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Organic semiconductors are widely investigated for their application in photovoltaics and photodetectors. We show that the efficiency of these devices is strongly influenced by the position of the space charge region, due to unintentional doping, and wavelength-dependent absorption properties in bulk heterojunctions. Spray-coated P3HT:PCBM bulk heterojunction photodiodes with thicknesses up to 4.2 μm and semitransparent top contact enable the characterization of exciton generation and separation in both irradiation directions. A large difference in external quantum efficiency (EQE) is observed for top and bottom illuminated configurations and is explained by a bias dependent arrangement of the space charge region at the two contact electrodes. Numerical drift–diffusion simulations allow to get insight into first order mechanisms behind the spectral features of EQE data in highly-doped organic photodiodes.

We have studied organic bulk heterojunction photovoltaic devices based on a bridged-bithiophene donor-acceptor type low-band gap polymer blended with PCBM and bis-PCBM. The impact of the molecular arrangement is discussed in terms of the correlation between the solar-cell performance and the degree of crystallization. Differential scanning calorimetry (DSC) and grazing-incidence X-ray diffraction (GIXRD) prove that films with bis-PCBM typically result in more amorphous blends than comparable films with PCBM. Electron tomography (ET) is used to visualize the three dimensional morphology of photoactive layers, confirming the presence of nanofibers, formed in different scales through the thickness in the blended films with mono and bis-fullerenes. (C) 2012 Elsevier B.V. All rights reserved

With the aid of optical modeling, the internal quantum efficiencies of organic Bulk Heterojunction (oBHJ) photovoltaic devices based on low band gap polymer of poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl] (Si-PCPDTBT) blended with the acceptors of 1-(3-Methoxycarbonyl) propyl-1-phenyl [6,6] C61 (PCBM) and bis–adduct (bis–PCBM) are determined. The Si-PCPDTBT:bis–PCBM devices show considerably lower short circuit current density (Jsc) as compared to the Si-PCPDTBT:PCBM devices. The results show that 30% of this smaller Jsc is due to the lower optical absorption of bis–PCBM, while the major losses originate from the electrical losses. It is found that for the best Si-PCPDTBT:bis–PCBM devices with an active layer thickness in the range of 70–100 nm, the inefficient charge generation within the bis–PCBM domains is the major contribution to the whole losses. Increasing the active layer thickness of Si-PCPDTBT:bis–PCBM device significantly enhances recombination losses in polymer/bis–fullerene matrix.

The effect of the additive 1,8-octanedithiol (ODT) on the nanometer-scale morphology and local photophysical properties of low-bandgap polymer blends of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b'] dithiophene)- alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl C(61) -butyric acid methyl ester (PCBM) is investigated. Phase separations of the PCPDTBT:PCBM blend film induced by ODT are visualized by the morphological changes from fibril-shaped features to spherical bumps, by the dramatically increased photoluminescence emission from PCPDTBT that was originally largely quenched, and by the fluctuations of spectral features at different locations of the sample surface. The correlations between the morphology and the local photophysical properties of the blend film with/without ODT at both the micrometer and nanometer scales are revealed by confocal and high-resolution near-field spectroscopic mapping techniques.

The effect of the addition of 1,8-octanedithiol (ODT) during processing on the microstructure of blend films of poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) and [6,6]-phenyl-C71 butyric acid methyl ester ([70]PCBM) is studied. Grazing incidence X-ray diffraction and absorption spectroscopy show that the crystalline order of PCPDTBT increases when ODT is introduced in the solution phase either to neat polymer systems or to blends with [70]PCBM. The increased crystalline order is accompanied by less dispersive hole transport in the polymer, and leads to a more efficient formation of a percolating fullerene network within the blend. This contributes to an increase in photocurrent generation. However, the bimolecular recombination rate as determined from photovoltage transients increases upon addition of ODT, limiting the power conversion efficiency to values well below those expected from the energy levels of PCPDTBT. We propose some explanations for this increase in bimolecular recombination, based also on variable angle spectroscopic ellipsometry measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011

Polymer:fullerene blends were screened in a combinatorial approach using inkjet printing thin film libraries for photovoltaic devices. The application of inkjet printing enabled a fast and simple experimental workflow from film preparation to the study of structure-property-relationships with a very high material efficiency. Inkjet printing requires less material for the preparation of thin film libraries in comparison to other dispensing techniques, like spin-coating. Two polymers (PCPDTBT, PSBTBT) and two fullerene derivatives (mono-PCBM, bis-PCBM) were investigated in various blend ratios, concentrations, solvent ratios, and film thicknesses. Morphological and optical properties of the inkjet printed films were investigated and compared with spin-coated films. This study shows the principle of an experimental setup from solution preparation to film characterization for the combinatorial investigation of large polymer:fullerene libraries.

We designed and synthesized a series of conjugated polymers containing alternating 4H-cyclopenta[2,1-b:3,4-b′]dithiophene units and comonomers consisting of 2,2′-bithiophene, 3″, 4″ -dihexyl-α -pentathiophene, 3,4-ethylenedioxythiophene and 5,5′ -bis(2-thienyl)-4,4′ -dihexyl-2,2′ -bithiazole. These polymers possess optical bandgaps in the range of 1.75 to 2.0 eV. The desirable absorption attributes of these materials make then excellent candidates for use in photovoltaic cells. Electrochemical studies indicate desirable HOMO-LUMO levels for use with fullerene derivatives as electron transporters. Field effect transistors made of these materials show hole mobilities in the range of 7.5 × 10−4 cm2/Vs to 2.0 × 10−3 cm2/Vs. Due to the combination of these characteristics, power conversion efficiencies up to 3.1% were achieved on devices made of bulk heterojunction composites of these materials with soluble fullerene derivatives.

Carbon bridged (C-PCPDTBT) and silicon-bridged (Si-PCPDTBT) dithiophene donor-acceptor copolymers belong to a promising class of low bandgap materials. Their higher field-effect mobility, as high as 10 -2 cm 2 V -1 s -1 in pristine films, and their more balanced charge transport in blends with fullerenes make silicon-bridged materials better candidates for use in photovoltaic devices. Striking morphological changes are observed in polymer:fullerene bulk heterojunctions upon the substitution of the bridging atom. XRD investigation indicates increased π-π stacking in Si-PCPDTBT compared to the carbon-bridged analogue. The fluorescence of this polymer and that of its counterpart C-PCPDTBT indicates that the higher photogeneration achieved in Si-PCPDTBT:fullerene films (with either [C60]PCBM or [C70]PCBM) can be correlated to the inactivation of a charge-transfer complex and to a favorable length of the donor-acceptor phase separation. TEM studies of Si-PCPDTBT:fullerene blended films suggest the formation of an interpenetrating network whose phase distribution is comparable to the one achieved in C-PCPDTBT-fullerene using 1,8-octanedithiol as an additive. In order to achieve a balanced hole and electron transport, Si-PCPDTBT requires a lower fullerene content (between 50 to 60 wt%) than C-PCPDTBT (more than 70 wt%). The Si-PCPDTBT:[C70]PCBM OBHJ solar cells deliver power conversion efficiencies of over 5%.

The charge transport and photogeneration in solar cells based on the low bandgap-conjugated polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H- cyclopenta[2,1-b; 3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and fullerenes is studied. The efficiency of the solar cells is limited by a relatively low fill factor, which contradicts the observed good and balanced charge transport in these blends. Intensity dependent measurements display a recombination limited photocurrent, characterized by a square root dependence on effective applied voltage, a linear dependence on light intensity and a constant saturation voltage. Numerical simulations show that the origin of the recombination limited photocurrent stems from the short lifetime of the bound electron-hole pairs at the donon/acceptor interface.

Conducting channel formation in organic field-effect transistors (OFETs) is considered to happen in the organic semiconductor layer very close to the interface with the gate dielectric. In the gradual channel approximation, the local density of accumulated charge carriers varies as a result of applied gate bias, with the majority of the charge carriers being localized in the first few semiconductor monolayers close to the dielectric interface. In this report, a new concept is employed which enables the accumulation of charge carriers in the channel by photoinduced charge transfer. An OFET employing C60 as a semiconductor and divinyltetramethyldisiloxane-bis(benzocyclobutene) as the gate dielectric is modified by a very thin noncontinuous layer of zincphthalocyanine (ZnPc) at the semiconductor/dielectric interface. With this device geometry, it is possible to excite the phthalocyanine selectively and photogenerate charges directly at the semiconductor/dielectric interface via photoinduced electron transfer from ZnPc onto C60. Thus the formation of a gate induced and a photoinduced channel in the same device can be correlated.

An experimental study of the transport properties of a low-bandgap conjugated polymer giving high photovoltaic quantum efficiencies in the near infrared spectral region (Eg-opt ∼ 1.35 eV) is presented. Using a organic thin film transistor geometry, we demonstrate a relatively high in-plane hole mobility, up to 1.5 · × 10−2 cm2 V−1 s−1 and quantify the electron mobility at 3 × · 10−5 cm2 V−1 s−1 on a SiO2 dielectric. In addition, singular contact behavior results in bipolar quasi-Ohmic injection both from low and high workfunction metals like LiF/Al and Au. X-ray investigations revealed a degree of interchain π-stacking that is probably embedded in a disordered matrix. Disorder also manifests itself in a strong positive field dependence of the hole mobility from the electric field. In blends made with the electron acceptor methanofullerene [6,6]-phenyl C61 butyric acid methyl ester (PCBM), the transistor characteristics suggest a relatively unfavorable intermixing of the two components for the application to photovoltaic devices. We attribute this to a too fine dispersion of [C60]-PCBM in the polymer matrix, that is also confirmed by the quenching of the photoluminescence signal measured in PCPDTBT [C60]-PCBM films with various composition. We show that a higher degree of phase separation can be induced during the film formation by using 1,8-octanedithiol (ODT), which leads to a more efficient electron percolation in the [C60]-PCBM. In addition, the experimental results, in combination with those of solar cells seem to support the correlation between the blend morphology and charge recombination. We tentatively propose that the drift length, and similarly the electrical fill factor, can be limited by the recombination of holes with electrons trapped on isolated [C60]-PCBM clusters. Ionized and isolated [C60]-PCBM molecules can modify the local electric field in the solar cell by build-up of a space-charge. The results also suggest that further improvements of the fill factor may also be limited by a strong electrical-field dependence of the hole transport.

Polymer/fullerene bulk heterojunctions have recently generated a lot of scientific interest due to their potential in low-cost photovoltaic applications. In this paper we detail the synthesis and characterization of two new low-band-gap polythiophenes, poly[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-4,7-bis(2-thienyl)-2,1,3-benzothiadiazole-5′,5′′-diyl] (PCPDTTBTT) and poly[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-2,3-dioctylquinoxaline-5,8-diyl] (PCPDTQ), for use in these applications. The PCPDTQ polymer did not produce efficient solar cells. A high power efficiency of 2.1% under one sun was found for a PCPDTTBTT/fullerene mixture. The high efficiency was achieved by alteration of the morphology using a solvent additive. Analysis of atomic force microscopy phase images shows that material phases with distinct mixing ratios are formed and altered with the addition of the solvent additive.

In organic bulk heterojunction solar cells (oBHJ) the blend morphology in combination with the charge transport properties of the individual components controls the extracted photocurrent. The organic field-effect transistor (OFET) has been proved as a powerful instrument to evaluate the unipolar carrier transport properties in a wide range of cases. In our work we extend the OFET concept to the evaluation of the bipolar transport properties in polymer-fullerenes blends and propose a method to improve the accuracy of the evaluation. The method is based on capacitance–voltage (C–V) measurements on MOS structures prepared on the same blends and delivers complementary information on the bulk heterojunction to the one obtained with FETs. The relevance for photovoltaic applications is investigated through the correlation between the current–voltage behavior of solar cells and the bipolar mobility for composites with varying polymer molecular weight and processed from different solvents. In particular the transport features of solar cells produced from o-Xylene (oX), a non chlorinated solvent more suitable to production requirements, have been compared to the one of devices cast from Chlorobenzene (CB) solution. For the P3HT-PCBM blend a consistent correlation between the mobility and the electrical fill factor and power performance was found. A significant asymmetry in the bipolar carrier mobility, together with low electron mobility dependent on the Mw value, affects the performances of thick o-Xylene cast devices. In the case of devices processed from Chlorobenzene the slower carrier has higher mobility and the small electrical losses detected are eventually more related to the formation of space-charge and eventually to surface recombination. This results in an efficient charge collection that is almost thickness independent. We report a dependence of the slow-carrier type (electrons or holes) and their mobility on the specific combination of molecular weight and solvent. The mobility data and the solar cell performance coherently fit to the prediction of a device model only based on the drift of carriers under the built-in electric field originated in the donor-acceptor oBHJ.

The hole mobility and power conversion efficiency of bulk heterojunction solar cells based on P3HT-type donor polymers and the soluble fullerene derivative [6,6]-phenyl C 61 butyric acid methyl ester (PCBM) as an acceptor both show a strong sensitivity to the introduction of interchain branches into the P3HT backbones. Branched B-P3HT copolymers display a distinctly decreased hole mobility and reduced solar cell power conversion efficiency with increasing amount of interchain 3.3'-bithiophene branches within the polythiophene macromolecules. The results illustrate the primary importance of proper solid state packing towards optimum charge transport and solar cell performance.

We designed and synthesized a series of conjugated polymers containing alternating electron-donating and electron-accepting units based on (4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene), 4,7-(2,1,3)-benzothiadiazole, and 5,5‘-[2,2‘]bithiophene. These polymers possess an optical band gap as low as 1.4 eV (i.e., in the case of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)]), and their absorption characteristics can be tuned by adjusting the ratio of the two electron-donating units: (4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b‘]dithiophene) and 5,5‘-[2,2‘]bithiophene. The desirable absorption attributes of these materials qualify them as excellent candidates for light-harvesting materials in organic photovoltaic applications allowing for high short-circuit current. Electrochemical studies indicate sufficiently deep HOMO/LUMO levels that enable a high photovoltaic device open-circuit voltage when fullerene derivatives are used as ...

Hydrogenated amorphous silicon solar cells have been realized in both a p-i-n configuration on Corning glass substrates, and a n-i-p configuration on stainless steel substrates. The performance degradation of the two kinds of cells under solar illumination has been examined over a 140 hour period. During degradation, the two devices have been kept under load in the maximum power condition that is normally used in a solar plant. The performance of the Corning glass deposited device exhibited a higher rate of degradation than did that of the other cell. A discussion of the possible reasons for this behaviour is given.

toactive layer deliver short circuit currents of up to 15.5 mA cm − 2 . Morphological studies show modest phase separation without the perturbation of the crystallinity of the P3HT:PC 61 BM matrix, in accordance with the measured acceptable fi ll factors. Picosecond time-resolved pump-probe spectroscopy reveals that the sensitization of P3HT:PC 61 BM with Si-PCPDTBT involves the transfer of photogenerated positive polarons from the low band gap polymer to P3HT within few hundreds of picoseconds. Intensity dependent experiments in combination with global fi tting show that the charge transfer from Si-PCPDTBT to P3HT competes with non-geminate charge carrier recombination of the holes in the Si-PCPDTBT phase with electrons in the PC 61 BM phase, both processes being of diffusive nature. At excitation densities corresponding to steady state conditions under one sun, modelling predicts hole transfer effi ciencies exceeding 90%, in accordance with IQE measurements. At higher pump intensities, bimolecular recombination suppresses the hole transfer process effectively.

[*] Prof. J. R. Durrant, Mr. A. Maurano, Dr. R. Hamilton, Dr. C. G. Shuttle, Dr. B. O’Regan, Dr. W. Zhang, Prof. I. McCulloch Departments of Chemistry, Imperial College London South Kensington SW7 2AZ (United Kingdom) E-mail: j.durrant@imperial.ac.uk Dr. A. M. Ballantyne, Prof. J. Nelson Departments of Physics, Imperial College London South Kensington SW7 2AZ (United Kingdom) Dr. H. Azimi, Dr. M. Morana, Prof. C. J. Brabec Konarka Austria, Altenbergerstrasse 69 A-4040 Linz (Austria) Dr. H. Azimi Christian Doppler Laboratory for Surface Optics Johannes Kepler University Linz (Austria)

There has been an intensive search for cost-effective photovoltaics since the development of the first solar cells in the 1950s [1-3]. Among all the alternative technologies to silicon-based pn-junction solar cells, organic solar cells are the approach that could lead to the most significant cost reduction [4]. The field of organic photovoltaics (OPV) is composed of organic/inorganic nanostructures, like the dyesensitized solar cell, multilayers of small organic molecules and mixtures of organic materials (bulk-heterojunction solar cell). A review of several so-called organic photovoltaic (OPV) technologies was recently presented [5].

The challenge to reversing the layer sequence of organic photovoltaics (OPVs) is to prepare a selective contact bottom cathode and to achieve a suitable morphology for carrier collection in the inverted structure. The authors report the creation of an efficient electron selective bottom contact based on a solution-processed titanium oxide interfacial layer on the top of indium tin oxide. The use of o-xylene as a solvent creates an efficient carrier collection network with little vertical phase segregation, providing sufficient performance for both regular and inverted solar cells. The authors demonstrate inverted layer sequence OPVs with AM 1.5 calibrated power conversion efficiencies of over 3%.

The challenge to reversing the layer sequence of organic photovoltaics (OPVs) is to prepare a selective contact bottom cathode and to achieve a suitable morphology for carrier collection in the inverted structure. We report the creation of an efficient electron selective bottom contact based on a solution-processed Titania layer on top of Indium Tin Oxide. The use of o-xylene as the casting solvent creates an efficient carrier collection network with little vertical phase segregation, providing sufficient performance for both regular as well as inverted solar cells. We demonstrate inverted layer sequence OPVs with AM 1.5-calibrated power conversion efficiencies of over 3%.

We developed a new method to accurately extract the singlet exciton diffusion length in organic semiconductors by blending them with a low concentration of methanofullerene[6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The dependence of photoluminescence (PL) decay time on the fullerene concentration provides information on both exciton diffusion and the nanocomposition of the blend. Experimentally measured PL decays of blends based on two narrow band gap dithiophene-benzothiadiazole polymers, C-PCPDTBT and Si-PCPDTBT, were modeled using a Monte Carlo simulation of 3D exciton diffusion in the blend. The simulation software is available for download. The extracted exciton diffusion length is 10.5 ± 1 nm in both narrow band gap polymers, being considerably longer than the 5.4 ± 0.7 nm that was measured with the same technique in the model compound poly(3-hexylthiophene) as a reference. Our approach is simple, fast and allows us to systematically measure and compare exciton diffusion length in a large number of compounds. cop. 2012 The Royal Society of Chemistry.

We present a novel double-gate structure for polymeric field-effect transistors produced from a solution of [9,9]-dioctylfluorene-co-bithiophene copolymer (F8T2) as the p-type organic semiconductor. The double-gate geometry adapts to different bias configurations and shows improved performances and higher flexibility of operation with respect to single-gate devices. The device characteristics show an increased on/off ratio and demonstrate the possibility to control the threshold voltage as well as the off current. The maximum hole mobility of 8×10−2cm2∕Vs measured for the F8T2 layer, in combination with the features of the double-gate structure, suggest the possibility to produce optimized devices with very high performances.