Red-shifting the surface plasmon resonance of silver nanoparticles for light trapping in

solar cells

Fiona Jean Beck1, and Kylie Catchpole2

1
Center for Sustainable Energy Systems, Australian National University, Room 216, Building
#32, Acton, Canberra, 0200, Australia
2
AMOLF, Amsterdam, Netherlands

ABSTRACT

Surface plasmons in metallic nanoparticle arrays have been shown to increase the
absorption of an underlying silicon substrate. This has wide ranging applications, not least in the
photovoltaic industry. Incident light excites localised surface plasmons in the silver
nanoparticles and is coupled into the silicon in trapped modes. The radiative behaviour of the
nanoparticle film is changed by the proximity of a high refractive index surface, causing
radiation to be directed into the silicon and providing a light-trapping layer. We investigate a
simple and effective method of tuning the surface plasmon resonance frequency, and hence the
spectral region at which the absorption enhancement is seen, by varying the underlying
dielectric. The particle geometry and distribution are modified by the surface conditions
provided by the dielectric layer, and both this and the change in refractive index alter the
resonance position. Three common dielectrics used in the photovoltaic industry were
investigated as surfaces on which to form arrays of self-assembled silver nanoparticles
atmospheric pressure chemical vapour deposited titanium dioxide (APCVD TiO2), low pressure
chemical vapour deposited silicon nitride (LPCVD Si3N4) and thermally grown silicon dioxide
(SiO2). We show, by optical and electrical measurements, that the red-shifted resonances
produced by nanoparticle films on APCVD TiO2, and LPCVD Si3N4 with relatively high
refractive indices, correspond to an increase in optical absorption and external quantum
efficiency in thin, crystalline solar cells at longer wavelengths.

INTRODUCTION

Solar energy has an important role to play in decreasing our reliance on fossil fuels for
energy production. Technological improvements and the massive expansion in the photovoltaic
(PV) industry in the last decade have reduced the cost of solar electricity to less than US 22 cents
per kWh for large installations in favourable, sunny locations 1 (correct for March 2008).
Further decreases are necessary to make solar energy commercially competitive across a broad
market.
Thin-film silicon solar cells are a promising candidate to drive down the cost of solar
energy generation. However, there are several intrinsic disadvantages with thin-film technology
that need to be overcome. Current commercial thin-film cells have a lower efficiency than
crystalline cells: up to 7% compared to 22% for wafer- based, monocrystalline cells in
production2. One of the most important considerations is light trapping; since silicon is a poor
absorber of long wavelength light it is desirable to confine the light within the active silicon
layer for as long as possible to promote absorption. Traditional techniques such as surface
texturing are not feasible for thin devices due to their small dimensions and the impact on device
performance caused by increased surface recombination resulting from the large surface area
exposed. Novel light-trapping techniques are needed for such devices. One method that is
gaining interest is the use of localised surface plasmons in arrays of metallic nanoparticles to
couple incident light into an underlying silicon.3

Surface plasmon theory

Of late there has been much interest in the field of plasmonics and the possibility of
manipulating light on the nanoscale; Maier and Atwater give a good review on the subject4.
The term nanoparticle is used throughout this work to refer to particles with a diameter that is
small compared to the wavelength of incident light. The confined geometry of the nanoparticle
allows the direct excitation of a localised surface plasmon. Free conduction electrons in the
nanoparticle respond to the oscillating electric field associated with the incident light, and a
dipole polarisation is built up. This produces a polarisation field that acts as an effective
restoring force. When the response of the electrons is π/2 out of phase with the driving field, the
oscillation becomes resonant. This occurs at the surface plasmon resonance wavelength (λSPR).
At resonance, the extinction cross-sections (the sum of the scattering and absorption
cross-sections) of the particles become larger than their geometric cross sections and the
electromagnetic fields near the particle are concentrated5. If the particle is in the vicinity of a
semiconducting surface with a high refractive index, a dipole image field is set up. This not only
affects the driving field, but also changes the polarisability of the particle, causing the angular
emission spectra of the induced dipole to be modified. For a nanoparticle within 30 nm of a
silicon substrate, the energy from the excited resonance is directed preferentially towards the
surface, in modes that confine the light in the silicon layer6. This increases the path length of the
light in the silicon, and hence the probability of absorption.
The λSPR is dependent on the material, size, geometry and filling factor of the
nanoparticle arrays, as well as the refractive index of the underlying media. Silver was chosen
over other noble metals for plasmon formation, due to its higher scattering efficiency in the
geometries and wavelength regions being studied7.

The resonance characteristics of particles that are much smaller than the wavelength of
incident light can be described by electrostatic expressions. In this regime, larger particles
generally show a stronger peak at resonance, as they provide a larger extinction cross-section,
but the position of resonance is not changed. However, as the diameter increases above 100 nm
the electrostatic assumption begins to fail. Retardation effects and the excitation of higher order
modes are seen to red-shift the resonance position, reduce the strength and broaden the peak. As
the particles deviate from perfect spheres, further red-shifting occurs. The resonance behaviour
of ellipsoidal particles can be found by introducing shape dependent depolarisation factors when
calculating the polarisibility8.
The λSPR will also be moved to longer wavelengths with increasing refractive index of the
medium surrounding, or partially surrounding the nanoparticles. In this instance the build up of
charges in the dielectric has a depolarising effect, weakening the restoring force. The ability to
vary λSPR by changing the refractive index of the underlying dielectric film has been investigated
by many authors; in particular, G. Xu et al.9 discuss particles with a diameter range similar to this
work.
 In this study, the effective Maxell-Garnett theory (equation 1) is used to predict the
deviation of λSPR from the bulk metal plasmon resonance wavelength λp. The relationship
demonstrates the dependence on the shape dependent depolarisation factor, L, the filling factor
of the nanoparticle array, f, and the effective dielectric constant, εav, calculated from the
refractive index of the underlying dielectric film. The high frequency dielectric constant, ε∞ is
due to intraband electron transitions and is not discussed here.
1
⎡ ε av ⎤2
λSPR = λp ⎢ − ε av + ε∞ ⎥ (1)
⎣ (1 − f ) L ⎦

Tuning the resonance position allows the design of an efficient light-trapping layer. However, it
is not only the final light trapping efficiency of the nanoparticle films that needs to be
considered: for this to be relevant to the PV industry, it has to be both cost effective and scalable
to commercial production. The fabrication procedure for the nanoparticle films must be
compatible with PV cell production, and should be as cheap and as simple to implement as
possible.
In this study the nanoparticle films were fabricated using a simple self-assembly method,
compatible with existing PV fabrication processes. A thin silver layer was first deposited by
vacuum evaporation on top of the dielectric layer, and then annealed at low temperatures. When
heated, the thin silver film breaks up under surface tension to form discrete islands. The shape
and size of these particles are dependent on the surface conditions of the dielectric layer. This
provides a simple and effective way of tuning the resonance position by forming the nanoparticle
arrays on different dielectric base coatings. This not only allows the underlying refractive index
to be varied, but also the final structure of the nanoparticle film.

EXPERIMENT

Silver films of 14 nm were deposited by thermal evaporation in a Varian vacuum

chamber with a background pressure of less than 3 µtorr. A quartz crystal oscillator was used to
track the thickness of the silver layer. The films were then annealed at 260°C for 30 minutes in
an atmosphere of forming gas.
The substrates used were microscope glass slides, 300 µm thick polished silicon wafers,
and 100 µm thick bifacial, crystalline silicon solar cells. The effect of the nanoparticles was
investigated using optical measurements for the samples with glass and silicon substrates, and by
taking spectral response measurements of the solar cells.
The tuning of λSPR was examined by forming the nanoparticle arrays on a range of
dielectric coatings: thermally grown silicon dioxide (SiO2), atmospheric pressure deposited
titanium dioxide (APCVD TiO2) and low-pressure chemical vapour deposited silicon nitride
(LPCVD Si3N4). The three different dielectrics were deposited on all sample substrates prior to
silver evaporation. All the bifacial solar cell samples had at least 15nm of thermally grown SiO2
to provide surface passivation. For consistency, the silicon wafer samples used for optical
measurements also had the same thin oxide layer grown in a dry oxygen environment, at
temperatures between 930 and 950ûC.
APCVD TiO2 (15 nm) was deposited on both sides of each sample, using a Sierra Therm
APCVD belt furnace10. The reactive gases were tetraisopropyltitinate as the titanium source, and
water as the oxygen source. These were delivered to the surface of the samples at 390°C in
nitrogen carrier gas under atmospheric pressure. Previous studies of films produced at this
temperature and in this manner suggest that the films produced are in the rutile phase and are
rough and porous11.
LPCVD Si3N4 (17 nm) was deposited in a low-pressure chamber at 0.45 Torr,.
Ammonia and dichlorosilane were introduced at elevated temperatures of 777°C. Previous
studies into this deposition method reported the film as stoichiometric Si3N412.
All samples were annealed at 400°C in forming gas after dielectric deposition.

Results

The TiO2 dielectric layers were measured with an ellipsometer using a mercury xenon
lamp, with a wavelength range of 400 to 800 nm. WVASE software was used to fit for
refractive indices and layer thickness. The refractive index (n) of the TiO2 was measured to be
2.5 at 600 nm, while stoichiometric Si3N4 and SiO2 was taken to be 2.05 and 1.46 from literature.
The particle formations were studied under a Hitachi S4500 Cold Field Emission
Scanning Electron Microscope and Matlab image recognition tools were used to gauge the filling
factor and size distribution. Nanoparticles on SiO2 had an average diameter of 135 nm with a
size variation of 35 nm and a filling factor of 26%. The structures formed on both Si3N4 and
TiO2 were bigger, with more irregular shapes. Roundness was quantified as the ratio of the
minor and major axes. The average roundness of the nanoparticles was 0.73 for TiO2 and 0.76
for Si3N4 undercoated films, with an average major axis length of 222 nm and 214 nm
respectively. The filling factor also varied between films, with TiO2 at 30% and Si3N4 at 28%.
Transmission measurements of nanoparticles were made on glass substrates, with the
three different undercoating layers. This approximates the resonance behaviour of particles in
free space due to the low refractive index of the glass. A dual beam
CARY 5000 Varian Spectrophotometer was used, with measurements taken over the wavelength
range 200 – 1300 nm. Extinction spectra (1-transmission) in Figure 1 (a) show that the Si3N4
and TiO2 undercoatings red-shift the λSPR from 490 nm on SiO2 to 595 nm and 700 nm
respectively.
For all optical and electrical measurements the effect of the nanoparticles on both the
front and the rear of the samples was investigated. Looking at both configurations allowed the
light-coupling effects of the nanoparticles to be studied, with light incident both from air and
from the silicon itself.
Optical absorption spectra (1-reflection and transmission) of the silicon substrates with
and without the nanoparticle films on the rear of the samples are shown in Figure 1(b).
 100

90
80

70

60

50

40

30

20 SiO2 Undercoating
Si3N4 Undercoating
10
TiO2 Undercoating
0
350 450 550 650 750 850 950 1050 1150
Wavelength (nm)

100
90
80
70
60
50
40 Silicon Reference
30 SiO2 Undercoating
TiO2 Undercoating
20 Si3N4 Undercoating
10
0
300 400 500 600 700 800 900 1000 1100 1200
Wavelength (nm)

Figure 1. (a)Top: Extinction spectra of nanoparticle films showing the bare particle resonances
red-shifting with increasing refractive index of the underlying dielectric. (b)Bottom: Absorption
spectra of nanoparticle films on the rear of samples, showing the increasing long wavelength
enhancements from films with red-shifted resonances.

Long wavelength light absorption in the silicon substrate was enhanced by all three
nanoparticle films. The absolute increase in absorption, quoted at a wavelength of 1050nm, was
2% for a SiO2 undercoated sample, 16% for Si3N4 and 23% for TiO2. When illuminated from
the front, similar long wavelength enhancements were seen. SiO2 samples showed an additional
large increase in absorption across the spectrum from 200 nm to 1200 nm, up to 23% at 800 nm.
In this wavelength region both Si3N4 and TiO2 samples had reduced absorption, corresponding to
an increase in reflection in this region.
Spectral response measurements were taken from 350 nm to 1200 nm by measuring the
short circuit current from the bifacial solar cell samples in 5nm wavelength increments and the
external quantum efficiency was calculated from the known illumination intensity.

SiO2 Undercoating

100
90
80
70
60
50
40
30 Withount Nanoparticles Front
20 Without Nanoparticles Rear
Nanoparticles on Front
10
Nanoparticles on Rear
0
350 450 550 650 750 850 950 1050 1150
Wavelength (nm)

Si3N4 Undercoating
100
90
80
70
60
50
40
30 Nanoparticles on Rear
20 Nanoparticles on Front
10 Without Nanoparticles Front
Without Nanoparticles Rear
0
350 450 550 650 750 850 950 1050 1150
Wavelength (nm)
 TiO2 Undercoating
100
90
80
70
60
50
40
30 Without Nanoparticles Rear
20 Without Nanoparticles Front
10 Nanoparticles on Front
Nanoparticles on Rear
0
350 450 550 650 750 850 950 1050 1150
Wavelength (nm)

Figure 3 (a) Top: %EQE for particles on SiO2, illuminated from both the front and the rear. (b)
Middle: Particles on Si3N4 and (c) Bottom: Particles on TiO2.

A large enhancement with nanoparticles on the front of SiO2 occurred between 525 nm
and 1050 nm. Si3N4 undercoated films showed increases above 640nm and improvements in
EQE for TiO2 coated bifacial solar cells were further red shifted to 890 nm. All samples showed
a decrease in EQE at wavelengths below λSPR. With particle arrays on the rear, SiO2 and Si3N4
coated bifacial solar cells showed little change while TiO2 samples increased from 14% EQE to
24% at 1050 nm.

DISCUSSION

The red-shifted resonances of nanoparticle arrays on high refractive index dielectrics

correspond to red-shifted absorption and EQE enhancements. Additionally, the surface
conditions of the three dielectrics form different films, with decreasing roundness and larger
particle diameters on TiO2 and Si3N4 contributing to the red shifting effects.
Measurements show that below λSPR all nanoparticle films on the front of samples
decreases absorption. This can be attributed to a measured increase in reflection off the silver.
Below the resonance wavelength, light that falls on the silver is not coupled into the silicon. By
placing particles on the rear of samples this decrease can be avoided while still achieving
enhancements at longer wavelengths. Spectral response measurements confirm that this
additional absorption is occurring in the silicon layer, where it increases the EQE of the bifacial
solar cells, and not in the nanoparticles themselves. At 1050 nm, nanoparticle films on the rear
of the solar cells, undercoated with TiO2, exhibited a relative increase in EQE of 1.4 compared to
an increase of 1.1 for Si3N4, and no increase at all seen for SiO2 (Figure 4). The enhancement
could be expected to be significantly higher still for thin-film silicon cells.

2.5

TiO2 Rear
2 SN Rear
SiO2 Rear

1.5

0.5
900 920 940 960 980 1000 1020 1040 1060 1080 1100
Wavlength (nm)

Figure 4. Relative EQE enhancements (EQE with nanoparticles / EQE without) due to the
application on nanoparticle arrays undercoated with different dielectrics on the rear surface of
thin bifacial solar cells.

Due to the need for a passivation layer the coupling effect of the nanoparticles may have
been reduced, leading to less EQE enhancement. Previous optical measurements by the author,
have shown further red-shifting and stronger absorption enhancements for 20-30 nm APCVD
TiO2 films. By undercoating with a dielectric that can provide both passivation and a high
refractive index surface, the spacing between the silicon and the nanoparticles could be
minimised and the coupling effects increased.

CONCLUSIONS

Localised surface plasmon resonances can be tuned towards longer wavelengths, where
silicon is a poor absorber of light, by undercoating the nanoparticles with dielectric layers of
relatively high refractive index.
The position of the surface plasmon resonance wavelength, λSPR, red-shifts as the
refractive index of the dielectric increases: from 490 nm for SiO2 (with n = 1.46), to 595 nm for
LPCVD Si3N4 (n = 2.05) and 700 nm for APCVD TiO2 (n = 2.5). Correspondingly, the EQE of
thin, bifacial crystalline silicon solar cells is shown to increase at 1050 nm from 14% to 20%
with a TiO2 undercoated nanoparticle film on the rear. This is compared to a negligible change
when the particles are formed on a SiO2 base coating.
This has a direct application as a simple and effective method of optimising light trapping
layers for thin film solar cells. Nanoparticle arrays formed on APCVD TiO2 could be used to
couple long wavelength light back into thin film cells that would normally be lost by
transmission. The placement of the particles on the rear would avoid any loss of short
wavelength light, which is already strongly absorbed in the silicon, to shading or absorption in
the silver. Furthermore, light trapping for other absorber layers could be engineered using this
method.

ACKNOWLEDGMENTS

This work is supported by the Center for Sustainable Energy Systems and the Department
of Engineering at the Australian National University. The author would like to thank Dr Evan
Franklin and Ms Nina De Caritat for providing solar cell test structures and Mr Andrew
Thomson for assistance with APCVD TiO2 depositions.

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