Thin Solid Films 387 Ž2001.

135᎐140

Characterisation and modelling of chalcopyrite solar cells

Reiner KlenkU
Hahn-Meitner-Institut, Glienickerstr. 100, D 14109 Berlin, Germany

Abstract

In this contribution, we have discussed current models of the chalcopyrite-based heterojunction solar cell and their
implications for achieving reliable and efficient devices. Numerical simulation of the device is an important tool for assessing the
influence of various parameters. It has been used here to provide examples for the topics discussed. The key points for the
minimisation of interface recombination are: doping of absorber and window; electrical charge and band line-up at the interface;
and interface recombination velocity. 䊚 2001 Elsevier Science B.V. All rights reserved.

Keywords: Chalcopyrite; Heterojunction; Recombination; Numerical modelling

1. Introduction
A significant part of photogeneration in a true ho-
mojunction solar cell takes place close to the surface of
the emitter. Avoiding current losses, especially for
high-energy photons, therefore, requires a careful de-
sign of the emitter depth and doping as well as good
surface passivation. It is an intrinsic advantage of the
window-absorber heterojunction cell that the genera-
tion maximum is shifted to the pn junction where the
electrical field is at its maximum and contributes to the
collection of photogenerated carriers. Due to the high
band gap window, only a few carriers are generated
close to the surface and the influence of surface recom-
bination can thus be neglected. In contrast to the
homojunction device, the heterojunction may exhibit a
high density of states at the interface. Nevertheless,
highly efficient chalcopyrite-based cells are dominated
by bulk rather than interface recombination. This has
been explained by a low interface recombination veloc-
ity Žlattice matching by a buffer layer. andror an
n-type absorber surface Žburied interface .. Numerical
examples Žcalculated with SCAPS w1x. based on a
generic cell concept using a window layer with a 3.3-eV
band gap and an absorber layer with a 1.5-eV band gap
and assuming otherwise ‘reasonable’ material proper-
ties 1 are presented in the following chapter for a more
general approach to the minimisation of interface re-
lated losses. As we will show, it can be achieved even in
presence of a high interface recombination velocity and
without an n-type absorber surface by adhering to a
few simple design criteria. In Section 3, we examine the
basic features of different chalcopyrite solar cells and
evaluate them in terms of the criteria for efficient
heterojunction solar cells derived in Section 2.
2. Guidelines for efficient heterojunction solar cells
The bucking current due to recombination at the
interface has to be minimised to achieve high open
circuit voltages. The recombination rate R within the
field zone of the diode is approximated by:
np
Rs Ž1.
␶ n q p.
Ž
Where n and p denote the concentrations of electrons
and holes, respectively, and where ␶ is the carrier
lifetime. The numerator in Eq. Ž1. depends on the

U
Tel.: q49-30-80622625; fax: q49-30-80623199.
1
E-mail address: klenk@hmi.de ŽR. Klenk.. Full parameter sets can be requested from the author.

0040-6090r01r$ - see front matter 䊚 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 0 . 0 1 7 3 6 - 3
136 R. Klenk r Thin Solid Films 387 (2001) 135᎐140
applied voltage U, but is nearly constant within the
field zone:
nps n2i exp ž qU
kT /
. Ž2.
Hence, the recombination rate as a function of position
has its maximum where n s p and decreases rapidly for
a high electron density or high hole density. In order to
minimise recombination for a given interface recombi-
nation velocity Si ; 1r␶, the heterojunction layout has
to be such that the Fermi-level at the interface is close
to either the conduction or the valence band. This can
be achieved by asymmetric doping. Then the open
circuit voltage loss is only in the order of a few mV
even for very high interface recombination velocity
Si s 0.1U carrier thermal velocity ¨ th ŽTable 1..
The current losses at the interface can be neglected
if the asymmetric doping is such that the interface is
inverted. For a chalcopyrite-based cell with a p-type
absorber, this means that the Fermi-level at the inter-
face should be close to the conduction band. In this
case, the minority carriers collected from the bulk are
majority carriers at the interface and are not subject to
significant recombination Žnq p in Table 1.. In conse-
quence, the performance of a carefully designed het-
erojunction solar cell is almost independent from the
interface recombination velocity. The situation changes
if the conduction bands are not aligned at the inter-
face. A small spike can be beneficial because it tends to
increase the inversion. It can be shown by analytical as
well as numerical calculations that a moderate spike
does not deteriorate the current collection w2x. On the
other hand, a cliff is undesirable because it reduces the
inversion and it also opens a recombination path with
decreased barrier Eb ŽFig. 1.. If the conduction band
line-up of a given structure cannot be modified by
preparation, it is advantageous to widen the absorber
band gap in the vicinity of the interface and to move
the valence band edge to lower energies in order to
re-establish the full barrier. In chalcopyrite-based cells,
this would be achieved by an OVC w3,4x layer or by
increasing the sulfur concentration at the absorber
surface, provided that the interface between the absor-
Table 1
Calculated device characteristics for varied doping ratio of p-type absorber and n-type window and varied band line-up at their interface a
Cell type Si s 0
Voc ŽmV. ff Ž%.
nsp 957 80
npq 1045 84
nq p 911 79
nq p 0.3 eV cliff 962 80
nq p 0.3 eV spike 911 80
a
Significant losses are highlighted.
ber bulk and surface has a low defect density. The
latter may be difficult to achieve with high gap chal-
copyrites w5x. Intermixing at the interface, as experi-
mentally observed by Heske et al. w6x, can also help to
close the recombination path over the reduced barrier
if the band discontinuity is spread over a certain dis-
tance. It has also been proposed to eliminate interface
recombination by doping the surface region of the
absorber to achieve a type conversion and, conse-
quently, a buried interface. In terms of the simple
models presented here, this approach is critical be-
cause it does not eliminate the main problem, i.e. the
reduced barrier. In addition, it tends to deteriorate the
photo current collection Žpoor blue response. because
a significant amount of light is absorbed in the n-type
absorber region. The carriers generated within this
surface region are minority carriers at the interface in
violation of the design rule stated earlier. It can be
seen that this device is similar in many respects to the
homojunction device and, consequently, does not ex-
ploit the inherent benefits of a heterojunction. For a
given amount of positive charge in the type inverted
surface region, the cell performance is maximised by
minimising the thickness of this layer. Taking this con-
sideration one step further, the charge should be lo-
cated at the interface itself.
Even a moderately charged interface can cause a
significant variation of the field zones extending to both
sides of the junction. Positive interface charge is desir-
able because it increases the band bending in the
absorber and, thereby, the inversion. A high defect
density at the interface can cause Fermi level pinning.
A simplified model can be treated in a clear manner by
analytic w7x as well as numeric calculations. It is charac-
terised by a charge neutrality level, where defects are
acceptors above and donors below the neutrality level.
Variation of the interface charge as a function of
Fermi level position and induced changes in the band
bending in the absorber and window lead to the coinci-
dence of charge neutrality and Fermi level at the
interface. Depending on the neutrality level, the inver-
sion can be enhanced or reduced leading to an im-
provement or deterioration of the open circuit voltage,
respectively.
Si s 0.1U ¨ th
jsc ŽmArcm2 . Voc ŽmV. ff Ž%. jsc ŽmArcm2 .
25.6 641 71 25.1
23.9 875 72 16.6
26.3 890 78 25.6
26.2 627 77 25.3
26.3 908 79 25.8
 R. Klenk r Thin Solid Films 387 (2001) 135᎐140
Fig. 1. Band diagrams in the vicinity of the interface.
In conclusion of the examples presented, a high
interface recombination velocity can be tolerated if the
following requirements for the minimisation of inter-
face recombination are met:
䢇 Fermi-level close to the conduction band at the
interface Žinverted interface .:
` an nq-windowrp-absorber design;
` appropriate interface charge Ž Q i G 0.;
` charge neutrality level close to the conduction
band if the Fermi level is pinned;
䢇 avoiding a barrier reduction Žcliff, segregation of
lower gap phases w8x..
Type inversion of the absorber surface by n-type
doping is neither required nor necessarily desirable. As
soon as the above criteria are fulfilled, the cell will
likely be limited by bulk properties and can be further
optimised through, e.g. high optical absorption and
good carrier lifetimes in the absorber Žnot shown here..
Tunnelling assisted recombination is known to play a
role in chalcopyrite based cells, especially those with
high gap absorbers. It has not been taken into account
Table 2
Characterisation methods for chalcopyrite solar cells
Method
Hall effect, conductivity, Seebeck
XPS, UPS, Kelvin probe
Quantum efficiency, electron beam induced current
jV curve analysis
Admittance spectroscopy, photoluminescence
Photoluminescence decay
137
here because it is not compatible with efficient devices.
Details can be found in the literature w9x.
3. Characterisation and modelling of chalcopyrite solar
cells
The most important characterisation methods for
chalcopyrite solar cells are those which allow an assess-
ment of the criteria mentioned above ŽTable 2.. Char-
acterisation methods that are well established for other
semiconductors Žsilicon. are sometimes problematic if
applied to chalcopyrite materials. For example, C Ž V .
curves and Mott᎐Schottky plots have to be measured
and interpreted by considering the high density of deep
defects. In more general terms, parameter extraction
requires a model that describes the correlation between
the property assessed by the measurement and the
underlying physical parameters. Due to the complexity
of the polycrystalline semiconductor films, the models
are often an approximation and the extracted parame-
ters have to be interpreted as effective parameters
bound to the specific model. They can be useful for
comparing different samples quantitatively but can be
misleading if used for calculations. Nevertheless, we
will use such data in the following to discuss the basic
features of different chalcopyrite solar cells and to
evaluate them in terms of the design criteria derived in
the previous chapter.
The principal band diagram for a low gap ŽCuInSe 2 .
cell is shown in Fig. 2. The interface is inverted and
there is no barrier reduction. Consequently, interface
recombination does not play a dominant role and the
calculation shows a bulk limited device in accordance
with the results of jV curve analysis w10x. The only
problem with this structure lies in the large distance
between the Fermi-level and the CdS conduction band
Žapprox. 0.6 eV in this calculation . which would cause a
poor fill factor due to series resistance and, in combina-
tion with the conduction band spike, a voltage depen-
dent photo current collection also. It is obvious that
Fig. 2 does not reflect the real situation because high
fill factors can be achieved in the experiment. There
are three possibilities to explain this discrepancy: Ža.
CdS is highly doped; Žb. the band offsets are somewhat
Extracted parameter
Majority carrier density and mobility
Band alignment
Minority carrier diffusion length, extension of field
Zone, interface recombination
Dominant recombination mechanism, barrier
Defects, density of states
Lifetime
138 R. Klenk r Thin Solid Films 387 (2001) 135᎐140

smaller than those postulated by Schmid et al. w3x and
used in this calculation; or Žc. there is a large density of
charged interface states. The latter two explanations
are in agreement with the analysis of a similar device
by Niemegeers et al. Žsee next paragraph.. Doping of
the CdS buffer layer is under discussion: CdS films on
glass show a very low lateral conductivity. This indi-
cates a low doping but it may also be due to depletion
induced by surface states. High carrier densities have
been deduced from capacitance spectroscopy in an
electrolyte w11x and from Schottky diodes w12x. Unfortu-
nately, there are no reliable data on the band offset
between the chalcopyrite and the ZnO. If the band
offsets are approximately linear with respect to a com-
mon reference, then this device should work well also
without the buffer layer. Indeed, this has been proven
in the experiment by using a proper conditioning of the
absorber surface Žpartial electrolyte w13x.. In view of
the considerations of the previous chapter it is believed
that the primary benefit of this treatment is appropri-
ate charges at the interface w7x rather than n-type
doping of the absorber surface Žformation of a thin
CdOH film cannot be excluded..
Widening the band gap of the absorber by incor-
porating moderate amounts of Ga leads to a reduced
spike at the absorberrbuffer interface. The interface is
Fig. 2. Calculated equilibrium band diagram and jV curves of a
ZnOrCdSrCuInSe2 thin film solar cell. The arrow highlights the
large distance between the CdS conduction band and Fermi-level at
the interface.
still inverted and there is no barrier reduction. Hence,
numerical calculations predict an efficient device with-
out any additional assumptions ŽTable 3.. These de-
vices, with an absorber band gap of approximately 1.2
eV, yield the highest conversion efficiencies in the
experiment. Niemeegers et al. w14x concluded from jV
curve analysis and admittance spectroscopy that the
band offset between CdS and ZnO cannot be larger
than 0.2 eV Žin contrast to 0.3᎐0.4 eV measured by
X-ray photoelectron spectroscopy.. They further postu-
lated that the Fermi level at the interface is pinned by
donor-like states and that there is a high density of
deep acceptors within the OVC layer. The charge state
of the latter varies with illumination, which results in a
barrier modulation and explains the cross-over of the
jV curves in the dark and under illumination. Variation
of the charge in deep defects has also been made
responsible for other non-ideal effects, such as the
roll-over of the jV curve as a function of temperature
and illumination conditions w15x, as well as various
meta-stabilities w16x, including changes in the device
performance with light soaking or annealing in air.
However, there is no general consensus on the nature
of these defects and their location within the device.
Assuming again a linear behaviour of the band offsets,
it should be more difficult to obtain an efficient buffer
layer free device with CuŽIn,Ga.Se 2 Žcliff to ZnO. in
comparison to pure CuInSe 2 , which is also indicated by
the experiment.
In high gap cells based on CuInS 2 or CuGaSe 2 , the
band line-up is not directly in favour of an inverted
interface and there is a conduction band cliff between
the absorber and buffer layer, leading to a reduced
barrier for recombination Eb ŽFig. 3.. Consequently,
the calculation predicts significantly lower efficiency
even for material properties similar to those of the
lower gap chalcopyrite due to interface recombination
ŽTable 3.. jV curve analysis of CuInS 2 solar cells shows
that the devices are dominated by tunnelling assisted
recombination in the dark. However, under illumina-
tion, the recombination is thermally activated. In the
latter case, extrapolation of the Voc ŽT . curve to 0 K is a

Table 3
Calculated device characteristics for chalcopyrite based cells a,b

Cell type NA EF CdS: SI ⌬ EC Voc ff jsc ␩ Ž%.

Žcmy3 . pinned ND Žcmy3 . Žcmrs. ŽeV. ŽmV. Ž%. ŽmArcm2 .

CuInSe2 1E16 no 1E14 1E6 y0.3 478 55 39.7 10.4

CuŽIn,Ga.Se2 1E16 no 1E14 1E6 y0.1 662 72 34.2 16.4
CuInS2 5E16 no 1E14 1E6 0.2 695 58 22.3 9.0
CuInS2 5E16 no 1E14 1E5 0.2 776 72 24.7 13.8
CuInS2 5E16 no 1E18 1E6 0.2 786 81 23.7 15.1
CuInS2 5E16 EC I 0.3 eV 1E14 1E6 0.2 762 82 23.1 14.5
a
The same bulk carrier life time Ž ␶ s 1 ns. and similar doping NA have been assumed for all absorbers.
b
The conduction band discontinuity CdSrZnO is 0.3 eV, the discontinuity at the absorber side of CdS ⌬ Ec is given in the table.
 R. Klenk r Thin Solid Films 387 (2001) 135᎐140 139

direct measure for the barrier. Recombination in the

bulk or at an interface without cliff should result in
Voc Ž0 K. s 1.5 V, corresponding to the band gap of the
absorber. Interface recombination at an interface with
a cliff gives Voc Ž0 K. s Ebrq. For CuInS 2 cells we find
Voc Ž0 K. f 1.3 V, which indicates that the CuInS 2 cells
are indeed limited by interface recombination over a
reduced barrier w17x. Nevertheless, an efficiency of al-
most 13% has been achieved in the experiment with
CuInS 2-based cells w18x. This could be explained by a
lower interface recombination velocity compared to the
assumption made in Fig. 3 or by an inverted interface
ŽTable 3.. In spite of the unfavourable band line-up, Fig. 3. Calculated band diagram and jV curves of a
inversion can be achieved by a highly doped buffer ZnOrCdSrCuInS2 heterojunction.
layer with sufficient thickness or by charges present at
the interface ŽFermi-level pinning.. As already ex- with theoretical estimations w22x. If, once more, band
plained, an inverted interface results in low recombina- offsets are assumed to be linear and if the band edges
tion rates for photo generated electrons. On the other of the window layer are not adapted w23x, then buffer
hand, this means that photo generated holes are likely layer free high gap chalcopyrite solar cells should show
to be lost at the interface, i.e. we expect that minority poor performance. The best CuInS 2rZnO that has
carriers generated in the n-type buffer layer do not been achieved even with partial electrolyte treatment
contribute significantly to the photocurrent. The situa- and with ZnO deposited by MOCVD has an efficiency
tion is reversed for the non-inverted interface: good of only 6% w24x.
collection from the buffer layer but poor collection
from the absorber. Examples of numerically calculated
4. Conclusions
quantum efficiencies of CuInS 2 cells are in good agree-
ment with this consideration ŽFig. 4.. Loss of carriers
generated in the CdS may also be due to recombina- It has been shown that efficient heterojunction solar
tion at the CdSrZnO interface, which has been taken cells can be achieved even in the presence of a high
into account in the calculations. In this experiment, we interface recombination velocity. Inversion of the het-
always observed poor collection from the buffer layer erointerface has to be achieved by suitable doping of
in both, CuInS 2 and CuGaSe 2 cells, indicating an in- the window and absorber and by an appropriate electri-
verted interface in spite of the unfavourable band cal charge at the interface. A barrier reduction has to
line-up. In principle, it is also possible to deduce the be avoided. Low gap chalcopyrite based solar cells need
band bending within the absorber from quantum effi- at least a Žwet chemical. conditioning of the absorber
ciency measurements performed at varied voltage bias surface to fulfil these criteria. As the absorber band
w19x. This has been demonstrated for CuGaSe 2 cells gap is increased, a buffer layer is required to move at
based on CVD grown absorbers where low absorber least part of the conduction band discontinuity away
doping, a moderate diffusion length and the variation from the absorber surface. Reliable data on the carrier
of the absorption coefficient due to valence band split-
ting make the parameter extraction feasible w20x. The
band bending in the absorber was found to be less than
half the absorber band gap, i.e. the interface appears to
be not in inversion. However, current collection from
the buffer layer was nevertheless not observed.
It has been shown that the band gap of CuInS 2
absorbers can be increased by alloying with Ga. The
open circuit voltage of CuŽGa,In.S 2 solar cells in-
creases at least linearly with the band gap Ž q⌬Voc G
⌬ Eg . up to a band gap of approximately 1.6 eV w21x.
This is surprising in view of the recombination model,
because a conduction band moving to higher energies
would only increase the cliff, leaving Eb and, therefore,
Voc unmodified. It has to be concluded that Ga in
CuInS 2 Žin contrast to Ga in CuInSe 2 . influences the Fig. 4. Calculated and measured quantum efficiency of
energy of the valence band, which is in good agreement CuInS 2 rCdSrZnO solar cells.
140 R. Klenk r Thin Solid Films 387 (2001) 135᎐140
density in the buffer layer as well as on the interfaces
between the buffer layer and ZnO and chalcopyrite
and ZnO would be helpful in refining the presented
models and to obtain high efficiency high gap and
buffer layer free solar cells.
Acknowledgements
J.L. Gray ŽADEPTF. and M. Burgelmann ŽSCAPS.
are gratefully acknowledged for providing software for
the numerical calculation of heterojunction solar cells.
The author thanks I. Hengel, Th. Matthes, J. Reiss and
R. Scheer for discussions.
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