Flexible thin-film InAs/GaAs quantum dot solar cells

Katsuaki Tanabe, Katsuyuki Watanabe, and Yasuhiko Arakawa

Citation: Applied Physics Letters 100, 192102 (2012); doi: 10.1063/1.4712597
View online: http://dx.doi.org/10.1063/1.4712597
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/100/19?ver=pdfcov
Published by the AIP Publishing
Articles you may be interested in
Multi-stacked InAs/GaAs quantum dots grown with different growth modes for quantum dot solar cells
Appl. Phys. Lett. 106, 222104 (2015); 10.1063/1.4922274
Enhancement of current collection in epitaxial lift-off InAs/GaAs quantum dot thin film solar cell and concentrated
photovoltaic study
Appl. Phys. Lett. 105, 113904 (2014); 10.1063/1.4896114
Challenges to the concept of an intermediate band in InAs/GaAs quantum dot solar cells
Appl. Phys. Lett. 103, 141113 (2013); 10.1063/1.4822322
InAs/GaAs quantum dot solar cell with an AlAs cap layer
Appl. Phys. Lett. 102, 163907 (2013); 10.1063/1.4803459
Reducing carrier escape in the InAs/GaAs quantum dot intermediate band solar cell
J. Appl. Phys. 108, 064513 (2010); 10.1063/1.3468520

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.199.63.237 On: Mon, 10 Aug 2015 09:31:50

APPLIED PHYSICS LETTERS 100, 192102 (2012)

Flexible thin-film InAs/GaAs quantum dot solar cells

Katsuaki Tanabe,1,a) Katsuyuki Watanabe,1 and Yasuhiko Arakawa1,2
1

Institute for Nano Quantum Information Electronics, University of Tokyo, 4-6-1 Komaba, Meguro,
Tokyo 153-8505, Japan
2
Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505, Japan

(Received 2 February 2012; accepted 23 April 2012; published online 8 May 2012)
Thin-film InAs/GaAs quantum dot (QD) solar cells on mechanically flexible plastic films are
fabricated. A 4.1-lm-thick compound semiconductor photovoltaic layer grown on a GaAs
substrate is transferred onto a plastic film through a low-temperature bonding technique. We also
fabricate thin-film InAs/GaAs quantum dot solar cells on Si substrates, as alternative low-cost,
lightweight, robust substrates. The open-circuit voltages of the thin-film cells on plastic and Si
substrates are equal to that of the as-grown bulk cell on a GaAs substrate, indicating that no
C 2012 American Institute of
material degradation occurs during our bond-and-transfer process. V
Physics. [http://dx.doi.org/10.1063/1.4712597]
Photovoltaic solar cells with semiconductor quantum
dots (QDs) can potentially realize ultrahigh-efficiency solarenergy conversion in single p-n junction structures utilizing
intermediate-level energy bands.1 Among the wide range of
semiconductor materials for QD solar cells currently under
intensive study,2 those using III-V semiconductor compound
InAs/GaAs QDs (i.e., InAs QDs embedded in GaAs matrices) have exhibited the highest efficiencies and robustness.3
However, expensive, heavy, thick, and solid GaAs wafers
have been used as the growth substrates for these QD cells,
hindering their commercialization. Solar-cell modules with
low-cost, lightweight, flexible support substrates are of particular interest for a number of practical applications.4 For
flexible-solar-cell production, the direct growth of photovoltaic semiconductor thin films on plastic films or metallic foils
as substrates would be the most desirable approach. Crystalline semiconductor materials, however, cannot be grown on
noncrystalline substrates; and therefore, this direct growth
scheme would inevitably result in poor-performance amorphous cells. Instead, crystalline cells on such noncrystalline
substrates can be prepared by transferring photovoltaic semiconductor layers grown in advance on proper crystalline substrates onto noncrystalline substrates.58
In this work, we fabricated thin-film InAs/GaAs QD solar cells on flexible plastic film substrates by layer transfer.
A 4.1-lm-thick compound semiconductor photovoltaic layer
was grown on a GaAs substrate, and then transferred onto a
plastic film through a bonding technique. Our bonding
scheme is mediated by a metalepoxy agent for the realization of bonding at low temperatures (below 200  C), enabling
the use of plastic materials as support substrates, as well as
preventing the degradation of the semiconductor photovoltaic layers including QDs. We also fabricated thin-film InAs/
GaAs QD solar cells on Si substrates, as alternative inexpensive, lightweight, robust substrates, using the same layertransfer scheme. Thus, we have demonstrated the validity of
this scheme for the formation of thin-film photovoltaics on
any kind of support plate or film with no degradation of the
semiconductor layers.
a)

E-mail: tanabe@iis.u-tokyo.ac.jp.

0003-6951/2012/100(19)/192102/4/$30.00

Figure 1 shows a schematic flow diagram of our fabrication process for thin-film InAs/GaAs QD solar cells on plastic films. The InAs/GaAs QD solar-cell structure was a p-i-n
GaAs/Al0.4Ga0.6As double heterostructure with a 440-nmthick i-GaAs layer embedding ten layers of self-assembled
InAs QDs. This cell structure was grown inversely as p-on-n
on a GaAs (100) substrate by molecular beam epitaxy with
an Al0.7Ga0.3As etch-stop layer immediately above the GaAs
substrate. This results in an n-on-p configuration in the final
transferred cell structure. Figure 2(a) shows an atomic force
microscope image of the as-grown InAs QDs, which are
seen to be uniformly sized, coalescence-free, high-density
(3.9  1010 cm2) QDs. The sizes of the InAs QDs were
observed as roughly 30 nm in diameter and 10 nm in height.
Figure 2(b) shows a photoluminescence spectrum from the
as-grown inverted cell structure. The photoluminescence
measurement was conducted at room temperature using a
640-nm-wavelength continuous-wave semiconductor laser
diode as the excitation source. The pump laser beam irradiated the sample surface with a spot size of 100 lm and a
power of 3 mW. The photoluminescence spectrum shown
in Figure 2(b) exhibits a peak associated with the groundstate emission of the InAs QDs at 1.28 lm with a full-width
at half-maximum of 25.1 meV.
Next, the QD solar-cell structure was layer-transferred
onto a plastic film through wafer bonding and subsequent removal of the GaAs growth substrate. We used a 130-lmthick polyimide film as the support substrate. A 30-nm-thick
AuGeNi alloy (80:10:10 wt. %) layer followed by a 150-nmthick Au layer were first deposited by electron-beam evaporation onto the bonding surfaces of both the QD cell structure
and the plastic film. In this work, we adopted an epoxy agent
containing Ag nanoparticle clusters to enable electrical contact as well as bonding at low temperatures, in order to avoid
degradation of the bonded materials, particularly the plastic
films. The diced cell wafer piece and plastic film were
brought into contact via the Agepoxy agent and annealed at
150200  C in ambient air for 1 h, with no pressure applied.
No significant difference in cell performance according to
bonding temperature was observed between 150 and 200  C,
except for a slightly higher degree of buckling of the plastic

100, 192102-1

C 2012 American Institute of Physics

V

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.199.63.237 On: Mon, 10 Aug 2015 09:31:50

192102-2

Tanabe, Watanabe, and Arakawa

Appl. Phys. Lett. 100, 192102 (2012)

FIG. 1. Schematic flow diagram of the

fabrication process for the InAs/GaAs
QD solar cells on plastic films.

film at 200  C, which was presumably due to the mismatch

of thermal expansion between the plastic and the metal.
After bonding, the GaAs substrate was removed at room
temperature by selective chemical etching with H3PO4/H2O2
(3:7 vol/vol) followed by 50% citric acid/H2O2 (4:1 vol/vol),
with the edges of the GaAs wafer coated with photoresist to
avoid undercutting of the cell structure. The H3PO4/H2O2
and citric acid/H2O2 solution compositions were chosen to
maximize the etching rate of GaAs and the etching selectivity between GaAs and AlGaAs, respectively.8 The
Al0.7Ga0.3As etch-stop layer was then removed with aqueous
hydrofluoric acid (HF) (20 vol. %) at room temperature. Following the bonding and layer transfer, the front surface of
the transferred photovoltaic thin film was partially metalized

FIG. 2. (a) Atomic force microscope image and (b) room-temperature photoluminescence spectrum of the InAs QDs grown in the InAs/GaAs QD
solar-cell structure.

with Au/AuGeNi. The nonmetalized part of the top n-GaAs

contact layer was removed by the citric acid/H2O2 solution,
and then an antireflection coating with MgF2/ZnS was
applied. The finished device was a 4.1-lm-thick thin-film
InAs/GaAs QD solar-cell structure bonded to a plastic film,
as shown in Figure 3. Using the same scheme, we also fabricated QD thin-film cells on Si substrates, which are strong
candidates as alternative support substrates with lighter
weight, higher mechanical robustness, thermal stability, and
conductivity relative to GaAs substrates.
Figure 4 shows the light currentvoltage (IV) characteristics of the highest-efficiency cells for each of the fabricated
thin-film InAs/GaAs QD solar cells on plastic films (active
area 0.0039 cm2) and Si substrates (0.059 cm2), as well as the
as-grown, bulk reference cells on GaAs substrates (0.21 cm2),
under AM1.5 G, 1-sun (100 mW cm2) illumination. Significantly, the thin film cells on plastic films can be easily cut
by household scissors into arbitrary shapes and sizes and
every separated piece exhibits photovoltaic operation, and we
intentionally cut the cells into smaller pieces to pick the bestefficiency data for Figure 4. Note that the open-circuit voltages (VOC)  0.6 V are commonly seen for such 1.3-lm-band
QD solar cells,3 in contrast to 1.0 V for GaAs cells without
QD, according to the bandgap offset. Table I summarizes the
cell performance parameters including the energy-conversion
efficiency g, VOC, short-circuit current JSC, and fill factor FF
for the highest-efficiency cells as well as the highest VOC values observed for each of the three types of cells under
AM1.5G illumination (1 sun). The highest VOC values of the
transferred thin-film cells on plastic films and Si substrates are
quite similar to that of the bulk reference cell. This result indicates that our bond-and-transfer process does not degrade the
quality of the cell material, since any generated crystal defects
that act as recombination centers would reduce VOC.9 In addition, the bonded interfaces have no significant carrier recombination rate to reduce VOC.
The transferred cells have larger photocurrents than the
bulk reference cell, as shown in Figure 4 and Table I. First of
all, note that this result is not due to light absorption by the
QDs because our transferred cells and bulk reference cells
are from the identical grown QD solar-cell wafer. The photocurrent difference is mainly because the bulk reference cell

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.199.63.237 On: Mon, 10 Aug 2015 09:31:50

192102-3

Tanabe, Watanabe, and Arakawa

Appl. Phys. Lett. 100, 192102 (2012)

FIG. 4. Light IV characteristics of the highest-efficiency cells for each of

the bulk reference cells and the thin-film cells on plastic films and Si substrates under AM1.5G, 1-sun illumination.

FIG. 3. (a) Cross-sectional schematic diagram, (b) scanning electron microscope image, and (c) photographs of the fabricated thin-film InAs/GaAs QD
solar cells on plastic films. Inset of (b) is a cross-sectional tunneling electron
microscope image of the InAs QD layers.

has an improperly deep p-n junction due to its inverted

growth and consequently exhibits inefficient carrier collection. Other potential reasons for the larger photocurrents of
the transferred thin-film cells are the efficient carrier collection in the thin-film photovoltaic layer structure thinner than
the minority-carrier diffusion length and the enhanced optical path length because of the metallic back reflectors implemented on the support substrates. In other words, the
metallic layer implemented between the semiconductor photovoltaic thin film and the support substrate has dual functions, acting as the bottom electrode of the solar-cell
structure and providing back-reflection and scattering at the
GaAs/metal interfaces at the bottom of the photovoltaic thin
film to increase the path length of the incoming photons to
be absorbed. However, this light-trapping effect by the back
reflector may have a minor contribution for the larger photocurrents for our relatively thick cell design in this work, but
would play more significant roles for thinner cells.7

The plastic film used in this work has a weight density of

1.4 g cm3, in contrast to the density of 5.4 g cm3 for GaAs.
Accounting for the difference in thickness of the substrates
used (130 lm and 450 lm for the plastic film and GaAs substrates, respectively), we reduced the cell weight to less than
1/10 by transferring the photovoltaic thin film (which was
much thinner and, therefore, had negligible weight relative to
the semiconductor and plastic substrates) from the GaAs
growth substrate onto the plastic support film. In principle,
we could reduce the cell weight even further by using thinner,
commercially available plastic films. For the thin-film cell on
a Si substrate, the Si density of 2.3 g cm3 provided a weight
of less than half that of the bulk cell on a GaAs substrate.
Our fabrication of thin-film QD solar cells on both plastic films and Si substrates is a strong demonstration of the validity of our bond-and-transfer scheme for the formation of
thin-film photovoltaics on any kind of support plate or film,
with no material degradation from the as-grown semiconductor layers. In this work, we adopted an etch-back method to
detach the GaAs growth substrate to simplify the fabrication
process. Alternatively, the incorporation of an epitaxial liftoff5,10 or ion-cutting7,11 technique would enable the reuse of
the GaAs substrates to reduce the production costs.
In summary, we have fabricated thin-film InAs/GaAs QD
solar cells on mechanically flexible plastic films by using a
bond-and-transfer technique as an approach for the production
of versatile QD solar cells. The use of a metalepoxy mediating agent enabled low-temperature bonding and layer transfer
onto plastic support substrates. We have also fabricated
TABLE I. Solar-cell performance parameters of the highest-efficiency cells
and the highest VOC values for each type of cell under AM1.5G, 1-sun
illumination.
Bulk reference Thin film on plastic Thin film on Si substrate
Highest g
4.69%
0.65 V
VOC
JSC
12.3 mA cm2
FF
0.58
Highest VOC
0.675 V

10.5%
0.64 V
23.5 mA cm2
0.70
0.673 V

8.45%
0.57 V
24.5 mA cm2
0.61
0.664 V

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.199.63.237 On: Mon, 10 Aug 2015 09:31:50

192102-4

Tanabe, Watanabe, and Arakawa

thin-film InAs/GaAs QD cells on Si substrates. No material

degradation was observed through our bond-and-transfer process, as verified by VOC measurements. The bond-and-transfer
process, without material degradation, thus provides a pathway for the production of lightweight, mechanically flexible,
low-cost, and highly efficient QD solar cells based on ultrathin
single-crystalline III-V semiconductors.
This work was supported by the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan,
through the Project for Developing Innovation Systems and
by the Japan Society for the Promotion of Science (JSPS)
through Grants-in-Aid for Young Scientists (B) 23760303.
1

A. Luque and A. Marti, Phys. Rev. Lett. 78, 5014 (1997); A. J. Nozik,
Physica E 14, 115 (2002); T. Nozawa and Y. Arakawa, Appl. Phys. Lett.
98, 171108 (2011).
2
J. M. Luther, M. Law, M. C. Beard, Q. Song, M. O. Reese, R. J. Ellingson,
and A. J. Nozik, Nano Lett. 8, 3488 (2008); G. Konstantatos and E. H.
Sargent, Nat. Nanotechnol. 5, 391 (2010).
3
S. M. Hubbard, C. D. Cress, C. G. Bailey, R. P. Raffaelle, S. G. Bailey,
and D. M. Wilt, Appl. Phys. Lett. 92, 123512 (2008); D. Guimard, R. Morihara, D. Bordel, K. Tanabe, Y. Wakayama, M. Nishioka, and Y. Arakawa,
Appl. Phys. Lett. 96, 203507 (2010); C. G. Bailey, D. V. Forbes, R. P.

Appl. Phys. Lett. 100, 192102 (2012)

Raffaelle, and S. M. Hubbard, Appl. Phys. Lett. 98, 163105 (2011); K. A.
Sablon, J. W. Little, V. Mitin, A. Sergeev, N. Vagidov, and K. Reinhardt,
Nano Lett. 11, 2311 (2011).
4
J. Yoon, A. J. Baca, S.-I. Park, P. Elvikis, J. B. Geddes III, L. Li, R. H.
Kim, J. Xiao, S. Wang, T.-H. Kim, M. J. Motala, B. Y. Ahn, E. B. Duoss,
J. A. Lewis, R. G. Nuzzo, P. M. Ferreira, Y. Huang, A. Rockett, and J. A.
Rogers, Nature Mater. 7, 907 (2008); G. Konstantatos, L. Levina, J. Tang,
and E. H. Sargent, Nano Lett. 8, 4002 (2008); J. Yoon, L. Li, A. V. Semichaevsky, J. H. Ryu, H. T. Johnson, R. G. Nuzzo, and J. A. Rogers, Nature
Commun. 2, 343 (2011).
5
M. Konagai, M. Sugimoto, and K. Takahashi, J. Cryst. Growth 45, 277
(1978).
6
K. Tanabe, A. Fontcuberta i Morral, H. A. Atwater, D. J. Aiken, and M.
W. Wanlass, Appl. Phys. Lett. 89, 102106 (2006); K. Tanabe, D. Guimard,
D. Bordel, S. Iwamoto, and Y. Arakawa, Opt. Express 18, 10604 (2010);
K. Tanabe, K. Watanabe, and Y. Arakawa, Sci. Rep. 2, 349 (2012).
7
J. M. Zahler, K. Tanabe, C. Ladous, T. Pinnington, F. D. Newman, and H.
A. Atwater, Appl. Phys. Lett. 91, 012108 (2007).
8
K. Tanabe, M. Nomura, D. Guimard, S. Iwamoto, and Y. Arakawa, Opt.
Express 17, 7036 (2009).
9
R. B. Bergmann, Appl. Phys. A 69, 187 (1999); R. Brendel, Jpn. J. Appl.
Phys., Part 1 40, 4431 (2001).
10
E. Yablonovitch, T. Gmitter, J. P. Harbison, and R. Bhat, Appl. Phys. Lett.
51, 2222 (1987).
11
M. Bruel, Electron. Lett. 31, 1201 (1995); P. Chen, Y. Jing, S. S. Lau, D.
Xu, L. Mawst, T. L. Alford, C. Paulson, and T. F. Kuech, Appl. Phys. Lett.
92, 092107 (2008); W. Chen, P. Chen, J. E. Pulsifer, T. L. Alford, T. F.
Kuech, and S. S. Lau, Appl. Phys. Lett. 92, 212109 (2008).

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.199.63.237 On: Mon, 10 Aug 2015 09:31:50