HIGH EFFICIENCY InAIN-BASED SOLAR CELLS

R.E. Jones'r', R. Broesler'", K. M. Yu 1, J. w. Ager 111 1, E. E. Haller 1,2 , W. Walukiewicz 1, X. Chen 3

and W. J. Schaff

1 Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA

2 Department of Materials Science and Engineering, University of California, Berkeley, CA
3 Department of Electrical and Computer Engineering, Cornell University, Ithaca, NY

ABSTRACT INTRODUCTION

The band gap energies of the In1-xAlxN alloys are The band gap energies of the group III-nitride
continuously tunable across the solar spectrum, making alloys (Le., In1-xGaxN and In1-xAlxN) are continuously
them good candidates for high efficiency solar cells. In tunable across the solar spectrum (Fig. 1). The band gaps
particular, multijunction solar cells could be fabricated of the In1-xGaxN alloys range from 0.7 eV (x =
0) to 3.4 eV
entirely from different compositions of this one alloy (x = 1) and the In1-xAlxN alloys from 0.7 eV (x =
0) to 6.2
system. From modeling experimental measurements of eV (x = 1). This makes the alloys promising materials for
the optical absorption coefficient in alloys with 0 s x s 0.6, high efficiency solar cells. Multijunction solar cells could
a band gap bowing parameter of 4.8 ± 0.5 eV is found for be fabricated entirely from different compositions of either
the alloy system. With this number, the alloy compositions of these single alloy systems. These cells should allow for
for two and three junction tandem cells with maximum simpler deposition processes than are used in today's high
theoretical power conversion efficiencies can be efficiency, multijunction cells, which use different materials
determined. Two junction InAIN I Si solar cells are also for each junction. The potential of InGaN as a solar cell
promising structures for high efficiency solar cells, due to material has been well established [2-4], and significant
the properties of the interface between n-type InAIN and p­ progress has been made toward understanding the
type Si, as well as the band gaps of the respective properties of this alloy system [5, 6]. Here we report our
materials. The theoretical efficiency (detailed balance) for studies on the structural, electrical and optical properties
the Ino.6oAloAoN I Si tandem cell is 410/0. of the InAIN alloy system and show that it is another good
candidate for solar cell applications.

4.0
3.5

, ,
3.0 , 3.0

,,
OJ
m
:::J
2,5 c..
2.5
>-..-.-
QJ , ~
G)
m
~

~
C1
2.0 ~ 2.0 m
::::J
~
~ CD

,,
QJ ~

r::: ~ to
w 1.5 1.5 '<

~
, ,-...

~
~

1.0 1,0

•
InAIN (experimental)
--lnAIN
0.5 FE
0.5
- -lnGaN
1 0,0
o 600 500 400 300 200 100 o 0.2 0.4 0.6 0.8
Solar Radiation (W/(m 2eV)) Fraction AI or Ga (x)
Figure 1: Band gap energies of the InAIN and InGaN alloys as a function of composition (right) compared to
the energy distribution of the solar spectrum (left). The lines give the band gaps calculated using bowing
parameters of 4.8 eV for InAIN and 1.4 eV [1] for InGaN. Experimental points determined from modeling the
optical absorption spectra of InAIN films are also shown.

978-1-4244-1641-7/08/$25.00 ©2008IEEE
 EXPERIMENTAL AND THEORY

The In1-xAl xN (0 s x S 0.6) films used in this study

were grown by molecular beam epitaxy on c-sapphire
substrates with an AIN buffer layer [7]. The films were
doped with Mg or were undoped. X-ray diffraction (XRD)
and Rutherford backscattering spectrometry (RBS) were
used to determine the compositions of the films. If the
values found from the two methods differed, their average • Experiment
was used. XRD was measured with a PANalytical X'Pert --Model
Pro Diffractometer, and the compositions were determined
from the position of the (0002) In1-xAl xN peaks in 28-w
scans, assuming Vegard's law. The (0002) AIN peak and
0
the (0006) peak of the Ab03 substrate were used as the 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
reference. The RBS measurements used a 2 MeV 4 He +
Energy (eV)
beam at a backscattering angle of 165°. Free electron
concentrations were determined from Hall effect 4
measurements using a 6000 gauss magnet and indium 510
contacts in the van der Pauw configuration. The b) InO.60Alo.40N
18
concentrations in the undoped films ranged from 2x10 to 410
4
18 18
7x10 ern", and were S 2x10 ern" in the Mg-doped films.
Optical absorption spectra were measured at room
temperature using a Perkin Elmer Lambda 950 NIR-VIS­ ..-.. 310 4
UV spectrophotometer in transmittance mode. The E
spectra were corrected for scattering and reflectance ,£,
4
losses by subtracting a constant baseline from the d 2 10
absorption coefficient. The band diagrams for the two
• Experiment
junction solar cells were calculated using the nextnano" --Model
4
software [8]. 1 10
Band gap energies are often determined by linear
extrapolation of the squared optical absorption coefficient
to O. However, this treatment assumes a parabolic band 0
0.5 1.5 2 2.5
structure, which is not accurate for narrow band gap
semiconductors such as In-rich InAIN. Instead, we Energy (eV)
extracted the band gap from the experimental optical Figure 2: Experimental and modeled absorption
absorption spectra and the measured electron
spectra for two InAIN films, a) Ino.88Alo.12N and b)
concentrations by modeling the spectra using the equation
InO.6oAloAoN.
developed by Kane for a nonparabolic band in the k-p
framework [9]. The absorption coefficient for a photon of shift. To account for this, we multiplied a(E) by the Fermi
energy E is: distribution function, with the Fermi level calculated from
the measured electron concentration. Finally, a(E) was
convoluted with a Gaussian function to include
(1) inhomogeneous broadening effects such as alloy disorder
and spatial variation of the donor distribution. The fitting
parameters for the modeling were the band gap, the
broadening parameter and a multiplicative constant
where e is the elementary charge, m is the electron mass,
(allowed to vary from 0.7 - 1.5) to account for
c is the speed of light, n, is the index of refraction, and uncertainties in n, and the effective masses. A more
Mj(E) is the optical matrix element averaged over direction
detailed discussion of the modeling can be found
and summed over degenerate bands (we assumed full
elsewhere [10]. The models and experimental data for two
conduction and valence bands), j is
coupling between the
an index that varies over the heavy hole, light hole and
representative films (x =
0.12 and 0.40) are shown in Fig.
2.
spin-orbit valence bands, and prE) is the density of states.
The high electron concentrations in the In-rich samples fill
RESULTS AND DISCUSSION
the lower states in the conduction band and cause a blue
shift of the absorption edge, known as the Burstein-Moss

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 sunlight. The ideal band gaps and compositions will vary
(0002) InN (0002)AIN (0006) AI 0
2 3
with the level of concentration and the incident spectrum

-2.0

..
.------r-----.-----r----1.------r-----.-----r-----1-----r-----.-----r----r-----r----r---r---T-----r----r--~

--Conduction band edge

E::J
-3.0 --Valence band edge
::J
~_ _-~ ~ -4.0
+-' >
·00 o
C +" -5.0
Q) Q)
+-'

->
L..
C
-6.0
0>
o ~
...J ~ -7.0
o L..
Q)
0:::
>< J] -8.0
-9.0
o
L...-...I----I..-..L..----l.---I---l.-..l..&--L---l...---l.--l....--....L...---I..-..L..----l.---I---l.-..I.--..L.--I

0.2 0.4 0.6 0.8 1

InN fraction AI (x) AIN
30 32 34 36 38 40 42
Figure 4: Conduction and valence band edge
Figure 3: Typical XRD 28-w scans around the (0002) positions as a function of composition in In1-xAlxN.
plane of In1-xAl xN. The peak positions of (0002) InN The band edge positions of Si, and the alignment of
and AIN and (0006) AI203 are shown by dashed the valence band edge of Si with the conduction band
vertical lines. Arrows indicate the In1-xAl xN peaks. edge of Ino.64Alo.36N are also shown.

All films used in this analysis showed a single In1­

xAlxN peak in the XRD; no evidence of phase separation In AI NISi Tandem Solar Cell
0.60 0.40
was observed. Representative scans are shown in Fig. 3.
The full width half max (FWHM) values were 10 - 14 ...-... p-In AI N -Conduction Band Edge
arcmin. Channeling RBS in the <0001> direction reveals
>Q)
0.6 0.4
--Valence Band Edge
'-'" 2
that the InAIN films are single crystal. We find that the Q)
crystalline quality of the InAIN film degrades as x >
Q) p-Si
increases. Minimum channeling yields (X) for low x 1
«0.10) are less than 0.05, similar to InN films grown on ·E
~ n-In AI N n-Si
GaN buffer layers. As x increases above 0.30, X also Q) 0.6 0.4
u, 0
increases to >0.4. This is consistent with the XRD results
0
that show an increase in the FWHM of the diffraction peak +oJ

as x increases. Q) -1
~
Figure 1 shows the band gaps of the In1-xAl xN ~
alloys determined from the modeling of the absorption C)
~

spectra and plotted as a function of composition. We can Q) -2

c:
find the composition dependence of the band gap (E g ) W
using the standard equation:

Figure 5: Band alignment of an Ino.6oAloAoN I Si two

junction solar cell. The free carrier concentration was
18
assumed to be 1x10 ern" in the n-type Ino.6oAloAoN
where b is the bowing parameter. Fitting our 17
layer and 1x10 ern" in all other layers.
experimental data gives b =4.8 ± 0.5 eV.
The composition dependence of the band gap
used.
allows for determination of the AI content (x) required for
The conduction and valence band edge positions
tandem solar cells with maximum theoretical power
for the alloy system (Fig. 4) were found using the
conversion efficiencies. A detailed balance efficiency
measured valence band offsets between InN and AIN [12]
(using only the band gaps of the cells as input parameters)
and assuming that the total bowing of 4.8 eV splits
of 420/0 is predicted for a two junction cell with x =0.44 and between the conduction and valence bands in proportion
0.20, and 490/0 for a triple junction cell with x =0.51, 0.32
to the ratio of the respective band offsets between the
and 0.11 under an unconcentrated 6000 K blackbody
binary endpoints. Due to their large electron affinities, the
spectrum [11]. Similarly, the ideal compositions can be
In-rich InAIN alloys have very low conduction band edges
determined for InAIN multijunction cells in concentrated

978-1-4244-1641-7/08/$25.00 ©2008IEEE
which are close to the valence band edges of many
semiconductors. In particular, the conduction band edge
in In1-xAl xN aligns with the valence band edge of Si for x
0.36 (Fig. 4). This has important implications for two
junction InAIN I Si solar cells. Typically multijunction solar
cells require the addition of heavily doped layers to create
tunnel junctions between the individual p-n junctions, in
order to facilitate efficient recombination of holes and
electrons from adjacent junctions. However, the alignment
of the valence band of Si with the conduction band of
Ino.64Alo.36N will produce a low resistance ohmic contact
between the adjacent junctions without heavily doped
layers. Further, the efficiency (detailed balance) of 390/0
predicted for Ino.64Alo.36N I Si tandem is near the maximum
of 420/0 for a two junction cell [11]. This number can be
improved with a small change in x to optimize the band
gap; an Ino.6oAlo.4oN I Si cell has a predicted efficiency of
410/0. At this composition, a simple tunnel junction is still
possible, as Fig. 5 shows. In addition, the electron
accumulation that plagues the surfaces of In-rich group 111-
nitrides [13] would be minimal at these values of x.
CONCLUSION
The In1-xAl xN alloys are promising materials for
high efficiency solar cells. Because their band gaps span
the solar spectrum, multijunction solar cells could be made
entirely from different InAIN compositions, simplifying the
deposition process. InAIN I Si two junction cells have the
advantage of a natural, low resistance tunnel junction
connecting them. Absorption spectra for alloys with 0 sx
s 0.6 were modeled to find the band gap bowing
parameter. The conduction and valence band edges were
also located as a function of composition in these alloys.
From this information, we calculated the band diagram for
a InAIN I Si two junction solar cell and the optimal
compositions for InAIN multijunction cells. However, it is
important to note that high quality, single phase InAIN films
have only recently been achieved; further development is
needed before the devices described above can be
realized. In particular, p-type doping is expected to be a
challenge, as it has been with InGaN.
[2] J. Wu, W. Walukiewicz, K. M. Yu, W. Shan, J. W. Ager
III, E. E. Haller, H. Lu, W. J. Schaff, W. K. Metzger, and S.
= Kurtz, Journal of Applied Physics 94,6477 (2003).
[3] S. C. Jain, M. Willander, J. Narayan, and R. Van
Overstraeten, Journal of Applied Physics 87,965 (2000).
[4] J. W. Ager Iii, K. M. Yu, R. E. Jones, D. M. Yamaguchi,
S. X. Li, W. Walukiewicz, E. E. Haller, H. Lu, and W. J.
Schaff, AlP Conference Proceedings 893,343 (2007).
[5] W. Walukiewicz, J. W. A. III, K. M. Yu, Z. Liliental­
Weber, J. Wu, S. X. Li, R. E. Jones, and J. D. Denlinger,
Journal of Physics D: Applied Physics 38, R1 (2005).
[6] B. Monemar, P. P. Paskov, J. P. Bergma, A. A.
Toropov, and T. V. Shubina, phys. stat. sol. (b) 244, 1759
(2007).
[7] K. D. Matthews, X. Chen, D. Hao, W. J. Schaff, and L.
F. Eastman, phys. stat. sol. (b), in press.
[8] The nextnano" software may be obtained from
http://www.wsi.tum.de/nextnan03 .
[9] E. O. Kane, J. Phys. Chem. Solids 1 (1957).
[10] R. E. Jones, R. Broesler, K. M. Yu, J. W. A. III, E. E.
Haller, W. Walukiewicz, X. Chen, and W. J. Schaff, in
preparation.
[11] A. D. Vos, J. Phys. D: Appl. Phys 13, 839 (1980).
[12] G. Martin, A. Botchkarev, A. Rockett, and H. Morkoc,
Applied Physics Letters 68,2541 (1996).
[13] S. X. Li, K. M. Yu, J. Wu, R. E. Jones, W.
Walukiewicz, J. W. Ager, III, W. Shan, E. E. Haller, H. Lu,
and W. J. Schaff, Physical Review B (Condensed Matter
and Materials Physics) 71, 161201 (2005).

ACKNOWLEDGMENTS

This work is supported by the Director, Office of

Science, Office of Basic Energy Sciences, Division of
Materials Sciences and Engineering, of the U.S.
Department of Energy under Contract No. DE-AC02­
05CH11231. REJ acknowledges as National Defense
Science and Engineering Graduate Fellowship.

REFERENCES

[1] J. Wu, W. Walukiewicz, K. M. Yu, J. W. Ager III, E. E.

Haller, H. Lu, and W. J. Schaff, Applied Physics Letters
80,4741 (2002).

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