A new approach to highefficiency multibandgap solar cells

K. W. J. Barnham and G. Duggan

Citation: J. Appl. Phys. 67, 3490 (1990); doi: 10.1063/1.345339
View online: http://dx.doi.org/10.1063/1.345339
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A new approach to multi-band-gap solar cells
K. w. J. Barnham
Blackett Laboratory, Imperial College a/Science, Technology, and Medicine, London SW7 2BZ,
United Kingdom
G. Duggan
Philips Research Laboratorit'S. Redhill RBi 5HA, United Kingdom
(Received 12 June 1989; accepted for publication 8 December 1989)
The advantages of using multi-quantum-well or superlattice systems as the absorbers in
concentrator solar cells are discussed. By adjusting the quantum-well width, an effective band-
gap variation that covers the high-efficiency of .solar spectrum can be obtained.
Higher efficiencies should result from the ablhty to current and. voltage
generating factors. Suitable structures to ensure good carner separation and collection and to
obtain higher open-circuit voltages are presented using the (AlGa) As/GaAsl (InGa) As
system. Efficiencies above existing single-band-gap limits should be achievable, with upper
limits in excess of 40%.
I. INTRODUCTiON
Rect'llt improvements 1 have taken the efficiency of sin-
gle-band-gap GaAs solar ceil;; a,l.l?ve 28%. under
o

tion, which is close to the theoretIcal maxlmum.- It IS there-
fore an appropriate time to consider afresh the problems
associated with the multi-band-gap approach to higher con-
version efficiencies. For Mli1ie time it has been appreciated
that a vertical stack of ceU,;, connected electrically in series,
with a band gap that as light penetrates into the
stack, offers the theoreticd of much higher effi-
ciency.2.' However, probl::m;; in making material and elec-
trical contacts between celh have meant that even the best
two-cell, tandem arrangcments
4
have, in practice, efficien-
cies comparable to thosf; that are possible with one compo-
nent.
In view of the advances in optoelectronic devices due to
progress in epitaxy (MBE) and metalor-
ganic chemical .J:por deposition (MOCVD) growth tech-
niques, it would also seem to consider whether
"low-dimension<l.l" structures (LDS) such as multi-quan-
tum-well (MQW) and superlattice C;';L) systems could pro-
vide a new approach to the highd1kiency, concentrator cell
problem. It has been materials with differ-
ent, but fixed, bulk g-ar", .connected by a strain;d-
layer SLs, Also a dopmg supen2,rf.lCe has been suggested as
a way to increa.c the roinority carrier lifetime by charge
separation. Here we point out the advantages of using the
quantum wells (QWs) themselves as the active region for
photon absorption in solar cells built from AIGaAs/GaAs
and InGaAs/GaAs MQW or SL systems.
In Sec. II we show rhflt in principle higher energy con-
version are possible in a LDS solar cell as the
factors determining cunt;,H and voltage generation can be
separately optimized. Calculations will be presented of the
upper limits to the energy efficiency that are possible in an
ideal LDS solar cell. They should be regarded as targets for
LDS solar cdl design to seek to achieve in the same way that
the calculations in Ref. 2 have served as the ideal for conve-
tional cells in the past decade. We point out that recombina-
tion effects must be minimized if these upper limits are to be
approached. In Sec. III we discuss one way to achieve high
carrier collection efficiencies by varying the well width in an
a periodic MQW or SL system.
II. ADVANTAGES OF A LOS SOLAR CELL
Some of the potential advantages of a LDS solar cell will
be illustrated with reference to Fig. 1 (a). The effective band
gap for absorption Ea will be determined by the lowest con-
fined states (or the associated excitons) of the quantum well.
This absorption band gap can be simply tailored by suitable
choice of quantum-well and barrier width [L
z
and L
b
, re-
spectively, in Fig. 1 (a)]. For example, Fig. 1 (b) shows the
range of photon energies that can be absorbed by the lowest
energy heavy hole to electron transition HHI-El simply by
varying the width L
z
of isolated quantum wells in
In035 Gilab5 As/GaAs and Al
a
.
3
Gila. 7 As/GaAs systems. It
can be seen that the peak in the conventional solar cell effi-
ciency curve
2
can be spanned simply by varying L
z
.
In Fig. 1 (a) the MQW or SL forms the intrinsic region
of a p-i-n diode. As will be demonstrated on the basis of a
simple superposition model, higher-energy conversion effi-
ciencies are possible in principle if L
z
, L
b
, barrier composi-
tion, and number of wells are all optimized so that the open-
circuit voltage VOL is determined primarily by the built-in
voltage due to the barrier regions of the MQW or SL. If this
is achieved, the factors that are primary determinants of ab-
sorption and v'K can be effectively decoupled and indepen-
dently optimized in a LDS solar cell, whereas in a conven-
tional cell they are both determined by the bulk band gap. It
will be shown that for this ideal situation to be achieved,
carrier recombination effects must be minimized. One possi-
ble LDS solar cell geometry that has the potential to achieve
this will be discussed in Sec. III.
The separation of current and voltage generation func-
tions in a LDS solar cell can be demonstrated using the stan-
dard superposition model of solar cells in which the current
density is
3490 J. Appl. Phys. 67 (7),1 April 1990
0021-8979/901073490-04$03,00 @ 1990 American Institute of Physics 3490
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_-..
pIn
60
b) C = 1x
40
-
-
-
-
20

eoA lOA 1:iOA lOA
o L-__ ___ -L ___ ___ _ _J ___
0.50 0.75 tOO 125 150 t75 2.00
AbsorptIon band-gap Eo (el/)
60
c) C = 1000x
g ------- .....
---
s::- 40
-
,
I
-
,
-
20
J
o
0.50 0.75 tOO 125 1.50 t75 2.00
Absorption band-gap Eo (rI)
FIG. 1. (a) Schematic representation of an equal-well-width LOS solar cell.
(b) Full line is maximum energy efficiency of a conventional single-band-
gap solar cell as a function of that band gap at I X concentration (from Ref.
2). Dashed line is maximum efficiency of an ideal LOS solar cell as in (a)
with Eb 20% greater than Ea' Dotted line is ideal LOS solar cell maximum
efficiency with Eb 40% greater than Ea. (c) As (b), but for 1000 X concen-
tration.
where the dark current density is given by the standard
Shockley form
Here Eb is the band gap controlling the dark saturation cur-
rent density, vand n are ideality factors, and prefactor A will
be discussed later. The short circuit current density is given
by
where N(Eo) is the number of photons per second per unit
area with energy greater than the effective band gap for ab-
sorption and Q is the quantum efficiency.
The current density J m and voltage V m at maximum
power are given in the standard way8 by
3491 J. Appl. Phys., Vol. 67, NO.7, 1 April 1990
QeN(Ea)
IJml=-----
1 + (nkT leV",)
where the open-circuit voltage is given by
eVoc =n[Eb/v-kTln(A/Jsc)]'
Hence, in the expression for energy efficiency 7] with Pin the
incident power per unit area,
JmV
m
7]=--.
Pin
J m is determined primarily by Eo , the effective band gap for
absorption, which in a LOS solar cell is the lowest confined
state, and V m is determined primarily by E
b
, the band-gap
controlling the dark saturation current density, which in a
well-designed LOS solar cell should be the band gap of the
barrier region. In a conventional solar cell, Eo = Eb = E
g
,
the semiconductor band gap.
In the ideal situation Q = n = v = 1 and the above ex-
pressions reduce to those in the standard work on maximum
solar cell efficiencies by Henry2 providing Eo = E
b
To dem-
onstrate the energy efficiency enhancement over the ideal
conventional cell which might be possible in an ideal LOS
solar cell, we compare in Figs. 1 (b) and 1 (c) Henry's calcu-
lation for the former under Air Mass 1.5 illumination at 1 X
and lOOOx concentration as a function of Eo with the maxi-
mum possible efficiency if the effective barrier band gap Eb
is 20% and 40% greater than Eo. For consistency we assume
the parametrization for A in the dark current density given
by Henry,
A = (A cm-
2
).
I t is clear from this derivation that if a LOS solar cell is
to attain efficiency enhancements approaching those indi-
cated in Figs. 1 (b) and 1 (c), the dark current should have
Shockley-type behavior with a "turn-on" voltage deter-
mined by the barrier band gap. It is well known that the dark
current characteristic ofMQW photodetectors reflect trans-
port across the entire device and are characterized by the
transport limiting structure which is generally the barrier
region in reverse bias. OUf expectation that in a well-de-
signed LOS solar cell this would also be true at forward bias
is strengthened by the observation that the Al
u25
Gaa75 As/
GaAs p-i-n MQW photodetectors of Ref. 9 have a dark cur-
rent characteristic with a forward bias "turn-on" voltage
between the values expected for wells and barriers.
The dark current will most closely approximate to the
Shockley form with current limited by the minority currents
outside the depletion regions if recombination effects in the
intrinsic region can be minimized. Preliminary results 10 on
Ala.3 Gaa.7 As/GaAs p-i-n photodiodes indicate that the ex-
ternal quantum efficiency remains high into the forward bias
region even with 50-A. barriers. In Sec. III we discuss a ge-
ometry in which rapid carrier collection should be possible.
In a conventional fixed or variable band-gap solar cell,
loss of energy by thermalization following the absorption of
a photon with energy greater than the band gap is one of the
main factors limiting efficiency. In a MQW or SL room-
temperature absorption at the lowest energy excitonic peak
K. W. J. Barnham and G. Duggan 3491
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is approximately twice as strong as in the continuum. II It
should therefore be possible to ensure, by altering the well
width systematically, that much of the absorption occurs at
these peaks, i.e., at the effective band edge. It will be impor-
tant that as many carriers as possible are then transported at
this energy and in Sec. III we discuss ways to arrange that
this occurs.
The (InGa)As system covers a range of band gaps of
particular importance for solar cells in the region of the sili-
con band gap. However, there are serious materials prob-
lems involved 12 in growing strained-layer SLs to link bulk
regions of GaAs and (InGa)As. Our proposal to use an
Iny Gal . y As strained-layer SL between GaAs or
Alx Gal x As barriers does not have this disadvantage. Pro-
viding the well widths are less than a critical thickness - 200
A (Ref. 13), the strain should be accommodated elastically
without generating deleterious misfit dislocations.
Finally it should be noted that in comparison with crys-
talline silicon at similar wavelengths, compositional MQW
and SL systems have high absorption coefficients II and ac-
tive regions only I ,urn thick are efficient absorbers.
III. METHODS FOR EFFICIENT CARRIER COLLECTION
A. Tunneling perpendicular to the quantum wells
In this geometry (an example is shown schematically in
Fig. 2) a well width vzriation is chosen so that the electron
levels are resonant at the operating bias. This device resem-
bles the SL of Summers and Brennan but
within a p-i-n structure rather than n-i-n (Ref. 14) and with
carriers being by absorption rather than electron in-
jection. Due to the smaller valence band discontinuity, holes
should be colketNi efficiently by thermal excitation from the
wells at room t.:mperature. This geometry shouid minimize
recombination in the intrinsic region as required in the ideal
LOS solar cell, as discussed in Sec. II.
The main problem with this geometry is to preserve the
resonant condition for e1ectn)Hs by varying well width while
p+
incorporating a sufficient number of wells to get high ab-
sorption. Calculations show that one can fit -100 wells into
> 1 ,urn using the two material systems of Fig. 1 (b) in a
single intrinsic region providing "clusters" of wells with
equal L
z
are used at the narrower well widths. This is where
the amount of absorbing material is smaller and the vari-
ation of the confined electron energy with L
z
faster. Within
these "clusters" the resonant condition will not hold. How-
ever, for narrow barriers the min bandwidths should lead to
efficient tunneling albeit at the expense of some thermaliza-
tion loss within the miniband.
B. Collection parallel to the wells
In the materials systems discussed here the room-tem-
perature mobility of the electrons parallel to the wells is rela-
tively high [9000 cm
2
V-I s -I (Ref. 15)]. Also MBE
growth usually results in a lightly p-type (N
A
..;;;10
14
cm-
3
)
intrinsic region and hence the hole lifetimes should be rela-
tively long. Charge separation and current collection paral-
lel to the wells becomes possible if selective contacts can be
fabricated as in Fig. 3. This geometry is similar to that ofthe
n-i-p-i doping superlattice cell of Ref. 7 in its inverted form as
in Ref. 16.
In this geometry the well width variation with depth can
be arranged for optimum absorption without the extra con-
straints imposed by resonant tunneling. The arrangement is
equivalent to a large number of cells in parallel and should
give a Voc that is approximately the average of that for each
cell and a current that is the sum of all the cells.
Although it is not possible to take advantage of the Voc
enhancement discussed in Sec. II above, this geometry
would be particularly useful in the Iny Gal v As!
GaAs
z
Sb
l
_ z type II MQW system where spatial carrier
separation occurs and carrier lifetimes are longer.
The main problem with this geometry is the need to
ensure that I < carrier diffusion lengths while l't> d to ensure a
large collecting area. For highest collection efficiency one
would like low background doping levels (N
A
< 10 14 em - ')
I
I
I
n+
GaAs AS,---i>IJ>+i ..:_-- AJO,3GaQ,7As/GaAs----i
FIG, 2. Schematic representation of possible h.igh collection efficiency MQW solar cell with carrier collection perpendicular to the wells,
3492 J, Appl Phys., Vol 67. No.7, 1 April 1990 K. W. J. Barnham and G, Duggan 3492
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I2ZZJ Al
o
.
3
Ga
O
.
r
As
c=J GaAs
~ InO.3SGaO.6SAs
- d _ ..... 1---------
with I < depletion length ( > 5 f-lm) to employ the drift field.
With ;;.100 short, wide channels in parallel, series resistance
should not be a problem given typical room-temperature
mobilities of two-dimensional systems under illumination. 15
One possibility is to use ion-implanted cylindrical contacts
in a square array with back-face contacting. Recent develop-
ments in growth on groove-etched substrates and of adding
in situ selective contacts by MBE (Ref. 17) may also prove
relevant. As technology develops on the micron scale, this
geometry should become more attractive.
We conclude that a variably spaced MQW or SL grown
in the (AlGa) As/GaAs/(lnGa)As system offers a new ap-
proach to the high-efficiency multi-band-gap solar cell prob-
lem. The effective band gap for absorption can be tailored by
varying well width alone or weII width and composition. The
current and voltage generation functions performed by the
band gap in a conventional cell should be capable of separate
optimization. Using technology that is currently being de-
veloped for other optoelectronic devices, solar cells with effi-
ciencies well above current single-band-gap limits should be
possible.
ACKNOWLEDGMENTS
We wish to thank Gareth Parry and Mark Whitehead
for communicating results prior to publication and Anders
Larsson for useful information. One of us (K.W.J.B) is
grateful for helpful discussions with Gene Blakeslee, Chris
3493 J. Appl. Phys., Vol. 67, No.7, 1 April 1990
--------.]00_ d -
FIG. 3. Schematic representation
of possible multi-quantum-well so-
lar cell with carrier collection par-
allel to the wells using the inverted
geometry of Ref. 16.
Jeynes, Jerry Olsen, Rob Stevens, Chris Summers, and Jan
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K. W. J. Barnham and G. Duggan 3493
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