Enhancing solar cells with photochemical upconversion

Tim Schulze, Klaus Lips and Timothy W. Schmidt

Triplet-triplet annihilation in organic molecules increases the photocurrent of thin-film solar cells.
17 March 2014, SPIE Newsroom. DOI: 10.1117/2.1201403.005390

Photovoltaics have the potential to become a major contributor to future sustainable energy generation. To
this end, device efficiency needs to be brought beyond present physical limits. Solar cells cannot absorb
light with less energy than the bandgap (absorption threshold of the photovoltaic absorber material), and
consequently this energy source is usually uncaptured. Upconversion (UC) devices harvest those unused
subthreshold photons behind the solar cell, create one higher-energy photon out of (at least) two
transmitted photons, and radiate upconverted light back toward the solar cell, thus expanding the usable
solar spectrum (see Figure 1). Key requirements for UC units are broad absorption and high UC quantum
yield under even the low-intensity incoherent illumination that is available to solar energy conversion
devices.

Figure 1. Principle of a solar cell assisted by upconversion (UC). The creation of usable electron-hole
pairs in the photovoltaic absorber material (left) is augmented by light, usually transmitted unused, which
is converted to higher photon energies in the UC unit (right).
Upconversion was proposed as a means to increase solar cell efficiency about a decade ago, 1 and
research has since then been primarily focused on UC processes occurring in lanthanide-doped glasses
or nanoparticles.2 Although transitions between the rare earth 4f orbitals lie in an energy range promising
for combination with common crystalline silicon solar cells, UC systems based on erbium (Er) or ytterbium
(Yb) suffer from weak absorption by Laporte-forbidden transitions, a narrow absorption bandwidth, and
the resulting low efficiency. Recently, triplet-triplet annihilation (TTA) in organic molecules has been
demonstrated to be an alternative UC mechanism highly promising for solar energy application. 3 It
proceeds efficiently even for low photon flux and displays highly tunable absorption characteristics.

The key to high quantum yield from TTA-UC lies in the combination of two different classes of organic
molecules dissolved together in organic solvents or in a polymeric host matrix. 4 A so-called sensitizer
species, which in many cases is a metalated porphyrin, absorbs a low-energy photon (process 1 in Figure
2) and undergoes fast intersystem crossing (ISC, process 2), whereby the spin of the exciton changes
from 0 (singlet, electron and hole spin cancel) to 1 (triplet, electron and hole spin add). This change of
spin state is facilitated by the heavy metal in the porphyrin center. The resulting triplet state cannot
radiatively relax back to the ground state and is therefore long-lived. Interaction with a second class of
molecule transfers the triplet energy to the so-called emitter species by triplet energy transfer (TET,
process 3). Successive interaction of two emitters yields TTA (process 4), which combines the two triplet
excitons to create one higher-energy singlet state. The singlet state quickly relaxes back to the ground
state under efficient emission of a high-energy photon (process 5).

Figure 2. Top: Working principle of triplet-triplet annihilation upconversion (TTA-UC) shown on a

schematic energy diagram. A key role is played by the long-lived triplet states T x of the organic molecules,
which cannot decay quickly due to quantum-mechanical laws. Bottom: Picture of the TTA-UC effect. ISC:
Intersystem crossing. Sx: Singlet states. TET: Triplet energy transfer.
We recently explored the feasibility of TTA-UC for expanding the spectral harvest of thin-film solar cells.
We combined TTA-UC systems comprising tailored molecular sensitizer species 5 with amorphous silicon
(a-Si) solar cells,6, 7 with organic bulk heterojunction solar cells,8 and with dye-sensitized solar cells.9 We
defined a figure of merit (FOM) for UC-assisted solar cells, which takes into account the inherent
nonlinearity of the UC process in the benchmarking of different UC systems. Usually, UC systems are
measured under highly concentrated illumination, which hinders a fair comparison of UC units measured
under different conditions. Our FOM traces the UC performance back to conditions equivalent to the
standard operation of a solar cell,6 and equals the photocurrent increase by UC under 1-sun conditions.
Using the FOM for guidance, we concentrated on increasing the performance of the solar cell/UC
assembly. Shifting the sensitizer absorption into the IR by extending the -system of the palladated
sensitizer porphyrin led to a fourfold increase of the FOM6 compared with the original sensitizer species,

using 130nm-thick hydrogenated a-Si (a-Si:H) cells. This preliminary result already beats the state of the
art for a-Si:H cells augmented by rare-earth UC by a factor of about 200. 10 Combining the UC unit with a
back-reflecting surface helps to multi-pass the incident light as well as to out-couple the upconverted light,
and led to a consecutive increase of the FOM7 by another factor of 3 to about 23104mA/cm2. Roughly
the same level of photocurrent enhancement could be obtained for organic bulk heterojunction solar cells 8
as well as for dye-sensitized solar cells with a fully device-integrated UC unit. 9 The latter result was
measured under illumination conditions very similar to device operation, reaching concentration factors as
low as 3 suns. Our current record FOM stands at 7.610 4mA/cm2, obtained with an a-Si:H solar cell
optimized for low parasitic absorption.8
In summary, we have shown cumulative FOM improvements of roughly three orders of magnitude
compared with lanthanide-based UC and a first move toward device-integrated UC units. However, the
photocurrent increase under 1 sun achieved to date is still far from commercially relevant. We are
therefore now working to increase the UC yield under low-illumination conditions. We are following two
strategies in parallel and have recently obtained initial, promising results. First, we are increasing the dye
concentration by tethering the UC-active molecules onto nanosized support structures to increase the
steady-state triplet density and therefore the UC yield.11 Second, we are focusing the incident light locally
in the UC layer using micro-optical structures such as parabolic back-reflectors. 12 In combination, these
strategies will enable us to exploit near-field optical effects such as plasmonic resonances or wave-guide
modes once characteristic absorption lengths in the 10100nm range have been reached, which should
make further increases in the UC yield possible. We are confident that TTA-UC will contribute significant
photocurrent to high-gap solar cells and photoelectrochemical devices for fuel production in the near
future.
T. F. S. acknowledges a Feodor-Lynen fellowship from the Alexander von Humboldt Foundation. T. W. S.
acknowledges Australian Research Council funding FT130100177, DP110103300, and project funding
from the Australian Renewable Energy Agency.

Tim Schulze, Klaus Lips

Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH
Berlin, Germany
Timothy W. Schmidt
The University of New South Wales
Sydney, Australia

References:
1. T. Trupke, M. A. Green, P. Wrfel, Improving solar cell efficiencies by up-conversion of sub-band-gap light, J. Appl. Phys. 92, p. 4117-4122,
2002.
2. M. Haase, H. Schfer, Upconverting nanoparticles, Angew. Chem. Int'l Ed. 50(26), p. 5808-5829, 2011.
3. S. Baluschev, T. Miteva, V. Yakutkin, G. Nelles, A. Yasuda, G. Wegner, Up-conversion fluorescence: noncoherent excitation by sunlight,
Phys. Rev. Lett. 97, p. 143903, 2006.
4. Y. C. Simon, C. Weder, Low-power photon upconversion through triplet-triplet annihilation in polymers, J. Mater. Chem. 22, p. 20817, 2012.

5. T. Khoury, M. J. Crossley, A strategy for the stepwise ring annulation of all four pyrrolic rings of a porphyrin, Chem. Commun. 46, p. 48514853, 2007.
6. Y. Y. Cheng, B. Fckel, R. W. MacQueen, T. Khoury, R. G. C. R. Clady, T. F. Schulze, N. J. Ekins-Daukes, et al., Improving the lightharvesting of amorphous silicon solar cells with photochemical upconversion, Energy Environ. Sci. 5, p. 6953-6959, 2012.
7. T. F. Schulze, Y. Y. Cheng, B. Fckel, R. W. MacQueen, A. Danos, N. J. L. K. Davis, M. J. Y. Tayebjee, et al., Photochemical upconversion
enhanced solar cells: effect of a back reflector, Aust. J. Chem. 65, p. 480-485, 2012.
8. T. F. Schulze, J. Czolk, Y.-Y. Cheng, B. Fckel, R. W. MacQueen, T. Khoury, M. J. Crossley, et al., Efficiency enhancement of organic and
thin-film silicon solar cells with photochemical upconversion, J. Phys. Chem. C 116(43), p. 22794-22801, 2012.
9. A. Nattestad, Y. Y. Cheng, R. W. MacQueen, T. F. Schulze, F. W. Thompson, A. J. Mozer, B. Fckel, et al., Dye-sensitized solar cell with
integrated triplet-triplet annihilation upconversion system, J. Phys. Chem. Lett. 4, p. 2073-2078, 2013.
10. J. de Wild, J. K. Rath, A. Meijerink, W. G. J. H. M. van Sark, R. E. I. Schropp, Enhanced near-infrared response of a-Si:H solar cells with
-NaYF4:Yb3+ (18%), Er3+ (2%) upconversion phosphors, Sol. Energy Mater. Sol. Cells 94, p. 2395-2398, 2010.
11. R. W. MacQueen, T. F. Schulze, T. Khoury, Y. Y. Cheng, B. Stannowski, K. Lips, M. J. Crossley, T. Schmidt, Nanostructured upconverters
for improved solar cell performance, Proc. SPIE 8824, p. 882408, 2013. doi:10.1117/12.2026907
12. T. F. Schulze, Y. Y. Cheng, T. Khoury, M. J. Crossley, B. Stannowski, K. Lips, T. W. Schmidt, Micro-optical design of photochemical
upconverters for thin-film solar cells, J. Photon. Energy 3(1), p. 034598, 2013.

2 Basic Principles of Photovoltaics

As the heading is telling, this section will focus on basic function of photovoltaics. This includes how
the solar resource works, types of solar energy converters, the principle of detailed balance, work
available from a PV cell and its efficiency.

2.1 Solar Radiation

To a good approximation, the Sun acts as a perfect emitter of radiation at a temperature close to 5800
K, and thus considered as a black body. The Sun emits electromagnetic light in various wavelengths:

UV (<400 nm)

Visible (400-800 nm)

Infrared (>800 nm)

Figure 2.1 shows the solar irradiance outside the earth's atmosphere, denoted byAM0, and at sea level,
denoted byAM1.5.

Figure 2.1 The solar spectrum. Hence the temperature for the black body, which is 5523 K in this case.
As the solar radiation passes the atmosphere, a part of the incident energy is removed by absorption or
scattering by molecules, clouds and aerosols. Wavelengths less than 300 nm is filtered out by molecules
like ozone, nitrogen and oxygen. Dips in the infrared area are caused by water and CO 2.
Did you know...
...that Earth receives more energy from the Sun in just one hour than the world uses in a whole year?

If the surface temperature on a black body is the same everywhere, the spectral photon flux normal to
the surface is

(2.1)
Fs is a geometrical factor, and is equal to just at the surface of the black body. Away from the
surface, the angular range is reduced and

(2.2)
On the earth Fs is reduced by a factor of 4.6 104, to 2.16 10-5 .
The total emitted power density is
(2.3)
where s is Stefan's constant:

At the sun's surface this power density is 62 MW/m2, and at a point just outside the atmosphere the
power density has shrunk to 1353 W/m2 because of the reduced angular range of the sun.

2.2 Solar Energy Converters

There are mainly three kinds of solar energy converters

The photovoltaic converter

The solar thermal converter

The photochemical converter

2.2.1 The Photovoltaic Converter

The photovoltaic converter transforms the photon energy into electrochemical potential energy. To
prevent the excited electrons from falling back into their ground state, there is some built-in
asymmetry that pulls the excited electrons away before they can relax. The extra energy of the
excited electrons generates a potential difference, , and it is this force that drives the electrons into
the external circuit and exerts work. The excited state (conduction band) and ground state (valence
band) are separated by an energy gap, also called band gap. The band gap's function is to maintain the
excited electrons at the high energy for a long time compared to the thermal relaxation time, so that
they can be collected. Note that electrons in each of the different bands relax to form aQTE with a
differentQFL.

Figure 2.2. A photon (yellow) excites

an electron (blue) to a higher energy and is pulled away by some mechanism of charge separation.
For a two band system, the Gibbs free energy represents the increase in electrochemical potential
energy:

where N is the number of promoted electrons, and is the difference in potential energy between
excited and ground state population.
In equilibrium, is zero. Thus, a ground state that is full initially and an excited state that is empty,
would give the best outcome in extraction of energy. This is one of many reasons why semiconductors
are beneficial among all the selections of materials.
You might think that solar cells cope well with increased temperature since they in fact are solar cells.
But the truth is that increased temperature can decrease the efficiency of photovoltaic conversion.
The most significant is the temperature dependence of the voltage which decreases with increasing
temperature. The temperature variation of the current or the fill factor are less pronounced. The
voltage decrease of a silicon cell is typiclly 2.3mV per C. Thus they are designed to be in good thermal
contact with the ambient.

Figure 2.3: This is an illustration on how the voltage will decrease with increasing temperature of the
cell.

2.2.2 The solar thermal converter

In a solar thermal converter, radiation absorbed is converted into internal energy and the temperature
of the cell is raised. Because of the difference in temperature between the cell and the surroundings,
the cell can now act as a heat engine and do work. In order to maximize the working temperature
difference, the cell is thermally insulated from the ambient.

2.2.3 Photochemical energy converter

A photochemical energy converter works almost exactly like a photovoltaic energy converter, the only
difference is that instead of converting the energy directly into electricity, the energy results in a
permanent increase in chemical potential.

2.3 Performances of a PV cell

The principle of detailed balance is utilised when describing the performance of a photovoltaic cell. As
the solar energy converter absorbes the radiant energy, it also emits thermal radiation to its
surroundings. The ratio between absorbtion and emission must be equal so that in the steady state the
concentration of electrons in the cell remains constant.

2.3.1 In equilibrium
Consider a cell in the dark and in thermal equilibrium with the ambient, which radiates like a black
body, then the equivalent current density absorbed from the ambient is
(2.4)
where a(E) is the probability of absorption, the absorptivity, of a photon of energy E, and R(E) is the
probability of photon reflection.
Let us take a look at some collectors of area A:

If the rear surface of the cell is in contact with air, the total equivalent current is

If the rear surface of a cell is in contact with a material of higher refractive index, n s, the total
equivalent current is

If the rear surface acts as a perfect reflector (capable of reflecting thermal photons), the
totalt equivalent current for absorbed thermal photons is

In the last case the device efficiency is greatest.

Emission of thermal photons by spontanious emission is necessary to maintain a steady state. If is the
emissivity, the equivalent current density for photon emission through the surface of the cell is
(2.5)
Steady state is maintained if (2.4) and (2.5) are balanced: (E)=a(E)

2.3.2 Illumination
The equivalent current density for photon absorption under illumination is given by

(2.6)
Under illumination the system develops a chemical potential, > 0. This results in increased
spontanious emission as more excited electrons causes more relaxation events. The photon flux
emitted normal to the surface

(2.7)
where

(2.8)
n0 is the refractive index of the ambient. If again is the probability of photon emission, the equivalent
current density for photon emission is
(2.9)
The net equivalent current density is then
(2.1
0)

2.4 Work from a PV cell

2.4.1 Photocurrent and dark current
We now have sufficient information to calculate the absolute limiting efficiency of a photovoltaic
converter. Assuming perfectly non-reflecing absorbing material, all incident photons of energy E > E g
are absorbed, and perfect charge separation, no radiative recombination, the maximumphotocurrent
for a given band gap is

(2.11)
Notice that thephotocurrent is a function only of the band gap and the incident spectrum. The lower E g
is, the greater Jsc will be.
Current that flows through the photovoltaic device when a bias voltage is applied in the dark is called
dark current. The output current J(V) is equal to the difference between the light-generated current
Jsc, and the diode current Jdark(V).

As V increases (larger Eg), the emitted flux, which is concentrated on photon energies near E g, will
increase and thus result in a decrease of the net current. Note that, under open circuit, when J(V) = 0,
all the light-generated current passes through the diode. Under short circuit (V = 0), all this current
passes through the external load. The upper limit on the voltage is V = Eg/q. This means that Voc must
always be less than this in order to avoid being a light emitting device.

2.4.2 Limiting efficiency

If it is assumed that no potential is lost through resistance anywhere in the circuit, all collected
electrons should have of electrical potential energy and deliver of work to the external circuit.
Since = q V, the power conversion, based on P = V J(V) from (1.3) and J(V), is

(2.12)
and with maximum efficiency when

(2.13)

2.5 Effects of band gap and spectrum

Given the earlier assumptions, and with a fixed incident spectrum,depends only on the band gap. If
the band gap is very small, the working value of V would be too small. If it is very large,
thephotocurrent would be too small. For the standardAM1.5 solar spectrum, the maximumis around
33% at an Eg about 1.4eV.

Limiting efficiency for a single band gap solar cell inAM 1.5

Figure 2.4:

List of band gaps

Material

Band gap (eV)

crystalline Si

1.12

amorphous Si

~1.75

CdTe

1.45

GaAs

1.42

CdS

2.4

The spectrum of a 5760 K black body shows a limiting efficiency around 31% at an Eg about 1.3eV
outside the Earth's atmosphere (AM0). By reducing the temperature of the radient source (more
reddish), the optimal energy gap and efficiency decrease. Similarly, by increasing the temperature of
the source, optimal energy gap and efficiency both increases. In the case where T a (ambient
temperature) is zero and the black body temperature is 6000K, the optimum V is Eg/q, which gives a
maximum efficiency around 44% at a band gap of 2.2eV.
Another way of improving the effiency through the spectrum is by concentrating the light, so that
absorbed flux will increase relative to the emitted flux. For light concentrated by a factor of 1000, a
limiting effiency around 37% at Eg about 1.1eV is predicted. And as for a concentration up to 4.6 104
(the maximum),is over 40%. But these estimates ignore the fact that under high concentration the
cell will be heated, and emit more strongly.

2.1 Solar Radiation

To a good approximation, the Sun acts as a perfect emitter of radiation at a temperature close to 5800
K, and thus considered as a black body. The Sun emits electromagnetic light in various wavelengths:

UV (<400 nm)

Visible (400-800 nm)

Infrared (>800 nm)

Figure 2.1 shows the solar irradiance outside the earth's atmosphere, denoted byAM0, and at sea level,
denoted byAM1.5.

Figure 2.1 The solar spectrum. Hence the temperature for the black body, which is 5523 K in this case.
As the solar radiation passes the atmosphere, a part of the incident energy is removed by absorption or
scattering by molecules, clouds and aerosols. Wavelengths less than 300 nm is filtered out by molecules
like ozone, nitrogen and oxygen. Dips in the infrared area are caused by water and CO 2.
Did you know...
...that Earth receives more energy from the Sun in just one hour than the world uses in a whole year?

If the surface temperature on a black body is the same everywhere, the spectral photon flux normal to
the surface is

(2.1)
Fs is a geometrical factor, and is equal to just at the surface of the black body. Away from the
surface, the angular range is reduced and
(2.2)
On the earth Fs is reduced by a factor of 4.6 104, to 2.16 10-5 .
The total emitted power density is
(2.3)
where s is Stefan's constant:

At the sun's surface this power density is 62 MW/m2, and at a point just outside the atmosphere the
power density has shrunk to 1353 W/m2 because of the reduced angular range of the sun.

2.2 Solar Energy Converters

There are mainly three kinds of solar energy converters

The photovoltaic converter

The solar thermal converter

The photochemical converter

2.2.1 The Photovoltaic Converter

The photovoltaic converter transforms the photon energy into electrochemical potential energy. To
prevent the excited electrons from falling back into their ground state, there is some built-in
asymmetry that pulls the excited electrons away before they can relax. The extra energy of the
excited electrons generates a potential difference, , and it is this force that drives the electrons into
the external circuit and exerts work. The excited state (conduction band) and ground state (valence
band) are separated by an energy gap, also called band gap. The band gap's function is to maintain the
excited electrons at the high energy for a long time compared to the thermal relaxation time, so that
they can be collected. Note that electrons in each of the different bands relax to form aQTE with a
differentQFL.

Figure 2.2. A photon (yellow) excites

an electron (blue) to a higher energy and is pulled away by some mechanism of charge separation.
For a two band system, the Gibbs free energy represents the increase in electrochemical potential
energy:

where N is the number of promoted electrons, and is the difference in potential energy between
excited and ground state population.
In equilibrium, is zero. Thus, a ground state that is full initially and an excited state that is empty,
would give the best outcome in extraction of energy. This is one of many reasons why semiconductors
are beneficial among all the selections of materials.
You might think that solar cells cope well with increased temperature since they in fact are solar cells.
But the truth is that increased temperature can decrease the efficiency of photovoltaic conversion.
The most significant is the temperature dependence of the voltage which decreases with increasing
temperature. The temperature variation of the current or the fill factor are less pronounced. The
voltage decrease of a silicon cell is typiclly 2.3mV per C. Thus they are designed to be in good thermal
contact with the ambient.

Figure 2.3: This is an illustration on how the voltage will decrease with increasing temperature of the
cell.

2.2.2 The solar thermal converter

In a solar thermal converter, radiation absorbed is converted into internal energy and the temperature
of the cell is raised. Because of the difference in temperature between the cell and the surroundings,
the cell can now act as a heat engine and do work. In order to maximize the working temperature
difference, the cell is thermally insulated from the ambient.

2.2.3 Photochemical energy converter

A photochemical energy converter works almost exactly like a photovoltaic energy converter, the only
difference is that instead of converting the energy directly into electricity, the energy results in a
permanent increase in chemical potential.