Bulk heterojunction polymer solar cells made from a novel low‐bandgap polymer show the highest photocurrent response so far for this class of materials (see figure). Efficiencies up to 3.2 % are realized, but this conjugated polymer has the intrinsic capability to reach 7 % efficiency because of its material properties. Possible loss mechanisms and improvements are discussed.
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%.
Solution processed organic solar cells based on blends of semiconducting polymers and soluble fullerene derivatives are showing impressive advances in photovoltaic power conversion efficiency, with recent reports of efficiencies in excess of 6%.[1]One of the key remaining factors limiting the performance of such blend or 'bulk heterojunction' solar cells is that they generally exhibit relatively modest voltage outputs, with the energy corresponding to the open circuit voltage, V OC , typically being less than half the optical gap. This V OC has been shown to be correlated to the energy levels of the donor and acceptor materials of the bulk heterojunction (BHJ). [2] In this paper, we compare the V OC of BHJ fabricated from four
Bulk heterojunction solar cells have attracted considerable attention over the past several years due to their potential for low-cost photovoltaic technology. The possibility of manufacturing modules via a standard printing/coating method in a roll-to-roll process in combination with the use of low-cost materials will lead to a watt-peak price of less than 1 US$ within the next few years. [1] Despite the low-cost potential, the power conversion efficiency of bulk heterojunction devices is low compared to inorganic solar cells. Efficiencies in the range of 5-6% have been certified at NREL and AIST usually on devices with small active areas.[2]The current understanding of bulk heterojunction solar cells suggests that the maximum efficiency is in the range of 10-12%.[3] Several reasons for the power conversion efficiency limitation have been identified.[1] Some of the prerequisites for achieving highest efficiencies are donor and acceptor materials with optimized energy levels [highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)], efficient charge transport in the donor-acceptor blend, efficient charge generation and limited recombination losses. Power conversion efficiency is strongly dependent on charge transport and charge generation, which are dominated by the phase behavior of the donor and acceptor molecules. The resulting, and often unfavorable, nanomorphology of this two-component blend limits the power conversion efficiency of bulk heterojunction solar cells. Precise control of the nanomorphology is very difficult and has been achieved only for a few systems. [4][5][6] The relation between the chemical structure of donor and acceptor materials and the nanomorphology that they form when they are blended is currently not well understood, and as will be shown in this paper, minor changes in the chemical structure can cause major changes in the performance of the materials in organic solar cells.
We designed and synthesized a series of conjugated polymers containing alternating electrondonating 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)), and their absorption characteristics can be tuned by adjusting the ratio of the two electrondonating 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 electron transporters. Field-effect transistors made of these materials show hole mobility in the range of 5 × 10 -4 -3 × 10 -3 cm 2 /(V s), which promises good device fill factor. Because of the combination of these characteristics, power conversion efficiencies up to 3.5% and an external quantum efficiency of at least 25% between 400 and 800 nm with a maximum of 38% around 700 nm were achieved on devices made of bulk heterojunction composites of these materials with soluble fullerene derivatives. Further improvement of the materials will include the modification of both the side chains and the backbone to effect change to the active layer morphology to maintain good charge carrier mobility in the composite.
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 donor/acceptor interface.
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-C 61butyric 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 dithiophenebenzothiadiazole 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 AE 1 nm in both narrow band gap polymers, being considerably longer than the 5.4 AE 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.
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 cm2 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%.
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