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1007/s003399900061
Applied Physics A
Materials
Science & Processing
Springer-Verlag 1999
places [1113]. Furthermore, Cu(In,Ga)Se2 thin-film modules show excellent outdoor stability [14] and radiation hardness [15, 16]. At a first sight, this achievement is somewhat
surprising in view of the complexity of the system and the
degree of understanding we actually have on the structural
and electronic properties of Cu(In,Ga)Se2 . The knowledge
on this material is still extremely low compared to what is
known from a-Si or c-Si. Hence, most of the achievements of
Cu(In,Ga)Se2 -based solar cells accumulated during the years
are thus initiated rather by intuition than by knowledge-based
technological design. Briefly: it worked first, and was explained later.
This review represents an attempt to equilibrate the balance between achievements and understanding of
Cu(In,Ga)Se2 -based heterojunction devices. We focus on
three points: (i) The description of the electronic transport
properties of these heterostructures and their dependence
on the different processing steps during device preparation.
(ii) The role of intrinsic defects in Cu(In,Ga)Se2 and their
implications for the device performance. (iii) The basic
options to influence and to design the material properties
of Cu(In,Ga)Se2 . For other important issues we refer the
reader to the literature. More about structural properties of
Cu(In,Ga)Se2 can be found, for example, in [1721]; interface properties of Cu(In,Ga)Se2 and related compounds
were recently reviewed by Scheer [22]; an overview on recent developments can be gained also from [2325]; for the
questions on up-scaling and module technologies see, for example, [26], and for economic aspects [3].
The review is organized as follows. In Sect. 1 we briefly
introduce the material and device properties of high-efficiency
Cu(In,Ga)Se2 heterojunction devices. Here, we restrict ourselves to those types of solar cells yielding the highest efficiencies; variations either in the deposition method and
material composition or in the device structure itself are only
briefly mentioned where it is necessary for completeness or to
assist the understanding of the high-efficiency devices. Section 2 deals with the electrical transport properties of the
heterostructure. Here, we start with an examination of the
limitations to the solar cell output parameters in terms of simple textbook knowledge before we summarize the present
132
Eg
eV
Voc
mV
jsc
mA/cm2
FF
%
A
cm2
Ref.
Cu(In,Ga)Se2
CuInSe2
CuGaSe2
CuInS2
Si
1.11a
1.04
1.68
1.57
1.15
17.7
15.4
8.3
11.1
24.4
647
515
861
728
696
34.0
41.2
14.2
21.24
42.0
77.2
72.6
67.9
70.9
83.6
0.414
0.38
0.471
0.48
4.00
[8]b
[30]c
[27]b
[28]b
[2]b
ence of Cu y Se (y < 2) [9]. This process is further supported by a substrate temperature close to the softening
point of the glass substrate [30].
(ii) The glass substrate was changed from Na-free glass to
Na-containing soda-lime glass [9, 30]. This change has
led to an enormous improvement of efficiency and reliability of the solar cells as well as to a larger process
tolerance. In contrast to first assumptions that this effect
is due to better match of thermal expansion coefficients,
the beneficial impact of Na diffusing from the substrate
through the Mo back contact on the growth of the absorber layer, its structural and electrical properties was
soon recognized. We will discuss the outstanding role of
Na in Sect. 4.1 in some detail.
(iii) Initially the absorbers consisted of pure CuInSe2 . The
partial replacement of In with Ga [31] is a further noticeable change which increases the band gap of the absorber
from 1.04 eV to 1.11.2 eV for the high-efficiency devices (cf. Table 1).
(iv) The counterelectrode for the CuInSe2 absorber of the
earlier cells was a 2-m-thick CdS layer obtained by
physical vapor deposition (PVD). This has been replaced
by a combination of a 50-nm-thin CdS buffer layer from
chemical bath deposition [3234] and a highly conductive ZnO window layer.
The consequences of the issues (i)(iv) on the electronic
properties and the performance of Cu(In,Ga)Se2 solar cells
will be discussed in detail below.
133
material with regard to the metals is controlled by the evaporation rates whereas Se is always evaporated in excess. Reasonable efficiencies are also obtained from absorber prepared
by the selenization of metal precursors in the presence of either H2 Se [3537] or elemental Se [38], and by rapid thermal
processing of stacked elemental layers [39]. On the laboratory scale the efficiencies of these preparation routes are
smaller by about 3% (absolute) when compared to the record
values. However, on the module level the differences are
much smaller and modules prepared by the selenization route
are, at the moment, the closest to commercialization [11]. The
advantage of co-evaporation is the flexibility of the method
with regard to variations in the material composition and
preparation conditions during processing.
Photovoltaic-grade Cu(In,Ga)Se2 films have slightly Inrich compositions. The allowed stochiometry deviations are
astonishingly large, thus yielding a wide process-window
with respect to composition. Devices with efficiencies above
14% are obtained from absorbers with a (In + Ga)/(In +
Ga + Cu) ratio between 52% and 64% if the sample contains
Na [40]. This issue has to be discussed in the context of the
phase diagram below. Cu-rich Cu(In,Ga)Se2 displays the segregation of a secondary Cu y Se (y < 2) phase preferably at
the film surface. Even after removal of the secondary phase
from the surface by etching the absorber in KCN, the use
of this material for photovoltaic applications is limited, most
probably due to the high doping density of 1018 cm3 in the
bulk and by the defects at the surface. However, the importance of the Cu-rich composition is given by its role during
film growth. Cu-rich films have grain sizes in excess of 1 m
whereas In-rich films have much smaller grains. A model for
the film growth under Cu-rich compositions comprises the
role of Cu y Se as a flux agent during the growth process of
co-evaporated films [29, 41]. This model for the growth of
Cu(In,Ga)Se2 in the presence of a quasi-liquid surface film of
Cu y Se is highlighted in Fig. 2. For Cu(In,Ga)Se2 prepared by
RTP the role of Cu y Se is similar [39]. Advanced preparation
sequences, therefore, always include a Cu-rich stage during
the growth process and end up with an In-rich overall composition in order to combine the large grains of the Cu-rich
stage with the otherwise more favorable electronic properties
of the In-rich composition. The first example for this kind
of procedure is the so-called Boeing or bi-layer process [42]
which starts with the deposition of Cu-rich Cu(In,Ga)Se2 and
Fig. 2. Model for the growth of polycrystalline Cu(In,Ga)Se2 in the presence of a quasi-liquid surface film of Cu y Se on top of the Cu(In,Ga)Se2
grains (according to [41])
134
ln
,
(1)
q
q
jsc NA L D
2 Electronic transport
2.1 Basic limitations
The system Cu(In,Ga)(S,Se)2 covers a wide range of band
gaps from 1.04 eV for CuInSe2 to 2.4 eV for CuGaS2 , thus,
including also the theoretical optimum of E g 1.4 eV for
single cells with a theoretical potential for the conversion efficiency of around 30% under one sun [57]. Nevertheless, the
Cu(In,Ga)Se2 solar cell in Table 1 is far from this theoretical
limit and also far from the best Si solar cell with a similar
band gap.
The current density available from the standard
100-mW cm2 solar spectrum (AM1.5) for a band gap of
1.11 eV (that of the best Cu(In,Ga)Se2 solar cell [8]) is about
43 mA cm2 [58]. If the CdS buffer layer would cause a sharp
Fig. 3. Detail of the band diagram of the ZnO/CdS/CuIn(Ga)Se2 heterostructure indicating the three relevant recombination paths recombination
in the neutral bulk (A), in the space-charge region (B), and at the interface
between the Cu(In,Ga)Se2 absorber and the CdS buffer layer (C). The dotted arrows stand for the tunneling enhancement of the recombination paths
B and C
135
where kT/q is the thermal voltage, Dn the diffusion constant for electrons, NC/V the effective density of states in
the conductance/valence band [62], NA the acceptor density,
and L D the diffusion length of the electrons. If this diffusion
length becomes comparable to the thickness d of the quasineutral zone of the absorber the recombination velocity Sb at
the back contact has to be taken into account and L D in (1) has
to be replaced by
L eff = L D
cosh(l 1 ) + sb sinh(l 1 )
,
sb cosh(l 1 ) + sinh(l 1 )
(2)
E g 2kT
kTDn NC NV
ln
.
Voc =
q
q
jsc Fm L 2D
(3)
Here Fm = (2qNA Vbm /s )1/2 is the electrical field at the position of maximum recombination. The quantity Fm depends
on the doping density NA and the band bending Vbm ; s is the
dielectric constant of the absorber. The dependence of (1) as
well as of (3) on the doping density NA is equal in that sense
that an increase of NA by one order of magnitude yields an
increase of Voc of Voc = kT ln(10)/q 60 mV. However,
improving the open-circuit voltage by increasing the doping
density finds its limitation by the increased Auger recombination in the neutral volume and by the enhancement of
tunneling in the SCR (see [63] and below).
We note further, that (1) and (3) may be written in the
same form also for polycrystalline materials if one uses the
Fig. 4. Functional dependence of the open-circuit voltage Voc on the diffusion length L D for electrons in the Cu(In,Ga)Se2 absorber according to
(1) L D > 0.7 m for and according to (4) for L D < 0.7 m. The assumed
doping density is NA = 1016 cm3 . The dashed lines reflect the influence
of the back-surface recombination velocity Sb for values of Sb = 102 cm/s
(upper curve) and of Sb = 105 cm/s (lower curve) according to (2). The
top axis shows the grain-boundary recombination velocity Sg leading for
poly
a grain size of g = 1 m by (3) to the effective diffusion length L eff of the
p
bottom axis. The right axis denotes the allowed barrier height b for a given
interface recombination velocity for holes of Sp = 104 cm/s according to (5)
(4)
kT
Voc = b
ln
,
(5)
q
q
jsc
where Sp is the interface recombination velocity for holes and
p
the barrier b as indicated in Fig. 1b. As (5) establishes a linp
ear relationship between b and Voc we have used the right
axis in Fig. 4 to demonstrate that for an assumed interface recombination velocity Sp = 104 cm3 already a relatively high
p
barrier b is needed to maintain Voc = 650 mV. A change of
Sp by one order of magnitude would shift the right axis in
p
Fig. 4 by b = kT ln(10) 60 meV.
Electronic loss in the early cells was essentially explained
by recombination at the buffer/absorber interface [66]. These
cells consisted of a thick CdS window layer deposited by
PVD on the CuInSe2 absorber. The doping density in the
CdS and in the CuInSe2 absorber were approximately equal.
Therefore, the band bending in both heterojunction partners
was also equal. In terms of (5) and the band diagram the openp
circuit voltage was determined by a relatively low value of b
and a high value of Sp . The use of a highly doped ZnO and
of only a several 10-nm-thin CdS buffer layer increased the
band bending in the absorber and decreased the recombination velocity for holes at the heterointerface such that in the
actual state-of-the-art high-efficiency devices it is commonly
believed that recombination in the bulk of the absorber is the
dominant electronic loss mechanism. We note that considerations [67, 68] similar to those sketched above lead to the conclusion that efficiencies close to or even above 20% are possible for ZnO/CdS/Cu(In,Ga)Se2 heterostructure solar cells.
The required open-circuit voltage is then about 700 meV. Figure 4 indicates that in this case the diffusion length becomes
136
p
The modeling and the analysis of the complicated heterostructure shown in Figs. 1b and 3 often requires numerical
analysis by means of device simulation programs. The programs ADEPT from Purdue University [69] and SCAPS from
the Ghent University [70] are especially suited and frequently
used for the simulation of the present heterostructures. However, the analysis of a larger amount of real devices is better
performed by means of analytical models. As we have seen
above understanding of the open-circuit voltage losses requires the understanding of the diode law underlying the
electron transport of the heterojunction. For the three models
mentioned in Sect. 2.1 and those discussed in the following one can write a general expression for the dark-current
density
qV
E a
qV
j = j0 exp
= j00 exp
exp
(6)
AkT
AkT
AkT
at forward voltage V > 3kT/q. Hence, for the open-circuit
voltage,
E a AkT
j00
Voc =
ln
.
(7)
q
q
jsc
The values for the diode ideality factors A, the activation
energy E a , and the weakly temperature-dependent reference
current density j00 for the thermal activation of the saturation
current density j0 can be obtained from (1), (3), (5) for either
case. The practical analysis of devices is performed by measuring currentvoltage characteristics under different illumination intensities rather than the dark characteristics [71]. By
a semilogarithmic plot of the short-circuit current densities
vs. the open-circuit voltages the saturation current density and
the ideality factor are obtained at a given temperature. This
method avoids complications from series resistance effects
which may heavily influence the dark characteristics as will
be discussed in Sect. 2.4. Furthermore, if the diode ideality
factor A is only weakly dependent or independent of temperature a plot of Voc vs. temperature allows one to extrapolate
the activation energy E a . It is found that for high-efficiency
Cu(In,Ga)Se2 and CuIn(Se,S)2 devices the activation energy
is close to the band gap energy of the respective material.
This indicates that Voc is dominated by recombination in the
SCR according to (2) rather than interface recombination
p
(with E a = b according to (3)) [71]. However the ideality factor of Cu(In,Ga)Se2 -based heterojunctions is not 2 but
generally around 1.5 at room temperature. Walter and coworkers [71, 72] proposed a model based on an exponential
distribution of trap states to explain the temperature dependence of the diode ideality factor. The expression derived
in [71, 72] may be written as
1
1
T
=
1+ ,
(8)
A 2
T
where kT is the characteristic energy of the distribution.
Thus, a plot of the inverse ideality vs. temperature should
137
138
139
that were actually achieved in recent years by the use of Nacontaining substrates as well as by the use of Cu(In,Ga)Se2
alloys.
3.2 Defect physics of Cu( In, Ga) Se2
The role of defects in the ternary compound CuInSe2 , and
even more in Cu(In,Ga)Se2 , is of special importance because of the large number of possible intrinsic defects and,
of course, because of the role of deep recombination centers
for the performance of the solar cell devices [113]. The 12
possible intrinsic defects in CuInSe2 are listed in Table 2. According to Zhang, Wei, Zunger, and Katayama-Yoshida [114]
the challenge of defect physics in Cu(In,Ga)Se2 is to explain
three unusual effects in this material: (i) the ability to dope
Cu(In,Ga)Se2 with native defects, (ii) the structural tolerance
to large off-stochiometries, and (iii) the electrical benign nature of the structural defects. It is obvious that the answer
to the questions (i)(iii) significantly contributes to the explanation of the photovoltaic performance of this material. It
is known that the doping of CuInSe2 is achieved by intrinsic defects. Samples with p-type conductivity are grown if
the material is Cu-poor and is annealed under high Se vapour
pressure, whereas Cu-rich material with Se deficiency tends
to be n-type [115, 116]. Thus, the Se vacancy VSe is held for
the dominant donor in n-type material (and also for the compensating donor in p-type material) and the Cu vacancy VCu
for the dominant acceptor in Cu-poor p-type material.
By calculating the metal-related defects in CuInSe2 and
CuGaSe2 Zhang et al. [114] found that the defect formation
energies for some intrinsic defects are so low that they can
be heavily influenced by the chemical potential of the components (i.e., by the composition of the material) as well as by
the electrochemical potential of electrons. For VCu in Cu-poor
and stochiometric material even a negative formation energy
is calculated. This would imply the spontaneous formation
of large amounts of this defect under equilibrium conditions.
Low (but positive) formation energies are also found for the
Cu on In anti-site CuIn in Cu-rich material (a shallow acceptor which could be responsible for the p-type conductivity of
Cu-rich, non-Se deficient CuInSe2). The dependence of the
defect formation energies on the electron Fermi-level could
explain the strong tendency of CuInSe2 for self-compensation
and the difficulties in achieving extrinsic doping. The results
of Zhang et al. [114] provide a good theoretical base on defect
formation energies and defect transition energies that exhibits
good agreement with experimentally obtained data.
Fig. 7. Detail of the phase diagram of CuInSe2 along the quasi-binary tie
line Cu2 Se-In2 Se3 according to [110, 111]
the preparation of thin films. Figure 7 shows the four different phases that have been found to be relevant in this range:
the -phase (CuInSe2), the -phase (CuIn3 Se5 ), the -phase
(the high-temperature sphalerite phase), and Cu2y Se. The
useful range of absorber compositions, in terms of the ratio
x = In/(In + Cu), of CuInSe2-based cells is limited by the
segregation of Cu2y Se on the copper-rich side and by a transition from p- to n-type conductivity with increasing x. The
phase diagram [111] suggests that the latter effect arises from
the occurrence of the secondary -phase which shows weak
n-type conductivity [112]. The existence range of the -phase
in pure CuInSe2 on the quasi-binary tie line Cu2 Se-In2Se3 extends from a Cu content of 24% to 24.5% (see Fig. 7). Thus,
the existence range of single-phase CuInSe2 is astonishingly
small and does even not involve the proper stochiometric
composition with 25% Cu. The Cu content of absorbers for
thin-film solar cells varies typically between 22 and 24 at. %
Cu. At the growth temperature this lies within the singlephase region of the -phase. However, at room temperature
one enters the two-phase + region in the equilibrium
phase diagram of Haalboom [111]. Hence, one would expect a tendency for phase separation in photovoltaic-grade
CuInSe2 after deposition. Fortunately, it turns out that partial
replacement of In with Ga as well as the use of Na-containing
substrates considerably widens the process window in terms
of (In+Ga)/(In+Ga+Cu) ratios [110]. Thus, the phase diagram already gives a hint to the substantial improvements
Table 2. Electronic transition energies (difference to the valence/conduction band energy
for acceptor/donor states) and the energies of
formation E for the 12 intrinsic defects in
CuInSe2 . Transition energies in italics are derived from [122] and the formation energies in
brackets from [119]. All bold numbers stem
from [114]. Here the defect-formation energy
is that of the neutral defect in stochiometric
material
VCu
0.03
0.03
(/2)
(2 /3)
(0/+)
VIn
0.17
0.04
0.41
0.67
Vse
0.04
Cui
Ini
Sei
0.07
0.2
0.11b 0.08
0.60
2.9
a) covalent, b) ionic
3.04
2.8
2.6
2.88
4.4
9.1
CuIn
0.29
0.05
0.58
0.25
0.04
0.34
0.07
(+/2+)
E/eV
InCu
22.4
3.34
1.4
0.08
0.06
1.54
1.5
7.5
InSe
0.09
7.5
5.5
5.0
140
A further important result in [114] are the formation energies of defect complexes as (2VCu ,InCu), (CuIn ,InCu ), and
(2Cui ,CuIn ). These are even lower than those of the respective isolated defects. Interestingly, the (2VCu ,InCu ) does not
exhibit an electronic transition within the forbidden gap, in
contrast to the isolated InCu anti-site which is a deep recombination center. As the (2VCu ,InCu ) complex is most likely
to occur in In-rich material it can accommodate for a large
amount of excess In (or likewise deficient Cu) and, at the
same time, maintain the electrical performance of the material. Furthermore, ordered arrays of this complex can be
thought of as the building stones of a series of Cu-In-Se compounds such as CuIn3 Se5 , CuIn5Se8 [117].
The work of Zhang and co-workers [114, 117] on formation energies of defects is based on computations from
first principles. However, as the algorithm used in [114, 117]
was not able to reproduce the proper band gap energy of
CuInSe2, assumptions had to be made to derive the ionization energies of the defects. Also the work does not cover
Se-related defects which however are considered to be important [21, 113, 118]. Earlier work of Neumann [119] and
other groups [120] used the simpler macroscopic cavity
model [119]. Table 2 summarizes the ionization energies and
the defect formation energies of the 12 intrinsic defects in
CuInSe2. The energies (bold values in Table 2) for VCu , VIn ,
Cui , CuIn , InCu , are obtained from a first-principles calculation [114] whereas the formation energies in italics (Table 2)
and for the other defects are calculated from the macroscopic
cavity model [119]. The ionization energies used in Table 2
are either taken from Zhang et al. [114] or from the data
compiled in [121]. Note that the data given in [119, 121] for
the cation defects differ significantly from those computed
in [114].
There are numerous experimental results on defects in
Cu(In,Ga)Se2 obtained from photoluminescence [121124],
Hall measurements [125], DLTS [126128], admittance
spectroscopy [129133], and positron annihilation [134, 135].
As these experiments are conducted on single crystals, epitaxial films, or polycrystalline thin films of different stochiometry, a comparison and a definite picture of the defects is
difficult to achieve. There are different and, unfortunately,
contradictory attempts for an assignment of the observed transitions to the respective defect levels [114, 120, 122].
Here we concentrate on the defects detected in photovoltaic-grade (and thus In-rich) polycrystalline films. In-rich material, in general, is highly compensated with a net acceptor
concentration in the order of 1016 cm3 . The shallow acceptor level VCu (around 30 meV above the valence band [121])
is assumed to be the main dopant in this material. As compensating donors the Se vacancy VSe and the double-donor
InCu are considered. The most prominent defect is an acceptor
level about 270 meV above the valence band which is reported
by several groups [122, 129, 130] and is also detected in single crystals [122, 126]. The transition exhibits a broadened
energy distribution with a tail in the defect density towards
larger energies [130]. This defect is detected not only in Inrich, but to equal amounts also in Cu-rich polycrystalline
materials [136]. Therefore, an assignment of this defect to the
CuIn anti-site is in agreement with the theoretical calculations
of Zhang and co-workers [114] as well as with the proposition of several experimenters [102, 109]. The importance of
this transition is given by the fact that its concentration is
141
material displays n-type conductivity, could yield the explanation for the type inversion. The findings of [53] led to an
increasing interest in the Cu(In,Ga)3 Se5 compound [143] and
also to the fabrication of solar cells based on Cu(In,Ga)3 Se5
absorbers [144].
Unfortunately, the existence of a separate phase on
top of standard Cu(In,Ga)Se2 thin films has to our knowledge not yet been confirmed by structural methods such as
X-ray diffraction, high-resolution transmission electron microscopy, or electron diffraction. Furthermore, if the surface
phase would exhibit the weak n-type conductivity of bulk
Cu(In,Ga)3 Se5 , this would not be sufficient to achieve the
type inversion, as can be concluded from simple chargeneutrality estimations [110]. Moreover, it has been shown
that exposure of the free thin-film surface to ambient air
immediately reduces the type inversion [48]. From surface
photovoltage measurements performed on samples stored in
air it is routinely found that the surface band-bending is below
50 meV, i.e., the Cu(In,Ga)Se2 surface after a long exposure
to air is nearly in flat-band conditions [145].
Based on these arguments, another picture of the surface of Cu(In,Ga)Se2 thin films and of junction formation
has emerged [48, 110]. As sketched in Fig. 8, the type inversion can be viewed as a result of Fermi-level pinning due
to shallow surface acceptors. The positively charged surface
acceptors in Fig. 8 are expected on theoretical grounds for
the metal-terminated (112) surface of CuInSe2 due to the
dangling bond to the missing Se [146, 147]. Under this assumption, the Cu-poor surface composition is a consequence
of the type inversion (rather than its origin) as the Cu is driven
away from the surface by the built-in electrical field [110].
The reason for the vanishing of the type inversion upon air exposure is given by the passivation of the surface donors due
to the reaction of oxygen with the metal terminated surface as
discussed in Sect. 4.1.
Now we are in the situation that, on the one hand, the
simple picture of a buried p/n junction as a consequence
of a segregated surface phase of the Cu(In,Ga)Se2 absorber
is misleading as it suggests that any change at the absorber
surface (air exposure, buffer deposition) would have only minor impact on the electronic properties of the device. This is
obviously not the case. On the other hand, electrical measurements indicate that the Cu-poor surface region (with thickness
> 0) has in fact different electronic properties compared to
the bulk of the absorber [148]. A possible way out is the assumption of a defect-rich, disordered surface layer [110, 136]
which can even have a larger band gap than that of the absorber material.
3.4 Heterojunction formation and the role of buffer
deposition
As mentioned above, one of the four most important technological steps which led to the actual high-efficiency devices
is the introduction of the chemical bath for the deposition
of the CdS buffer layer. The benefit of the CdS layer is
manifold: (i) CBD deposition of CdS provides complete coverage of the rough polycrystalline absorber surface already
at a film thickness of 10 nm [149]. (ii) The layer provides
a protection against damages and chemical reactions resulting from the subsequent ZnO-deposition process. (iii) The
chemical bath removes the natural oxide from the film surface [150] and, thus, re-establishes positively charged surface
states and, as a consequence, the natural type inversion at
the CdS/Cu(In,Ga)Se2 interface. (iv) The Cd ions, reacting
first with the absorber surface, remove elemental Se possibly
by the formation of CdSe. (v) They also diffuse to a certain
extent into the Cu-poor surface layer of the absorber material [151, 152] where they possibly form CdCu donors, thus
providing additional positive charges enhancing the type inversion of the buffer/absorber interface. (vi) As we have discussed above the open-circuit voltage limitations by interface
recombination require also a low surface-recombination velocity in addition to the type inversion of the absorber surface.
Thus one might conclude that also interface states (except
those shallow surface donors responsible for the type inversion) are also passivated by the chemical bath.
4 Film modification options
The purpose of this section is to discuss the fundamental
options that were used so far to modify and to design the
electronic properties of the Cu(In,Ga)Se2 during and after
preparation. We will show that a number of ingredients such
as Na, Ga, O, S (note that we use the symbols of the chemical
in the following, regardless of ionization states or chemical
bindings of the atoms) can be utilized to optimize the electronic properties of the material. However, our present picture
of the impact of these materials is far from being complete
and the interactions to be considered are in any case manifold.
4.1 Influence of sodium
142
means of XPS and concluded that the Na is built into the lattice replacing In or Ga. The extrinsic defect NaIn/Ga should
then act as an acceptor and improving the p-type conductivity. The incorporation of Na into the Cu(In,Ga)Se2 lattice is
supported by X-ray diffraction measurements indicating an
increased volume of the unit cell [157]. The authors of [157]
assume the Na on a Cu place preventing the formation of
the deep double-donor InCu which would also have a beneficial effect. Schroeder and Rockett [170] found that Na
driven into epitaxial Cu(In,Ga)Se2 films at a temperature of
550 C decreased the degree of compensation by up to a factor 104 . Schroeder and Rockett attributed their findings to
a Na-enhanced re-organization of the defects, which allows
the defects to built electrically passive clusters [170].
We see from the numerous approaches that, despite the
significance of Na incorporation, the benefit is far from being
explained in terms of simple models. However, we feel that in
view of the amounts of Na (0.1 at. %) necessary for optimum
film preparation arguments considering the effect on the film
growth are slightly in favor with respect to those dealing with
the incorporation of Na into the completed film.
4.2 Influence of oxygen
Air-annealing has been one important process step crucial
for the efficiency especially of the early solar cells based
on CuInSe2 [171, 172]. Also often not mentioned explicitly,
an oxygenation step is still used for most of the present-day
high-efficiency devices [8]. The beneficial effect of oxygen
was explained within the defect chemical model of Cahen
and Noufi [146]. In this model the surface defects at grain
boundaries are positively charged Se vacancies VSe . During air-annealing, these sites are passivated by O atoms. By
the decreased charge at the grain boundary the band bending as well as the recombination probability for photogenerated electrons is reduced [146]. As we have already seen
above the surface donors and their neutralization by oxygen are also important for the free Cu(In,Ga)Se2 surface as
well as for the formation of CdS/Cu(In,Ga)Se2 interface [48].
Electrical analysis of oxidized and unoxidized samples revealed the validity of the CahenNoufi model for the earlier
CdS/CuInSe2 devices [173] as well as for the more recent
ZnO/CdS/Cu(In,Ga)Se2 heterostructures [174]. Also the extension of this model for the catalytic effect of Na [163] could
be verified [174].
The intriguing interplay between surface oxygenation and
the deposition of the CdS buffer layer (cf. Sect. 3.4) is visualized in Fig. 9. In the initial state (Fig. 9a) the film surface as well as the grain boundaries are electrically active
due to the positively charged dangling bonds. These charges
cause a large space-charge region within the grain. Airannealing passivates the dangling bonds at both interfaces.
The bands essentially become flat: space-charge essentially
vanishes (Fig. 9b). Eventually, the chemical bath removes the
passivating oxygen and thus re-establishes the beneficial type
inversion of the film surface (Fig. 9c).
4.3 Influence of gallium
The best Cu(In,Ga)Se2 -based solar cells (efficiency of 17.7%)
have Ga contents between 10% and 30% with respect to
143
a)
b)
c)
Fig. 9ac. Illustration of the effect of air-annealing of polycrystalline
Cu(In,Ga)Se2 films and that of subsequent CdS deposition by the chemical
bath. a In the initial state grain boundaries and the film surface are positively charged. The space-charge region within the grains counterbalances
these charges. b Air-annealing passivates both surfaces. c The chemical bath
during CdS deposition re-establishes positively charged donors at the film
surface only
144
Three out of the four cornerstones (i)(iv) for the recent achievements mentioned in Sect. 1.1 concern the growth
of the films: the optimized deposition conditions (i) and the
incorporation of Na (ii) and Ga (iii). However, no detailed
model is available to describe conclusively the growth of
Cu(In,Ga)Se2 and, especially, the impact of Na which in our
opinion is the most important under the different ingredients
available to tune the electronic properties of the absorber.
A clearer understanding of the Cu(In,Ga)Se2 growth would
allow us to find optimized conditions in the wide parameter
space available and, thus, reduce the number of recombination centers and compensating donors and to optimize the
number of shallow acceptors.
The deposition of the buffer layer, or more generally
speaking, the formation of the heterojunction is another critical issue. The surface chemistry taking place during heterojunction formation and also during post-deposition treatments
is decisive for the final device performance. Both processes
heavily affect not only the surface defects (i.e., recombination and charge) and therefore the charge distribution in the
device but also immediately the defects in the bulk of the
absorber material. As recombination under open-circuit conditions takes place only some 50100 nm away from the
surface it is well understood that mastering of the (near) surface chemistry is an extremely challenging business in the
future. Concentrated effort and major progress in these tasks
would not only allow us to push the top efficiencies further
towards 20% but is also required to provide a sound knowledge base for the various attempts for commercialization of
Cu(In,Ga)Se2 solar cells.
Note added in proof : during proof-reading of the article
we learned that a new record efficiency for Cu(In,Ga)Se2 of
18.8% was achieved by the group at the National Renewable
Energy Laboratories (Golden, USA) [187].
Acknowledgements. The authors thank all our colleagues in the IPE for various discussions and the fruitful collaboration with all the groups at our
institute. We are especially grateful to J.H. Werner for his continuous support and his interest in this work. Critical reading of the manuscript by
D. Braunger, A. Jasenek, and M. Grauvogl is especially acknowledged. This
work is to a great part supported by the German Ministry of Research,
Technology, and Education (BMBF) under contract 0328059F. Collaborations with D. Cahen, J.-F. Guillemoles, L. Kronik, and D. Lincot are also
acknowledged. U.R. also thanks colleagues at the University Oldenburg and
the various groups of the FORSOL project (supported by the Bayerische
Forschungsstiftung) for collaboration and discussions.
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