Core-Shell Gold Nanoparticle for Enhanced Near-Infrared Silicon

Solar Cell Response

Di Qu, Fang Liu*, Jiafan Yu, Wanlu Xie, Qi Xu, and Yidong Huang
Department of Electronic Engineering, Tsinghua University, Beijing, 100084, China

ABSTRACT

Near-infrared silicon solar cell response enhanced by gold nanoparticles with core-shell structure has been studied
experimentally. The colloidal core-shell gold nanoparticles are synthesized by the standard sodium citrate
reduction method. The enhanced photocurrent response of silicon solar cell is obtained over almost the entire
silicon response spectrum, and the obvious enhancement is observed when λ0 > 800nm. The highest value 12%
near λ0=1160nm is obtained.

Keywords: Surface plasmon, gold nanoparticle, core-shell structure, silicon solar cell

1. INTRODUCTION
The enhanced optical absorption in solar cells utilizing metal nanoparticles with surface plasmon effects has
received a lot of attention in recent years1. There are usually two methods to improve the optical absorption of
solar cells by applying metal nanoparticles, including inside and outside the active materials2-6. For the latter
method, the scattering effect based on the surface plasmon resonance is dominant in the enhancement performance.

Surface plasmon (SP) is the local oscillations between the collective electron charge and the electromagnetic field,
which could also be supported by metal nanoparticles. It was reported that the gold nanoparticles with diameter
about 100nm can enhance the photocurrent response of silicon solar cell in the visible region3-5. This paper reports
the experimental results on the notable photocurrent enhancement in the near-infrared wavelength range, when the
core-shell gold nanoparticles with diameter about 15-100nm are deposited on the surface of silicon solar cell.

2. STRUCTURE AND FABRICATION

2.1 Structure and fabrication of silicon solar cell
Figure 1 shows the schematic structure of the silicon solar cell with core-shell gold nanoparticles on the surface. To
fabricate the solar cell, a p-type Si wafer with 525 μm thickness is selected as the substrate, and the ion
implantation method is adopted to realize the pn-junction. Then, the electrodes are fabricated on both sides of the
solar cell.

*liu_fang@tsinghua.edu.cn; yidonghuang@tsinghua.edu.cn phone: +86-10-62797073

Display, Solid-State Lighting, Photovoltaics, and Optoelectronics in Energy II, edited by Heonsu Jeon, et al.,
Proc. of SPIE-OSA-IEEE Asia Communications and Photonics, SPIE Vol. 7991, 799103
© 2011 SPIE-OSA-IEEE · CCC code: 0277-786X/11/$18 · doi: 10.1117/12.890126

SPIE-OSA-IEEE/ Vol. 7991 799103-1

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx

 Fig. 1 Schematic of device and experimental geometry

2.2 Synthesis of colloidal core-shell gold nanoparticles

The colloidal gold nanoparticles with Au-citrate core-shell structure are synthesized by the standard sodium citrate
reduction method7. Figure 2 shows the experimental setup. After dissolving the HAuCl4 into the pure water, the

solution is heated to near 100℃, and sodium citrate is added to the HAuCl4 solution with continuous stirring. The

reaction formulas are

COO COO
Au 3+
HO COO OH Au + CO2 H2O
O
COO
COO (1)
and

COO

Au+ HO COO Au0

COO . (2)
The radius of gold nanoparticles is controlled by adjusting the ratio of HAuCl4 and sodium citrate, the reactant
concentration, reaction temperature and reaction time. Then, the stable, purple solution of the citrate coated gold
nanoparticles is obtained and shown in Fig. 3.

SPIE-OSA-IEEE/ Vol. 7991 799103-2

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx

 Fig. 2 Experimental Setup

Fig. 3 Photo of the colloidal gold nanoparticles

Further, the colloidal gold nanoparticles with Au-citrate core-shell structure are deposited on the surface of the
prepared solar cell. The photograph of scanning electron microscope (SEM) is shown in Fig. 4(a), which illustrates

that the size of core-shell gold nanoparticles is within the range of 15-100nm and the concentration is about 1.6×

109cm-2. Figure 4(b) shows the magnifying core-shell structure.

SPIE-OSA-IEEE/ Vol. 7991 799103-3

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx

 Fig. 4(a) SEM photo of the nanoparticles on the surface of solar cell

Fig. 4(b) SEM photo of the magnifying core-shell structure

3. MEASUREMENT RESULTS
3.1 Measurement system
The photocurrent response spectrum (PRS) of the silicon solar cells (with and without Au-citrate core-shell
nanoparticles) is measured by the standard solar cell relative spectral response measurement system, including a
tungsten-halogen lamp (OSRAM), a grating monochromator providing monochromatic light, a filter wheel for the
elimination of multi-spectral, a reference Si photodiode, a Si photodetector, and a lock-in amplifier. With this
system, the photocurrent response of the device under the wavelength range from 300nm to 1800nm can be
obtained with high measurement repeatability (the error < 1%).

SPIE-OSA-IEEE/ Vol. 7991 799103-4

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx

 3.2 Measurement results
Figure 5 shows the photocurrent response ratio (Iph Ratio) of devices with and without gold nanoparticles as a
function of wavelength. The photocurrent is essentially the same when λ0 < 800nm, while there is a notable
increase when λ0 > 800nm. The enhancement on photocurrent response reaches 12% surrounding the wavelength
of λ0 =1160nm. This improvement mainly results from the changing of the local dielectric environment of the gold
nanoparticles because the core-shell structure leads to the redshifting of resonance, and accordingly results in an
increase in scattering cross section at longer wavelengths, which would be beneficial for increasing the absorption
of silicon solar cell.

Fig. 5 Measured photocurrent response ratio as functions of wavelength for the devices

4. CONCLUSIONS
In summary, the enhancement effect of the silicon solar cell with core-shell gold nanoparticles has been studied
experimentally. The results show that the core-shell gold nanoparticles with diameter between 15-100nm play a
significant role in improving the conversion efficiency of the silicon solar cell in the near-infrared range. The
obvious enhancement on photocurrent response is observed when λ0 > 800nm, and the highest enhancement of
12% near λ0=1160nm is obtained.

SPIE-OSA-IEEE/ Vol. 7991 799103-5

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx

 5. ACKNOWLEDGEMENT
The authors would like to acknowledge Limin Xiong and Hao Sun of National Institute of Metrology, China, for
their advice and help in measurement. This work is supported by the National Basic Research Programs of China
(973 Program) under Contract No. 2010CB327405 and 2007CB307004, and the National Natural Science
Foundation of China (NSFC-60877023).

REFERENCES

[1] H. A. Atwater and A. Polman, “Plasmonics for improved photovoltaic devices”, Nature Mater. 9, 205 (2010).
[2] B. P. Rand, P. Peumans, and S. R. Forrest, “Long-range absorption enhancement in organic tandem thin-film
solar cells containing silver nanoclusters”, J. Appl. Phys. 96, 7519 (2004).
[3] D. M. Schaadt, B. Feng, and E. T. Yu, “Enhanced semiconductor optical absorption via surface plasmon
excitation in metal nanoparticles”, Appl. Phys. Lett. 86, 063106 (2005).
[4] S. H. Lim, W. Mar, P. Matheu, D. Derkacs, and E. T. Yu, “Photocurrent spectroscopy of optical absorption
enhancement in silicon photodiodes via scattering from surface plasmon polaritons in gold nanoparticles”, J.
Appl. Phys. 101, 104309 (2007).
[5] P. Matheu, S. H. Lim, D. Derkacs, C. McPheeters, and E. T. Yu, “Metal and dielectric nanoparticle scattering
for improved optical absorption in photovoltaic devices”, Appl. Phys. Lett. 93, 113108 (2008).
[6] S. Pillai, K. R. Catchpole, T. Trupke, and M. A. Green, “Surface plasmon enhanced silicon solar cells”, J.
Appl. Phys. 101, 093105 (2007).
[7] B. V. Enustun and J. Turkevich, “Coagulation of colloidal gold”, J. Am. Chem. Soc. 85, 3317 (1963).

SPIE-OSA-IEEE/ Vol. 7991 799103-6

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 07/18/2016 Terms of Use: http://spiedigitallibrary.org/ss/TermsOfUse.aspx