Superlattices and Microstructures 75 (2014) 99–104

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Superlattices and Microstructures

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

Influence of pH on the performance of ZnO

nanocrystal based dye sensitized solar cells
V. Devabharathi a,⇑, K.L. Palanisamy b, N. Meenakshi Sundaram c
a
Department of Physics, KSR Institute for Engineering and Technology, Tiruchengode 637 205, India
b
Department of Physics, Sengunthar Engineering College, Tiruchengode 637 205, India
c
Department of Biomedical Engineering, PSG College of Technology, Coimbatore 641 004, India

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

Article history: ZnO nanocrystals have been synthesized via simple precipitation
Received 28 June 2014 method at different pH values. The synthesized nanocrystals are
Received in revised form 19 July 2014 annealed at three different temperatures such as 400, 500 and
Accepted 21 July 2014
600 °C respectively. The X-ray diffraction pattern shows that
Available online 30 July 2014
synthesized ZnO nanocrystals are of hexagonal structure and the
grain size was found to be in the range of 30–60 nm. The results also
Keywords:
pH values
indicated that the crystallinity of the nanocrystals improved with
ZnO nanocrystals increase of pH values and annealing temperature. Scanning electron
Precipitation method microscopic image shows that the surface morphology improves
Dye sensitized solar cells with increase of pH values. Optical absorption studies show that
the band gap has been found to lie in the range of 3.62–3.72 eV
depending on pH suggesting the formation of ZnO nanocrystals.
Dye sensitized solar cells prepared using ZnO nanocrystals synthe-
sized at pH = 9 exhibits an enhanced short-circuit current density
of 5.06 mA/cm2, open-circuit photo voltage of 0.61 V, fill factor of
0.65, and overall power conversion efficiency of 2.05%.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction

In recent years ZnO nanocrystals have attracted much interest for solar cell applications due to its
wide direct band gap and large exciton binding energy. Not only ZnO, all other wide band gap

⇑ Corresponding author. Tel.: +91 99426 19776.

E-mail address: devabharathi@gmail.com (V. Devabharathi).

http://dx.doi.org/10.1016/j.spmi.2014.07.028
0749-6036/Ó 2014 Elsevier Ltd. All rights reserved.
100 V. Devabharathi et al. / Superlattices and Microstructures 75 (2014) 99–104

semiconducting materials have attracted much attention in recent years due to novel optical, electri-
cal and mechanical properties, which results from quantum confinement effects compared with their
bulk counterparts. Compared with all semiconductor nanoparticles, zinc oxide (ZnO) nanocrystals are
the most frequently studied because of their interest in fundamental study and applied aspects in
many areas, such as ultraviolet (UV) light emitting devices, sensors, laser diodes and other high speed
electronic devices [1–4]. Wurzite ZnO nanocrystal having Wannier-Mott excitons, these excitons are
stable at room temperature with extremely large oscillator strength and emit blue light. This makes
ZnO an excellent potential candidate for the fabrication of room-temperature lasers where the coher-
ent light amplification is ruled by the fascinating mechanism of the Bose condensation of exciton
polaritons [5]. ZnO semiconductor has several favorable properties such as good transparency, high
electron mobility, wide band gap and strong room temperature luminescence. The room temperature
luminescence is due to the radiative recombination of free excitons, this radiative recombination
directs the quantum well photoluminescence even at room temperature [6]. ZnO is also a material
which is being used in non-electronic applications like optical brightener in wall colours, ingredient
in sun cream and bone implants [7]. Several researchers have also investigated the different properties
of ZnO nanocrystals including ultra violet and visible region emission. It is reported that structural
imperfection and defects generally deteriorate exciton related recombination process and it is neces-
sary to grow high quality crystals for all applications. ZnO nanocrystals have been synthesized by
many research workers using different techniques like, molecular beam epitaxy [8], chemical vapor
deposition [9], aerosol pyrolysis [10], electrodeposition [11], sol–gel and precipitation method
[12–16]. Out of these methods, the precipitation method is simple, inexpensive, non-vacuum and
low temperature technique for synthesizing nanocrystals. This technique offers many advantages like,
excellent control of the stoichiometry of precursor solutions, easy to modify the compositions, cus-
tomizable microstructure, ease of introducing various functional groups, requires relatively low
annealing temperatures and possibility of preparing over large volumes. In the present study, ZnO
nanocrystals have been prepared using zinc acetate dehydrate and 2-methoxy ethanol by the simple
precipitation method at room temperature. An attempt has been made to control the hydrolysis/con-
densation reaction in the precipitation of ZnO using mono ethanolamine. The effect of preparative
parameter, pH, of the sol on the properties of the prepared ZnO nanocrystals has been studied. There
is no detailed study on the effect of pH on the performance of ZnO nanoparticles based dye sensitized
solar cells. The present work therefore focuses on the influence of pH on the structural, optical prop-
erties and power conversion efficiency (CE) of ZnO nanoparticle based dye sensitized solar cells.

2. Experiment

All chemicals used in this study were of high purity which was purchased from Sigma Aldrich. To
synthesis ZnO nanocrystals zinc acetate dehydrate (Zn(CH3COO)22H2O) was used as zinc precursor.
The required amount of zinc acetate dehydrate was mixed with 50 ml double distilled water and a
small amount of NaOH was dissolved in 50 ml double distilled water and then this solution was added
drop wise in the first solution; the slow addition yields a milk white solution. The obtained white solu-
tion was placed at room temperature for 24 h and then aged at an elevated hydrothermal temperature
of 100 °C for desired period of 48 h for the nucleation and growth of ZnO nanoparticles. The resulting
nanoparticles was washed with distilled water and the obtained solution was centrifuged at 5000 rpm
for 10 min, the washing and centrifuging was repeated until solution had a pH of 5.0, and then the
sample was dried at 100 °C for 1hr. The ZnO nanocrystals have been prepared for another pH (=9)
by using the same experimental procedure. The prepared nanocrystals are annealed at three different
temperatures such as 400, 500 and 600 °C respectively for 30 min using a heating rate of 2 °C/min.
To prepare dye sensitized solar cells, ZnO paste was prepared by mixing 2.0 g of synthesized pow-
ders (annealed at 500 °C) using with a mixture consisting of 5.0 g of a-terpineol, 0.5 g of cellulose, and
20 ml of ethanol, which was sonicated for 24 h at 1200 W cm2 [17]. By using the prepared paste ZnO
thin films were prepared by coating the paste on a FTO conducting glass plate (Hartford FTO,
30 X cm2, 80% transmittance in visible region) using the doctor blade technique. The prepared films
were annealed at 450 °C for 30 min to remove the additives.
 V. Devabharathi et al. / Superlattices and Microstructures 75 (2014) 99–104 101

To assemble the dye sensitized solar cells, the prepared thin film electrodes were immersed in a
(3.0  104 M) N719 dye solution at room temperature for 24 h, rinsed with anhydrous ethanol,
and dried. A platinum coated FTO electrode was then placed over the dye adsorbed electrode, and
the edges of the cell were sealed with a sealing sheet (PECHM-1, Mitsui-Dupont Polychemical). A
redox electrolyte consisting of 0.5 M KI, 0.05 M I2, and 0.5 M 4-tertbutylpyridine was used as a solvent
and it was injected sufficiently into the cell.
To identify the crystal structure, X-ray diffraction studies have been carried out using a PANalytical
X-ray diffractometer with nickel-filtered Cu Ka (30 kV, 30 mA) and surface morphology of the film
was studied using scanning electron microscopy (SEM; S-4100, Hitachi). Optical characterization of
the films was carried out using UV–VIS–NIR spectrophotometer (Jasco V-570). The current–voltage
(I–V) characteristics were measured using white light from a xenon lamp (max. 150 W) using a sun
2000 solar simulator (ABE technologies). Light intensity was adjusted using a Si solar cell to AM-
1.5. Incident light intensity and active cell area were 100 mW cm2 (one sun illumination) and
0.25 cm2 (0.5  0.5 cm), respectively.

3. Results and discussion

X-ray diffraction pattern has been used to investigate the phase and particle size of the synthesized
ZnO nanocrystals. Fig. 1(a, b) shows the X-ray diffraction pattern of the ZnO nanocrystals prepared
using pH = 5 & pH = 9 and annealed at different temperatures. All the diffraction peaks can be indexed
to the wurtzite structure (hexagonal phase) of ZnO with fine crystallinity. The diffraction peaks pres-
ent at 31.7°, 34.6°, 36.2°, 47.5°, 56.7°, 63.2°, 66.4, 68.0°, 69.1°, 72.3° and 76.9° are respectively indexed
to (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2), (2 0 1), (0 0 4) and (2 0 2) planes of ZnO. The
calculated lattice parameters are a = 3.26 Å and c = 5.22 Å and the values are in good agreement with
the standard values (JCPDS No. 36-1451). The results indicate that the products were consisted of pure
phases. For all the annealing temperatures and pH values there is no additional peaks related to impu-
rities. ZnO nanocrystals synthesized at both the pH values have the same hexagonal wurtzite struc-
ture. The growth rate of (0 0 2) peak has been found to increase with increase of pH; it is clearly
shown in Fig. 1(b). The increase in intensity of (0 0 2) peak at higher pH values reveals high [0 0 1]
growth orientation of the ZnO nanocrystals [18]. Furthermore, it could be seen that the diffraction
peaks shown in both the figures are more intensive and narrower, implying a good crystalline nature
of the as-synthesized ZnO nanocrystals.
In addition, the broadening at the bottom of diffraction peaks shown in the figures also denotes
that the crystalline sizes were small and in good agreement with the characteristic of nanosized par-
ticles reported in literature [12]. The average crystalline size (D) of the ZnO nanocrystals can be
obtained from the Debye–Scherrer formula [19],

pH=9
(010)

pH=5
(101)

(a) (b)
(002)
(100)
Intensity (a. u.)

(002)

Intensity (a. u.)

(100)

(110)

(103)
(103)

(110)
(102)

(112)

(112)
(102)

(201)
(201)
(200)

(200)

(004)
(202)

(202)
(004)

(600 °C) (600 °C)

(500 °C) (500 °C)
(400 °C) (400 °C)

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2θ (degree) 2θ (degree)

Fig. 1. X-ray diffraction patterns of ZnO nanocrystals synthesized at (a) pH = 5 and (b) pH = 9.
102 V. Devabharathi et al. / Superlattices and Microstructures 75 (2014) 99–104

D ¼ 0  94k=b cos h

where D is the mean crystallite size, b the full width at half maximum of the diffraction line, h the
angle of diffraction, and k the wavelength of the X-ray radiation. The calculated average crystallite
sizes for (1 0 1) planes are shown in Table 1. From the table it is observed that both the pH values
the particle size increases with increase of annealing temperature. For a particular pH value, the inten-
sity of the diffraction peak increases with an increase of the heat treatment temperature, which is evi-
dent from increased intensity of (1 0 1) reflection and reduced full width at half maximum (FWHM).
This is due to the transformation from amorphous to crystalline on heat treatment.
The scanning electron microscope images of the synthesized ZnO nanocrystals are shown in Fig. 2.
The image clearly shows that the size and morphology of the synthesized nanocrystals were highly
dependent on the pH value used. When the pH value is low, the nanocrystals smooth surface but at
higher pH there is a small amount of nanorods agglomerated horizontally. This result shows that to
synthesize nanorods higher pH value should prefer. At higher pH, the morphology of particles is to
be found roughly spherical and homogenous; some of the particles have agglomerated.
Fig. 3 shows the UV–Vis absorption spectra of the ZnO nanocrystals prepared at different pH values
and annealed at different temperatures. All the samples show sharp absorption in UV region and high
transparency in the visible region. The absorbance of the ZnO nanocrystals is observed to decrease
with increase in annealing temperature. This can be ascribed to the formation of larger particles with
increase of annealing temperature which causes scattering of light.
By the extrapolation of the absorption edge onto the x-axis, band gap of the samples have been cal-
culated and its values are tabulated in Table 1. It should be noted that the band gap decreases with
increase of annealing temperature. This may be due to the formation of larger nanocrystals at higher
temperatures. The UV–Vis absorption spectra shows that absorption edge shifts to longer wavelength
with increase of pH values and the red-shift of absorption edge can be attributed to the increase of ZnO
nanoparticle sizes (formation of rod like structures) on increasing pH values. This absorption in the UV
region was attributed to the transition from the ground state to a few defect related deep states. How-
ever absorption graph for both the pH values show excitations of unequal tail towards the higher
wavelength regions it is due to scattering of light from the crystals.
Fig. 4 shows the photocurrent–voltage curves of the DSSCs assembled by using ZnO thin films. The
film thickness was in the range of 10.0–12.0 mm. A DSSCs assembled with ZnO nanocrystals prepared
at pH = 5 had a Voc of 0.60 V and a Jsc of 2.53 mA cm2 at an incident light intensity of 100 mW cm2.
The power conversion efficiency was 1.04%, which was increased to 2.05% in the DSSC fabricated by
the ZnO nanocrystals prepared at pH = 9, with a Jsc of 5.06 mA cm2 and a Voc of 0.61 V. It is observed
that DSSCs using ZnO nanocrystals prepared at pH = 9 shows higher short-circuit current density (Jsc)
and conversion efficiency (CE) compared to the solar cells prepared using ZnO nanocrystals prepared
at pH = 5. The reason for the higher Jsc is the formation of small rod like structures on the surface; it
may increase the dye absorption area. But in the case of ZnO nanocrystals prepared at pH = 5 having
particle like structures gives lesser power conversion efficiency. It is due to the presence of very small
grains adsorb lesser dye molecules, resulting in a reduced electron–hole pairs and therefore the short-
circuit current density. The higher current density and overall conversion efficiency originated from
the improvement of the dye absorption area and the light harvesting [20].
The efficiencies obtained in the dye sensitized solar cells prepared using ZnO nanocrystals are less
for practical applications. But the obtained efficiencies are better than the ZnO nanorod based dye sen-
sitized solar cells prepared by Thambidurai et al. [21] and Suh et al. [22]. Thambidurai et al. have

Table 1
Particle size and band gap of ZnO nanocrystals synthesized at different pH values.

Annealing temperature (°C) Particle size (nm) Band gap (eV)

pH = 5 pH = 9 pH = 5 pH = 9
400 34.5 40.6 3.72 3.66
500 45.5 42.3 3.68 3.63
600 50.7 44.2 3.63 3.62
 V. Devabharathi et al. / Superlattices and Microstructures 75 (2014) 99–104 103

Fig. 2. SEM image of ZnO nanocrystals synthesized at (a) pH = 5 and (b) pH = 9.

(a) Absorbance (a.u.) (b)

Absorbance (a.u.)

(600°C)
(600°C)
(500°C) (500°C)

(400°C) (400°C)

300 400 500 600 700 800 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)

Fig. 3. UV–Visible spectra of the ZnO nanocrystals synthesized at (a) pH = 5 and (b) pH = 9.

6
pH=5
pH=9
5
η=2.05%
Current Density (mA/cm )
2

η=1.04%
2

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Voltage (V)

Fig. 4. J–V characteristics of ZnO nanocrystal based dye sensitized solar cells.

reported 0.78% of power conversion efficiency value for dye sensitized solar cell based on flower like
ZnO nanorods. Suh et al. have reported about the synthesis and preparation of dye sensitized solar
cells with pillar and branch shaped ZnO nanowires grown onto the FTO substrates by thermal evap-
oration process and have obtained an overall solar energy conversion efficiency of 0.46% for branched
104 V. Devabharathi et al. / Superlattices and Microstructures 75 (2014) 99–104

Table 2
Photovoltaic performance of ZnO nanocrystal based dye sensitized solar cells.

pH Voc (V) Jsc (mA/cm2) FF CE

5 0.60 2.53 0.67 1.04
9 0.61 5.06 0.65 2.05

ZnO nanowires. Table 2 shows the photovoltaic performance of ZnO nanocrystals synthesized at
pH = 5 & 9 and annealed at 500 °C.

4. Conclusion

Using different pH values ZnO nanocrystals have been synthesized via simple precipitation
method. The synthesized nanocrystals are annealed at different temperatures such as 400, 500 and
600 °C respectively. The X-ray diffraction pattern shows that synthesized ZnO nanocrystals are of hex-
agonal structure and the grain size was found to be in the range of 30–60 nm. The results also indi-
cated that the crystallinity of the nanocrystals improved with increase of pH values and annealing
temperature. Scanning electron microscopic image shows that the surface morphology improves with
increase of pH values. Optical absorption studies show that the band gap has been found to lie in the
range of 3.62–3.72 eV depending on pH suggesting the formation of ZnO nanocrystals. Dye sensitized
solar cells prepared using ZnO nanocrystals synthesized at pH 9 exhibits an enhanced short-circuit
current density of 5.06 mA/cm2, open-circuit photo voltage of 0.61 V, fill factor of 0.65, and overall
power conversion efficiency of 2.05%.

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