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An approach to high efficiencies using GaAs/GaInNAs multiple quantum

well and superlattice solar cell


Maykel Courel, Julio C. Rimada, and Luis Hernández

Citation: J. Appl. Phys. 112, 054511 (2012); doi: 10.1063/1.4749418


View online: http://dx.doi.org/10.1063/1.4749418
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Published by the American Institute of Physics.

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JOURNAL OF APPLIED PHYSICS 112, 054511 (2012)

An approach to high efficiencies using GaAs/GaInNAs multiple quantum


well and superlattice solar cell
Maykel Courel,1 Julio C. Rimada,1 and Luis Herna
ndez2,a)
1
Solar Cell Laboratory, Institute of Materials Science and Technology (IMRE), University of Havana,
Zapata and G, 10400 La Habana, Cuba
2
General Physics Department, Faculty of Physics, University of Havana, Colina Universitaria,
10400 La Habana, Cuba

(Received 8 March 2012; accepted 9 August 2012; published online 13 September 2012)
A new type of photovoltaic device where GaAs/GaInNAs multiple quantum wells (MQW) or
superlattice (SL) are inserted in the i-region of a GaAs p-i-n solar cell (SC) is presented. The
results suggest the device can reach record efficiencies for single-junction solar cells. A
theoretical model is developed to study the performance of this device. The conversion efficiency
as a function of wells width and depth is modeled for MQW solar cells. It is shown that the MQW
solar cells reach high conversion efficiency values. A study of the SL solar cell viability is also
presented. The conditions for resonant tunneling are established by the matrix transfer method for
a superlattice with variable quantum wells width. The effective density of states and the
absorption coefficient for SL structure are calculated in order to determinate the J-V
characteristic. The influence of superlattice length on the conversion efficiency is researched,
showing a better performance when width and cluster numbers are increased. The SL solar cell
conversion efficiency is compared with the maximum conversion efficiency obtained for the
MQW solar cell and shows an efficiency enhancement. V C 2012 American Institute of Physics.

[http://dx.doi.org/10.1063/1.4749418]

I. INTRODUCTION between adjacent wells is greatly increased and the carriers


are no longer localized in individual wells. Thus, carriers are
The inability of a single-gap solar cell (SC) to absorb
easily spread throughout whole SL via continuous mini-
energies less than the band-gap energy is one of the intrinsic
bands.4 These outcomes result in the high conductivity and
loss mechanisms which limits the conversion efficiency in
improved performance of SL solar cells.
photovoltaic devices. New approaches to “ultra-high” effi-
GaAs solar cells currently retain the world efficiency re-
ciency solar cells include devices such as multiple quantum
cord for single junction photovoltaic cells. The enhancement
wells (MQW) and superlattices (SLs) systems in the intrinsic
of GaAs solar cell efficiency is therefore important to
region of a p-i-n cell of wider band-gap energy (barrier or
improve solar cell performance, and then to include quantum
host) semiconductor. These configurations are intended to
wells in GaAs, as semiconductor host, would be the best
broaden the absorption band beyond the one of the host cell
option. However, the lattice mismatch places an upper limit
semiconductor. In simple terms, the MQW or SL solar cell
on the number of quantum wells that can be accommodated
(MQWSC, SLSC) is a structure of sandwiched layers between
before strain relaxation takes place, compromising the open
two n and p doped bulk semiconductors. This idea was pio-
circuit voltage. The first attempts included strained GaAs/
neered by Barnham et al. in 1990.1 A common feature of
InGaAs QWSCs, but they have not possessed sufficient quan-
these new approaches is that they rely on quantum-based
tum well absorption to increase the short-circuit current to
devices for their implementation. Hence, the inclusion of
overcome the loss in the open circuit voltage resulting from
quantum effects in the calculation of solar cell parameters is
dislocations.5 Another more successful approach has been to
of increasing importance. The quantized energy levels in
include strain-balanced GaAsP/InGaAs multiple quantum
quantum structures become the driving force for next-
wells in the intrinsic region.6 The strain-balanced absorbers
generation solar cells by means of the light absorption range
constructed with alternate tensile and compressively strained
control.
layers have demonstrated remarkably improved photovoltaic
In the MQW solar cell, the presence of the built-in elec-
performance for the MQW cell design, comparable in effi-
tric field in the depletion layer leads to the collection of car-
ciency to a homogeneous GaAs control cell.
riers photo-generated in the wells, leading to an enhanced
The dilute nitride (GaIn) (NAs) is a novel material sys-
current.2 Early quantum efficiency (QE) modeling showed
tem grown lattice matched to GaAs. This compound is gain-
that escape efficiency is essentially 100%.3 On the other
ing increasing interest in recent years due to its very unique
hand, SL is obtained by reducing layer barrier; which origi-
physical properties and a wide range of possible device
nates that the tunnel probability of photogenerated carriers
applications.7 The band gap of GaAs decreases rapidly with
the addition of small atomic fractions of N,8,9 moreover, the
a)
Author to whom correspondence should be addressed. Electronic mail: addition of In to GaNAs does not only provide a lattice
luisman@fisica.uh.cu. matched to GaAs but also decreases the band gap. This

0021-8979/2012/112(5)/054511/7/$30.00 112, 054511-1 C 2012 American Institute of Physics


V
054511-2 ndez
Courel, Rimada, and Herna J. Appl. Phys. 112, 054511 (2012)

property makes very attractive the use of GaInNAs materials and well band gap EgW was studied in a previous work.16
to fabricate multiple quantum wells and superlattice to Under these conditions, the current–voltage relation of the
improve the GaAs solar cell conversion efficiency. MQW cell is given by
A scheme, involving the use of GaInNAs subcells, has
been formulated to enhance the efficiency of existing triple J ¼ J0 ð1 þ rR bÞ
and quadruple junction solar cells.10 Nonetheless, up to now,        
qV qV
poor minority carrier properties11 and doping issues12 specific  exp  1 þ arNR exp  1  JPH ;
to bulk dilute nitrides have hindered the success of this kT 2kT
approach.13 A different strategy has been published,14 where (1)
GaAsN multiple-quantum wells are embedded within the
intrinsic region of conventional GaAs p–i–n solar cells. The where q is the electron charge, V is the terminal voltage, kT
qWB n2
authors reported a current output about 25 A m2 in absence is the thermal energy, a ¼ qWAB niB and b ¼ J0B iB are pa-
of anti-reflection coating (ARC) and output voltages around rameters defined by Anderson.17
0.6 V for a 1.1 eV MQW cell. These short circuit current and J0 is the reverse saturation current density.
open circuit voltage values are much smaller than those AB is the nonradiative coefficient for barriers in the
reported for conventional GaAs solar cells, surely due to high depletion region, which is related to barrier non-radiative
interface recombination as consequence of the lattice mis- lifetime sB by AB ¼ 1/sB.
match between GaAs and GaNAs layers. BB is the radiative barrier recombination coefficient,
In the present work, we extend a new approach, whose which includes the charge-neutral Shockley injection cur-
first results were reported by Courel et al.15 where GaAs/GaIn- rent, and the space-charge region radiative current.
NAs multiple-quantum wells and superlattice are added within niB is the equilibrium intrinsic carrier concentration for
the intrinsic region of conventional GaAs p–i–n solar cells. the barrier material.
First, a GaAs/GaInNAs MQWSC is described in order to rR and rNR are the radiative enhancement ratio and non-
research the conversion efficiency as a function of wells width radiative enhancement ratio, respectively, and represent the
and depth. A discussion about N fraction and quantum well fractional increase in radiative and non-radiative recombina-
width to reach the maximum of the solar cell performance is tion in the intrinsic region, due to the insertion of the quan-
addressed. Second, a theoretical study of the GaAs/GaInNAs tum wells. These parameters are given by the following
SLSC viability is considered where the effective density of expressions:
states and the absorption coefficient for the SL structure are    
calculated in order to determinate the J-V characteristic. The DE  qFx
rR ¼ 1 þ fW cB c2DOS exp 1 ; (2)
influence of the superlattice width and number on the conver- kT
sion efficiency is discussed. The SLSC conversion efficiency
is compared with the maximum conversion efficiency    
DE  qFx
obtained for the MQWSC. Finally, we present GaAs/GaInNAs rNR ¼ 1 þ fW cA cDOS exp 1 ; (3)
2kT
SLSC conversion efficiency as a function of solar concentra-
tion, showing an amazing increment in its performance.
where DE ¼ EgB  EgW, fW is the fraction of the intrinsic
region volume replaced by quantum well material,
II. MODEL DETAILS
cDOS ¼ gW/gB is the density of states enhancement factor,
In this paper, we made the common assumptions of ho- with gW and gB as the effective density of states for the wells
mogeneous composition in doped and intrinsic layers, the and barriers, and cB, cA are “oscillator enhancement factor”
depletion approximation in the space-charge region, and total and “lifetime reduction factor,” respectively.17 The built in
photogenerated carrier collection. field is denoted by F and x is the position in the wells, so rR
The first cell characteristic simulated was the spectral and rNR are position dependent. The photocurrent JPH is cal-
response, yielding the cell quantum efficiency and short circuit culated from the quantum efficiency of the cell. The p-region
current for a given spectrum. Transport and Poisson equations and n-region contribution to QE was classically evaluated
were used to compute the quantum efficiency in the charge- solving the carrier transport equations at room temperature
neutral layers. The fit to the QE determines the recombination within the minority carrier and depletion approximations.18
characteristics independently in charge neutral and space- The contribution of photo-generated carriers in the intrinsic
charge regions. This determines the radiative and non-radiative region to QE values is calculated by the expression
recombination currents in these regions as a function of applied ( )
X 3
bias. The overall photocurrent is simply expressed in terms of QEðkÞ ¼ ½1  RðkÞexp  ai zi
superposition, adding photocurrent to the dark current in order i¼1
to ascertain the light current characteristic. At the same time,
 ½1  expðaB W  NW aW Þ; (4)
we assumed an equal carrier temperature in all regions.
where R(k) is the surface reflectivity spectrum of the antire-
A. Multiple quantum well solar cells (MQWSC)
flection layer. The first exponential factor is due to the
A MQW solar cell with NW wells each of length LW in attenuation of light in the layers between the surface of the
the intrinsic region of length W with barrier band gap EgB cell and the depletion layer (see Figure 1). The layers
054511-3 ndez
Courel, Rimada, and Herna J. Appl. Phys. 112, 054511 (2012)

FIG. 1. Sketch of energy band diagram of a GaAs p-i-n


solar cell with quantum wells inserted within the intrin-
sic region.

considered in our calculus, which are depicted in Figure 1 by becomes extended over the whole superlattice, and the
numbers, are: (1) antireflection layer, (2) emitter layer, and discrete levels in isolated quantum wells spread into a mini-
(3) space-charge region from the emitter layer. On the other band. In presence of electric field across the intrinsic region,
hand, ai and zi are the absorption coefficient and the width of perpendicular to the layers, the superlattice minibands split
these precedent layers, respectively, the aB is the absorption into a band energy ladder and as the electric field is increased,
coefficient of the bulk barrier material, and aW is the dimen- considering wells of equal width with a single energy level;
sionless quantum well absorption coefficient, used for ener- an alignment between the energy subbands is getting worse.
gies below the barrier band gap. When mixing between light On the other hand, when wells have more than a single quan-
and heavy valence sub-bands is neglected, the absorption tum energy level, it is expected that the bands move in and
coefficient can be calculated as follows:19 out of alignment as the field is varied. This effect reduces tun-
neling current causing a decrease of the solar cell perform-
aW ¼ aW K; (5) ance. This way, the electric field causes a localization of the
electron in the quantum well that produces vanishing of the
aW ðEÞ ¼ Raen hhm ðEÞ þ Raen lhm ðEÞ; (6)
miniband, and then the superlattice advantages disappear.
Hence, the major challenge is to achieve the conditions for
where Raen hhm ðEÞ and Raen lhm ðEÞ are sums over well states
resonant tunneling for a specific value of the electric field
n and m, which depend on the quantum wells width and
which allow the escape of the carrier from the superlattices.
depth, aen hhm ðEÞ and aen lhm ðEÞ are the absorption coeffi-
This difficulty is overcome fabricating variable spaced super-
cients due to electron-heavy hole and electron-light hole
lattice where a well width variation is chosen so that the elec-
transitions to conduction band, respectively; aW is the well
tron levels are resonant at the operating bias.1
absorption coefficient and K is the “quantum thickness of the
In a SLSC, the optical transitions take place between
heterostructure.” To match accurately with experimental
minibands and not between quantum levels, so optical tran-
data in the long wavelength region, the exciton absorption is
sitions between electron, heavy, and light holes minibands
considered in the theoretical calculation.
must be included in the J-V characteristic. Equation (1) can
The exciton binding energies are analytically evaluated
be extended to describe a SLSC taking into account that the
in the framework of fractional-dimensional space.20 Once
coefficients (Eqs. (2) and (3)) and the photocurrent JPH
the total QE is calculated, by means of the AM1.5 solar spec-
should be related to superlattice structure. Now, the fW fac-
trum F(k), the photocurrent is determined by integration
tor is the intrinsic region fraction replaced by superlattices,
ð k2 with gSL and gB as the effective density of states for super-
JPH ¼ q FðkÞQETOTAL ðkÞdk; (7) lattices and barriers, cB ¼ BSL/BB and cA ¼ ASL/AB are the
k1 radiative and non radiative recombination coefficients
which are referred to superlattices and barriers, respec-
where k1 and k2 are limits of the taken solar spectrum. Then, tively. The photocurrent is evaluated including the mini-
Eq. (1) is completely determined and conversion efficiency band absorption coefficients. We calculated the effective
(g) can be evaluated. The present model was previously cor- density of states, the absorption coefficient, the radiative
roborated comparing experimental quantum efficiency and recombination coefficient, and the photocurrent in a super-
open circuit voltage with the corresponding calculated values lattice system in order to determine the J-V characteristic
using AlGaAs/GaAs MQWSC.16,21 for a SLSC.
The density of states N(E), for a superlattice was esti-
mated considering that each state of energy in a single quan-
B. Superlattice solar cells (SLSC)
tum well becomes the bottom of a two dimensional subband
In a MQWSC, the different quantum wells are independ- in the density of states. In the same way, each Bloch state in
ent and there is no coupling between neighboring quantum a superlattice behaves as the bottom of a subband. The co-
wells. However, for the superlattice solar cell, there is an sine approximation for a singe miniband of width C was con-
interaction between neighboring wells and the wave function sidered. Once N(E) is known, assuming an instantaneous
054511-4 ndez
Courel, Rimada, and Herna J. Appl. Phys. 112, 054511 (2012)

transition at the barrier band edge to the usual three dimen- Boltzmann approximation to the Fermi-Dirac distribution,
sional density of states, considering that the miniband energy we previously found the effective density of states for
extends only the length of the cluster LSL and making the electrons4

2 0 0 11 3
ð
Ce Ce       
m 6 B1 1 E  E þ Ee Ee þ Ce DEc 7
B 2C C
gSle ¼ 2 e 4 @ þ arcsin@ AAexp  dE þ kT exp   exp  5
p
h dSL 2 2 Ce kT kT kT
0
2
 3=2 " rffiffiffiffiffiffiffiffiffi   rffiffiffiffiffiffiffiffiffi#
2pme kT DEc DEc DEc
þ2 2 exp  þ erfc ; (8)
h2 pkT kT kT

ð2
E
where Ee is the electron miniband bottom, erfc is the comple- 8pn2 aSL E2 dE
B¼ 2 3 r E : (12)
mentary error function, me is the electron effective mass, c h n0 p0 exp kT 1
E1
DEc ¼ Qc(EgB – EgW) is the conduction band well depth, Qc
is the band offset, dSL is the superlattice period, and Ce is the
Equation (4) should be modified to consider the absorption
conduction miniband width. Analogous expressions are held
of photons through a miniband and not by means of the
for the heavy hole and light hole effective density of states
quantum well discreet levels. The contribution of photo-
(g SL , g SL ). We then calculated the total superlattice effec-
hh lh generated carriers in the intrinsic region to QE values is cal-
tive density of states as
culated by the expression
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ( )
X 3
gSL ¼ g SLe ðg SL þ g SL Þ: (9) QEðkÞ ¼ ½1  RðkÞexp  ai zi
lh hh
i¼1
We also found the absorption coefficient for the transitions  ½1  expðaB W  NLSL aSL Þ; (13)
between light hole and electron minibands as a function of
their widths, Clh and Ce where LSL is the superlattice width or cluster width and N is
the number of clusters.
q2 mlh þ me Once the expressions for the effective density of states,
alhe ðEÞ ¼ jhf ja:pjiij2  the absorption coefficient, the radiative recombination coeffi-
cm2e e0 nr dSL h2 x mlh  me
8 2 39 cient, and photocurrent were found for SLSC, it is possibly
> Ce þ Clh > to evaluate the J-V characteristic (Eq. (1)). It is then possible
<1 1 E  Eg0  =
6 2 7 to calculate the conversion efficiency.
 þ arcsin4 5 ;
>
:2 p Ce þ Clh >
;
2
(10) III. RESULTS AND DISCUSSION
A. GaAs/GaInNAs MQWSC
where jhf ja:pjiij is the matrix element between the initial i
and the final f states, a is a unit vector in the direction of A GaAs p-i-n solar cell is modeled where the i-region is
propagation, the momentum p is a differential operator, nr is filled with GaAs/GaInNAs multiple quantum wells. The
the heterostructure refraction index, e0 is the vacuum dielec- electron and hole concentrations, in base and emitter regions
tric constant, x is the radiation frequency, mlh is the light are 1.8  1017 cm3 and 2.3  1018 cm3, respectively, while
hole effective mass, Eg0 ¼ EgW þ Ee þ Elh , and Elh is the their width are 0.15 lm (p-region), 0.60 lm (i-region), and
light hole miniband top. A similar expression of the absorp- 0.46 lm (n-region). A 40 nm Al0.8Ga0.2As window layer was
tion coefficient is found for the transitions between heavy incorporated into the p region to reduce front surface recom-
hole and electron minibands (ahhe ). Hence, the superlattice bination and a 70 nm MgF:SiN layer as antireflection coating
absorption coefficient can be written as was used. The MQW energy diagram is schematically repre-
sented in Figure 1.
In order to investigate the GaAs/Ga1xInxNyAs1y
aSL ðEÞ ¼ alhe ðEÞ þ ahhe ðEÞ: (11) MQWSC conversion efficiency, small nitrogen concentrations
were considered to modify the quantum well depth. Also, the
The absorption allows us to evaluate the radiative recombi- x ¼ 2.85y condition was satisfied so that Ga1xInxNyAs1y lat-
nation loss in Eq. (1). According to detailed balance theory, tice matches to GaAs. GaInNAs parameters were taken from
assuming a quasi-Fermi level separation constant and equal Ref. 22. High values of conversion efficiency are reached up
to the applied voltage V, the radiative recombination coeffi- to 3% N composition, as depicted in Figure 2. The maximum
cient is given by values of efficiency are obtained for a narrow region around
054511-5 ndez
Courel, Rimada, and Herna J. Appl. Phys. 112, 054511 (2012)

FIG. 4. A variably spaced multiple quantum well (cluster) which enhances


the resonant tunneling between adjacent wells.

B. GaAs/GaInNAs SLSC
GaAs/GaInNAs solar cells were studied inserting now
superlattices in the i-region of a GaAs p-i-n solar cell, keep-
ing the other device parameters identical as shown in Figure
3. The conditions for resonant tunneling were computed by
the well-known transfer matrix method (TMM) without
FIG. 2. Contour plot of GaAs/GaInNAs QWSC efficiency as a function of back-scattered wave. A variably spaced multiple quantum
the quantum well width and the nitrogen composition.
well or superlattice was considered to enhance the resonant
tunneling between adjacent wells following the method
reported by Reyes-Gomez et al.23 Figure 4 shows this partic-
1% of nitrogen composition and narrow quantum well widths. ular superlattice that we refer as a cluster, in which the reso-
These N compositions correspond to shallow quantum wells, nant tunneling conditions were obtained. The resonance
where the carrier generation overcomes the recombination. takes place at 12 kV/cm, which was evaluated taking into
Also, for these N fractions a second quantum level appears in account the uniform doping levels, p and n-regions, and
the heavy hole band slightly increasing photon absorption. intrinsic region width. We have used a fixed field (a parame-
When the quantum wells are deeper (nitrogen percent ter in our model), which is not such a difficult thing to do
increases) the carrier recombination is increased and the con- experimentally, once that doping levels and intrinsic thick-
version efficiency falls. Figure 2 also shows the conversion ef- ness are as those reported here.
ficiency dependence on quantum well width. For 1% nitrogen To research the GaAs/GaInNAs SLSC performance,
composition, g is practically insensitive to quantum well some different arrangements with ten variably spaced multi-
width because there is a compensation effect. This result ple quantum wells (clusters) were optimized to enhance the
could be explained because there is a trade-off between quan- resonant tunneling between adjacent wells. These clusters
tum well width and quantum well number, for wider quantum are composed by quantum wells of 1% nitrogen composition
wells the photons absorption is greater, but the quantum well and barriers of 1 nm wide. A series of clusters are inserted in
number inserted in the constant intrinsic region (0.6 mm) is the i-region, independent from each other, in such a way that
smaller. On the other hand, narrow quantum wells absorb less there is no coupling between neighboring clusters. Figure 5
photon but it is possible to insert more of them in the intrinsic shows a contour plot of the conversion efficiency for the
region, then the absorption overcomes the recombination at SLSC as a function of the width and the number of clusters.
the 1% N concentration. For any nitrogen compositions higher The first thing to highlight is that the SLSC conversion effi-
than 1%, the efficiency falls when the quantum well width ciencies are as much as 3% higher than those of the
increases since the carrier recombination is increased. MQWSC. The AB contour in Figure 5 corresponds to the

FIG. 3. Sketch of energy band diagram of a GaAs p-i-n


solar cell with superlattices inserted within the intrinsic
region.
054511-6 ndez
Courel, Rimada, and Herna J. Appl. Phys. 112, 054511 (2012)

originating a decrease of the photogenerated carriers. For


this reason, the indefinite incorporation of clusters does not
mean that the photocurrent also increases, but spreading to
saturation as long as the open-circuit voltage falls due to the
increment of the recombination. This behavior is shown in
Figure 6, where we also research the conversion efficiency
as a function of solar concentration for ideal GaAs/GaInNAs
solar cell without electric resistance. Note that at 1000 solar
concentration, the conversion efficiency could increase
until 6%.

IV. SUMMARY
We have shown a new type of photovoltaic device
where GaAs/GaInNAs multiple quantum wells or superlat-
tice are inserted in the i-region of a GaAs p-i-n solar cell. A
theoretical model was developed to study the performances
of these devices. A study of conversion efficiency as function
of nitrogen composition and quantum well width was pre-
FIG. 5. Contour plot of GaAs/GaInNAs SLSC efficiency as a function of the sented which allowed determining the range of these param-
cluster width and number. eters where high conversion efficiencies in MQWSC are
reached. In order to research the GaAs/GaInNAs SLSC per-
formance, it was necessary to determine the conditions for
pair of values (cluster number and cluster width) where the
resonant tunneling which were established by the matrix
highest conversion efficiency is reached. It can be also
transfer method for a superlattice with variable quantum
observed that while the width and the number of cluster
wells width. The effective density of states and the absorp-
increase, the conversion efficiency is increased because the
tion coefficients for superlattice structure were calculated to
photon absorption is higher. For this reason, it is suitable to
evaluate the J-V characteristic. The cluster width influence
add smaller clusters length in the intrinsic region, keeping
on the conversion efficiency was researched showing a better
wide wells, to enhance the conversion efficiency.
performance when width and the number of cluster are
It could be though that it is possible to increase the con-
increased.
version efficiency by adding more clusters in the intrinsic
Our results show that conversion efficiencies can be
region but it is not true at all because when more clusters are
reached which have never been obtained before for a single-
inserted the recombination process is increased, being neces-
junction solar cell. Because of the results that our model pre-
sary to get a balance between generation and recombination.
dictions are neither compared nor confirmed experimentally,
Besides, with the incorporation of more clusters in the
it would be interesting to see if future experiments will cor-
intrinsic region, the absorption processes increase, moving
roborate our outcomes.
forward less photon to the deepest layers in the device,
Solar cell efficiency potential remains far greater than
solar cell efficiencies, including those achieved in research
laboratories. New approaches are necessary in order to
increase the conversion efficiency and the GaAs/GaInNAs
solar cells could be a road to reach this goal.
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