Preparation of Au@TiO2@SiO2 core-shell

nanostructure and their light harvesting

capability on DSSC (dye sensitized solar cells)
Cite as: AIP Conference Proceedings 2088, 060007 (2019); https://doi.org/10.1063/1.5095355
Published Online: 29 March 2019

Nur Fadhilah, Detak Yan Pratama, Dyah Sawitri, and Doty Dewi Risanti

AIP Conference Proceedings 2088, 060007 (2019); https://doi.org/10.1063/1.5095355 2088, 060007

© 2019 Author(s).
 Preparation of Au@TiO2@SiO2 Core-Shell Nanostructure
and Their Light Harvesting Capability on DSSC (Dye
Sensitized Solar Cells)

Nur Fadhilah1, a), Detak Yan Pratama 1, b), Dyah Sawitri 1), Doty Dewi Risanti 1,c)
1
Department of Engineering Physics, Faculty of Industial Technology, Institut Teknologi Sepuluh Nopember,
Kampus ITS Keputih, Sukolilo, Surabaya, 6011, Indonesia
a)
nurfadhilah321@gmail.com
b)
detak@ep.its.ac.id
c)
d.d.risanti@gmail.com

Abstract. One of the methods to enhance the performance of Dye-Sensitized Solar Cell (DSSC) is by adding SiO2
nanoparticles and Au nanoparticles. Au is known to be able to increase light harvesting while silica acts as scatterer and
back recombination inhibitor. Gold nanoparticles should be fabricated in core-shell nanostructure to prevent corrosion,
recombination and back reaction of excited electron because of direct contact between metal nanoparticles and liquid
electrolyte. In this study, the core-shell characteristics of Au@TiO2@SiO2 and their effects on DSSC performance were
investigated. The fractions of SiO2 extracted from Sidoarjo mud to Au and TiO2 were varied. The result revealed that the
addition of SiO2 above a certain level leads to agglomeration and uneven distribution of core-shell. Only for 90 ml SiO2
addition can form intended core-shell nanoparticles. Compared to DSSC using basic photoanode TiO2, the core-shells have
increased the efficiency of 92.9%. This enhancement was mainly because of the scattering effect of SiO2 while the presence
of Au is too small to promote the localized surface resonance.

INTRODUCTION

DSSC modified with the addition of SiO2 and gold nanoparticles have an efficiency enhancement of 44.8% and
20%, respectively 1,2. SiO2 has a refractive index of 1.46, while TiO2 has a refractive index of about 2.56. According
to the Mie Scattering theory 1,3, the larger difference in refractive index between particle and surrounding media, the
greater the effective light scattering. SiO2 acts as a scattering material can increase the absorption of light, which
indirectly increases the value of the photocurrent and the voltage generated 3,4.
Au nanoparticles behave as plasmonic material, i.e. when they interact with light a collective oscillation of
conduction band electrons known as the localized surface plasmon resonance (LSPR) occur. The LSPR effect can also
increase the absorption of visible light 5,6. Moreover, it can also accelerate the transfer of electrons to the electrodes so
that the transfer of charge becomes efficient and decreases load recombination7. On the other hand, DSSC loaded
with Au in the form of core-shell nanostructure has a higher efficiency compared to pristine Au, i.e. efficiency increase
of Au@SiO2 and Au@TiO2 are 85.7% and 23% respectively1,8. Likewise, core-shell with Au in the inner layer have
enhanced power conversion efficiency about 1.2 times higher than core-shell with Au in the outer layer. Using core-
shell nanostructures into DSSC is beneficial to provide a more effective distribution of far-field and optical path
lengths 9,10. Many researchers have utilised TiO2 and SiO2 to cover Au. Addition of Au@TiO2 core-shell in DSSC
raised Voc as a result of photocharging11. The addition of Au@SiO2 core-shell tends to increase the Jsc as a contribution
of the plasmon effect12. While the SiO2/TiO2 coating Au has a larger dipole to produce a wider local field, so that the
obtained Jsc is higher than those coated by TiO2 or SiO2 only13.

Advanced Industrial Technology in Engineering Physics

AIP Conf. Proc. 2088, 060007-1–060007-7; https://doi.org/10.1063/1.5095355
Published by AIP Publishing. 978-0-7354-1818-9/$30.00

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 Earlier findings have noted the importance of the right shell composition to form a core-shell. Ariesta et al.,
synthesized TiO2@SiO2 and SiO2@TiO2 core-shell structure nanoparticles from Sidoarjo Mud Extraction14. Their
results showed that the core is not fully coated by the shell is due to the large volume of SiO2 addition. The core-shell
with a thickness of 2-3 nm silica layer can induce the highest current density of 21.2 mA.cm-2 and photon
conversion efficiency (PCE) 9.55%. In contrast, with a shell thickness of 38 nm, PCE and Jsc significantly decreased
to 8.25% and 18.5 mA.cm-2, respectively.
The aim of this paper is to synthesize Au@TiO2@SiO2 core-shell nanostructure under various fractions of SiO2
and analyze their effects on dye-sensitized solar cells performance.
.

METHODS

A gold solution was prepared using Turkevich method 8,9. 0.4 μL MUA solution was added to the 30ml gold
solution and incubated for 2 h. The concentrations of Ti4+ in solution were adjusted to 0.3 mM17. Subsequently the
SiO2 nanoparticles were extracted from Sidoarjo mud also using co-precipitation method by a modified procedure
previously reported by Budiarti et al. 10,11. SiO2 solution was added. Volume of SiO2 solution was varied, i.e. 30ml,
60ml, 90ml and 120ml. The synthesized samples with different volume ratios were denoted as 30-Au@TiO2@SiO2,
60-Au@TiO2@SiO2, 90-Au@TiO2@SiO2, and 120-Au@TiO2@SiO2. HCl [2M] was added to the filtered solution
until pH = 7 was reached and white precipitaon was obtained. The resulting suspension was maintained at room
temperature for 24 hours and subsequently filtered and washed several times with distilled water to remove the acid,
alkali, and salt contents, then dried for 24 hours at 80°C.
Composite paste was made from 0.25gram grounded photoanode nanoparticles mixed with 87 μL distilled water,
125 μL CH3COOH, and 12.5 μL ml Triton X-100 under stirring until the paste was completely formed. The paste was
then coated onto FTO glass by using doctor blade technique. The size of photoanodes was controlled at 0.5 x 0.5 cm2.
The films were immersed in N719 ethanol solution for 12 h to obtain the dye sensitized photoanodes. The electrolyte
used was a redox (I-/I3-) gel electrolyte.
The crystal structure of the powders was determined by powder X-ray diffraction (XRD) using a Phillips X’pert
MPD (40 kV, 30 mA) with Cu Kα radiation (λ = 0.154 nm). Diffraction patterns were obtained for 15o – 90o (2).
Morphology of core-shell nanoparticles was thoroughly examined by Field-Emission Scanning Electron Microscope
using FEI Quanta 400F FESEM equipped with EDX. PSA (Particle Size Analyzer) characterization using Malvern
Zetasizer was carried out on core-shell powder samples to determine particle size. Photocurrent – voltage curves were
measured under 100 mW/cm2 using solar simulator connected to PXI-E1073 & SMU PXI-4130 and LabView
Software. Incident photon to current conversion efficiency (IPCE) in visible light spectrum was obtained by adjusting
wavelength of incident light, i.e. series connection of halogen lamp (GR-150 Halogen Flood Light 150W) and
monochromator (CT-10T, JASCO). The value of incident light power was measured by using optical power meter
(Thorlab S-120C)

RESULTS AND DISCUSSION

Based on the diffraction pattern in Fig 1, Au@TiO2 core-shell has peak of TiO2 anatase phase at 2θ = 25,869 °,
and Au peak at 2θ = 38,296 °. Additional peaks were observed and attributed to Al2O3 in 2θ = 31.7°, which is known
as the remnant of extraction process 20. The main peak of anatase which is initially located at 25,869°, was eventually
shifted towards the longer angles, following SiO2 addition, i.e 26,692 °. Hence, the peak located at 2θ of ~26,692° is
a convolution of anatase and SiO2 peaks. Compared to Au@TiO2 core-shell, Au@TiO2@SiO2 core-shell spectra has
a lower peak intensity of Au and TiO2. This study may suggest that SiO2 has covered the Au@TiO2 core-shell. This
result is supported by the characterization of the PSA in Fig 2. Au@TiO2@SiO2 core-shell has a larger particles size
distribution than core-shell Au@TiO2.

060007-2
 120-Au@TiO @SiO
2 2
90-Au@TiO @SiO
SiO 2 2
2
60-Au@TiO @SiO
2 2
Au TiO 30Au@TiO @SiO
2 2 2
TiO
2 Au@TiO
2

intensity a.u
Al2O3

Al2O3

TiO
2
TiO
2
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90


FIGURE 1. XRD pattern of Au@TiO2@SiO2 core-shell nanostructure synthesized under various SiO2 volume

The overall particles size distribution of Au@TiO2@SiO2 nanostructure was bimodal distribution. The bimodal
distribution can be interpreted that not all of core-shell were successfully synthesized. The multi-shell structure is
prone to agglomeration. From Fig 2, it is seen that only 90-Au@TiO2@SiO2 shows the smallest particle size
distribution.

25

120-Au@TiO @SiO
2 2
20 90-Au@TiO @SiO
2 2
60-Au@TiO2@SiO2
Intensity (percent)

30-Au@TiO2@SiO2
15
Au@TiO2

10

0
100 1000 10000
Size d (nm)

FIGURE 2. Particle size distribution of Au@TiO2@SiO2 core-shell nanostructure synthesized under various SiO2 volume

Fig 3 presents the FESEM images of core-shell Au@TiO2@SiO2 under various SiO2 volume. Gold nanoparticles
are marked with the bright round particles. TiO2 and SiO2 nanoparticles show as irregular shapes white and grayish
in color. For 90-Au@TiO2@SiO2, there is no visible Au nanoparticles, whereas for others Au nanoparticles were
observable as loose or partially covered particles. Particularly on the surface of 30-Au@TiO2@SiO2 Au was present
since the SiO2 fraction is very small and unable to cover the core. According to EDX characterization (Table 1), all
samples studied show the presence of Au in a small fraction. Except for 90-Au@TiO2@SiO2, Au traces cannot be
detected. This may indicate that Au core has been covered by the shells with the thickness beyond resolution of EDX
depth penetration.

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 FIGURE 3. FESEM images of (a) 30 (b) 60 (c) 90 (d) 120 Au@TiO2@SiO2 core-shell nanostructure

TABLE 1. Percentage of subtance Au@TiO2@SiO2 core-shell from EDX characterization

Volume Wt %
of SiO2 O Ti Si Au
30ml 51,7 41,2 7 0,1
60ml 60,1 31,1 8,6 0,2
90ml 51,8 35,1 13,1 0
120ml 53,4 30,6 15,8 0,2

The normalized UV-Vis absorption spectra of Au@TiO2@SiO2 core-shell are provided in Fig 4. All samples
indicate a strong absorption peak at 300nm as indicative of the presence of SiO2. On the other hand, Au absorption
peak which usually observable at wavelength of 500-550 nm cannot be detected. There are two possible reasons for
this, either the diameter of Au core is too small or the SiO2 and TiO2 shells are too thick so that the LSPR occured at
the Au interface cannot reach the outer shell surface.

0.90
0.85 30-Au@TiO @SiO
2 2
0.80 60-Au@TiO @SiO
2 2
0.75 90-Au@TiO @SiO
2 2
0.70 120-Au@TiO @SiO
Absorbance (a.u)

2 2
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25

300 350 400 450 500 550 600 650 700

Wavelength (nm)

FIGURE 4 Normalized UV-Vis absorption spectra of the of Au@TiO2@SiO2 core-shell

According to Cai et al., the presence of SiO2 in the core-shell can widen energy gap21. The larger the SiO2 size, the
higher the energy gap. Our result in Fig 5 shows that the optical band gap of the core-shell increases from 1.6 eV to
2.58 eV with SiO2 volume increase from 30-120 ml.

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 120000

110000

100000

90000

80000

2
70000

h) (eV/m)
60000

2
50000

40000 30-Au@TiO@SiO (1,6 eV)

2
60-Au@TiO@SiO (1,92 eV)
30000 2
90-Au@TiO@SiO (2.25 eV)
20000 2
120-Au@TiO@SiO (2.58)
2
10000
Au@TiO (2.00 eV)
2
0
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
hev)

FIGURE 5. Tauc plot of Au@TiO2@SiO2 core-shell nanostructure synthesized under various SiO2 volume

The photocurrent density-voltage curve of the DSSC is shown in Fig 6, while the open circuit voltage (VOC),
current density (JSC), fill factor (FF), and power conversion efficiency (η) are summarized in Table 2. No significant
differences were found between DSSC using Au@TiO2 and DSSC using the bare TiO2 sample. The highest
photovoltaic parameters are obtained from DSSC using 90-Au@TiO2@SiO2; Jsc = 0.0595 mA.cm-1; Voc = 0.6188 V,
efficiency (η) = 0.0162%. Compare with pristine TiO2, the efficiency of modified photoanode has been increased by
92.9 %.

0.14
0.135 TiO
2
0.060 Au@TiO
2
0.055 30-Au@TiO @SiO
2 2
Current Density (mA.m )

0.050 60-Au@TiO @SiO

-2

2 2
0.045 90-Au@TiO @SiO
2 2
0.040 120-Au@TiO @SiO
2 2
0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Voltage (V)

FIGURE 6. Photocurrent density – voltage curve of the DSSCs Au@TiO2@SiO2 core-shell nanostructure synthesized under
various SiO2 volume
TABLE 2. Summary of the DSSC parameters
Volume Voc Isc Jsc Pmax FF η
Core-shell
of SiO2 (V) (mA) (mA.cm-1) (mW) (%) (%)
TiO2 0,4736 0,0093 0,0371 0,0021 47,5984 0,0084
Au@TiO2 0,4823 0,0508 0,0417 0,0146 41,6415 0,0084
30ml 0,5460 0,0108 0,0430 0,0024 41,6595 0,0098
60ml 0,5733 0,0122 0,0488 0,0031 43,7662 0,0123
Au@TiO2@SiO2
90ml 0,6188 0,0149 0,0595 0,0040 43,9677 0,0162
120ml 0,4642 0,0088 0,0352 0,0017 41,6791 0,0068

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 The IPCE plots determined the variation with the wavelength for all sample studied were shown in Fig 7.
Obviously, IPCE percent value increase with increasing wavelength up to about ~500 nm followed by a continuous
drop to higher wavelength. Unlike the UV-Vis results, the IPCE values reveal the peak of Au absorption (~550 nm).
Among all studied samples, only 90-Au@TiO2@SiO2 shows a stronger absorption in the range of 510-550 nm and
almost double those without addition (85.7%). These results inform that the N-719 allows enhanced solar energy
absorption leading to shift of the peak at 500 nm to 460 nm for samples without core-shell addition. Whereas the peak
remains at ~530 nm for those with core-shell addition. The former shift confirms strong interaction between dye and
photoanode, where the latest verifies the stronger absorption of Au core.
In this result, the current of IPCE was dominated by SiO2 which is similar to Wang, et al research. SiO2 which acts
as scattering particle can boost the light harvesting capability for dye and long light path way22. All samples have
similar trend, as Au@TiO2@SiO2 core-shell nanostructure was embedded in the photoanodes the peaks tend to shift
to the longer wavelength (red shift). This shift was also observable for core-shell Puspitasari et al.,23.

0.011

0.010

0.009 Au@TiO @SiO 30ml

2 2
Au@TiO @SiO 60ml
0.008 2 2
Au@TiO @SiO 90ml
0.007 2 2
Au@TiO @SiO 120ml
2 2
IPCE (%)

0.006
TiO /SiO
2 2
0.005 TiO
2
0.004

0.003

0.002

0.001

0.000
400 450 500 550 600 650 700 750
Wavelenght (nm)

FIGURE 7. IPCE curves for Au@TiO2@SiO2 core-shell nanostructure synthesized under various SiO2 volume

CONCLUSIONS

Only for 90 ml SiO2 addition can form intended core-shell nanoparticles. The addition of SiO2 below 90 ml results
in partially or uncovered core, while above 90ml leads to agglomeration and uneven distribution of core-shell.
Compare with pristine TiO2, the efficiency of modified photoanode has been increased by 92.9%. this enhancement
was dominant contributed by scattering effect of SiO2.

ACKNOWLEDGMENTS

This research was supported by Research Institutions and Community Service of Institut Teknologi Sepuluh
Nopember Surabaya through local funding of Engineering Physics Department contract number 1745/PKS/ITS/2018.

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