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This PDF file contains the front matter associated with SPIE Proceedings Volume 7052, including the Title Page, Copyright information, Table of Contents, and the Conference Committee listing.
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Charge Injection and Transport in Organic Light Emitting Diodes and Solar Cells: Joint Session with Conference 7051
Synchrotron induced photoelectron spectroscopy on in situ
co-evaporated blends of CuPc and TCNQ and on
TCNQ/CuPc interfaces is applied for monitoring the electronic interaction indicated in systematic shifts of the CuPc and
TCNQ HOMO and core orbitals. These shifts correspond to a movement of the Fermi level within the HOMO LUMO
energy gap. The shifts in CuPc induced by the interaction with TCNQ are similar in the composites and in the interface
model experiment. At the interface an additional induced dipole potential can be measured. The interface-dipole plus the
Fermile level shift add up to the work function difference of pure CuPc and TCNQ. We conclude that TCNQ forms a
separate phase in CuPc rather than single isolated acceptor molecules. Charge transfer at the bulk hetero-junction
induces the Fermi level variations, which may be called doping.
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Reliability of Flexible Packaging: Joint Session with Conference 7048
Large area organic photovoltaic modules have been fabricated with 232.8 cm2 of total area with 108 cm2
of photoactive area. Efficiencies up to 2.3% by active area (1.1% by total area) demonstrate operation of a multicell module with configurable voltage and current output. NREL certification
is reported and is an example of the largest OPV module certified by NREL, as well as the only polymer:fullerene-based module tested. Module lifetime data were collected and with ca. 550 h of
light-soaking, > 2000h of lifetime is expected based on extrapolation. The conditions of the test were 100% duty cycle, ~ 1 Sun Xe-arc lamp, KG5-Si reference, ~25 °C controlled
temperature. The lifetime data were normalized with respect to the variations and fade of the Xe-arc lamp source.
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Accurate Measurement of the Efficiency of Organic Photovoltaic Devices
We discuss the measurement and analysis of current vs. voltage (I-V) characteristics of organic and dye-sensitized
photovoltaic cells and modules. A brief discussion of the history of photovoltaic efficiency measurements and
procedures will be presented. We discuss both the error sources in the measurements and the strategies to minimize their
influence. These error sources include the sample area, spectral errors, temperature fluctuations, current and voltage
response time, contacting, and degradation during testing. Information that can be extracted from light and dark I-V
measurement includes peak power, open-circuit voltage, short-circuit current, series and shunt resistance, diode quality
factor, dark current, and photo-current. The quantum efficiency provides information on photo-current nonlinearities,
current generation, and recombination mechanisms.
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Organic solar cells (OSCs) have been extensively studied and significant improvements have been demonstrated in
recent years. Along with the excitement in technology development, the accurate measurement of OSCs has become
critical for the healthy development of this promising technology. The limited absorption and spectral response of
organic based solar cells could lead to significant derivation in solar cell measurement. In this paper, we will discuss
several issues in the measurement of organic solar cells, including spectral mismatch factor, elimination of the
mismatch by proper selection of reference cell, external quantum efficiency testing, device area issue etc. Results on
both polymer based bulk hetero-junction solar cell and small molecule based solar cell will be presented.
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Performance characterization of the dye-sensitized solar cells (DSC) and organic polymer solar cells (OSC) has been
investigated, in order to clarify how to accurately determine their performance. Accurate characterization of DSC
requires consideration on the very slow temporal response, and variation of the quantum efficiency spectrum for the bias
light. The I-V curves of the DSC are clearly dependent on the voltage sweep direction, even when the sweep time is the
order of seconds. The quantum efficiency spectra shows irradiance-dependence in the wavelength range of <500 nm.
Also, the temporal response is dependent on the wavelength of the incident light. On the other hand, the characterizationrelated
features for measuring the I-V curves and quantum efficiency spectra of OSC are rather similar to conventional
crystalline Si or amorphous silicon devices. Although their characteristics can be strongly dependent on the device
design, the present results can be utilized for precisely characterizing the I-V curves and spectral responses of DSC and
OSC.
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Multilayer Organic Photovoltaics with a p-i-n Structure
Fullerene (C60) samples purified to seven-nine level by single-crystal formed sublimation were incorporated into i-layer
of p-i-n organic solar cells. Fill factor hardly decreased even for the very thick C60: metal-free phthalocyanine (H2Pc)
codeposited i-interlayer reaching 1.2 µm. For 1 µm thick i-layer, short-circuit photocurrent density of 18.3 mAcm-2 and
photo-electric conversion efficiency of 5.3% was observed. Very large photocurrent density is mainly due to nearly
100% utilization of solar light in the visible region by 1 µm-thick i-layer.
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We have fabricated organic photovoltaic cell using tetrabenzoporhyrin (BP) as a donor material. Tetrabenzoporhyrin is
formed by thermal conversion of the soluble precursor that has four bicyclo rings. Upon heat treatment above 150°C, the
precursor molecule is converted to semiconductive tetrabenzoporphyrin, which is insoluble against conventional organic
solvents. Taking advantage of this insoluble character of BP, p-i-n bulk heterojunction photovoltaic cell is successfully
fabricated from solution, with BP/BP:fullerene/fullerene trilayer, where p-layer is crystal BP, i-layer consists of both BP
and fullerene, and fullerene acts as n-layer. We have reported the
p-i-n photovoltaic cell using [6,6]-phenyl-C61-butyric
acid n-butyl ester (PCBNB) as an acceptor. This solution-processed
p-i-n device has achieved power conversion
efficiency as high as 3.4% (Jsc=9.8mA/cm2; Voc=0.62V; FF=0.56). The performance of BP device with p-i-n junction is
further improved by introducing a new fullerene for the i- and
n-layers. Taking into consideration LUMO level,
solubility and thermal properties, a novel fullerene derivative,
1,4-bis(dimethylphenylsilylmethyl)[60]fullerene (SIMEF),
is designed and synthesized. This new di-adduct fullerene , SIMEF, improves power conversion efficiency up to 4.1%
(Jsc=9.1mA/cm2; Voc=0.76V; FF=0.59). This improvement is largely due to an increased Voc. We have analyzed
BP:fullerene composite films to find that formation of meta-stable phase of BP is fully suppressed by SIMEF. Depth
profile of this p-i-n cell is measured by means of TOF-SIMS method to observe the expected vertical distribution of the
donor and acceptor that has been designed.
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Physics of Multi- and Bulk Heterojunction Solar Cells
Studying polymer:fullerene solar cells, we find that the bimolecular recombination is much lower than the anticipated
Langevin recombination. In our study, we investigate the performance of annealed P3HT:PCBM bulk
heterojunction solar cells by current-voltage characterisation, and complement these measurements with
photo-CELIV experiments. We find that at room temperature the bimolecular recombination rate is reduced by a
factor of about 50 as compared to the Langevin rate. We discuss the implications of this reduction on the solar
cell performance, using a one-dimensional numeric simulator to analyse the experimental results, and compare
the reduced recombination rates with the Langevin rates.
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In this study we present research results on interdigitated organic / small molecule photoconductors. We investigated
photoconductivity in interdigitated lateral photoconductors with aluminum contacts, using (1) a spin-coated organic
blend and (2) evaporated organic multilayers as the active layer. The spin-coated devices were made with a blend of a
poly[2-methoxy-5-(2-ethylhexyl-oxy)-1,4-phenylene-vinylene]
[MEH-PPV] and {6}-1-(3-(methoxycarbonyl)
propyl)-{5}-1-phenyl-[6,6]-C61 [PCBM]. In spin-cast devices, the quantum efficiency was limited by the dissociation of the
excitons. The field dependence of the dissociation of the excitons was explained using a modified Onsager model for
charge dissociation. The evaporated devices were made from layers of alpha-sexithiophene [α-6T] and C60. In the
evaporate devices, trap sites in the active layer limited the quantum efficiency. By modeling the quantum efficiency
based on exciton diffusion to the interface and the dissociation of the excitons, the experimental quantum efficiency was
explained by a trapping model with a charge carrier lifetime of 0.002s.
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Hybrid Solar Cells with Organic and Inorganic Components
In this article, the polymer photovoltaic devices based on the poly(3-hexylthiophene)/TiO2 nanorods hybrid material is present. An enhancement in the device performance can be achieved by removing or replacing the insulating surfactant on the TiO2 nanorods surface with a more conductive ligand, which can play the role to assist charge separation efficiency or also to prevent from back recombination, giving a large improvement in the short circuit current and fill factor. The relatively high power conversion efficiency of 2.2 % under simulated A.M. 1.5 illumination (100mW/cm2) can be achieved, providing a route for fabricating low-cost, environmentally friendly polymer photovoltaic devices by all-solution processes.
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We report the synthesis and photovoltaic properties of poly[2,7-(9,
9-di-n-octyl-silafluorene)-alt-5,5''-(4',
7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PSiF-DBT). The polymer heterojunction solar cells fabricated from PSiF-DBT as the electron
donor blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as the electron acceptor exhibited a high powerconversion
efficiency up to 5.4% with an open-circuit voltage of 0.90 V, a short-circuit current density of 9.5 mA cm-2
and a fill factor of 50.7% under the illumination of AM 1.5 G from a solar simulator (800 W m-2). A comparative study
between PSiF-DBT and its polyfluorene analogous PFDTBT and PFO-DBT demonstrates that the high performance of
PSiF-DBT originated from its red-shifted absorption spectrum up to 680 nm and high mobility of 1 × 10-3 cm2 V-1 s-1 compared with 645 nm and 3 × 10-4 cm2
V-1 s-1 for corresponding polyfluorene derivatives, respectively. These results indicate polysilafluorene derivatives are a promising new class of donor materials for polymer solar cells.
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We report the development of a fully regioregular Poly(3-Dodecyl-2,5-thienylenevinylene)
(HT-HT PDDTV) using the Horner-Emmons reaction, and studies using proton and carbon
NMR spectroscopy, UV-vis absorption spectroscopy, fluorescence spectroscopy,
cyclovoltametry, thermal analysis (DSC & TGA) and XRD. The HT-HT PDDTV developed has
practically no solubility in boiling hexane, in sharp contrast to the literature PDDTV prepared
from the Stille coupling reaction, which is mostly soluble in hexanes (an indication of high
content of structural defects). The optical energy gaps are 1.80 eV in chloroform solution and
1.65 eV in film. The HOMO/LUMO of the film were -5.03 eV and
-3.63eV, respectively. The
electrochemical energy gap in the film is 1.4 eV. XRD study shows that a decent crystalline
structure was formed without any annealing of the as-cast films. The lamellar sheets (formed
from π. π. stacking) preferentially are oriented in parallel to the substrate surface with an
interlayer spacing of 17.6 angstrom.
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A composite of polyaniline (PANI) containing iron oxides (Fe3O4) with nanometer size was prepared by a chemical method. The electrical properties of (PANI-Fe3O4) sandwich structure using ohmic gold and blocking aluminium electrodes were studied. The current density - voltage (J-V) characteristics for the device resemble the typical dark current versus applied voltage characteristic for conventional Schottky diode. Electronic parameters have been calculated using J-V and capacitance-voltage (C-V) measurements.
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A series of dye-sensitized solar cells (DSSCs) were fabricated using ZnO nanorod arrays as the anode electrode.
The ZnO nanorod arrays were grown on the fluorine doped tin dioxide (FTO) substrates by a hydrothermal method.
The scanning electron microscopy (SEM) images indicated that the ZnO nanorod arrays were highly oriented on
FTO substrates with an average diameter of ~40 nm and an average length of ~1 μm. After sensitized by Z-907
dye via impregnation in solution, ZnO nanorod arrays changed the color from white to pink. This indicated that the
dye had been successfully attached to ZnO nanorods. The high-aspect-ratio (~25) ZnO nanorod arrays are expected
to improve charge transport through the formation of continuous channels along the nanorods. We fabricated
photovoltaic cells based on these ZnO nanorod arrays and found the deposition time and effective area were two
important factors affecting short circuit current densities and cell efficiencies. The device performance (Voc = 0.48
V, Jsc = 5.39 mA/cm2, η = 0.73 %) showed a great potential for solar energy conversion.
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Four different perylene-based electron-acceptors having similar electron affinities, but different thermotropic phases are blended with nematic liquid crystalline electron-donors with a
fluorene-thiophene structure to form single layer photovoltaic devices. Best results are obtained when the nematic donor is mixed with an amorphous acceptor to give a supercooled nematic glass at room temperature. Atomic force microscopy operating in the phase contrast mode reveals phase separation on a nanometer scale with a broad distribution of domain sizes peaking at 26 nm. We correlate the
morphology of the different blends with the performance of the photovoltaic devices. Power conversion efficiencies up to 0.9 % are obtained with excitation at 470 nm.
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A distribution-controlled bulk heterojunction (dc-BHJ) photovoltaic cell where the distribution of an electron donor and
acceptor is controlled across the film was fabricated by Evaporative Spray Deposition using Ultradilute Solution
(ESDUS) method, which can build a layered structure of polymer semiconductors soluble in a same solvent, and the
energy conversion efficiency, PCE, of the dc-BHJ was significantly improved compared with a conventional BHJ cell.
The dc-BHJ cells were fabricated by changing the ratio of a donor, regioregular poly(3-hexyl-thiophene-2,5-diyl)
(P3HT), and an acceptor, a fullerene derivative (PCBM), from 2:1 to 1:2. The short circuit current, Jsc, and PCE of a dc-BHJ cell having P3HT-rich BHJ/PCBM-rich BHJ structure was 6.06 mA/cm2 and 2.15 %, respectively, while those of a
conventional BHJ cell having P3HT:PCBM=1:1 layer were 5.26 mA/cm2, 1.71 %. In the dc-BHJ cells, the introduction
of composition gradient brought about the increase in conversion efficiency. The transportation of photogenerated charge
carriers to the collecting electrodes was improved because the better pathways should be formed in the dc-BHJ cells.
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CdSe/ZnS core/shell quantum dots have been decorated on thin multiwalled and singlewalled carbon nanotubes (CNTs)
by chemical functionalization and substrate gate-bias control. CdSe quantum dots were negatively charged by adding
mercaptoacetic acid (MAA). The silicon oxide substrate was decorated by octadecyltrichlorosilane (OTS) and converted
to hydrophobic surface. The negatively charged CdSe/ZnS NCs were adsorbed on the SWCNT surface by applying the
negative gate bias. The selective adsorption of CdSe/ZnS quantum dots on SWCNTs was confirmed by confocal laser
scanning microscope. Quantum dots decorated carbon nanotubes have been used for effective photogenaration and
carrier transport through the organic photovoltaic device which has fabricated using effective polymers. The results
clearly indicate the efficient photocurrent generation and carrier transport which effectively increased the efficiency of
the device for the next generation organic solar cell applications.
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Tandem solar cells, in which two individual cells are stacked on top of each other, offer the potential to increase the
efficiency significantly compared to a single cell on the same area. To reach maximum efficiency, each cell in the stack
must have a distinctive spectral response and the current in each cell must be similar. This requires smart selection of
materials, proper cell design and appropriate layer thickness. Tandem polymer solar cells can be made by processing two
individual cells from solvent based liquids, separated by a recombination layer. Potential candidates for the
recombination layer are 1) a combination of a ZnO layer and a pH-neutral PEDOT:PSS layer, 2) a TiOx layer combined
with a normal PEDOT:PSS layer. We will discuss the properties of the suggested recombination layers. To determine the
performance of tandem cells, accurate spectral response measurements are crucial. Spectral response measurements of a
polymer tandem cell show that the response of each subcell can be measured only when a bias light with sufficient
intensity and suitable spectrum is applied. We will discuss the special requirements for the spectral response set-up that
are needed in order to successfully discriminate between the responses of each subcell.
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The solution processable poly(3-hexylthiophene)(P3HT)/TiO2-nanorod hybrid material for solar cells has been
successfully demonstrated. A critical issue for using hybrid heterojunction concept is the interface properties which
affect the exciton separation efficiency and bi-carrier transport. To improve the interface properties, we replace the
insulating surfactant on TiO2 nanorod surface with a more conductive oligomer, carboxylate terminated 3-hexylthiophene (P3HT-COOH). The enhancement of exciton separation efficiency due to better organic-inorganic
interfacial compatibility can be obtained. The electron mobility for transporting in the TiO2 network is improved. A
power conversion efficiency has been increased 3 times by using this new hybrid material without optimization as
compared with the hybrid without P3HT-COOH modification.
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Poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonic acid) (PEDOT:PSS) is a common material of hole
injection layer used in polymer light emitting diodes (PLEDs) and organic solar cells. It can improve the efficiency of the
charge collection at the anode. It has been reported that adding glycerol to PEDOT:PSS could increase the conductivity
and improve the efficiency of PLEDs and organic solar cells. However, it is less noticed that the conductivity could be
improved when the solution of PEDOT was heated before deposition. Here we experimented different concentrations of
glycerol into PEDOT:PSS to make G-PEDOT:PSS solution, and heated the G-PEDOT:PSS solution at different
temperatures before deposition. The solutions are then spin-coated on the glass and annealed at 140 °C. The conductivity
was then measured and compared. The experiments showed that the conductivity of pure PEDOT:PSS slightly increased
for 2-3 times, while the G-PEDOT:PSS increased over two orders of magnitudes. The conductivity increased with the
heating temperature before deposition. The enhancement of the conductivity of the G-PEDOT:PSS film was higher than
that of the pure PEDOT:PSS film. The overall conductivity increase for over three orders of magnitude. The reason is
because the high temperature causes the glycerol and PEDOT:PSS to mix evenly. This is helpful for the swelling and
aggregation of colloidal PEDOT-rich particles, forming a highly conductive network. When G-PEDOT:PSS resistance is
reduced, it may not only increase the hole collection ability, but also replace ITO as the anode layer due to its advantages
of low production cost and high work function.
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PPV derivatives, polymers with vinylene units, have their tendency to exhibit degradation, after irradiation with white
light or operation of the device, resulting in the appearance of a shifted absorption and emission band in the short
wavelength regions of the spectra. In order to reduce oxidation of the vinylene group, the vinylene group was cyclized
using two 5-membered rings. In this paper, we report the synthesis and properties of new copolymers utilizing
poly(5,5,10,10-tetrakis(2-ethylhexyl)-5,10-dihydroindeno[2,1-a]indene-2,7-diyl) (PININE) and benzothiadiazole (BT).
PININE copolymers with BT and thiophene units exhibit high PCE for polymer solar cells (PSCs). Under white light
illumination (AM 1.5 G, 100 mW/cm2), the cell based on PININEDTBT/PCBM as the active layer has a short circuit
current density (Isc) of 5.93 mA/cm2, a fill factor (FF) of 43 %, and PCE of 1.88 %. These copolymers have not only
good processability due to indenoindene unit, in which four alkyl groups can be incorporated, but also the strong and
uniform absorbance in the whole visible region.
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We introduce a novel nanostructuring method for bulk heterojunction solar cells which is aimed at overcoming current
limitations associated with short exciton diffusion lengths and poor charge transport. By employing a nanosphere
templating technique porous interconnected films of copper phthalocyanine (CuPc) have been prepared. Subsequent
infiltration of the CuPc structures with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) results in the formation of
three dimensionally structured nanocomposites, consisting of interpenetrating and interconnected networks. The
lengthscale separation in the composite can be engineered to match exciton diffusion lengths and the interconnectivity is
compatible with good charge transport. We propose this templating strategy as a widely applicable solution to the
continued development of low-cost organic photovoltaics.
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We report a study on solar cells using pentacene derivatives with triisopropylsilylethynyl substitution at the
6,13-position and 1,3-dioxolane substitution to the terminal benzenoid rings of pentacene as the electron donor and C60 as the electron acceptor. A significant increase in the open circuit voltage (Voc) was obtained in all the
pentacene-derivative
based cells with the highest Voc as high as 0.90 V, compared to a 0.24 V value for pentacene. The variation in the Voc of
the cells is in qualitative agreement with the larger offset between ionization potential of the electron donor and the
electron affinity of C60. The power conversion efficiency (η) at 100 mW/cm2 of EtTP-5/C60 cells reached 0.74%, which
is comparable to that of a pentacene/C60 cell (0.82%).
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