Multiple Exciton Generation Solar Cells: Effects of Nanocrystal Shape

on Quantum Efficiency
Ashley R. Marshall,1,2 Matthew C. Beard,2 and Joseph M. Luther2
1
University of Colorado Boulder, Boulder, Colorado, 80302, USA
2
National Renewable Energy Laboratory, Golden, Colorado, 80401, USA

Abstract — Semiconductor nanocrystals (NCs) have the of MEG and carrier mobility can be used to enhance device
ability to perform a process, termed multiple exciton generation performance.
(or MEG), which produces two electrons for every absorbed This work utilizes a p-n junction device structure, as seen in
photon. This has been experimentally confirmed using ultrafast
spectroscopic techniques for many semiconductor NC families. Fig. 1, to compare different shapes of NCs and mixtures of NC
The shape of the NCs has been found to play an important role in shapes.
the efficiency of MEG. Spherical PbSe NCs have been used to
fabricate devices that exhibit greater than 100% quantum
efficiencies, here we report on the use of NC morphologies and
hybrid NC assemblies that can increase the power conversion
efficiency in a device.
Index Terms — Lead chalcogenides, multiple exciton
generation, nanocrystals, photovoltaic cells..

I. INTRODUCTION
Photovoltaic power conversion efficiency has an upper
limit of ~32% for single junction devices as determined by the
Shockley-Queisser analysis [1]. There are a limited number of
ways to circumvent this upper limit including generating
multiple electrons per photon, hot carrier extraction and
tandem devices [2]. This work focuses on exploiting the
formation of multiple electrons per photon in order to improve
the photocurrent in devices. Bulk semiconductors can generate
multiple electron-hole pairs per absorbed photon through
impact ionization, but this process is inefficient enough to be
neglected for photovoltaic cells [3]. Due to consequences of
quantum confinement, nanocrystals (NCs) undergo a similar
process called multiple exciton generation (MEG) with higher
efficiency than bulk materials[4]-[8].
MEG was shown to increase the external quantum efficiency
to greater than 100% in PbSe quantum dot (QD) solar cells
using spherical nanocrystals and a two-step ligand treatment
[9]. In addition, the MEG onset and efficiency has been shown
to be dependent on the PbSe NC shape using spectroscopic
techniques [10]-[11]. Shape can also influence the transport of
carriers through a device, since carriers travel through films by
tunneling or “hopping” from NC to NC. Therefore, devices
made out of small structures require carriers to make many
hops before being collected. This slows transport and
increases the probability of trapping carriers in surface trap
states. Elongated structures, such as nanorods (NRs), allow
carriers to travel longer distances before requiring them to hop
to the next NC, thus improving the transport through the
absorber layer film. Here we study how the shape dependence
Fig. 1. SEM image of a standard PV device fabricated from NCs.
II. EXPERIMENTAL
PbSe QDs and NRs are fabricated using previously
published syntheses [12]-[13]. In general, PbO, oleic acid, and
1-octadecene were heated to the desired temperature (140-
190°C) using standard Schlenk line techniques. Then,
trioctylphosphine:selenium or tri(diethylamino)phosphine:
selenium was injected and the reaction was allowed to run for
1-3 minutes. The resulting NCs were washed by three
iterations of dissolution/precipitation using hexane and ethanol
as the solvent/nonsolvent pair. The NCs were then stored, air-
free, in hexane or chloroform.
Devices were fabricated starting with glass superstrates
patterned with a 150nm film of ITO, spin coating ZnO from a
solution of diethylzinc (DEZ) (10% in toluene) and
tetrahydrofuran, then annealing at 130°C for 15 minutes. The
NC layer was deposited using a layer-by-layer technique, i.e.
dipping in a solution of NC in hexane or chloroform, then 1,2-
ethanedithiol (EDT) in acetonitrile repeatedly in order to build
up a film. The last four layers of the NC layer were dipped
with hydrazine instead of EDT as this was shown to improve
device performance in devices made from PbSe QDs [9]. For
the back contact, 100nm of gold is thermally evaporated. All

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device fabrication and testing after the deposition of the ZnO standard ligand used for QDs we looked for other ligands that
layer, is performed in air-free, He- or N2-filled gloveboxes. could potentially be better for devices made with NRs. Using

Fig. 2. JV-curves and data for PbSe NC devices fabricated A) with QDs only and predominately QDs with some NRs compared to
B) hybrid devices using similar amounts of QDs and NRs. Due to a much lower concentration of NRs, each of the devices are
approximately the same thickness despite the different number of cycles. One cycle of QDs is equivalent to about 4 cycles of NRs.

time-resolved microwave conductivity (TRMC) the carrier

mobility in films of QD and NRs with a variety of ligands was
III. RESULTS
measured and the results are reported in Table 1.
Using the devices fabricated from spherical PbSe QD as a
reference, new shapes such as nanorods (NRs) were
incorporated into the device structure to exploit the heightened
MEG efficiency shown in spectroscopic studies [10]-[11].
Incorporating PbSe NRs into the QD devices leads to
improved device efficiency for low band-gap QDs, as shown
in Fig. 2. The open circuit voltage (VOC) is improved upon the
addition of NRs in the NC film, most likely due to the bigger
band gap of the NRs used in this study. The increased VOC
improves the power conversion efficiency slightly, but at high
NR ratios the short circuit current (JSC) declines, counter-
acting the increased VOC.
When the NRs included in the device have a smaller
bandgap than the QD, the overall VOC of the device is greatly
diminished, shown in Fig. 3. This shows that the bandgap of
the NRs plays a significant role in device performance.
Since the improvement seen from including NRs in the PbSe
QD devices was in the VOC instead of the JSC as expected, the
optimized fabrication conditions for QD devices may not be Fig. 3. NRs with a smaller bandgap than the QDs in the original
the best for devices using NRs. While EDT has been a device decrease the VOC significantly.

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TABLE I
TRMC MOBILITY VALUES FOR PBSE NC FILMS FROM
VARIOUS SHAPES AND LIGANDS
IV. CONCLUSION
In conclusion, incorporating NRs into traditional QD
devices can lead to higher power conversion efficiencies.
Devices with too high of a NR content suffer from a drop in
JSC, which may mean the fabrication process is not optimal for
the NR shape. Mixing NCs of different bandgaps has a big
influence on the resulting VOC of the device.
ACKNOWLEDGEMENT
The authors would like to thank Bobby To for help with
SEM measurements and Ryan Crisp for help with TRMC
measurements. Funding for this work was provided by the
Center for Advanced Solar Photophysics (CASP), an Energy
Frontiers Research Center from the U.S. Department of
Energy, Office of Science, Basic Energy Sciences.
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