APPLIED PHYSICS LETTERS 98, 171108 共2011兲

Detailed balance limit of the efficiency of multilevel intermediate band

solar cells
Tomohiro Nozawa1,2 and Yasuhiko Arakawa1,3,a兲
1
Institute for Nano Quantum Information Electronics, The University of Tokyo, Komaba, Meguro-ku,
Tokyo 153-8505, Japan
2
Advanced Technology Research Laboratories, Sharp Corporation, 2613-1 Ichinomoto-cho, Tenri,
Nara 632-8567, Japan
3
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
共Received 28 December 2010; accepted 30 March 2011; published online 27 April 2011兲
Intermediate-band solar cells 共IBSCs兲 promise ultrahigh solar-electricity energy conversion. We
have calculated the detailed balance limit of the efficiency for IBSCs with multiple intermediate
bands by optimizing IB’s energy levels. The results indicate that thermodynamic limit of IBSCs with
4 IBs is 74.6% which far exceeds 63% calculated in a previous study for the single IB case. By
further increasing the total number IBs, the thermodynamic limit of IBSCs can ultimately approach
nearly 80%. © 2011 American Institute of Physics. 关doi:10.1063/1.3583587兴

Intermediate-band solar cells 共IBSCs兲 are a promising
technology for realizing ultrahigh efficiency of solar energy
conversion. In 1997, Luque and Martí1 predicted a 63% ef-
ficiency as the thermodynamic upper limit in IBSCs relative
to 41% for conventional single-junction cells under full
concentration, i.e., 46 000 suns. This intermediate-band ap-
proach has been intensively studied these days by experi-
mentally adopting quantum well2,3 and quantum dot4,5 struc-
tures in photovoltaic active layers.
Luque et al.6 recently applied a detailed balance limit
calculation model to investigate IBSCs for their experimental
sample solar cells. They calculated the efficiency of an IBSC
with four intermediate bands 共IBs兲 for a matrix band gap and
IBs’ energy levels measured. Their calculation showed an
efficiency of 40.0%, which is smaller than the thermody-
namic upper limit efficiency of 63% for an IBSC with a
single IB. The reason for this poor efficiency is that Eg and
IBs’ energy levels are unoptimized. Green reported on the
general theory of impurity photovoltaic solar cells with mul-
tiple bands 共N-band cells兲 and mentioned that the perfor-
tively. Inter IB transitions have spectra with infinitesimal
linewidths and absorbed photon fluxes between IBs are much
smaller compared to the other transitions shown in Fig. 1共a兲.
For this reason, those transitions were ignored. Solid and
dotted arrows represent carrier generation and recombina-
tion, respectively. Figure 1共b兲 shows energy gaps Ei between
VB and IBi 共i = 1 , 2 , 3 , 4兲 and that of matrix semiconductor
Eg. It should be noted that more than one set of Ei’s result in
a same energy conversion efficiency for a given Eg due to
symmetrical equivalency between the first excitation from
VB to Ei and the second from Ei to CB. We assume that
interband transitions have no overlap for wavelengths of the
photon fluxes one another as Luque et al. supposed.1,6
Namely, we divide the whole incident solar spectrum into
nine parts 共double the number of IBs+ 1兲 in wavelengths and
each wavelengths component contributes only to a single
interband transition. We assume that the photon flux with
energies between Eini and Efin 共Efin ⬎ Eini兲 from a matter
obeys Planck radiation and is given by
2␲
冕 Efin
E2

冉 冊
mance limit of an N-band cell can approach that of an Ṅ共T, ␮,Eini,Efin兲 = dE, 共1兲
h 3c 2 Eini E−␮
N-band tandem as N approaches infinity. However, the effi- exp −1
ciency of an N-band cell was not calculated.7 In this letter, kT
we discuss the detailed balance limit of the efficiencies for where T is the temperature of the matter, ␮ is the photon
IBSCs with multiple IBs, calculating the efficiencies by op- chemical potential equal to the separation of quasi-Fermi
timizing Eg and IB energy levels for each case of various
numbers of IBs. We show that the maximum theoretical ef-
ficiency of the IBSCs is well above 63% obtained in Ref. 1,
approaching 80% by increasing the number of intermediate
levels.
The detailed balance limit represents the thermodynamic
energy conversion efficiency limit of solar cells accounting
for black-body radiation. 共See Refs. 8 and 9 for details of the
theory and formalism.兲 We followed the calculation condi-
tions in Ref. 1. In the following the calculation method for
IBSCs with 4 IBs 共i.e., 6-level IBSCs兲 is explained as an
example. A schematic diagram of carrier transitions between
one energy level and another is depicted in Fig. 1共a兲, where
CB and VB are the conduction and valence band, respec-
FIG. 1. Schematic diagram of 共a兲 carrier transitions and energy levels and
a兲
Electronic mail: arakawa@iis.u-tokyo.ac.jp. 共b兲 energy gaps.

0003-6951/2011/98共17兲/171108/3/$30.00 98, 171108-1 © 2011 American Institute of Physics

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 171108-2 T. Nozawa and Y. Arakawa
FIG. 2. 共Color online兲 Calculated detailed balance limit of the efficiencies
for various types of solar cells as a function of the bandgap energy of matrix
semiconductor, Eg, under 共a兲 full concentration and 共b兲 no concentration. IB
energies, Ei’s, are optimized to maximize the efficiency for each Eg.
levels, h is the Planck’s constant, c is the speed of light, k is
the Boltzman constant. Using Eq. 共1兲, the photon fluxes of
GCV, RCV, GVI4, and RVI4 are written as
GCV = C0HṄ共Ts,0,Eg,⬁兲,
RCV = Ṅ共T0,qV,Eg,⬁兲,
GVI4 = C0HṄ共Ts,0,E4,Eg兲,
RVI4 = Ṅ共T0, ␮5,E4,Eg兲,
where C0 is the concentration ratio 共C0 suns illumination兲, Ts
is the sun temperature, T0 is the solar cell temperature, H is
sin2 ␪s, ␪s is the sun’s semiangle of vision determined by the
sun’s radius and its distance to the Earth, 0.267°.
Other photon fluxes are described similarly. No carrier is
extracted from any IB, which is mathematically expressed as
0 = GVI1 − GCI1 − RVI1 + RCI1 ,
0 = GVI2 − GCI2 − RVI2 + RCI2 ,
0 = GVI3 − GCI3 − RVI3 + RCI3 ,
0 = GVI4 − GCI4 − RVI4 + RCI4 .
The solar cell output voltage is the sum of the five chemical
potentials 共␮ j for j = 1 , 2 , 3 , 4 , 5兲. Therefore, the chemical po-
tential ␮ j can be obtained from Eqs. 共6兲–共9兲 for a given qV.
With these parameters the current output of the solar cell is
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Appl. Phys. Lett. 98, 171108 共2011兲
FIG. 3. 共Color online兲 Calculated variation in optimal Eg’s to maximize the
limit efficiency for each Ntotal under varied sunlight concentrations.
calculated. The current-voltage characteristic of the solar cell
is described as
J
= GCV + GCI1 + GCI2 + GCI3 + GCI4 − RCV − RCI1 − RCI2
q
− RCI3 − RCI4 . 共10兲
From this equation the maximum power of JV and the effi-
ciency of the solar cell are obtained. By the calculation
scheme above, detailed balance limits of the efficiencies for
IBSCs with 0, 1, 2, 3, and 4 IBs were simulated for Ts of
6000 K and T0 of 300 K. Each IBSC with 0, 1, 2, 3, and 4
IBs has the number of total 共CB+ VB+ IBs兲 energy levels/
bands 共Ntotal兲 of 2, 3, 4, 5, and 6, and is named as No-IB solar
cell, 3-, 4-, 5-, and 6-level IBSC, respectively. Figure 2
shows the calculation results of limit efficiencies for various
types of solar cells as a function of the bandgap of matrix
semiconductor, Eg, under 共a兲 full concentration and 共b兲 no
concentration, with IBs optimized to maximize the limit ef-
共2兲 ficiency for each Eg. It should be noted that our calculation
results for 3-level IBSC under full concentration shown in
Fig. 2共a兲 are quite consistent with those obtained in Ref. 1.
共3兲
From this figure it can be seen that the limit efficiencies
significantly increase with increasing Ntotal except for small
共4兲 Eg’s, especially below approximately 1.2 eV, where the effi-
ciencies of IBSCs are almost independent on Ntotal. The in-
共5兲 crease in limit efficiency in this region is insensitive to Eg,
which we interpret as resulting from the smaller potential for
共6兲
共7兲
共8兲
共9兲
FIG. 4. 共Color online兲 Calculated detailed balance limit of the efficiencies as
a function of Ntotal for each sunlight concentration. Eg and Ei are optimized
to maximize the efficiency for each Ntotal and sunlight concentration.
 171108-3 T. Nozawa and Y. Arakawa Appl. Phys. Lett. 98, 171108 共2011兲

TABLE I. Limit efficiencies, optimal Eg’s and Ei’s for each sunlight con- In Fig. 4, we summarize the limit efficiencies depending
centration in each type of solar cells. Note that more than one set of Ei’s on Ntotal for each sunlight concentration. It can be seen from
result in a same energy conversion efficiency for a given Eg due to sym-
metrical equivalency between the first excitation from VB to Ei and the
this figure that the limit efficiency under full concentration
second from Ei to CB. We show only one set of Ei’s for each Eg in descend- approaches 80% with increasing Ntotal.
ing order in this table. For each sunlight concentration in each type of solar
cells, the limit efficiencies, optimal Eg’s and Ei’s are summa-
No concentration rized in Table I. Again, it should be noted that more than one
set of Ei’s result in a same energy conversion efficiency for a
Efficiency Eg E4 E3 E2 E1
共%兲 共eV兲 共eV兲 共eV兲 共eV兲 共eV兲
given Eg due to symmetrical equivalency between the first
excitation from VB to Ei and the second from Ei to CB. We
No-IB solar cell 31.0 1.30 ¯ ¯ ¯ ¯ show only one set of Ei’s for each Eg in descending order in
3-level IBSC 46.8 2.39 1.48 ¯ ¯ ¯ this table. From this table, we notice that the limit efficiency
4-level IBSC 53.0 2.58 1.80 1.44 ¯ ¯ for 6-level IBSC reaches approximately 75% under full con-
5-level IBSC 55.5 2.63 1.93 1.63 1.41 ¯ centration. Even for 4-level IBSC, the limit efficiency is cal-
6-level IBSC 56.8 2.68 1.99 1.73 1.55 1.41 culated to be as high as 70% under full concentration, 64%
under 1000 suns and 53% without concentration. Further-
1000 suns more, the limit efficiency of over 77% is obtained for an
Efficiency Eg E4 E3 E2 E1 IBSC with 15 IBs under full concentration.
共%兲 共eV兲 共eV兲 共eV兲 共eV兲 共eV兲 In conclusion, we have calculated detailed balance limit
No-IB solar cell 37.1 1.19 ¯ ¯ ¯ ¯ of the efficiencies for IBSCs with increased numbers of IB
3-level IBSC 57.3 2.09 1.32 ¯ ¯ ¯ energy levels. The limit efficiency of a 6-level IBSC 共i.e.,
4-level IBSC 63.8 2.30 1.65 1.30 ¯ ¯ IBSC with four IBs兲 is found to be 74.6% and approaches
5-level IBSC 66.5 2.38 1.81 1.51 1.29 ¯ 80% by further addition of IBs. These limit efficiencies far
6-level IBSC 67.9 2.44 1.90 1.63 1.44 1.29 exceed the 63% calculated in Ref. 1 for an IBSC with a
single IB 共i.e., 3-level IBSC兲. This work is a strong implica-
Full concentration tion of the potential of multilevel IBSCs to realize ultrahigh
Efficiency Eg E4 E3 E2 E1
efficiency.
共%兲 共eV兲 共eV兲 共eV兲 共eV兲 共eV兲
The authors would like to thank S. Iwamoto and M.
No-IB solar cell 40.7 1.10 ¯ ¯ ¯ ¯
Kitamura for their useful discussions and K. Tanabe for his
3-level IBSC 63.2 1.95 1.24 ¯ ¯ ¯
4-level IBSC 70.1 2.19 1.59 1.24 ¯ ¯
invaluable comments on our manuscript as well as useful
5-level IBSC 73.1 2.25 1.73 1.44 1.23 ¯
discussions. The authors also would like to acknowledge A.
6-level IBSC 74.6 2.29 1.82 1.56 1.38 1.22 Takahashi, Y. Tomomura, S. Aomori, and M. Izumi for their
encouragement and support to this work. This work was sup-
ported in part by the Special Coordination Funds for Promot-
ing Science and Technology by the Ministry of Education,
current increase for low Eg’s. On the other hand, higher Eg’s Culture, Sports, Science and Technology 共MEXT兲, Japan.
give larger efficiency increment with increased Ntotal and
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4
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