Energy Conversion and Management 52 (2011) 426–430

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Cadmium sulfide enhances solar cell efficiency

Karl W. Böer *
Department of Physics and Astronomy, University of Delaware, Newark, DE 19711, United States

a r t i c l e i n f o a b s t r a c t

Article history: A thin layer of CdS of about 200 Å enhances the solar conversion efficiency of CdS/CdTe solar cells from 8%
Received 4 June 2010 to 15%. A similar enhancement of the efficiency is observed on other solar cells, based on CuInSe2 or sim-
Accepted 8 July 2010 ilar compounds. The reason for this efficiency enhancement that is typical for CdS, but not observed with
Available online 31 July 2010
similar semiconductors, is briefly described. The technical and economical importance of these solar cells
on the energy conversion market is summarized.
Keywords: Ó 2010 Elsevier Ltd. All rights reserved.
CdS
Solar cell efficiency
CdS/CdTe
Cd toxicity
Te supply
Solar cell economy

1. Introduction to the CdS/CdTe solar cell
Since the early 1950’s, cadmium telluride has been known as a
good candidate for solar cells since it could be doped n- and p-
type and its band gap at 1.45 eV is close to optimal for solar en-
ergy conversion [1,2]. A decade later it was observed that a layer
of cadmium sulfide on top could increase the conversion effi-
ciency from about 5% to about 8% [3–6]. Only in the 1980’s were
solar cells made by close spaced sublimation of a CdS/CdTe sand-
wich that achieved 12% conversion efficiency [7]. It took another
10 years before one learned that the thickness of the covering CdS
layer could be reduced to below 1 lm to prevent it from filtering
out a significant part of the solar spectrum beyond its band gap of
2.4 eV [8–19]. The next step was to deposit this sandwich on top
of a conducting glass (CTO) layer and further improve the current
collection capacity in larger cells and increase the efficiency fur-
ther. It was in 1991 that Ting L. Chu reached 15% efficiency
[20,21,10,22,12,13,23,15,16,24,18,25–28]. This opened the poten-
tial for significant commercial interest that was captured by a
dozen new start-up companies. However, a continuous produc-
tion process was not developed, and the early cells showed early
degradation problems.
The maximum solar conversion efficiency of the CdS/CdTe cell
that was already achieved in 2001 now stands, as confirmed by
NREL at 16.5% [29–31]. With further improved production and cell
stability, the conditions were given for a major commercial take-
* Tel.: +1 610388 0560.
E-mail address: solpax@aol.com
off, that, after several set-backs, was achieved by First Solar in
2005 to reach a production capacity of 25 MW/year.
For comparison, another group of promising thin-film solar cells
is the CIS group, with its first entrance as CdS/CuInSe2. Soon there-
after, other cells of similar type where produced in which In and Se
was replaced by homologous elements or their alloys. The best of
these cells surpassed CdS/CdTe cells by a few percentage points
(approaching almost 20%), However, the CdS/CdTe cell became
the preferred commercial solar cell because of the ease of repro-
ducible fabrication of large area cells, and their better long-term
stability. The production of a large area of these solar cells by rel-
atively simple vacuum deposition has lead to a further rapid devel-
opment of a thin-film solar cell industry.
The CdS/CdTe solar cell is produced by evaporation of a thin CdS
layer on top of a conductive glass substrate, followed by another
evaporation of a typically 2 lm thick CdTe layer and the deposition
of a metal contact layer to complete the initial process. The cell is
then treated for a short time at a temperature of about 450 °C, usu-
ally with a CdCl2 flux that causes a partial crystallization of the two
semiconductors, and this allows for the copper doping of the CdS in
the same process (the flux or other components at the outer inter-
face of the CdTe layer provides the source for this doping) [32]. All
of these procedures can be performed economically on a semi-
automatic production line.
In the last two decades numerous other compounds were inves-
tigated in an attempt to replace CdS and achieve similar conversion
efficiency improvements, or even surpass the efficiency of CdS. All
these attempts failed and only a few materials showed some, but
insignificant, improvements of the CdTe or CIS type solar cells
[33–35].

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.07.017
 K.W. Böer / Energy Conversion and Management 52 (2011) 426–430
The reason why CdS is a good partner to CdTe was first thought
to be the enhanced optical transmission through the covering CdS
layer, that is caused by the lower index of refraction of CdS com-
pared to CdTe, hence one experiences a lower light reflection from
the cell surface. However, this ‘‘window effect” from which an
improvement of the current is expected, is by far surpassed by
the substantial increase of the open circuit voltage and the fill fac-
tor in the current–voltage characteristics. Thereby the electric
power output of these solar cells under solar illumination is almost
doubled [36–40].
This remarkable fact of the conversion efficiency enhancement
by a thin layer of CdS was known for almost three decades, but
an explanation of the reasons for it was elusive. In addition, more
recently, it was observed that the thickness of this layer can be re-
duced to 200 Å while remaining effective [41]. Only recently, a
more thorough analysis of the physical behavior of copper-doped
CdS has helped to clear up this puzzle [42,43], as we will discuss
in the next section.
2. Why cadmium sulfide?
Since the replacement of CdS with other compounds was unsuc-
cessful, it became important to find out why CdS is so beneficial.
All earlier attempts of explanation had failed, mostly because one
tried to model the actual cell that is polycrystalline and has a com-
plicated morphology. The involved processes are seemingly too
complex to permit a reasonable model computation that shows
encouraging agreement with the experiments, i.e. mostly with
the measured current–voltage characteristics.
Only recently [42,43] was it recognized that the cause of the
enhancement should be researched within the CdS itself, and that
the cause should be substantiated with sufficient careful experi-
mental evidence. One, therefore, has to first proceed with a simple
one-dimensional model, that is, by replacing the actual CdS layer
with a thin CdS platelet. Here, ample experiments have been per-
formed in the 1950’s and 1960’s, and they provide the basis for
an attempt to explain the behavior (for a comprehensive review
see [44,45]). From these results, it is known that CdS is an n-type
semiconductor that, when doped with copper becomes highly pho-
toconductive. With an optical excitation, as it is exposed in a solar
cell, the electron density is on the order of 1018 cm 3. Such photo-
conductivity can easily be quenched (i.e. the electron density can
be reduced) by additional low energy excitation, as, e.g., by infra-
red light, or, what becomes important in the case of the solar cell,
by an intermediate electric field. This field causes a Frenkel-Poole
excitation [46] of trapped holes1 (that stem from the optical excita-
tion) from Coulomb attractive hole centers into the valence band.
The now set-free holes can be trapped by fast recombination centers
from which they can interact with the conduction electrons, permit-
ting enhanced recombination/and thereby reducing their density
[47]. These intermediate electric fields can be reached at the CdS side
of the junction to the CdTe, causing, in the corresponding thin CdS
layer, such ‘‘field quenching” to occur [48].
It can be shown that the field quenching is one of the reasons
for the cell improvement since it can reduce the electron density
at the junction interface and hence its back-diffusion into the CdTe,
that would represent a junction leakage. Such a leakage conse-
quently would result in a lower solar conversion efficiency, as it
is observed in the uncoated CdTe cells. However, one must now in-
clude several other important factors to explain the behavior more
quantitatively.
1
Frenkel-Poole excitation is caused by the lowering of the Coulomb funnel in field
direction by an electric field due to the tilting of the bands in this field, thereby
reducing the energy necessary to thermally excite the holes into the valence band.
427
1. The electric field at the CdS side of the junction is a function of
the voltage drop that is observed at various points of the
current–voltage characteristics: It is generally low (below
20 kV/cm) in forward bias and increases rapidly when
approaching the open circuit voltage, and beyond in reverse
bias. This means, for sufficient forward bias, there is no field
quenching, and hence electrons can travel through the junction
easily. However, as the field increases when Voc is approached,
field quenching sets-in and substantially reduces such electron
leakage [43].
2. CdS in the quenched region shows a negative differential con-
ductivity, that is, the photocurrent decreases with increasing
applied voltage. When the field quenching is strong enough, a
high-field domain is created in which the field is limited to
approximately 50 kV/cm. This field is approximately the same
as that in which substantial field quenching is observed. In fact,
the field quenching is the cause of the negative differential con-
ductivity that is necessary to initiate the high-field domain [47].
This maximum field near the CdS/CdTe interface is too low to
permit electron tunneling through the junction, which other-
wise would shunt the junction and reduce the solar cell
efficiency.
3. The field quenching near the CdS/CdTe interface can be strong
enough to turn the CdS into a p-type layer [49]. This causes
the Fermi level in this layer to move much closer to the valence
band. Since the Fermi level at open circuit condition must
remain horizontal, this means that both the valence and con-
duction bands curve up in the field quenched region and the
conduction band at the interface must disconnect from the con-
duction band of the CdTe, to which it was connected in forward
bias [43]. This again limits the electron back-diffusion into the
CdTe.
4. To permit such relative shift of the bands between CdS and
CdTe, a change of the dipole moment at the interface, which
determines the band connection (or the band offset), is
required. There is experimental evidence that in copper-doped
CdS platelets, the dipole moment that is involved in a Schottky
barrier to a metal electrode can be changed by changing the
photoconductivity [50]. That seems to justify the assumption
that such a change of the dipole moment at an even ‘softer’
interface can occur.
With these conditions, one can draw the band diagram of a CdS/
CdTe solar cell close to the junction interface [43] as it is shown in
Fig. 1. By interpretation of this figure, one should recognize that the
influence of the outer electrodes is omitted, and so is any addi-
tional junction recombination. This is a qualitative drawing that
also does not show the quasi-Fermi levels that need to be consid-
ered2 but for which additional information on the defect structure
on both sides of the junction is required, which is presently not
available. The model picture should therefore only be considered
to point attention to the involved basic physics and is no attempt
to quantitatively model an actual CdS/CdTe solar cell.
Finally, one has to explain why it is CdS that permits such an
improvement. For this, it is essential that the field quenching be
initiated efficiently and at a field of about 50 kV/cm. Field quench-
ing is quite sensitive to the distance between the Coulomb attrac-
tive centers that are produced by copper doping3 [48]. If this
density is too low, then the quenching is not efficient enough to re-
duce the electron density markedly. If, on the other hand, the density
2
More precisely, one should discuss the connection of quasi-Fermi levels for
electrons and holes. However, in the absence of more information about the defect
level distribution this cannot be done properly. Therefore, the Fermi level discussion
is used here to describe the involved principle.
3
Saturation can be shifted by adding co-activators, e.g., Al during doping.
428 K.W. Böer / Energy Conversion and Management 52 (2011) 426–430
Fig. 1. Preliminary band diagram, schematically, of the central part of the CdS/CdTe solar cell.
is too high, then these centers become too close and the critical field
for Frenkel-Poole excitation becomes much higher. Accidentally, the
saturation level of copper in CdS is about 100 ppm, which brings the
distance between the copper atoms to its optimal value [46].
Though in some other semiconductors one can induce such field
quenching and consequently negative differential conductivity,
one must design the doping just to the right level. This is too com-
plicated to achieve over large enough areas, causing this alterna-
tive layer to become highly inhomogeneous and its beneficial
effect limited to a small percentage of the solar cell area.
3. Economical aspects of thin-film solar cells
Compared with the classical silicon solar cells, these CdS/CdTe
or other CdS/CIS type solar cells have a somewhat smaller conver-
sion efficiency but a substantially lower material electrical power
demand for production. Specifically, laboratory size thin-film cells
have approximately 15% while single crystal silicon cells often ex-
ceed 20% efficiency. Large panels, fully assembled, of thin-film cells
have approximately 10% while silicon panels have approximately
17% and panels assembled from polycrystalline silicon have about
12% efficiency [51,52].
However, the material demand for silicon cells is at least 10
times that of thin-film cells, and the energy consumption per unit
area of the final panel is at least twice as large. This relates to a sub-
stantial cost advantage for the thin-film material, even though the
material supply of the raw material for silicon cells is of unlimited
supply (sand and charcoal) while some of the other elements such
as Cd, Te, In, Ga and As have limited supply in the minable earth
crust, but are still plentiful for decades of future thin-film produc-
tion. The limited supply compensates for some of the material de-
mand factors. In addition, the necessary encapsulation, e.g. glass
and framing of the panels tend to even out some of the costs.
Therefore, presently the selling price for the assembled panels is
approximately $2 for thin-film and $4 for crystalline silicon cells
per peak Watt. Taking the larger area into consideration to achieve
the same wattage of the installed panels, which is larger by the in-
verse ratio of the efficiency, this tends to further even out the cost
for the consumer. Furthermore the silicon cell panels are on the
market now for at least four decades, while large scale CdS/CdTe
panels have taken off into the multi-Megawatt per year production
range only less than a decade ago. This has an impact on the reli-
ability confidence that is guaranteed for silicon, often to 25 years,
with older panels on rooftop exposure having exceeded mostly
that warranty range significantly. Even though the manufacturers
of the CdS/CdTe cells claim confidence in their product, one simply
has to await actual field data to gain such experience.
Dependent on the size and the place of the installation, one has
to add approximately $2–$5 per Watt to the cost of the total instal-
lation. These added costs result in a cost for the consumer on his
house roof of about $7000–$9000 per installed kW, minus a per-
centage for tax incentives that differ from state to state, which, to-
gether with federal tax incentives, can amount to 30–50% of this
value.
Depending on the geographic location and assuming an average
50% of utility electric power savings this means the need of a
2–5 kW installation on a single family home, or a $14,000–$45000
initial cost, with an average of 40% tax savings to about $5,000–
$30,000 initial capital outlay,
Giving an electric power saving of, on average 10 cents
per kW h and an annual average of 3 h per day total sunshine,
one obtains, with $100 per year savings, an amortization period
of about 10–15 years for such an installation4.
For large area installations the prorated installation costs are
smaller, but then again, dependent on the state and other local
considerations, the tax incentives are smaller. It exceeds the intent
of this presentation to go further into the economical detail.
4
This number was calculated for cells of 10.7% efficiency, yielding 107 W/m2
multiplied with a $1.04 per Watt , yielding $111 per m2.
 K.W. Böer / Energy Conversion and Management 52 (2011) 426–430
Irrespective of the unquestionable advantage of the installation
of solar panels by reducing the emission of greenhouse gases, the
investment into such solar system may already make economical
sense, recognizing that it will increase the value of the house and
the electrical energy harvested will be essentially free after the
amortization period.
4. Cd toxicity and Te supply
Cadmium is one of the most toxic metals and has long ago been
banned for use as sulfide or selenide in the pigments of paint. Its
use was consequently banned by the European Union’s RoHS reg-
ulation. Consequently, the use in solar cells is subject to stringent
recycling procedures5. The additional costs for recycling, including
transport is estimated at $0.05 per Watt. Also exposure to fire of
the glass encapsulated cells does not allow cadmium release.
The tellurium supply is still questionable, since presently only
800 metric tons per year is available, since it was not in high de-
mand in the past. In 2007, the global production has increased to
135 metric tons [53] but was barely sufficient for much more than
1 GW CdS/CdTe solar panel installation6. However in the meantime
new tellurium rich ore has been discovered in Xinju, China [53] and
at several other places in the world. Other resources of abundant tel-
lurium are now discovered on undersea ridges which promise a fur-
ther increased supply potential, sufficient for more solar cell panels
than can be expected to be produced to supply most of the global
electric energy demand [54].
5. Larger recent CdS/CdTe panel deployments
Up to the writing of this paper, more than 2 GW of CdS/CdTe
panels have been deployed, the latest part of it from First Solar:
40 MW at Waldpolenz in Germany at a price of €3250 per kW,
and the 7.5 MW system installed in Blythe, CA, where the Califor-
nia Public Utility Commission hast an agreed power delivery price
of 12 cent per kW h. Other large installations of First Solar include a
contract with Southern California Edison to install a total of
250 MW, at an installation price of $3.50/W with tax incentives.
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