Fabrication and Efficiency Enhancement of Z907 Dye

Sensitized Solar Cell Using Gold Nanoparticles

Nabeel A. Bakr1*. Abdulrahman K. Ali 2 . Shaimaa M. Jassim1

1
Department of Physics, College of Science, University of Diyala, Diyala, IRAQ

2
Department of Applied Science, University of Technology, Baghdad, IRAQ

*Email: nabeelalibakr@yahoo.com

Abstract In this study, Z907 dye sensitized solar cell was fabricated using gold

nanoparticles which were prepared by pulsed Nd:YAG laser ablation in ethanol at

wavelength of 1064 nm. The prepared nanoparticles were added to Z907 dye to study

their effect on the efficiency of the fabricated dye-sensitized solar cell (DSSC). SEM

image showed that the TiO2 layer was porous and the XRD analysis confirmed that it

has a polycrystalline structure belonging to anatase phase. The average particle size of

the gold nanoparticles was estimated by TEM imaging technique and it was found to

be 50 nm. UV-Vis investigation shows that the absorption of the Z907 dye increases

with adding the gold nanoparticles. Solar cells with efficiency as high as 1.284 % and

2.357 % have been achieved without and with Au NPs respectively. The enhanced

performance is attributed to plasmons of Au NPs that may scatter more photons to the

substrate in comparison to the particle free solar cell, leading to increase the optical

path length in the solar cell which subsequently resulted in efficiency enhancement of

about 84 %.

Keywords: DSSC; Z907 dye; Gold nanoparticles; Efficiency

1

1 Introduction

The increasing energy demand has promoted the creation of devices that are able to

convert alternative source of energy, such as solar energy [1]. The conversion of solar

radiation to electricity has become more and more important, because sunlight is a clean

and limitless energy source compared to the traditional fossil energy source [2-3]. The

dye sensitized solar cell (DSSC) is a low cost solar cell which belongs to the thin film

solar cells [4]. The DSSC can be classified as a photoelectrochemical (PEC) solar cell

due to its utilization of photons, charges, and electrolyte in its basic operation [5]. This

type of solar cells was firstly reported by Gratzel in 1991 and since that time the DSSC

technology has been developed very quickly [1]. Dye-sensitized solar cells have been

extensively studied because of their high energy conversion efficiency, simple

fabrication processes, low-cost and environmentally benign [6]. DSSCs are also

attractive due to their transparency and their stylish color design [1]. Conventional

DSSCs consist of five components: transparent conducting oxide (TCO) glass, a wide

band gap semiconductor film such as TiO2, a sensitizer such as Ruthanium dye, redox

electrolyte and a counter electrode such as Pt [7]. Figure 1 shows a schematic diagram

of DSSC.

Fig. 1 Schematic diagram showing the structure of conventional DSSC

Fig. 1 Schematic diagram showing the structure of conventional DSSC

2

In the present decade, the surface modification of TiO2 with noble metal nanoparticles

such as gold (Au) and silver (Ag) have been regarded as an attractive approach to boost

the efficiency of DSSCs. These noble metal nanoparticles play an interesting role in the

DSSC performance, including the enhancement of the absorption coefficient of the dye

and the optical absorption due to surface plasmon resonance [8]. Moreover, they also

play an important role in improving the interfacial charge transfer process, and

minimize the charge recombination, thereby in DSSC [9].

In this work, we investigate the performance improvement of Z907 DSSC with addition

of gold nanoparticles prepared by pulsed laser ablation in liquid (PLAL) method.

2 Experiment

All the materials used in this experiment were supplied from Dyesol

Company/Australia. The materials were as follows: Fluorine Tin Oxide (FTO) coated

glass substrates, TiO2 paste (18-NRT), Z907 dye, organic solvent based electrolyte (EL-

HSE), platinum paste and high purity of 99.99 % gold plate as target. The pulsed laser

ablation in liquid technique is employed to synthesize colloidal gold nanoparticles (Au

NPs) using gold target and ethanol at room temperature. The gold target was placed in

glass vessel containing Z907 dye solution and the ablation was achieved using focused

output of pulsed Nd:YAG laser of 1064 nm wavelength at fluence of 13.27 J/cm2 (type

DELIXI, DZ47-63, C10) operating with a repetition rate of 1 Hz and pulse width of 10

ns. Ablation is carried out with laser. For the preparation of the photoanode, FTO glass

substrate with size of (2.5 cm 2.5 cm) was used. The FTO glass was cleaned in

ultrasonic bath for 5 minutes in distilled water and for 5 minutes in acetone. The TiO2

paste was deposited on FTO glass by Doctor-blade method and the thickness of the

titania layer was determined by the thickness of scotch tape which has a thickness of

10 m placed on the left and right sides of the conductive face of substrate. Then the
3

scotch tape was removed and the films were left to dry for 30 minutes in a covered Perti

dish. Thereafter, the films were annealed at 350 oC and 550 C for 30 minutes. Finally,

the photoanodes were allowed to cool at room temperature. After cooling, the

photoanodes were immersed in a 0.25 mM Z907 dye solution with and without Au NPs

for 24 hours. For the preparation of the counter electrode, two holes of 1 mm diameter

were drilled to enable a later injection of electrolyte and platinum (Pt) paste was

deposited on conductive side of FTO glass by Doctor-blade method, and the electrodes

were then annealed at 450 C for 30 minutes. This leads to homogenous distributed

platinum with good catalytic activity.

The two electrodes were assembled into a sandwich structure using thermoplastic

sealant, with a thickness of 30 m as spacer. The sealant gasket was placed around TiO2

paste and the counter electrode was put on it while the Pt film faces the TiO2. Finally,

the electrolyte was filled through the holes in the counter electrode by a pipette, and the

holes were covered by plaster to prevent evaporation.

The crystallite phase of TiO2 was identified by X-ray diffractometer (Shimadzu 6000,

Japan) using CuK radiation (= 1.5406 ). The surface morphology of TiO2 was

investigated by SEM (JSM-7000F) type. The UVVis absorption spectra of TiO2 layer

and the Z907 dye, with and without Au NPs, were measured by UVVISNIR

spectrophotometer (Shimadzu, UV-1800). High resolution image of Au NPs was

obtained by TEM (type CM10 pw6020, Philips-Germany). The photovoltaic

performance of the DSSCs was measured using Keithley 2400 multimeter and tungsten

halogen lamp. Based on IV curve, the fill factor (FF) was calculated according to the

following equation:
.
FF (1)
.

4

Where Jmax is the maximum photocurrent density, Vmax is maximum photovoltage, Jsc

is the short-circuit photocurrent density and Voc is the open-circuit photovoltage. The

overall energy conversion efficiency ()was calculated according to the formula:

. .
% 100 (2)

Where Pinp is the incident power.

Two sets of dye sensitized solar cells has been prepared, each set of six samples, using

the same procedure and conditions described above to check the reproducibility of the

route used in this study and it was found that the photovoltaic performance values of

all cells are the same within an experimental error not more than ~ 8%.

3 Results and discussion

3.1 Structure analysis

Structure characterization of TiO2 films with thickness of 10 m deposited by Doctor-

blade technique on FTO glass substrate was carried out by X-ray diffraction (XRD)

technique. Figure 2 shows the XRD diffraction patterns of the as-deposited and

annealed TiO2 films. From the figure, it was confirmed that all patterns are indexed to

the anatase phase with polycrystalline structure according to the ICDD standard card

no. (21-1272) [12]. From the figure, it is clear that all films exhibit diffraction peaks of

anatase crystal planes (101), (004), (200), (105), (211), (204) and (215) and this result

is in agreement with the results reported by Hasan [13]. The highest and strongest peak

of all TiO2 thin films was at 2 25.4 corresponding to (101) direction [14]. The

average crystallite size of TiO2 films of (101) peak was calculated by Scherrers

formula given by the following equation [15]:

D 0.9 / Cos (3)

5

Where D is the crystallite size, is the X-ray wavelength of Cu K radiation, is the

full width at half maximum (FWHM) and is the Braggs angle. The calculated

crystallite size of TiO2 films is shown in Table 1. The annealing temperature of 550 C

was chosen as the optimum annealing temperature for the synthesis of TiO2

nanomaterials since it gives the minimum crystallite size. It is reported that the anatase

TiO2 with small size has shown better photocatalytic activity as it leads to increase in

the surface area of TiO2 film and resulting in an increase of dye absorption amount.

[16]. The lattice parameters a and c are calculated using the following equation and they

are given along with other XRD results in Table 1.

(4)

The calculated lattice constants a and c are found to agree well with the standard values

(a 3.781 nm and c 9.51 nm) [17].

Fig. 2 XRD patterns of TiO2 thin films

Table 1 XRD results of TiO2 films

Annealed Annealed
TiO2 thin film As-deposited
at 350 C at 550 C
2 (deg) 25.4007 25.3983 25.3720

6

 hkl 101 101 101
FWHM (rad) 0.009319 0.010327 0.011456
D (nm) 15.252 13.763 12.406
Lattice constants a 3.781 3.787 3.781
()
c 9.476 9.466 9.477

3.2 Morphological analysis

The surface morphology of TiO2 thin film was characterized by SEM. Figure 3 displays

the SEM image of TiO2 film of 10 m thickness which has been deposited on the FTO

glass after annealing at 550 C for 30 minute. The SEM micrograph shows a spongy

shape with reduction in the number of open pores making easy for dye adsorption and

electron transport [10]. The average particle size of TiO2 NPs is about 20-40 nm. The

small particles of TiO2 film have larger surface area and subsequently absorb more dye

molecules. Subsequently, this may lead to improved DSSC performance [11].

Fig. 3 SEM image of TiO2 thin film at 30,000X

3.3 Optical properties

7

Figure 4 shows the optical absorption spectra of Au NPs prepared by PLAL, Z907 dye

solution and their mixed solutions (1:1 v/v) in the wavelength range of (350-700) nm.

From the figure, it is clear that Au NPs has single absorption peak located at round 530

nm, due to surface plasmon resonance [18], while Z907 dye solution and the mixed

solution have two absorption peaks located at (370 and 510 nm) and (371 and 517 nm)

respectively. It can be noticed that the optical absorption increases when Au NPs were

added to Z907 dye. This enhancement is attributed to the surface plasmon resonance of

Au NPs. Moreover, an absorption tail in the red zone of the Au NPs spectrum was also

observed,which indicates particle assembling and instability [19].

Figure 5 illustrates the UVVis absorption spectra of TiO2 films with thickness of 10

m deposited on glass substrates annealed at 550 C and 350 C for 30 minutes under

ambient conditions. It can be noticed that the absorbance increases with increasing

annealing temperature. Furthermore, in the UV region, the absorption is very high in

comparison with that of the visible region, due to which TiO2 can be used as UV blocker

in inverted organic solar cells which avoids solar cells from degradation as UV rays

have negative impact on the cells [20]. When annealing temperature is increased, the

absorption edge is shifted to a shorter wavelengths (high energy) and this result is in

agreement with the results reported by Muaz et al. who found that the absorption edge

is shifted to a shorter wavelengths due to the quantum-size effect when the particle size

was very small [21].

Tauc model is employed to quantify the optical band gap of TiO2 films using the
equation:

n
h A h Eg (5)

Where is the absorption coefficient, h is the photon energy, Eg is the optical band

gap, A is a constant which does not depend on photon energy and n has four numeric
8

values (1/2 for allowed direct, 2 for allowed indirect, 3 for forbidden direct and 3/2 for

forbidden indirect optical transitions) [22]. Figure 6 shows Tauc plots where the direct

band gap of the TiO2 thin films can be estimated by the intercept of the extrapolation

of straight line portion of the plot at (h)2=0. From the figure, it was observed that

direct optical band gap for annealed TiO2 thin films increases from 2.31 eV to 3.12 eV

with the increase in annealing temperature and this result is in agreement with the

results reported byRashad et al. [15]. It is reported that the decrease in the crystallite

size leads to the increase in the band gap energy and caused a gradual shift of the

absorption edge towards shorter wavelengths [23].

0.35

Au NPs
0.30

0.25
Absorbance

0.20
0.30

0.20
Z907 Dye + Au NPs

0.10

Z907 Dye Solution

0.00
300 350 400 450 500 550 600 650 700 750

Wavelength (nm)
Fig. 4 Optical absorption spectra of Au NPs (upper), Z907 dye solution and

Z907+Au NPs mixed solution (1:1 v/v)

9

 Fig. 5 UV-Vis absorption spectra of TiO2 films

6
9x10

6 as-deposited
8x10 350 OC
6 550 OC
7x10
2
eV)

6
6x10
-1

6
5x10
h cm

6
4x10

6
3x10

6
2x10

6
1x10

0
1.0 1.5 2.0 2.5 3.0 3.5 4.0

h (eV)

Fig. 6 Taucs plots of TiO2 films

3.4 TEM analysis for Au NPs

To identify the number, shape and size distribution of Au NPs present in the prepared

samples, they were characterized by transmission electron microscope (TEM). The

TEM image and size distribution of Au NPs produced by PLAL method is shown in

Fig. 7a. The TEM image confirmed that the particles are spherical in shape of nanosize

[24]. It can be also observed that interconnect NPs lead to agglomeration. On the basis

of the TEM image the size distribution of NPs was calculated. The precise size

10

distribution of NPs is presented in Fig. 7.b, and it is clear that the nanoparticles

diameters are in the range of (10-90) nm and the average particle size is about 50 nm.

Fig. 7 a TEM image of gold nanoparticles produced by PLAL,

b Corresponding size distribution histogram of the particles

3.5 Current voltage analysis

Figure 8 shows the current density-voltage characteristics of DSSC with Au NPs. For

comparison, the current density-voltage characteristic of the reference DSSC without

Au NPs is also shown. Table 2 lists the cells performance data obtained from the J-V

curve measurements. From the results, it was found that photocurrent density (JSC) and

11

open-circuit voltage (VOC) increase for DSSC with Au NPs compared to the DSSC

prepared without Au NPs. An increase in JSC leads directly to an increase in the power

conversion efficiency. The enhanced performance was largely attributed to plasmons

of Au NPs that may scatter more photons to the substrate in comparison to the particle

free solar cell, leading to increase the optical path length in the solar cell [19]. The

efficiency achieved by the DSSC using Au NPs was 2.367 % with an efficiency

enhancement of ~84 % compared to the particle free DSSC.

Fig. 8 J-V curves of DSSCs with and without Au NPs

Table 2 The photovoltaic parameters of DSSCs with and without Au NPs

4 Conclusions

In this study, DSSCs with and without the addition of Au NPs to the dye have been

successfully synthesized using simple technique. Solar cells with efficiency as high as
DSSC VOC JSC Vmax Jmax
FF (%)
Type (V) (mA/cm2) (V) (mA/cm2)
Without Au 0.513 3.949 0.298 2.155 0.317 1.284
NPs
With Au 0.606 5.859 0.304 3.893 0.333 2.367
NPs
1.284 % and 2.357 % have been achieved without and with Au NPs respectively. The

12

enhanced performance is attributed to plasmons of Au NPs that may scatter more

photons to the substrate in comparison to the particle free solar cell, leading to increase

the optical path length in the solar cell which subsequently resulted in efficiency

enhancement of about 84 %.

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