
support in the form of JRF from UGC, New Delhi. The authors
also wish to acknowledge the partial nancial support from
University of Delhi for the strengthening of research program.
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