32nd European Photovoltaic Solar Energy Conference and Exhibition

FABRICATION OF STRAIN-COMPENSATED HETEROJUNCTION GE/SI1-XCX

QUANTUM DOT SOLAR CELLS

Kazuhiro Gotoh1, Ryuji Oshima2, Takeshi Tayagaki2, Takeyoshi Sugaya2, Koji Matsubara2, and Michio Kondo1,3
1
Department of Innovative and Engineering Materials, Interdisciplinary Graduate School of Science and Engineering,
Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503, Japan
2
Research Center for Photovoltaics, National Institute of Advanced Industrial Science and Technology (AIST),
1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan
3
Fukushima Renewable Energy Institute, AIST (FREA), 2-2-9 Machiikedai, Koriyama, Fukushima 963-0298, Japan

ABSTRACT: Heterojunction 50-layer-stacked Ge quantum dot solar cells (QDSCs) were fabricated via molecular
beam epitaxy using a strain-compensation technique. Si1-xCx materials consisting of a Si matrix with a small amount
of carbon (~0.05%) were used as strain-compensating layers (SCLs). In the 50-layer-stacked Ge QDs, large coalesced
islands with a density of 4.0  108 cm-2 were observed for QDs stacked with Si spacer layers, whereas the formation
of coalesced islands was effectively suppressed for QDs stacked with Si1-xCx SCLs. The external applied bias voltage
dependence on the short circuit current was calculated from external quantum efficiency measurements. This study
revealed that the carrier collection efficiency Ge/Si1-xCx QDSCs was superior to Ge/Si QDSCs, possibly due to the
reduction of non-radiative recombination centers associated with coalesced islands. As a result, the open circuit
voltage increased from 0.38 V for Ge/Si QDSCs to 0.42 V for Ge/Si1-xCx QDSCs.
Keywords: Silicon, Germanium, Carbon, Quantum Dots and Solar Cell

1 INTRODUCTION

Recently, self-assembled quantum dots (QDs), which

were formed via the Stranski-Krastanov growth mode in
lattice-mismatched hetero-epitaxy, were employed in
intermediate band solar cells (IBSCs). In IBSCs, an
additional photocurrent is generated by utilizing two-step
optical transitions via IB states (transitions from the
valence band (VB) to the IB and from the IB to the
conduction band (CB)). This current adds to the
conventional direct optical transition from the VB to the
CB (Fig. 1). IBSCs may ideally achieve higher
conversion efficiency than the single-junction Shockley-
Queisser limit of ~30% [1,2].
In the Ge QDs in the Si matrix, the photo-generated
electron-hole pairs can be efficiently separated in real and
k spaces, because they have type-II heterointerfaces and
indirect band structures [3,4]. These characteristics may
lead to an improvement of the collection efficiency of
carriers. In order to realize practical QD-IBSCs, QDs
should be dense, homogeneous in size, and periodically
distributed to form the mini-bands utilized as IB states.
Increasing the number of stacked, self-assembled QDs is
a promising way to increase the total QD density,
although some difficulties may arise from the
Figure 2: Schematic concept of strain compensation
in multi-stacked Ge QDs on Si substrate.
accumulation of compressive strains induced by QD
layers. If the host material used for burying the QDs was
the same as the substrate, the QDs in a stacked
configuration would be generally accompanied by an
increase in size [5] and, in case their thickness exceeded a
critical value, they would generate misfit dislocations. To
address this issue, a strain-compensation growth
technique was recently developed for GaAs-based [6-8]
and InP-based QD [9] systems, in which the compressive
strain induced by the QDs was compensated by the
tensile strained spacer layers. In the case of Ge/Si QDs,
we have developed strain-compensated Ge QDs buried in
Si1-xCx strain compensating layers (SCLs) with a small
amount of carbon (x = 0.05%) [10]. Fig. 2 shows the
schematic concept of strain compensation in multi-
stacked Ge QDs on Si substrates with Si spacer layers or
Si1-xCx SCLs. This work characterizes the carrier
collection efficiency of strain-compensated Ge/Si1-xCx
QDSCs.

2 EXPERIMENTAL

All QD samples were grown by solid-source

molecular beam epitaxy (SS-MBE) on 350 m-thick p+-
Figure 1: Schematic band diagram of Ge/Si QDSCs.
Si (001) substrates (resistivity: ~10-3 cm). The typical
base pressure of the growth chamber was 310-10 Torr.

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 32nd European Photovoltaic Solar Energy Conference and Exhibition

150 C and 20-nm-thick n-type a-Si:H deposited at 180

C by PECVD. An indium tin oxide (ITO) layer was used
as transparent conductive oxide (TCO); silver and
aluminum were deposited for the front and rear contact
electrode, respectively. The cell size was 0.25 cm2. For
the solar cell characterization, the current-voltage (I-V)
characteristic was measured under air mass 1.5 global
(AM1.5G), 100 mW/cm2 at 25 C. External quantum
efficiency (EQE) measurements were performed at room
temperature under a constant monochromatic photon
irradiation of 1014 cm−2 using a standard lock-in
configuration.

3 RESULTS AND DISCUSSION

Fig. 4 shows the AFM images of the topmost surface

Figure 3: Schematic structure of 50-layer-stacked
Ge/Si1-xCx QDSCs.
Both Si and Ge sources were heated by an electron beam
gun. A Ga dopant cell and a C filament cell were
installed. The Si substrate was chemically cleaned by
RCA cleaning methods [11] and then was set to the
growth chamber. After the deposition of a 1-µm-thick p-
type (1  1016 cm-3) Si base layer at 700 °C, 50-layer-
stacked 4.6 monolayer (ML) Ge QDs were grown at 500
C. Composite structures of a 6-nm-thick Si1-xCx SCL
were sandwiched by 2-nm-thick Si mediating-layers [10],
which resulted in a total spacer layer thickness of 10 nm.
The growth rates of Ge QDs and Si1-xCx SCLs were 2.6
Å/s and 2.0 Å/s, respectively. The C filament cell was
heated at 1400 C for the growth of Si1-xCx SCLs. The C
content in the Si1-xCx SCLs, x, was determined to be
0.05% by X-ray diffraction measurements. A 50-layer-
stacked Ge/Si QD sample was fabricated using an
identical structure, except for 10-nm-thick Si spacer
layers instead of Si1-xCx. For solar cells, multi-stacked Ge
QD structures were buried by a 750-nm-thick intrinsic Si
layer. The surface morphology was studied by atomic
force microscopy (AFM).
Heterojunction Ge/Si1-xCx QDSCs using
hydrogenated amorphous silicon (a-Si:H) emitter layers
were fabricated, as shown in Fig. 3. The use of a-Si:H as
an emitter layer is advantageous for the suppression of
interdiffusion of Ge atoms during deposition [12]. In
order to form p-n junction, the deposition of a-Si:H is
typically employed by plasma-enhanced chemical vapor
deposition (PECVD) at a temperature of as low as 200 C,
in comparison with the conventional phosphorous
dopant-diffusion process processed at ~900 C in a
furnace [13]. MBE-grown epi-layers were finished with a
combination of 10-nm-thick intrinsic a-Si:H deposited at
measured for 50-layer-stackedGe/Si1-xCx QDs and Ge/Si
QDs. Average height, average lateral size, fluctuation in
lateral size and areal density were 1.5 nm, 28.1 nm,
13.6% and 6.5 × 1010 cm-2 for Ge/Si1-xCx and, 1.8 nm,
29.3 nm, 14.5% and 4.4 × 1010 cm-2 for Ge/Si,
respectively. Almost identical Ge QDs were observed
for both samples, except for the occurrence of large
coalesced islands with a lateral size of 600 nm and a
density of 4.0  108 cm-2 in the Si/Ge samples. The
generation of coalesced islands was probably caused by
exceeding the local critical thickness, due to the
accumulation of compressive strain [14,15]. These
coalesced islands contained misfit dislocations, resulting
in generation of non-radiative recombination centers.
Although x = 1.7% would be necessary to exactly
compensate the compressive strain induced by Ge QDs
in the Ge/Si1-xCx QD configuration [16], the partial
strain-compensation with x = 0.05% could result in the
suppression of the formation of coalesced islands.
Fig. 5 shows EQE spectra of (a) Ge/Si1-xCx QDSC,
(b) Ge/Si QDSC and (c) p+-Si cell. For the fabrication of
a p+-Si cell, the bare p+-Si substrate without any
epilayers was processed by identical heterojunction
procedures with QDSCs, and was used as a reference.
Lower EQE in shorter wavelength region from 300 to
700 nm for both QDSCs, which are mainly contributed
from the absorption of the Si layers, was observed
compared with the p+-Si cell. Moreover, the EQE for
Ge/Si1-xCx cells was slightly higher than that for Ge/Si
cells in the entire wavelength range. These results
suggest that carriers generated in Si layers are trapped in
both QD states and non-radiative recombination centers
generated in the stacked QD structure [17,18]. Thus, the

Figure 4: 5 µm  5 µm AFM images of topmost

surface for 50-layer-stacked (a) Ge/Si1-xCx QDs Figure 5: EQE spectra of 50-layer-stacked (a)
and (b) Ge/Si QDs. The insets show 1 µm  1 µm Ge/Si1-xCx QDSCs, and (b) Ge/Si QDSCs and (c)
enlarged views for each sample. p+-Si cell as a reference.

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 32nd European Photovoltaic Solar Energy Conference and Exhibition
Figure 6: Normalized ISC of (a) Ge/Si1-xCx QDSC
and (b) Ge/Si QDSC and (c) p+-Si cell as function of
bias voltage. Dot lines are guides for each sample.
slight increase in EQE for Ge/Si1-xCx cells was probably
due to the suppression of coalesced islands by strain
compensation. Conversely, an increased EQE in the
longer wavelength region up to 1100 nm for both
QDSCs was attributed to additional absorption by the
insertion of stacked Ge QD structures.
Fig. 6 shows the normalized short-circuit current
(ISC) calculated from the EQE measurements for the (a)
Ge/Si1-xCx QDSC, (b) Ge/Si QDSC and (c) p+-Si cell as
a function of the external bias voltage applied. The ISC
was calculated from the EQE spectrum measured at
each applied voltage by using following equation:
1 𝜆 ∙ EQE(𝜆)∙𝑏𝑠 (𝜆)
𝐼SC = ∫ 𝑑𝜆 (1)
1000 1240
where λ and bs(λ) are the wavelength and spectral
irradiance, respectively. The ISC was normalized with
the 0 V value for each cell. In the forward applied bias
region, a significant decrease in ISC with increasing
applied voltage was observed for all cells due to the
weakened electric field in the intrinsic region, resulting
in the enhancement of recombination in the junction.
Conversely, in the reverse applied bias region, the
degree of ISC increase significantly depends on the kind
of cell measured. Especially, the p+-Si cell showed
almost no change in ISC in the reverse bias region,
indicating that p+-Si SCs contained few recombination
centers in the junction. The fact that the degree of
increase for the Ge/Si1-xCx and the Ge/Si cells were
greater than that for the p+-Si cell indicates poor carrier
collection efficiency for both QDSCs due to the
increased recombination in the Ge QD structures. Since
both the radiative recombination via quantum states in
Ge QDs and non-radiative recombination associated
with the misfit dislocations seem to be dominant in
QDSCs, the smaller degree of ISC increase for Ge/Si1-xCx
compared to Ge/Si is probably due to the reduction of
non-radiative recombination centers.
Fig. 7 compares the light I-V curves measured for
50-layer-stacked Ge QDSCs grown with (a) Si1-xCx
SCLs and (b) Si spacer layers. The short-circuit current
density (ISC), open-circuit voltage (VOC), fill factor (FF)
and conversion efficiency () were 6.23 mA/cm-2, 0.42
V, 0.73 and 1.91% for the Ge/Si1-xCx cell and 6.20
mA/cm-2, 0.38 V, 0.70 and 1.62% for the Ge/Si cell.
Note that the VOC was increased from 0.38 V for the
Ge/Si cell to 0.42 V for the Ge/Si1-xCx cell. From the
diode equation, the VOC is given by
30
Figure 7: I-V curves of 50-layer-stacked Ge
QDSCs grwon with (a) Si1-xCx SCLs and (b) Si
spacer layers.
𝑘𝑇 𝐼SC
𝑉OC = ln (1 + ) (1)
𝑞 𝐼0
where k, T, q, and I0 are the Boltzmann constant,
temperature, elementary charge, and reverse saturation
current density, respectively [19]. The I0 for Ge/Si1-xCx
QDSCs was estimated from dark I-V measurements to
be 5.48  10-7 mA/cm2, which was smaller than that of
2.56  10-6 mA/cm2 for Ge/Si QDSCs. Thus, the
enhancement of VOC is a result of the reduction of I0,
indicating suppression of recombination losses due to
strain compensation. However, the difference in ISC
between Ge/Si1-xCx and Ge/Si QDSCs was negligibly
small, since the radiative recombination via quantum
states in Ge QDs may play a dominant role in carrier
recombination at short circuit conditions.
4 SUMMARY
We fabricated 50-layer-stacked heterojunction
Ge/Si1-xCx QDSCs via SS-MBE. The formation of
coalesced islands was effectively suppressed via strain-
compensation techniques. The EQE response extended
up to 1100 nm due to the contribution of Ge QD layers
compared with that of the p+-Si cell. From the applied
external bias voltage dependence on the ISC calculated
from the EQE, a smaller increase in ISC was observed
for Ge/Si1-xCx QDSCs in the reverse applied bias region
than that for Ge/Si QDSCs. Moreover, a reduced I0 of
5.48  10-7 mA/cm2 was observed for Ge/Si1-xCx QDSCs.
These results suggest that the strain compensation
effectively reduced the non-radiative recombination
centers, although the radiative recombination via
quantum states in Ge QDs may play a dominant role in
carrier recombination at short circuit conditions. Thus,
the VOC was improved from 0.38 V for the Ge/Si QDSC
to 0.42 V for the Ge/Si1-xCx QDSC. This initial
demonstration of Ge/Si1-xCx QDSCs is an important step
toward the development of highly efficient, cost-
effective Si-based QDSCs.
ACKNOWLEDGEMENTS
This work was supported by the New Energy and
Industrial Technology Development Organization
(NEDO) under the Ministry of Economy, Trade, and
 32nd European Photovoltaic Solar Energy Conference and Exhibition

Industry (METI). One of the authors (K. G) was

supported by Research Fellowships of Japanese Society
for Promotion of Science (JSPS) for Young Scientists
(Grant-in-Aid for Fellows: grant number 26010268).

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