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Solar Energy Materials & Solar Cells 90 (2006) 23292337


www.elsevier.com/locate/solmat

Enhancing the performance of silicon solar cells


via the application of passive luminescence
conversion layers
B.S. Richards
Centre for Sustainable Energy Systems, The Australian National University, Canberra ACT 0200, Australia
Available online 2 May 2006

Abstract
This paper discusses ways of reducing the two major losses encountered in a single-junction
photovoltaic (PV) devicethat of sub-band gap transmission and lattice thermalisation lossesvia
the application of passive luminescent devices called up- and down-converters, respectively. Downconversion (DC) results in the generation of more than one lower energy photon being generated per
incident high-energy photon, while up-conversion (UC) generates one photon with energy for every
two or more sub-band gap photons absorbed. A related process of wavelength down-shifting (DS) is
similar to DC except that the external quantum efciency of the DS process is less than unity.
Crown Copyright r 2006 Published by Elsevier B.V. All rights reserved.
Keywords: Solar cells; Up-conversion; Down-conversion; Luminescent solar concentrator; Silicon; Photovoltaics

1. Introduction
Photovoltaic (PV) devices fabricated from silicon (Si) wafers dominate the marketplace
and comprised 94% of all module shipments in 2004 [1]. In addition, the dominance of
bulk Si over other thin-lm technologies has been increasing year by year. While it is
acknowledged that thin-lm and more advanced third generation solar cells [2]
undoubtedly have an important role to play in the future, manufacturers of Si solar cells
are presenting the more recent generations of PV with a rapidly moving target.

Tel.: +61 2 6125 9741; fax: +61 2 6125 8873.

E-mail address: bryce.richards@anu.edu.au.


0927-0248/$ - see front matter Crown Copyright r 2006 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2006.03.035

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B.S. Richards / Solar Energy Materials & Solar Cells 90 (2006) 23292337

For any single-junction solar cell, the band gap energy (Eg) of the semiconductor from
which the PV device is fabricated establishes a fundamental upper limit for its conversion
efciency. The two major loss mechanisms that need to be overcome to signicantly
enhance device efciencies are lattice thermalisation and transparency to sub-band gap
photons. For the case of lattice thermalisation, a photon with high energy creates an
electronhole (e h) pair, however, the photoexcited pair quickly loses energy in excess of
the band gap and the extra energy is lost as heat within the device. This is illustrated by
process 1 for a typical pn junction band diagram in Fig. 1, while the transparency of the
semiconductor to sub-band gap photons is denoted as process 2 in Fig. 1. A further loss
mechanism is the recombination of photoexcited eh pairs (see 3 in Fig. 1), however, the
impact of this parameter can be minimised by maintaining high minority carrier lifetimes
in the semiconducting material and does not contribute greatly to the theoretical efciency
limit. Using the principle of detailed balance between incident and escaping photons and
extracted electrons, Shockley and Queisser demonstrated that the one-Sun efciency limit
for a single-material cell is around 31% with an optimal band gap of 1.3 eV [3]. This
assumes that the only unavoidable losses from the device are the emission of photons
produced by radiative recombination, and includes voltage drops across the contacts and
junction, denoted by processes 4 and 5 in Fig. 1. With a slightly non-optimal band gap,
the ShockleyQueisser one-Sun efciency limit of a silicon (E g 1:12 eV) device is further
reduced to 30% [3].
The only existing PV device that addresses lattice thermalisation and sub-band gap
losses is the tandem solar cell, a series-connect stack of twove junctions made from
semiconducting materials with a decreasing band gap. Green has described the theoretical
upper efciency limits of tandem devices, being able to achieve efciency limits ranging
from 31% to 68.2% for one and an innite number of band gaps, respectively, using
unconcentrated sunlight [2]. When operating under the maximum theoretical solar
concentration of around 46,000 times, these values increase to 40.8% and 86.8%,
respectively [2].
The best lab-scale Si solar cells with a one-Sun efciency of Z 24:7% have already
achieved results that are very close to their theoretical limit. Motivated by the predicted
dominance of Si PV technologies for the next decades, research has been performed on the
application of luminescence up-conversion (UC) [46] and down-conversion (DC) [7] to

electron (e-)

p-type
material

Energy
photon
absorption

n-type
material
4

Conduction
5 Band (CB)

3
2
3

5
1

hole (h+)

Valence
Band (VB)

Fig. 1. Loss processes in a single-junction solar cell: 1 lattice thermalisation loss; 2 transparency; 3
recombination loss, 4 junction loss and 5 contact voltage loss.

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single-junction PV devices in an effort to bridge the gap between the realisable efciencies
on Si devices and the ultra-high efciencies expected of third generation PV.
There are both benets and challenges in successfully applying UC and DC to PV
technologies. Both UC and DC components are passive, optical devices with carrier
collection still performed via the single PV junction. Therefore, they have a distinct
advantage over tandem solar cells, where the photocurrents generated in upper and lower
cells must match throughout the day in order to avoid signicant mismatch losses. In
addition, the application of UC and DC layers, at least initially, to PV does not require
modication of the existing solar cell as the layers are passive and purely optical in
operation.
2. Impact of varying solar air-mass on UC and DC

Spectral Irradiance (kW/m2/m)

Before describing the mechanisms via which UC and DC can be applied to Si solar cells,
it is rst informative to determine what fraction of sunlight can make a useful contribution
to UC and DC throughout the day. Fig. 2 plots the spectral irradiance of the solar
spectrum modelled by a 6000 K black body, the extraterrestrial solar spectrum of air-mass
zero (AM0), and also the terrestrial solar spectrum for various positions of the sun
throughout the day, reected by the solar air-mass [8,9]. The total power density is also
displayed in Fig. 2. While the power contained in the AM10G spectrum is only one-fth of
that in the AM1G spectrum, the most important difference is the reduced spectral
irradiance at ultraviolet (UV) and visible wavelengths. Finally, a typical spectrum taken on
a totally overcast day is plotted in Fig. 2. This spectrum is blue-shifted due to the higher
component of scattered light under cloudy skies.
Fig. 3 plots the AM1.5G spectrum and the fraction of this light that can be absorbed by
a bulk Si device. Since silicon possesses an indirect band gap, a value of 1150 nm (dotted
white line) is used in this work as the cut-off response. To achieve two-photon emission via
DC, each incident high-energy photon must possess energy of at least twice the Si band
gap, or a wavelength of shorter than 550 nm. This extra fraction of the AM1.5G spectrum
that is available to a DC is plotted in Fig. 3. Likewise, for the UC of two sub-band gap

6000K black body


AM0
1367 W/m2
AM1G 1086 W/m2
AM1.5G 982 W/m2
AM1D 868 W/m2
AM3G 696 W/m2
AM10G 207 W/m2
Overcast 104 W/m2

2.0
1.5
1.0
0.5
0.0
0.2

0.6

1.0

1.4

1.8

2.2

Wavelength, (m)
Fig. 2. Spectral irradiance and power contained within various solar spectra including global (G) and direct (D)
(data taken from Bird et al. [8,9]).

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B.S. Richards / Solar Energy Materials & Solar Cells 90 (2006) 23292337

Fig. 3. AM1.5G spectrum showing the fraction that is currently absorbed by a thick silicon device and the
additional regions of the spectrum that can contribute towards up- and down-conversion.

Table 1
Comparison of the fraction of spectral irradiance that is available to be absorbed by a thick silicon wafer, as well
as the extra spectral irradiance that is suitable for an up- and down-converter attached to a silicon solar cell
Air-mass
spectrum

Total intensity
(W/m2)

Extraterrestrial spectruma
AM0
1367
Terrestrial spectraclear sky
AM1D
868
AM1G
1086
AM1.5Gb
982
AM3G
696
AM10G
207

Intensity
o1.15 mm
(W/m2)

Fraction of
intensity absorbed
by silicon (W/m2)

Extra intensity available for

DC o0.55 mm
(W/m2)

UC
1.152.21 mm
(W/m2)

1035

590

247 (42%)

222 (38%)

691
891
807
539
122

413
513
468
334
86

124 (30%)
185 (36%)
149 (32%)
75 (22%)
7 (8%)

157 (38%)
172 (34%)
164 (35%)
139 (42%)
74 (85%)

149

86

31 (36%)

18 (21%)

Terrestrial spectracloudy skyc


Overcast
166

Note: for the case of down-conversion, the extra intensity available is that which is normally lost to a silicon solar
cell in lattice thermalisation.
The values in parentheses are the percentage of DC or UC light compared to the fraction of the light that is
absorbed by silicon.
a
Data taken from Bird et al. [8].
b
Not normalised to 1000 W/m2.
c
Data taken from Bird et al. [9].

photons resulting in the emission of a single above-band gap photon, the former must
exhibit an energy of at least half the Si band gap, or longer than 2210 nm. This fraction of
the AM1.5G spectrum then becomes available to a Si solar cell with an up-converter
located at the rear is plotted in Fig. 3.

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The integrated intensity of fraction of light absorbed by Si and the extra intensity
available for UC and DC of different solar spectra is compared in Table 1. Naturally, the
power density available for UC and DC is greatest under extraterrestrial AM0 irradiation
and least under AM10G radiation when the Sun is low in the sky. While similar intensities
are expected for both DC and UC light under AM0, AM1G and AM1.5G, at higher airmasses the fraction of sunlight that is useful for DC drops signicantly, to as low as 8%,
whereas for UC this fraction increases signicantly up to 85%. This is due to spectral
differences, with a large red-shift occurring at higher AM. The difference in the available
intensity for UC and DC in the AM1D spectrum, where the DC fraction is lower and the
UC fraction higher than the AM1G spectrum, respectively, is due to the greater fraction of
shorter wavelength radiation in scattered (diffuse) light (as can be seen in Fig. 2).
Therefore, it would appear that the greatest benets of applying of luminescent wavelength
shifting devices to PV would be in the:
(1) DC of extraterrestrial sunlight or diffuse sunlight, and
(2) UC of the direct radiation, especially at higher AM.
Further evidence that these are the two best scenarios will be presented later, where it
will be discussed that DC luminescence varies linearly with incident intensity, whereas UC
luminescence is nonlinear.
3. UC for photovoltaics (UC-PV)
Three advantages of applying UC to PV are, rstly, a large body of research has already
been performed on the topic of UC, albeit primarily for achieving visible light output
rather than the near-infrared (NIR) light with E4E g best-suited for Si solar cells.
Secondly, an UC layer can be placed upon the rear of a bifacial solar cell without
disturbing the performance of the device for incident photons with energy E4E g . In this
manner, any UC photocurrent is a real gain. Thirdly, with a reector placed behind the
UC layer, no luminescence can escape out of the rear. However, the major disadvantage of
UC is that it is a nonlinear optical process. Thus, for the minimum UC process of twosteps, the intensity of UC light (I) is related to the incident light intensity (I0) by I / I 20 ,
while for a three-step UC process I / I 30 .
In a recent research we have reported results from application of UC layers based on
rare-earth luminescence centres contained within polymer sheets [46]. The UC layers were
made from 5 mm-diameter erbium-doped sodium yttrium uoride (NaY0.8F4:Er3+
0.2 )
phosphors dispersed into a mixture of white oil and a rubberizer at a weight ratio of
fours parts phosphor to one part white oil [5]. As illustrated in the left of Fig. 4, the UC
layer was attached to the rear of a bifacial Si solar cell with a front and rear side one-Sun
conversion efciency of 15% and 12%, respectively. A layer of evaporated silver was
applied to the rear side of the of UC layer to create a rear specular reector.
When the UC-PV device is illuminated with a 1.5 mm tunable laser, the light passes
straight through the Si wafer and is absorbed by the Er3+ ions in the UC layer. Two- and
three-step UC processes then result in a photoluminescence spectrum with emission peaks
at 550, 660, 810 and 980 nm [5]. Fig. 5 plots the enhanced spectral response of the UC-PV
device at wavelengths around 1.5 mm. The peak external quantum efciency (EQE) of the
UC-PV device is 3.4%, occurring at 1523 nm [5], as is also shown in Fig. 5. The internal

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Si solar cell

Down-converter

Up-converter
Rear reflector

Si solar cell

EQE (%)

Log [EQE] (%)

Fig. 4. Diagram of (left) a bifacial solar cell with an UC layer placed at the rear to capture sub-band gap light;
and (right) a DC layer placed at the front of a monofacial solar cell to convert each high-energy photon into
multiple low-energy photons. Once optimised, both UC and DC layers could be placed on the front and rear of a
bifacial silicon solar cell, respectively).

1.0

2
1
0

0.1
0

1540
1560
1520
1580
Excitation wavelength (P=2 mW), (nm)

2
3
4
5
Excitation Power at 1523 nm, P (W)

Fig. 5. Variation of the EQE of the silicon UC-PV device with incident laser power at the peak response
wavelength of 1523 nm and (inset) the spectral response over the l 151021590 nm range.

quantum efciency (IQE) of the luminescence process, however, is estimated to be 5.7%


due to various reectance losses at the surfaces and interfaces within the device and also
absorption losses in the phosphor host material [5]. While the EQE of the UC-PV device
appears to be low, it can be put into perspective somewhat by comparing this device with
high efciency Si solar cells that have been ion-implanted with Er3+ ions, which achieved
an EQE of 1.8  104% [10].
4. DC for photovoltaics (DC-PV)
Whereas UC is a nonlinear process, DC can be a linear process, suggesting that it will be
easier to gain a performance advantage using the Earths Sun as the illumination source.
The schematic diagram in Fig. 4 shows a DC layer attached to the front of a solar cell.
While some inorganic phosphors have achieved EQEs of 130 [11], these require excitation
with vacuum ultraviolet photons (lp200 nm), which are not present in the solar spectrum.
Initially, the DC mechanism whereby one thulium (Tm3+) or terbium (Tb3+) ion (2.6 eV)
gives up its energy to two ytterbium (Yb3+) ions (1.2 eV) seemed promising, resulting in a
narrow emission peak at 970 nm [12,13]. However, a recent literature survey performed
on DC-PV by the author did not identify any promising rst-order linear DC processes
that would be applicable to Si PV [7]. In addition, it should be pointed out that since a
fraction of the luminescence will escape back out the front top surface of the DC layer. If

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the luminescent species are contained within a host material with a refractive index of
n 1:5, this amounts to a 12.7% loss, meaning that a DC with an EQE of 4115% is
required just to break even [6]. Thus, due to the lack of apparent DC mechanisms that are
relevant to Si devices operating under terrestrial sunlight, DC-PV devices will not be
discussed further here.
5. DS for photovoltaics (DS-PV)
DC processes that occur with a sub-unity efciency can still be interesting for
application to silicon solar cells, and are referred to as luminescence (or wavelength) downshifting (DS). To date, two general kinds of DS-PV devices have been investigated,
including luminescent solar concentrators (LSC) and wavelength DS to overcome solar cell
limitations. These different applications of DS-PV will be discussed in greater detail below.
5.1. Luminescent solar concentrators
A cross-sectional diagram of an LSC is shown in Fig. 6, where solar cells are now
attached to the thin edges of the sheet. With the LSC, light is incident on the front surface
and is then absorbed and subsequently re-emitted isotropically by a luminescence centre.
The luminescence is then transported to solar cells at the edges of the sheet by total internal
reection (TIR). While the DS inherently results in the loss of energy as heat, and hence a
reduction in the achievable energy conversion efciency, the total power (P) generated by
the LSC system can be much greater than that of the PV cell alone because of the
concentration of light at the edge of the module by TIR. The primary motivation to move
towards a LSC conguration is when the cost of solar cells contributes a signicant
fraction of the nal module cost. Benets that can be gained by moving to a LSC
conguration include:

The concentrator is static, thus no tracking mechanism is required to follow the Sun,
and good performance is achieved even under cloudy conditions.
The upper limit on the concentration ratio is given by the geometric ratio of the sheet,
G Afront surface/Aperimeter, however, in practice the maximum concentration expected is
Escape Cone Losses

Incident Light
Reflection

Surface Scattering

Re-absorption
TIR

t
Absorption
L

PV Cell

Escape Cone

Fig. 6. Cross-sectional diagram of a LSC with luminescence centres (K) contained within thin, large-area
transparent sheets with PV cells attached to the edge. Light is transported to the edge via TIR, incurring some
losses along the way, such as self-absorption, scattering and the escape of light emitted within the critical angle (w).

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B.S. Richards / Solar Energy Materials & Solar Cells 90 (2006) 23292337

up to 20 Suns. Therefore, the LSC technology can rely on existing silicon solar cells,
such as the Sliver cell, which exhibit ideal aspect ratios [14].
The large sheets of the LSC technology are ideally used as a building-integrated
photovoltaic (BIPV) product, replacing the large sheets of glass used in the fac- ades of
ofce buildings, thus offsetting further costs on new installations.
As the solar cell see only cold light, the PV cells at the edge operate cooler and
therefore more efciently.

While the rst papers on LSCs appeared in the mid-1970s [15,16], renewed interest in
these devices has been driven by the development in new materials that were not available
two decades ago, such as semiconductor quantum dots [17] and new NIR emitting organic
dye molecules [18]. One unique kind of LSC proposed is the use of DS luminescent bres
connected to solar cells to recharge lithium ion batteries in unattended ground sensors [19].
In this case, uorescent bres are used to overcome the challenge of avoiding shadowing of
a series-connected array of solar cells, and the uniform illumination afforded by the bres
resulted in a measured output power density of up to 75 mW/cm2 for the 20.5 mm2 PV
array [19].
5.2. DS to overcome device limitations
In the late 1970s, Hovel et al. [20] realised that instead of concentrating the sunlight, the
wavelength shifting property could also be used to overcome poor solar cell performance
to UV/blue light. In this scenario, the glass or polymeric sheet containing the luminescent
species replaces the cover sheet used in at-plate PV modules. High-energy light is
absorbed, and subsequently re-emitted at a slightly longer wavelength where the EQE of
the solar cells is much higher. For example, thin lm solar cells that rely on cadmium
sulphide (CdS) window layers actually exhibit a large amount of parasitic absorption at
wavelengths shorter than 510 nm, however, by DS these photons to longer l a 33%
increase in power has been achieved [21]. In the case of Si solar cells, DS can overcome the
effects of poor front surface passivation, however, the increase in device performance was
not as dramatic [22]. Once again, it should be remembered that a fraction of the
luminescence will be lost via the escape cone at the front surface.
6. Conclusions
The application of luminescent devices to existing silicon solar cells have the potential to
enhance their performance by overcoming the traditional loss mechanisms of single
junction devices. This paper describes three ways in which luminescence devices can be
used to alter the solar spectrum, with the ultimate aim of enhancing the energy conversion
efciency. Initial promising results are presented in the areas of UC, however, this will
always be a nonlinear process and perhaps, at the end of the day, more applicable to
enhancing the spectral response of silicon photodiodes. There seem to be limited options
for the DC of higher-energy sunlight to a wavelength just above the Si band gap with an
EQE4100%. However, luminescent DS can offer several advantages in the form of LSCs
and overcoming device limitations, and research is being further pursued in this area.

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Acknowledgements
The author would like to gratefully acknowledge the funding assistance provided by the
CASS Foundation Limited (Australia). In addition, the author would like to thank the
following people for their contribution to the experimental work on up-conversion: Avi
Shalav (Centre of Excellence for Advanced Silicon Photovoltaics and Photonics,
University of New South Wales, Sydney, Australia); and Daniel Biner, Karl Kramer
and Hans Gudel (Department of Chemistry, University of Bern, Switzerland).
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