1100
4, JULY 2014
Nanostructured Electrodes Improve the Fill Factor
of Organic Photovoltaics
Jonathan H. Beck, Student Member, IEEE, Biswajit Ray, Member, IEEE, Richard R. Grote,
Richard M. Osgood, Jr., Fellow, IEEE, Charles T. Black, Senior Member, IEEE,
Muhammad Ashraful Alam, Fellow, IEEE, and Ioannis Kymissis, Senior Member, IEEE
Abstract—In this study, we demonstrate that suboptical-
wavelength nanostructured electrodes (NEs) improve fill factor
(FF) in organic photovoltaic devices without compromising open-
circuit voltage or short-circuit current. We attribute this improve-
ment to efficient charge collection by the NEs, which reduce recom-
bination in low-mobility organic semiconductors. NEs increase the
FF of planar heterojunction devices with boron subphthalocyanine
chloride (SubPc)/C6 0 from 28% to 40%. Optical simulations and
external quantum efficiency measurements show that improved
charge collection, rather than light trapping, is the mechanism for
device improvement. Our findings suggest that NEs can be opti-
mized for a given material set to improve FF performance, which
is important for improving organic photovoltaic power conversion
efficiency.
Index Terms—Fill factor (FF), nanolithography, nanostructured
electrodes (NEs), organic photovoltaic (OPV) cell.
I. INTRODUCTION
RGANIC photovoltaics (OPVs) are a promising renew-
O able energy technology because of their potential low
cost, compatibility with roll-to-roll processing, and demon-
strated power conversion efficiencies above 10% [1], [2]. Com-
mercial and novel device architectures enabled by OPV cells
include columnar strands, partially transparent sheets for ar-
chitectural surfaces, and flexible plastic panels [3], [4]. De-
spite these desirable properties, OPVs often have poor fill
factor (FF) due to low charge carrier mobility and high bi-
molecular recombination rates. The FF describes the efficiency
Manuscript received October 10, 2013; accepted March 20, 2014. Date of
publication April 25, 2014; date of current version June 18, 2014. This work
was supported as part of the Center for Re-Defining Photovoltaic Efficiency
Through Molecule Scale Control: an Energy Frontier Research Center funded
by the U.S. Department of Energy, Office of Science, Office of Basic Energy
Sciences, under Award Number DE-SC0001085. The work carried out in part at
the Center for Functional Nanomaterials, Brookhaven National Laboratory, was
supported by the U.S. Department of Energy, Office of Basic Energy Sciences,
under Contract DE-AC02-98CH10886.
J. H. Beck, R. R. Grote, R. M. Osgood, Jr., and I. Kymissis are with
the Department of Electrical Engineering, Columbia University, New York,
NY 10027 USA (e-mail: jhb2158@columbia.edu; richard.r.grote@gmail.com;
osgood@columbia.edu; johnkym@ee.columbia.edu).
B. Ray and M. A. Alam are with the School of Electrical and Com-
puter Engineering, Purdue University, West Lafayette, IN 47906 USA (e-mail:
ray0@purdue.edu; alam@purdue.edu).
C. T. Black is with the Center for Functional Nanomaterials, Brookhaven
National Laboratory, Upton, NY 11973 USA (e-mail: ctblack@bnl.gov).
Color versions of one or more of the figure in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/JPHOTOV.2014.2315436
2156-3381 © 2014 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
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IEEE JOURNAL OF PHOTOVOLTAICS, VOL. 4, NO.
of charge extraction in the photovoltaic device and is de-
fined as FF ≡ (J · V )m pp /Jsc · Vo c , where Vo c is the open-
circuit voltage, Jsc is the short-circuit current density, and
mpp indicates the maximum power point. The FF is an impor-
tant characteristic because power conversion efficiency, ηp =
FF · Vo c · Jsc /Pincident , is directly proportional to FF.
One of the primary challenges facing OPV is low FF, which
results because most organic semiconductors have low mobil-
ity [5], [6]. OPV devices often have FFs of 40–60%, while
traditional silicon devices have FF >80% beacuse of high mi-
nority charge carrier mobility and long minority carrier lifetime
which enables carrier diffusion lengths up to ∼ 400 μm [7], [8].
Donor materials used in OPVs such as boron subphthalocya-
nine chloride (SubPc), squaraine, and MDMO-PPV have hole
mobilities in the range of 10−5 − 10−8 cm2 ·V−1 ·s−1 , which are
much lower than the electron mobility of the common acceptor
material C60 , i.e., ∼ 10−2 cm2 ·V−1 ·s−1 [9]–[12]. Recombina-
tion increases and FF decreases when organic semiconductor
films are thicker than the donor/acceptor (D/A) carrier diffu-
sion lengths [13]. Improving hole extraction is a priority for
improving the cell because performance is limited by the lower
mobility among the two materials [11], [14]. The open-circuit
voltage and short-circuit current are limited by the organic semi-
conductor material set. The maximum Vo c is constrained by the
energy difference between the highest occupied molecular or-
bital of the donor and the lowest unoccupied molecular orbital
of the acceptor. The maximum Jsc depends on the molecule’s
spectral absorption profile [13], [15], [16].
Previous investigations have improved OPV FF through bal-
ancing the electron and hole mobilities. Chen et al. increased
the FF and Jsc of a CuPc/C60 OPV by doping the low-mobility
CuPc with high-mobility pentacene in order to improve hole
extraction in the donor [17]. Li et al. showed that FF was max-
imized by optimizing the BHJ mixing conditions to achieve
an electron/hole mobility close to unity [18]. Additional stud-
ies improved the mobility balance by modifying material crys-
tallinity, modifying the organic–electrode interfaces, and intro-
ducing conductive molecules [19]–[22]. Although the previous
studies demonstrate increased FF, a universal, material-agnostic
technique to improve charge collection efficiency would benefit
the majority of OPV devices.
Nanostructured 3-D electrodes improve effective mobility in
organic films by providing efficient hole- or electron-collection
paths within donor and acceptor films, respectively [14]. Several
groups have previously improved OPV device performance
by integrating advanced electrodes. Textured electrodes have
BECK et al.: NANOSTRUCTURED ELECTRODES IMPROVE THE FILL FACTOR OF ORGANIC PHOTOVOLTAICS
previously been shown to improve optical absorption in OPV de-
vices [23]–[25]. Nanostructured electrodes (NEs) that improve
light trapping have been investigated and may enable ultra-thin
OPV devices with high FF and Jsc [26]. Micrometer-scale struc-
tured electrodes do not improve charge collection because the
electrode pitches are too large; inserted nanostructures must be
in the subwavelength scale to improve charge carrier transport.
Dispersed carbon nanotubes in solution-processed OPV devices
were shown to improve effective mobility [20]. Confined NEs
fabricated using templating achieve improved bulk heterojunc-
tion OPV charge transfer [27]. Additional studies of embedded
conductive NEs were shown to improve FF [28]–[31]. Most
recently, Pegg and Hatton increased the FF and Jsc of a bulk
heterojunction OPV device with NEs that provided a geometric
electric field enhancement [32]. Previous studies found that pre-
cise control of the nanoelectrode geometry and density strongly
influenced performance improvements [14], [32], [33]. Ray
et al. previously developed simulations revealing the potential
for optimized NEs to increase OPV FF [14]. In this investiga-
tion, we integrate an innovative device structure that improves
OPV FF through the implementation of optimized NEs.
A. Simulation and Theory
Investigations of optimized NEs for OPVs via optoelectronic
simulations by Ray et al. found that NEs improve carrier ex-
traction efficiency when added to planar heterojunction OPV
devices [14]. The inserted electrodes improve carrier extraction
at the maximum power point by reducing the carrier collection
length. The NEs also redistribute the electric field within the
bulk, which attracts carriers to the electrode. The design rules
for inserted electrodes stipulate that the electrode pitch needs
to be small—100 nm or less—and the electrode height needs
to be about 80% of the film thickness and contained within one
material. An electrode height of zero corresponds to a planar
electrode and is the basis for our reference device. NEs that
cross the D/A junction decrease Jsc and FF by introducing an
electric field that causes local charge accumulation. We designed
the inserted electrode to collect holes in the SubPc donor mate-
rial because mobility is lower in SubPc (10−6 –10−8 ) than in C60
(10−2 ). The inserted electrodes redistribute the active materials
during deposition, which results in improved charge extraction
and causes Jsc to increase by a small percentage. Via the design
rules summarized in the previous study, we fabricated an NE
device with a 100-nm 2-D electrode pitch and a 30-nm elec-
trode pillar height, optimized for an existing boron SubPc/C60
planar heterojunction device. The device structure, with NEs
confined to the low-mobility SubPc donor film, is shown in
Fig. 1(a). Based on the NE dimensions, OPV structure, and ma-
terial electrical and optical properties, our simulations predict
that FF should increase from 33% to 47%, while maintaining
similar Vo c and Jsc .
II. EXPERIMENTAL DETAILS
A. Fabrication
The NE OPV device is shown in Fig. 1(b) and described
herein: Fused-silica wafers were coated with 50 nm of ZEP520A
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1101
Fig. 1. (a) Schematic of an NE device. (b) Cross-sectional SEM micrograph
of an NE device. The NEs are 30 nm tall and 30 nm in diameter and are repeated
in a 2-D square lattice with a period of 100 nm. The scale bar is 100 nm.
Fig. 2. Energy band diagram for the OPV device. All energy levels are relative
to the vacuum level and measured in electronvolts [34]–[36].
electron beam resist. Thirty-nanometer diameter single-shot
voids were exposed with a JEOL JBX-6300FS electron beam
lithography system and developed. A 7-nm Cr film was ther-
mally deposited and then lifted off for 1 h at 60 ◦ C in Nano
Remover PG to produce a Cr etch mask. The fused-silica pillars
were etched in an Oxford Instruments PlasmaLab System 100
using a CHF3 /O2 chemistry. An advantage to this electrode fab-
rication process is that lithography and etching are performed
on standard fused-silica substrates before the deposition of or-
ganics or electrodes. The NEs are 30 nm tall, 30 nm in diameter,
and repeated in a 2-D square lattice with a 100-nm pitch. SEM
micrographs of the electrode structure can be found in Fig. 1(b)
and the inset of Fig. 6.
The OPV device consists of a planar heterojunction with a
SubPc donor and C60 acceptor. SubPc/C60 -based OPV have
recently attained ηp of 4.5 ± 0.1% [37]. SubPc has a high ab-
sorption coefficient of α−1 = 53.4 nm, as measured in deposited
films, broad visible absorption, and a high Vo c (>1 V) [35]. The
NE and planar electrode devices have identical electrode metals
and active layer films: 3-nm Cr adhesion layer, 10-nm Au trans-
parent anode, 5-nm MoO3 (molybdenum oxide) hole injection
layer, 40-nm SubPc electron donor, 40-nm C60 electron ac-
ceptor, 10-nm TPBi (2,2’,2”-(1,3,5-benzinetriyl)-tris(1-phenyl-
1-H-benzimidazole)) exciton blocking layer, and a 100-nm Al
cathode [38] (see energy diagram in Fig. 2). The Cr/Au anode
was deposited on a rotating stage to achieve a conformal coating
of the nanostructured fused-silica pillars. The anode has a sheet
resistance of 68 Ω·−1 . All electrodes, inorganic, and organic
films were deposited by thermal physical vapor deposition using
shadow masks. The SubPc layer preferentially fills the troughs
between nanopillars to planarize the SubPc/C60 junction [see
1102
Fig. 3. Measured J–V curve of an NE and planar electrode devices. The solid
red line represents the light current curve of the NE device. The dashed blue
line represents the light current curve of the reference planar electrode device.
The inset dashed squares show the definition of 100% FF and the FF of each
device type at the maximum power point.
Fig. 1(b)]. Lin et al. proposed that SubPc’s crystalline structure
and high deposition temperature cause molecules to migrate and
aggregate upon interacting with the substrate [9]. MoO3 , SubPc,
C60 , and TPBi were used as received from Luminescence Tech-
nology Corp. All depositions were performed at a rate of 1.0
Å·s−1 at a pressure below 2 × 10−6 Torr with the stage rotation
turned ON. The device area is 0.01 cm2 . We verified film thick-
nesses and nanostructure geometries using cross-sectional SEM
in a Hitachi 4800 FE-SEM.
B. Electrical Measurements
J–V characterization is performed using a Keithley 2400
source meter and a Newport solar simulator with an AM1.5
global tilt filter in an N2 environment. The dark current curves
(see Fig. 4) are taken in low-light conditions. The series re-
sistance is calculated by taking the inverse slope of the linear
portion of the light current curve at 2 V, which is well above
Vo c , RS = ( VJ )−1 . The shunt resistance is calculated by taking
the inverse slope of the J–V curve at 0 V, Rsh = ( VJ )−1 [39].
External quantum efficiency (EQE) is defined as the fraction
of incident photons that produce electrons at the device con-
˙
tacts, i.e., EQE = SR(λ)hc/qλ, where SR(λ) = Jsc (λ)/Φ(λ).
The EQE spectra shown are averaged over two reference planar
devices and two NE devices.
C. Optical Measurements and Simulations
The absorption profiles of the NE and planar OPV devices are
simulated using rigorous coupled-wave analysis (RCWA) [40].
RCWA simulations are performed using the commercially avail-
able DiffractMOD simulation package from the RSoft Design
Group [40]. The cell absorption is simulated with 220 + 1 har-
monics in the x- and y-directions. The spectral step size for
the simulations is 5 nm. The material optical properties were
taken from the literature [41]–[44] or, in the case of TPBi,
measured using a J. A. Woollam M-2000 ellipsometer. Film
and nanostructure dimensions are taken from cross-sectional
SEM micrographs. The absorption of neat SubPc and C60 films
was measured using a Perkins Elmer Spectrometer with an
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IEEE JOURNAL OF PHOTOVOLTAICS, VOL. 4, NO. 4, JULY 2014
Fig. 4. Measured dark J–V curve of NE and planar electrode devices. The
solid red line represents the dark current curve of the NE device. The dashed
blue line represents the dark current curve of the reference planar electrode
device. Inset photograph: 2 × 2 cm substrate with eight devices.
integrating sphere and absorption was calculated as 1 − T − R.
The absorption of the fused-silica substrate was subtracted.
III. RESULTS AND DISCUSSION
A. Electrical Characterization
Experimental current–voltage (I–V) measurements show that
NEs increase the FF of the OPV device from 28% to 40% (see
Fig. 3). Higher FF causes an improvement in average ηp from
0.65% to 1.18%. NEs also increase Jsc by an average of 17%.
A summary of the NE and planar electrode device performance
is listed in Table I. The experimentally measured FF increased
by 12 percentage points, showing a close match to the 14 point
improvement predicted by the device simulations.
We note that the FF and Jsc of our reference device are lower
than SubPc/C60 devices in the literature, because of a rela-
tively thick SubPc donor layer and nonmixed/graded device
structure [9], [35], [37]. However, we have shown that a pla-
nar heterojunction device with poor charge collection efficiency
can be improved by the addition of NEs. Our fabricated devices
achieve similar benefits to FF (12% pts) as the improvement in
simulated devices (14% pts). The carrier collection efficiency of
high-performance devices simulated by Ray et al. also increases
because of NEs, in which the FF of an optimized OPV device
improved from 70% to 75% [14]. NEs have the potential to
improve thinner planar heterojunction OPV devices which have
mobility imbalances. Chen et al. found charge extraction to be
a limiting factor in thin, optimized CuPc/C60 OPV devices and
improved FF by effectively increasing the CuPc hole mobility
with a pentacene dopant [17].
The EQE is 2% higher in the NE devices than in the pla-
nar electrode devices (see Fig. 5). The EQE behavior for the
reference planar device is consistent with previously measured
SubPc/C60 devices [41]. Despite the redistribution of active
material during film deposition, the charge collection at the
short-circuit condition is similar across both devices. Ray et al.
previously concluded that NEs reduce bulk charge carrier re-
combination in the short-circuit condition. We conclude that
the NE slightly increases EQE as a result of improved charge
collection efficiency and generates increased Jsc . We simulated
BECK et al.: NANOSTRUCTURED ELECTRODES IMPROVE THE FILL FACTOR OF ORGANIC PHOTOVOLTAICS
TABLE I
PERFORMANCE CHARACTERISTICS OF NE AND PLANAR DEVICES
Electr
t ode typ
Electrode ttypee Voc [V] Jsc [mA cm−2 ]
Planar 0.95 ± 0.09 2.48 ± 0.29
Nanostr
tructu
t red
Nanostructured 1.01 ± 0.05 2.90 ± 0.22
Fig. 5. EQE of NE and planar electrode devices. The EQE spectra are averaged
for two identical planar electrode devices and two NE devices.
Fig. 6. RCWA simulation of active layer absorption in NE and planar elec-
trode OPV devices. The spectral resolution is 5 nm. The optical properties
for each material were measured using ellipsometry or taken from the litera-
ture [41]–[44]. Inset: SEM micrograph of the NE array before deposition of
organic material.
the optical absorption of each device architecture to show that
increased light trapping is not the cause of the increased EQE.
B. Optical Characterization
Optical absorption simulations show that NEs do not sig-
nificantly alter the device absorption profile or introduce any
additional resonance peaks. The simulated absorption profiles
of the NE and planar electrode devices are shown in Fig. 6.
The RCWA absorption simulations converge to within ±0.26%
when integrated over the AM 1.5 solar spectrum. The NE gener-
ates a resonant peak around 625 nm, which is not large enough
to be visible in Fig. 6. The small resonant peak around 625 nm
is outside the absorption range of SubPc/C60 and, therefore,
does not contribute to the photocurrent [45]. The absence of
significant additional absorption in the NE device shows that
improvements in FF and Jsc cannot be attributed to additional
light trapping. RCWA simulations show that the difference be-
tween NE and planar device absorption is less than 4%, as de-
termined by averaging the simulated absorption (A, %, Fig. 6)
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1103
ηp [%] FF [%] Rsh [Ω cm2 ] Rs [Ω cm2 ]
0.65 ± 0.06 28.0 ± 2.1 752 ± 106 27.4 ± 1.16
1.12 ± 0.12 40.3 ± 2.7 1490 ± 203 4.16 ± 0.57
Fig. 7. Absorption profile of neat SubPc and C6 0 films on fused-silica. The
substrate absorption has been subtracted. Films are 23 nm thick, as measured
by AFM and X-ray reflectivity.
from 300 to 800 nm. The difference in absorptions is within the
margin of error introduced by device geometry measurements
and differences between the literature and fabricated film optical
properties.
The EQE spectra for the NE device do not show any reso-
nant peaks because of increased light trapping. The EQE in-
crease is broadband (300–620 nm) and minor (2%) and can-
not be correlated with any additional resonant peaks in the
device absorption. The definition of EQE can also be written
as EQE = ηA (λ)ηC C (V ), with contributions from the absorp-
tion efficiency ηA and charge collection efficiency ηC C , assum-
ing unity exciton dissociation. The improved charge collection
in the NE device manifests as increased photogenerated cur-
rent, which is measured as EQE. Thinner NEs, which have been
demonstrated in previous OPV electrode studies, would displace
less active material volume and may simultaneously improve
ηA and Jsc [28], [32]. Future OPV device architectures may
incorporate both NEs within the active layer to improve charge
collection and larger nanostructures to improve light trapping.
The UV/Vis absorption data for neat SubPc and C60 films on
fused-silica are shown in Fig. 7. The SubPc and C60 absorp-
tion spectra closely match measurements performed in previous
investigations [9], [12].
IV. CONCLUSION
In this paper, we show that inserted NEs significantly improve
the FF of planar heterojunction OPV devices. We demonstrate
improved FF in a small-molecule OPV device by increasing
the charge extraction efficiency from a low-mobility film. The
addition of NEs increases the FF of a SubPc/C60 OPV de-
vice from 28% to 40%. We show that open-circuit voltage and
short-circuit current are not adversely affected by the inserted
NEs. Via simulations of optical absorption, we show that the
improved performance of NE devices cannot be attributed to
1104
increased light trapping or other optical effects. These electrode
improvements can be optimized for any planar heterojunction
device with low FF caused by an imbalance in charge carrier
mobility. Improved charge extraction can enable the use of thick
low-mobility films in OPV devices for more complete optical
absorption.
ACKNOWLEDGMENT
The authors would like to thank M. Y. Sfeir, A. Stein, and
D. Nykypanchuk with the Center for Functional Nanomaterials,
Brookhaven National Laboratory, for their assistance in measur-
ing absorption of OPV structures, optimizing nanofabrication
processes, and measuring film thicknesses.
REFERENCES
[1] R. F. Service, “Outlook brightens for plastic solar cells,” Sci., vol. 332,
no. 6027, p. 293, 2011.
[2] L. Dou, J. You, J. Yang, C.-C. Chen, Y. He, S. Murase, T. Moriarty,
K. Emery, G. Li, and Y. Yang, “Tandem polymer solar cells featuring a
spectrally matched low-bandgap polymer,” Nat. Photon., vol. 6, pp. 180–
185, Mar. 2012.
[3] B. O’Connor, K. P. Pipe, and M. Shtein, “Fiber based organic photovoltaic
devices,” Appl. Phys. Lett., vol. 92, no. 19, p. 193306, 2008.
[4] R. F. Bailey-Salzman, B. P. Rand, and S. R. Forrest, “Semitransparent
organic photovoltaic cells,” Appl. Phys. Lett., vol. 88, no. 23, p. 233502,
2006.
[5] J. Yu, Y. Zang, H. Li, and J. Huang, “Fill factor enhancement of organic
solar cells based on a wide bandgap phosphorescent material and c60,”
Thin Solid Films, vol. 520, no. 21, pp. 6653–6657, 2012.
[6] C. M. Proctor, C. Kim, D. Neher, and T.-Q. Nguyen, “Nongeminate
recombination and charge transport limitations in diketopyrrolopyrrole-
based solution-processed small molecule solar cells,” Adv. Funct. Mater.,
vol. 23, no. 28, pp. 3584–3594, 2013.
[7] J. Zhao, A. Wang, P. P. Altermatt, S. R. Wenham, and M. A. Green, “24%
efficient perl silicon solar cell: Recent improvements in high efficiency
silicon cell research,” Sol. Energy Mater. Solar. Cells, vol. 41–42, pp. 87–
99, 1996.
[8] M. Green, J. Zhao, A. Wang, and S. Wenham, “Very high efficiency
silicon solar cells-science and technology,” IEEE Trans. Electron Devices,
vol. 46, no. 10, pp. 1940–1947, Oct. 1999.
[9] C.-F. Lin, S.-W. Liu, C.-C. Lee, J.-C. Hunag, W.-C. Su, T.-L. Chiu,
C.-T. Chen, and J.-H. Lee, “Open-circuit voltage and efficiency improve-
ment of subphthalocyanine-based organic photovoltaic device through de-
position rate control,” Sol. Energy Mater. Sol. Cells, vol. 103, pp. 69–75,
2012.
[10] G. Wei, S. Wang, K. Renshaw, M. E. Thompson, and S. R. Forrest,
“Solution-processed squaraine bulk heterojunction photovoltaic cells,”
ACS Nano, vol. 4, no. 4, pp. 1927–1934, 2010.
[11] C. Melzer, E. J. Koop, V. D. Mihailetchi, and P. W. M. Blom, “Hole trans-
port in poly(phenylene vinylene)/methanofullerene bulk-heterojunction
solar cells,” Adv. Funct. Mater., vol. 14, no. 9, pp. 865–870, 2004.
[12] R. Pandey, A. A. Gunawan, K. A. Mkhoyan, and R. J. Holmes, “Efficient
organic photovoltaic cells based on nanocrystalline mixtures of boron
subphthalocyanine chloride and c60,” Adv. Funct. Mater., vol. 22, no. 3,
pp. 617–624, 2012.
[13] S. R. Forrest, “The limits to organic photovoltaic cell efficiency,” MRS
Bull., vol. 30, pp. 28–32, Jan. 2005.
[14] B. Ray, M. Khan, C. Black, and M. Alam, “Nanostructured electrodes for
organic solar cells: Analysis and design fundamentals,” IEEE J. Photo-
volt., vol. 3, no. 1, pp. 318–329, Jan 2013.
[15] K. Vandewal, K. Tvingstedt, A. Gadisa, O. Inganas, and J. V. Manca, “On
the origin of the open-circuit voltage of polymer-fullerene solar cells,”
Nat. Mater., vol. 8, pp. 904–909, 2009.
[16] B. Ray, M. S. Lundstrom, and M. A. Alam, “Can morphology tailoring
improve the open circuit voltage of organic solar cells?,” Appl. Phys. Lett.,
vol. 100, no. 1, p. 013307, 2012.
[17] W.-B. Chen, H.-F. Xiang, Z.-X. Xu, B.-P. Yan, V. Roy, C.-M. Che,
and P.-T. Lai, “Improving efficiency of organic photovoltaic cells
Authorized licensed use limited to: Concordia University Library. Downloaded on January 29,2022 at 19:05:20 UTC from IEEE Xplore. Restrictions apply.
IEEE JOURNAL OF PHOTOVOLTAICS, VOL. 4, NO. 4, JULY 2014
with pentacene-doped cupc layer,” Appl. Phys. Lett., vol. 91, no. 19,
pp. 191109-1–191109-3, 2007.
[18] G. Li, V. Shrotriya, J. Huang, Y. Yao, T. Moriarty, K. Emery, and Y. Yang,
“High-efficiency solution processable polymer photovoltaic cells by self-
organization of polymer blends,” Nat. Mater., vol. 4, no. 11, pp. 864–868,
2005.
[19] C.-W. Chu, H. Yang, W.-J. Hou, J. Huang, G. Li, and Y. Yang, “Control of
the nanoscale crystallinity and phase separation in polymer solar cells,”
Appl. Phys. Lett., vol. 92, no. 10, p. 103306, 2008.
[20] C.-Y. Nam, Q. Wu, D. Su, C.-Y. Chiu, N. J. Tremblay, C. Nuckolls, and
C. T. Black, “Nanostructured electrodes for organic bulk heterojunction
solar cells: Model study using carbon nanotube dispersed polythiophene-
fullerene blend devices,” J. Appl. Phys., vol. 110, no. 6, p. 064307,
2011.
[21] M.-S. Kim, B.-G. Kim, and J. Kim, “Effective variables to control the fill
factor of organic photovoltaic cells,” ACS Appl. Mater. Interfaces, vol. 1,
no. 6, pp. 1264–1269, 2009.
[22] J. Wagner, M. Gruber, A. Hinderhofer, A. Wilke, B. Bröker, J. Frisch,
P. Amsalem, A. Vollmer, A. Opitz, N. Koch, F. Schreiber, and W. Brütting,
“High fill factor and open circuit voltage in organic photovoltaic cells with
diindenoperylene as donor material,” Adv. Funct. Mater., vol. 20, no. 24,
pp. 4295–4303, 2010.
[23] Z. Hu, J. Zhang, and Y. Zhao, “Effect of textured electrodes with light-
trapping on performance of polymer solar cells,” J. Appl. Phys., vol. 111,
no. 10, pp. 104516-1–104516-7, 2012.
[24] B. Niesen, B. P. Rand, P. Van Dorpe, D. Cheyns, L. Tong, A. Dmitriev, and
P. Heremans, “Plasmonic efficiency enhancement of high performance
organic solar cells with a nanostructured rear electrode,” Adv. Energy
Mater., vol. 3, pp. 145–150, 2012.
[25] M. Niggemann, M. Glatthaar, A. Gombert, A. Hinsch, and V. Wittwer,
“Diffraction gratings and buried nano-electrode—Architectures for or-
ganic solar cells,” Thin Solid Films, vol. 451–452, pp. 619–623, 2004.
[26] Z. Yu, A. Raman, and S. Fan, “Fundamental limit of nanophotonic light
trapping in solar cells,” Proc. Nat. Acad. Sci., vol. 107, no. 41, pp. 17491–
17496, 2010.
[27] J. E. Allen and C. T. Black, “Improved power conversion efficiency in
bulk heterojunction organic solar cells with radial electron contacts,” ACS
Nano, vol. 5, no. 10, pp. 7986–7991, 2011.
[28] M.-H. Hsu, P. Yu, J.-H. Huang, C.-H. Chang, C.-W. Wu, Y.-C. Cheng, and
C.-W. Chu, “Balanced carrier transport in organic solar cells employing
embedded indium-tin-oxide nanoelectrodes,” Appl. Phys. Lett., vol. 98,
no. 7, p. 073308, 2011.
[29] M. K. Fung, Y. C. Sun, A. Ng, A. M. C. Ng, A. B. Djurisic, H. T. Chan,
and W. K. Chan, “Indium tin oxide nanorod electrodes for polymer pho-
tovoltaics,” ACS Appl. Mater. Interfaces, vol. 3, no. 2, pp. 522–527,
2011.
[30] J. H. Lee, D. W. Kim, H. Jang, J. K. Choi, J. Geng, J. W. Jung, S. C. Yoon,
and H.-T. Jung, “Enhanced solar-cell efficiency in bulk-heterojunction
polymer systems obtained by nanoimprinting with commercially avail-
able AAO membrane filters,” Small, vol. 5, no. 19, pp. 2139–2143,
2009.
[31] H. K. Lee, J. H. Jeon, D. H. Wang, O. O. Park, J.-K. Kim, S. H. Im, and
J. H. Park, “Enhanced charge collection via nanoporous morphology in
polymer solar cells,” Appl. Phys. Lett., vol. 96, no. 10, p. 103304, 2010.
[32] L.-J. Pegg and R. A. Hatton, “Nanoscale geometric electric field enhance-
ment in organic photovoltaics,” ACS Nano, vol. 6, no. 6, pp. 4722–4730,
2012.
[33] P. Yu, C.-H. Chang, M.-S. Su, M.-H. Hsu, and K.-H. Wei, “Embedded
indium-tin-oxide nanoelectrodes for efficiency and lifetime enhancement
of polymer-based solar cells,” Appl. Phys. Lett., vol. 96, no. 15, p. 153307,
2010.
[34] D. Y. Kim, J. Subbiah, G. Sarasqueta, F. So, H. Ding, and Irfan, Y. Gao,
“The effect of molybdenum oxide interlayer on organic photovoltaic
cells,” Appl. Phys. Lett., vol. 95, no. 9, pp. 093304-1–093304-3,
2009.
[35] K. L. Mutolo, E. I. Mayo, B. P. Rand, S. R. Forrest, and M. E. Thompson,
“Enhanced open-circuit voltage in subphthalocyanine/c60 organic pho-
tovoltaic cells,” J. Amer. Chem. Soc., vol. 128, no. 25, pp. 8108–8109,
2006.
[36] Z. Gao, C. S. Lee, I. Bello, S. T. Lee, R.-M. Chen, T.-Y. Luh, J. Shi,
and C. W. Tang, “Bright-blue electroluminescence from a silyl-substituted
ter-(phenylene–vinylene) derivative,” Appl. Phys. Lett., vol. 74, no. 6,
pp. 865–867, 1999.
[37] R. Pandey, Y. Zou, and R. J. Holmes, “Efficient, bulk heterojunction or-
ganic photovoltaic cells based on boron subphthalocyanine chloride-c70,”
Appl. Phys. Lett., vol. 101, pp. 033308-1–033308-4, Jul. 2012.
BECK et al.: NANOSTRUCTURED ELECTRODES IMPROVE THE FILL FACTOR OF ORGANIC PHOTOVOLTAICS
[38] J. Yu, N. Wang, Y. Zang, and Y. Jiang, “Organic photovoltaic cells based
on TPBi as a cathode buffer layer,” Sol. Energy Mater. Sol. Cells, vol. 95,
no. 2, pp. 664–668, 2011.
[39] S. K. Hau, H.-L. Yip, O. Acton, N. S. Baek, H. Ma, and A. K.-Y. Jen, “In-
terfacial modification to improve inverted polymer solar cells,” J. Mater.
Chem., vol. 18, pp. 5113–5119, 2008.
[40] Synopsis. RSoft [computer software]. Available from http://optics.
synopsys.com/rsoft/
[41] R. Pandey, Y. Zou, and R. J. Holmes, “Efficient, bulk heterojunction or-
ganic photovoltaic cells based on boron subphthalocyanine chloride-c70,”
Appl. Phys. Lett., vol. 101, no. 3, pp. 033308-1–033308-4, 2012.
[42] A. D. Rakic, A. B. Djurišic, J. M. Elazar, and M. L. Majewski, “Optical
properties of metallic films for vertical-cavity optoelectronic devices,”
Appl. Opt., vol. 37, pp. 5271–5283, Aug. 1998.
[43] F. Hamelmann, A. Brechling, A. Aschentrup, U. Heinzmann, P. Jutzi,
J. Sandrock, U. Siemeling, T. Ivanova, A. Szekeres, and K. Gesheva,
“Thin molybdenum oxide films produced by molybdenum pentacarbonyl
1-methylbutylisonitrile with plasma-assisted chemical vapor deposition,”
Thin Solid Films, vol. 446, no. 2, pp. 167–171, 2004.
[44] H. H. P. Gommans, D. Cheyns, T. Aernouts, C. Girotto, J. Poortmans,
and P. Heremans, “Electro-optical study of subphthalocyanine in a bilayer
organic solar cell,” Adv. Funct. Mater., vol. 17, no. 15, pp. 2653–2658,
2007.
[45] S. A. Mann, R. R. Grote, R. M. Osgood, and J. A. Schuller, “Dielectric
particle and void resonators for thin film solar cell textures,” Opt. Exp.,
vol. 19, pp. 25729–25740, Dec. 2011.
Jonathan H. Beck (S’13) received the B.S. and M.S.
degrees in electrical engineering from Columbia Uni-
versity, New York, NY, USA, in 2009 and 2011,
where he has been working toward the Ph.D. degree
in electrical engineering since 2009.
His research interests include thin-film semicon-
ductor systems, organic electronics, and renewable
energy technology.
Biswajit Ray (M’11) received the B.Tech. degree
from the National Institute of Technology, Trichy,
India, in 2002, the M.Sc.(Eng.) degree from the In-
dian Institute of Science, Bangalore, India, in 2008,
and the Ph.D. degree from Purdue University, West
Lafayette, IN, USA, in 2013, all in electrical engi-
neering.
His research interests include understanding elec-
tronic transport in organic and amorphous semicon-
ducting materials.
Dr. Ray received the Technoinventor Award from
the Indian Semiconductor Association for his master’s thesis in 2009. He also
received the Best Poster Award in the area of Organic Photovoltaics at the 38th
IEEE Photovoltaic Specialist Conference in 2012.
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1105
Richard R. Grote received the B.Sc. and M.Sc. de-
grees in electrical engineering from Drexel Univer-
sity, Philadelphia, PA, USA, in 2008. He is currently
working toward the Ph.D. degree in electrical engi-
neering with the Department of Electrical Engineer-
ing, Columbia University, New York, NY, USA.
His research interests include nanophotonic
light trapping for photovoltaics, silicon-based opto-
electronics, and deprecated technologies for guitar
amplification.
Mr. Grote is a Student Member of the Optical So-
ciety of America.
Richard M. Osgood, Jr. (F’87) received the Ph.D.
degree in physics from Ali Javan’s Group, Mas-
sachusetts Institute of Technology, Cambridge, MA,
USA, in 1973.
He has worked on a broad variety of optical mate-
rials and devices and is a Coinventor of several major
laser systems for Department of Defense (DoD) and
Department of Energy (DOE) applications, includ-
ing the high-power CO laser, the electrical-initiated
high-frequency laser, and a deep-ultraviolet solid-
state laser system. He is also a Pioneer in laser pro-
cessing, numerical optical simulation, laser surface interactions, and Si linear
and nonlinear optical-guided wave devices. He has been a major Advisor to
many DoD and DOE organizations and directed and participated in many tech-
nology studies for DARPA and the National Academy of Engineering. From
2000 to 2002, he served as an Associate Lab Director with Brookhaven National
Laboratory, Upton, NY, USA, where he established the BNL Nanocenter and
the Materials Sciences Department. He is also a co-Founder of the Columbia
Microelectronics Sciences Laboratories and has directed four DARPA and two
AFOSR sponsored center programs at Columbia. He has published 460 journal
articles on laser science and materials science and optical devices and physics.
He has maintained a major program on active and passive Si photonics devices
for 15 years. He, his group, and groups at IBM recently authored several major
review papers on the subject of nonlinear Si photonics, which are focused on
the “fiber-on-a-chip” applications.
Dr. Osgood is a Fellow of the American Physical Society and the Optical
Society of America. He serves as a Consultant to numerous research institutions
and government agencies. In 1991, he received the R.W. Wood Award from
the Optical Society of America and Japanese Honorary Lectureship for OITDA
(Optical Device Association). Research in his group contributed to the formation
of four start-up companies, including RSoft, Litel, Telephotonics, and Revise.
In addition, a number of his 57 graduated Ph.D students have been selected for
graduate student awards and fellowships from the IEEE Photonics Society and
the Optical Society of America.
Charles T. Black (SM’14) received the Ph.D. degree in physics from Harvard
University, Cambridge, MA, USA, in 1996.
He is a Scientist and Group Leader for Electronic Nanomaterials with the
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton,
NY, USA, where he researches applications for nanostructured materials in
photovoltaic devices. From 1996 to 2006, he was a Research Staff Member
with the IBM Thomas J. Watson Research Center, Yorktown Heights, NY. His
research at IBM involved using self-assembly to address device fabrication
challenges in high-performance semiconductor electronics.
Dr. Black is a Fellow of the American Physical Society.
1106
Muhammad Ashraful Alam (F’06) received the
Masters and Doctoral degrees from Clarkson Uni-
versity, Potsdam, NY, USA, and Purdue University,
West Lafayette, IN, USA, in 1991 and 1995, respec-
tively.
He is currently a Professor of electrical and com-
puter engineering and a University Faculty Scholar
with Purdue University, where his research and teach-
ing focus on physics, simulation, characterization,
and technology of classical and emerging electronic
devices. From 1995 to 2001, he was with Bell Labo-
ratories, Murray Hill, NJ, USA, as a Member of Technical Staff in the Silicon
ULSI Research Department. From 2001 to 2003, he was a Distinguished Mem-
ber of Technical Staff with Agere Systems, Murray Hill. After joining Purdue
University in 2004, his research has broadened into nanocomposite flexible
electronics, organic solar cells, and performance limits of nanobiosensors. He
has published more than 180 papers in international journals and has presented
many invited and contributed talks at international conferences.
Dr. Alam is a Fellow of the American Physical Society and the American
Association for the Advancement of Science. He received the 2006 IEEE Kiyo
Tomiyasu Award for contributions to device technology for communication
systems.
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IEEE JOURNAL OF PHOTOVOLTAICS, VOL. 4, NO. 4, JULY 2014
Ioannis Kymissis (SM’10) received the S.B., M.Eng., and Ph.D. degrees from
the Massachusetts Institute of Technology (MIT), Cambridge, MA, USA. His
M.Eng. thesis was performed as a co-op at the IBM T. J. Watson Research Lab
on organic thin-film transistors, and his Ph.D. degree was in the Microsystems
Technology Lab at MIT, where at worked on field emission displays.
After graduation, he spent three years as a Postdoctoral Researcher
with MIT’s Laboratory for Organic Optics and Electronics, working on
a variety of organic electronic devices and as a Consulting Engineer for
an MIT-based startup which is developing and commercializing a novel
light-emitting architecture. He joined the faculty of Columbia University,
New York, NY, USA, in 2006, in the Electrical Engineering Department,
where he heads the Columbia Laboratory for Unconventional Electronics,
which is developing a variety of thin-film sensing, display, and actuation
systems.
Dr. Kymissis has received several awards, including the IVNC Shoulders-
Spint-Grey medal, the IEEE EDS Paul Rappaport Award, the NSF CAREER
Award, a Google Faculty Award, an IBM Research Outstanding Technical
Achievement Award, and the Vodafone Foundation Wireless Innovation award.