WHITE PAPER

THIRD GENERATION PHOTOVOLTAICS: RECENT THEORETICAL PROGRESS

Martin A. Green
Special Research Centre for Third Generation Photovoltaics,
University of New South Wales,
Sydney, Australia, 2052
Telephone: +61-2-9385-4018; Facsimile: +61-2-9662-4240; Email: m.green@unsw.edu.au


ABSTRACT: A common perception in photovoltaics has been that first generation silicon wafer-based solar cells
eventually would be replaced by a second generation of lower cost thin-film technology, probably also involving a
different semiconductor. Historically, CdS, a-Si, CuInSe
2
, CdTe and, more recently, thin-film Si have been key thin-
film candidates. Since mature mass-produced technologies usually evolve to the stage where costs are dominated by
those of the constituent materials, be it silicon wafers or glass sheet, it is argued that photovoltaics will evolve, in its
most mature form, to a third generation of high-efficiency thin-film technology, with energy conversion values
double or triple the 15-20% range presently targeted. Tandem cells provide the best known example of such high
efficiency approaches, where efficiency can be increased merely by adding more cells of different bandgap to a stack.
However, several more parallelled approaches are possible that offer similar efficiency to an infinite stack of
tandem cells. Efficiency limits for several such options are analysed on a self-consistent basis.
Keywords: Fundamentals 1: High Efficiency 2: Thin Film - 3


1. INTRODUCTION

Most solar cells on the market are based on silicon wafers,
dubbed first generation technology. For the past 15
years, the industry has seemed on the verge of switching to
a second generation of thin-film cell technology.
Regardless of semiconductor, thin-films offer prospects for
a major reduction in material costs by eliminating the
silicon wafer. Thin-films also offer other substantial
advantages, such as the increase in the manufacturing unit
from a silicon wafer (~ 100 cm
2
) to a glass sheet (~ 1 m
2
),
about 100 times larger. In terms of energy conversion
efficiency, this second generation technology, with time,
may largely bridge the present gap between it and first
generation product.
As thin-film second generation technology matures,
costs will become progressively dominated by those of the
constituent materials, in this case, the top cover sheet and
other encapsulants required for a 30-year operating life. To
progress further, conversion efficiency needs to be
increased substantially. The Carnot limit on the conversion
of sunlight to electricity is 95% as opposed to the
theoretical upper limit of 33% for a single junction cell,
such as silicon and most present thin film cells. This
suggests performance could be improved 2-3 times if
different concepts were used to produce a third
generation of high performance, low-cost photovoltaic
product [1].
In the following, photovoltaic performance limits and
possible third generation approaches are reviewed.


2. PHOTOVOLTAIC EFFICIENCY LIMITS

The conversion efficiency of energy from a source at 6000
K with a sink at of 300 K is limited by the Carnot
efficiency (1 T
sink
/T
source
) to 95.0%. However, this value
does not count the photons emitted by the converter as a
waste, since it assumes they get back to the sun, helping it
to maintain its temperature! A limit that regards these
photons as a loss while assuming the conversion process is
reversible, as in the Carnot limit, is 93.3% [2].
However, this result overlooks the fact that there is an
unavoidable rate of entropy generation associated with any
steady-state absorption process. There is no way of
avoiding this entropy production when an attempt is made
to extract energy from a conversion device, no matter how
perfect its design.
A new principle [3] allows the minimum possible
entropy generation rates associated with a finite absorption
rate to be calculated under conditions of interest in
evaluating limiting efficiencies. This principle states that
absorption sites over the absorption volume for each
photon energy (hf) must be emitting radiation at a uniform
photon spontaneous emission rate [or, more correctly,
chemical potential
sp
(hf)] (Figure 1).



Figure 1: Conditions for minimising entropy production
during absorption, i.e., constant spontaneous emission rates
over the absorption volume (see text).
Applying this principle shows that the maximum power
-
W
that can be extracted from any solar converter is given by:
) ( )] ( ) ( )[ (
}
=
- - -
o
out in
sp
hf d hf n hf n hf W (1)
where
in
n
-
and
out
n
-
are the input and emitted photon flux.
In the idealised conditions leading to maximum possible
efficiencies, ) (hf n
out
-
is given by a generalised form of the
black-body Plankian emission expression:
1 ] / ) exp[(
) ( ) ( 2
) ( ) (
2
2 3

=
-
kT hf
hf d hf
c h
A
hf d hf n
sp
out

t
(2)

where A is cell area, c the vacuum light velocity, T the cell
temperature and h and k are Planck and Boltzmann
constants. If the sun is modelled as a black-body at
temperature T
s
and the sunlight is fully concentrated, as
consistent with obtaining maximum efficiency,
in
n
-
is
given by an identical expression, but with
sp
= 0 and T
replaced by T
s
. In an arbitrary case, the reverse procedure
can be used. The value of an effective temperature T
s
(hf)
corresponding to
in
n
-
can be found. Simply by
differentiating Eq. (1) with respect of
sp
, its optimum
value can be found implicitly as[3]:

+
+

=
] / ) exp[( ] 1 ) / [( 1
] / ) exp[( ) / ( 1
ln ) / (
) / 1 (
kT hf kT
kT hf kT
q kT
T T hf
sp sp
sp sp
s sp

(3)

The approximate form of this solution is shown in Fig. 2.
For constant T
s
, optimum
sp
is a monotonically increasing
function of hf, always less than the first term on the right
hand side. Inserting the solution to this equation back into
Eq. (1) allows the maximum efficiency to be calculated
(86.8% for a sun at 6000 K and an ambient of 300 K).

E(1-T/T
s
)

opt
Optimum
Chemical
Potential
hf, Photon Energy


Figure 2: Optimum chemical potential versus photon
energy (black-body source; schematic only).

The form of Eq. (3) suggests that a reasonable
approximation for the optimum
sp
would be to keep it a
fixed fraction of hf. This gives 85.4% for the limiting
efficiency for the optimum fraction, quite close to the
unconstrained optimum efficiency.
However, using a
sp
that steps from zero to a constant
value at the bandgap, as in a single junction cell, gives an
efficiency of 40.7% under the best conditions. This shows
the potential for greater than 2 times higher efficiency
using third generation approaches.


3. TANDEM CELLS

The tandem cell concept, as in Fig. 3, allows a staircase
approximation to the optimal chemical potential, with
variable step size (Fig. 4).
Performance increases as the number of cells in the
stack increases, with a direct sunlight conversion efficiency
of 86.8% calculated for an infinite stack of independently
operated cells [4], the highest possible value.
Solar cells
Sunlight
Decreasing band gap

Figure 3: Tandem cell approach.

Having to independently operate each cell is a
complication best avoided. Usually cells are designed with
their current outputs matched so that they can be connected
in series. This constraint reduces achievable performance.
More importantly it makes the design very sensitive to the
spectral content of the sunlight. Once the output current of
one cell in a series connection drops more than about 5%
below that of the next worst, the best for overall
performance is to short-circuit the low output cell,
otherwise it will consume, rather than generate power.
Tandem cells are now in commercial production.
Double and triple junction cells based on GaInP/GaAs/Ge
have been developed for use on spacecraft with terrestrial
efficiencies approaching 30%. Quadruple junction devices
with efficiencies approaching 40% are presently under
development. Tandem cells are also used to improve the
performance and reliability of terrestrial amorphous silicon
cells with stabilised efficiencies up to 12% confirmed for
triple junction cells based on the Si:Ge:H alloy system.
Modules with efficiencies up to 6-7% are available
incorporating double and triple junction devices.

E(1-T/T
s
)

opt

j
(tandem)
E
1
E
2
E
3
E
4
E
5 E,Energy
Optimum
Chemical
Potential


Figure 4: Staircase approximation to optimum using
tandem cells (cells with bandgap E
i
used).


4. MULTIPLE ELECTRON-HOLE PAIRS

If, instead of giving up their excess energy as heat, the high
energy electron-hole pair used it to create additional pairs,
higher efficiency would be possible (Fig. 5). Evidence for
the creation of more than one pair by high energy photons
is documented, attributed to impact ionisation by the
photoexcited carriers.
On energy grounds at least, many electron-hole pairs
could be generated by each incident photon. Ideally, the
quantum conversion efficiency of an ideal device would
appear as in Fig. 5(b). In reality, the measured effect to
date is so weak so as to produce only modest increases
above unity, even at short wavelengths. Competitive
processes for the relaxation of the high energy
photoexcited carriers are too efficient.
In the ideal case, spontaneous emission of a single
photon would involve the simultaneous recombination of
several lower energy electrons. The corresponding
chemical potential is therefore multiplied by the number of
electrons recombination events per photon. This allows a
staircase approximation (constant step size) to the optimum

sp
variation with hf.

3.0
2.0
1.0
0
IQE

G


Figure 5: (a) Multiple electron-hole pair generation; (b)
Internal quantum efficiency versus wavelength.

For bandgaps approaching zero, the staircase approximates
a straight line, leading to 85.4% as for the constant fraction
case of Section 2. A slightly better approximation is
obtained with the fine staircase obtained with a bandgap of
only 50 meV, giving an efficiency of 85.9% [5].


5. HOT CARRIER CELLS

When photoexcited carriers collide elastically with one
another, no energy is lost. It is inelastic collisions with the
atoms of the cell material that result in an energy loss
(through phonon emission). In principle, if such atomic
collisions can be avoided during the time it takes a
photogenerated carrier to cross the cell, such thermalisation
loss can be avoided.
Carriers either have to traverse the cell very quickly or
cooling rates have to be slowed in some way. Radiative
recombination rates also need to be faster than cooling
rates for maximum efficiency. Carriers can only be
extracted at a single energy if maximum performance is to
be obtained.
In a previous analysis of hot carrier cells [6], both
bands were assumed at a constant temperature. This allows
a linear
sp
increase with increasing hf. The chemical
potential associated with each band can also be adjusted
independently in principle. With this zero, the limiting
efficiency is 85.4%. The extra adjustment possible by
having a finite potential increases the limiting efficiency to
86.2% [7].
In our recent work, we have shown that control of the
effective mass as in Fig. 6, plus different carrier
temperatures in each band gives an abundance of
parameters in controlling the spontaneous emission
chemical potential. This allows the limiting efficiency of
86.8% to be obtained by hot carrier cells in principle.

E
G
E
T


Figure 6: Band structure required for limiting hot carrier
solar cell performance (schematic only).


6. MULTIBAND CELLS

Standard cells rely on excitations between the valence and
conduction band. A recent analysis [8] has shown
advantages if a third band, nominally an impurity band, is
included in the analysis (Figure 7).

1 2
3
finite
band
width


Figure 7: Three band solar cell. The finite bandwidth
reduces efficiency below calculated limits but allows the
required photon absorption selectivity to be implemented.

This theory has been extended to an n-band cell and
additional implementation approaches discussed [9]. These
include using excitations between minibands in
superlattices, if phonon relaxation processes can be
controlled, the use of semiconductors with multiple narrow
bands, such as I-VII and I
3
-VI compounds or the use of
high concentrations of impurities such as rare-earths to
form multiple impurity bands in wide bandgap
semiconductors. In some configurations, multiple quantum
well devices can also be described by this theory.
The limiting efficiency for an n-band cell is identical to
the 86.8% figure for a large stack of tandem cells.

7. IMPURITY PHOTOVOLTAIAC EFFECT

Cells relying on the impurity photovoltaic effect are closely
related to multi-band cells. The new entropy generation
principle shows that each defect site must be at the same
chemical potential for optimum performance. Fortunately,
this requirement greatly simplifies the analysis.
With one single impurity type, the efficiency limit is
the same as for a single band. However, since optical
excitations between impurity levels, only transitions
between impurity levels and the conduction or valence
band need be considered. This difference restricts the
efficiency of a device with an infinite number of optimally
selected defect level energies to a more modest 77.2% [10].


8. THERMOPHOTOVOLTAIC AND THERMO-
PHONIC DEVICES

Thermophotovoltaics is a well-established branch of
photovoltaics where a light from a heated body other than
the sun is used as the illumination. A development of this
approach has been dubbed thermophotonics.
Figure 8 shows the basic arrangement which is nearly
symmetrical. Two diodes acting as solar cells/light
emitters face each other, connected by a load. Heat is
supplied to one to heat it hotter than the other and heat is
extracted from the other to cool it. The devices are
optically coupled but thermally isolated. The combination
is able to convert heat supplied to the hotter device to
electricity in the load with an efficiency approaching the
Carnot efficiency, in principle. Basically, the heated
device acts as an emitter of narrow bandwidth light within
an energy, kT, of its bandgap energy. This near-
monochromatic light can be converted very efficiently by
the cell. Moreover, light emitted by the cell is recycled
back to help drive the light emitting diode. Since the same
current flows in the cell and source diode, the voltage
across the diode will be smaller than that across the cell
when the diode is at higher temperature. This results in
power dissipation in the load.

N P P N
I
L
I
C
Q
C
Q
L
T
L
T
C
R
I


Figure 8: Thermophotonic conversion (conceptual only).

Both experimental solar cells and light emitting diodes are
approaching the stage where internal recombination can be
limited by radiative processes, a prerequisite for this
scheme. If used to convert solar radiation in conjunction
with a thermal absorber, energy conversion efficiency up to
85.4% is obtainable in principle. Alternatively, the
approach could be used for maximally efficient conversion
of fossil fuels or waste heat, particularly when the heat is
available at low temperature.


8. CONCLUSION

Unavoidable entropy production associated with light
absorption that limits solar energy conversion efficiency to
86.8% (6000 K sun, 300 K sink). To reach this efficiency,
converters must be perfectly absorbing but re-emit light
with a specific spectral content. The chemical potential
associated with spontaneous emission for each photon
energy must have a particular value and be constant
throughout the absorption volume.
Several advanced conversion approaches are shown
capable, in principle, of meeting these requirements
(tandems, hot carrier, multiple band cells). Others are
bound by a slightly low energy conversion efficiency of
85.4% (thermophotovoltaic). A third group (multiple
electron-hole pairs) has intermediate bounds, while the
impurity photovoltaic effect has an efficiency bound of
77.2%. All are appreciably higher than the bound for a
conventional cell (40.7%).


9. ACKNOWLEDGEMENTS

The author gratefully acknowledges the contributions of
many others particularly the following associated with the
Centre for Third Generation Photovoltaics: Andrew Brown,
Kylie Catchpole, Richard Corkish, Eun-Chel Cho, Nils
Harder, Albert Lin, Holger Neuhaus, and Thorsten Trupke.
The author is supported by an Australian Research Council
Senior Research Fellowship. The Centre for Third
Generation Photovoltaics is supported by the Australian
Research Councils Special Research Centres Scheme.


10. REFERENCES

[1] M.A. Green, Third Generation Photovoltaics:
Ultra-High Conversion Efficiency at Low Cost,
Progress in Photovoltaics 9, (2001) 123.
[2] P.T. Landsberg, Thermodynamics and Statistical
Mechanics, Dover, New York, 1990
[3] M.A. Green, unpublished work.
[4] A. Marti and G.L. Araujo, Limiting Efficiency for
Photovoltaic Energy Conversion in Multigap
Systems, Sol. En. Mats. Sol. Cells 43 (1996) 203.
[5] A. De Vos and B. Desoete, Sol. En. Mat. Sol. Cells
51 (1998) 413.
[6] R.T. Ross and A.J. Nozik, Efficiency of Hot-
Carrier Solar Energy Converters, J. Appl. Phys. 53
(1982) 3813.
[7] P. Wurfel, Solar Energy Conversion with Hot
Electrons from Impact Ionisation, Sol. En. Mats.
and Sol. Cells 46 (1997) 43.
[8] A. Luque and A. Marti, Increasing the Efficiency
of Ideal Solar Cells by Photon Induced Transitions
at Intermediate Levels, Phys. Rev. Lett. 78 (1997)
5014.
[9] M.A. Green, Prog. Photovoltaics 9 (2001) 137.
[10] A. Brown and M.A. Green, these proceedings.