23 research outputs found
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Reduced Recombination and Capacitor-like Charge Buildup in an Organic Heterojunction
Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination—poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient 20 Stark effect, caused by nanoscale electric fields of ~487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ~2000 times less than predicted by Langevin theory. This in turn leads to the build-up of electric charge in donor and acceptor domains—away from the interface—resistant to bimolecular recombination. 25 Interestingly, this signal is only experimentally obvious in thick films, due to the different scaling of electro-absorption and photo-induced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of > 8 % because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies, the bulk heterojunction can go beyond its established role in charge photogeneration, and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination
Efficient light harvesting of a luminescent solar concentrator using excitation energy transfer from an aggregation-induced emitter
The compromise between light absorption and reabsorption losses limits the potential light conversion efficiency of luminescent solar concentrators (LSCs). Current approaches do not fully address both issues. By using the excitation energy transfer (EET) strategy with a donor chromophore that exhibits aggregation-induced emission (AIE) behaviour, it is shown that both transmission and reabsorption losses can be minimized in a LSC device achieving high light collection and concentration efficiencies. The light harvesting performance of the LSC developed has been characterized using fluorescence quantum yield measurements and Monte Carlo ray tracing simulations. Comparative incident photon conversion efficiency and short-circuit current data based on the LSC coupled to a silicon solar cell provide additional evidence for improved performance
Concentrating Aggregation-Induced Fluorescence in Planar Waveguides: A Proof-of-Principle
The photophysical properties of fluorescent dyes are key determinants in the performance of luminescent solar concentrators (LSCs). First-generation dyes--coumarin, perylenes, and rhodamines--used in LSCs suffer from both concentration quenching in the solid-state and small Stokes shifts which limit the current LSC efficiencies to below theoretical limits. Here we show that fluorophores that exhibit aggregation-induced emission (AIE) are promising materials for LSC applications. Experiments and Monte Carlo simulations show that the optical quantum efficiencies of LSCs with AIE fluorophores are at least comparable to those of LSCs with first-generation dyes as the active materials even without the use of any optical accessories to enhance the trapping efficiency of the LSCs. Our results demonstrate that AIE fluorophores can potentially solve some key limiting properties of first-generation LSC dyes
Emissive Molecular Aggregates and Energy Migration in Luminescent Solar Concentrators
Luminescent solar concentrators (LSCs) are light harvesting devices that are ideally suited to light collection in the urban environment where direct sunlight is often not available. LSCs consist of highly luminescent compounds embedded or coated on a transparent substrate that absorb diffuse or direct solar radiation over a large area. The resulting luminescence is trapped in the waveguide by total internal reflection to the thin edges of the substrate where the concentrated light can be used to improve the performance of photovoltaic devices. The concept of LSCs has been around for several decades, and yet the efficiencies of current devices are still below expectations for commercial viability. There are two primary challenges when designing new chromophores for LSC applications. Reabsorption of dye emission by chromophores within the waveguide is a significant loss mechanism attenuating the light output of LSCs. Concentration quenching, particularly in organic dye systems, restricts the quantity of chromophores that can be incorporated in the waveguide thus limiting the light absorbed by the LSC. Frequently, a compromise between increased light harvesting of the incident light and decreasing emission quantum yield is required for most organic chromophore-based systems due to concentration quenching. The low Stokes shift of common organic dyes used in current LSCs also imposes another optimization problem. Increasing light absorption of LSCs based on organic dyes to achieve efficient light harvesting also enhances reabsorption. Ideally, a design strategy to simultaneously optimize light harvesting, concentration quenching, and reabsorption of LSC chromophores is clearly needed to address the significant losses in LSCs.
Over the past few years, research in our group has targeted novel dye structures that address these primary challenges. There is a common perception that dye aggregates are to be avoided in LSCs. It became apparent in our studies that aggregates of chromophores exhibiting aggregation-induced emission (AIE) behavior are attractive candidates for LSC applications. Strategic application of AIE chromophores has led to the development of the first organic-based transparent solar concentrator that harvests UV light as well as the demonstration of reabsorption reduction by taking advantage of energy migration processes between chromophores. Further developments led us to the application of perylene diimides using an energy migration/energy transfer approach. To prevent concentration quenching, a molecularly insulated perylene diimide with bulky substituents attached to the imide positions was designed and synthesized. By combining the insulated perylene diimide with a commercial perylene dye as an energy donor–acceptor emitter pair, detrimental luminescence reabsorption was reduced while achieving a high chromophore concentration for efficient light absorption. This Account reviews and reinspects some of our recent work and the improvements in the field of LSCs
Cobalt(III) complexes of monobenzyl-cyclam macrocycle derivatives
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