School of Chemistry - Research Publications
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ItemHighly Efficient Luminescent Solar Concentrators by Selective Alignment of Donor-Emitter Fluorophores(AMER CHEMICAL SOC, 2019-04-23)Vertically aligning fluorophores to the surface of a waveguide is known to be an effective approach to improve the optical quantum efficiency (OQE) of luminescent solar concentrators (LSCs). While the chromophore alignment assists waveguiding of the emitted photons to the LSC edges, it also significantly reduces the light-harvesting properties of the LSC. We report here a fluorophore pair consisting of a sphere-shaped energy donor and a rod-shaped emitter that was incorporated in LSCs to provide selective fluorophore alignment to address the reduced incident-light absorption issue. A liquid-crystal polymer matrix was used to perpendicularly align the rod-shaped acceptors to a favorable orientation for light guiding, while the sphere-shaped donor was randomly oriented to maintain its light-absorbing properties. The OQE of LSC devices with this selectively aligned donor-acceptor fluorophore system is 78% without significant loss of light-harvesting capability.
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ItemCompetitive Triplet Formation and Recombination in Crystalline Films of Perylenediimide Derivatives: Implications for Singlet Fission(AMER CHEMICAL SOC, 2020-05-28)Developing photostable compounds that undergo quantitative singlet fission (SF) is a key challenge. As SF necessitates electron transfer between neighboring molecules, the SF rate is highly sensitive to intermolecular coupling in the solid state. We investigate SF in thin films for a series of perylenediimide (PDI) molecules. By adding different substituents at the imide positions, the packing of the molecules in the solid state can be changed. The relationship between SF parameters and the stacked geometry in PDI films is investigated, with two-electron direct coupling found to be the main SF mechanism. Time-resolved emission and transient absorption data show that all of the PDI films undergo SF although with different rates and yields varying from 35 to 200%. The results show that PDI1 and 2, which are stacked PDI pairs twisted out of alignment along the highest occupied molecular orbital to lowest unoccupied molecular orbital transition, exhibit faster and more efficient SF up to 200% yield. We demonstrate that both triplet formation and decay rates are highly sensitive to the ordering of the molecules within a film. The results of this study will assist in the design of optimized structures with a fast SF rate and low recombination rate that are required for useful light harvesting applications.
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ItemFRET-enhanced photoluminescence of perylene diimides by combining molecular aggregation and insulation(Royal Society of Chemistry, 2020-07-14)The photoluminescence quantum yield (ϕPL) of perylene diimide derivatives (PDIs) is often limited by aggregation caused quenching (ACQ) at high concentration or in the neat solid-state. Energy transfer in high dye concentration systems is also a key factor in determining ϕPL as a result of energy funneling to trap sites in the sample. By tuning the substituents, we present two classes of PDIs with aggregation and insulation of the PDI core. By combining these fluorophores in a polymer film, we demonstrate highly emissive samples (85% ϕPL) at high concentration (140 mM or 20% w/w). Experimental and theoretical studies provide insight into why such a combination is necessary to achieve high ϕPL. While insulated fluorophores maintain respectable ϕPL at high concentration, an improved ϕPL can be achieved in the presence of appropriately oriented fluorophore aggregates as emissive traps. The theoretical calculations show that the relative orientation of aggregated monomers can result in energetic separation of localized states from the charge-transfer and bi-excitonic states thereby enabling high ϕPL.
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ItemLiquid Crystallinity as a Self-Assembly Motif for High-Efficiency, Solution-Processed, Solid-State Singlet Fission Materials(WILEY-V C H VERLAG GMBH, 2019-08)Abstract Solution and solution‐deposited thin films of the discotic liquid crystalline electron acceptor–donor–acceptor (A‐D‐A) p‐type organic semiconductor FHBC(TDPP)2, synthesized by coupling thienyl substituted diketopyrrolopyrrole (TDPP) onto a fluorenyl substituted hexa‐peri‐hexabenzocoronene (FHBC) core, are examined by ultrafast and nanosecond transient absorption spectroscopy, and time‐resolved photoluminescence studies to examine their ability to support singlet fission (SF). Grazing incidence wide‐angle X‐ray (GIWAX) studies indicate that as‐cast thin films of FHBC(TDPP)2 are “amorphous,” while hexagonal packed discotic liquid crystalline films evolve during thermal annealing. SF in as‐cast thin films is observed with an ≈150% triplet generation yield. Thermally annealing the thin films improves SF yields up to 170%. The as‐cast thin films show no long‐range order, indicating a new class of SF material where the requirement for local order and strong near neighbor coupling has been removed. Generation of long‐lived triplets (µs) suggests that these materials may also be suitable for inclusion in organic solar cells to enhance performance.
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ItemSolution-Processable, Solid State Donor-Acceptor Materials for Singlet Fission(WILEY-V C H VERLAG GMBH, 2018-10-25)Abstract The exploitation of singlet fission (SF) materials in optoelectronic devices is restricted by the limited number of SF materials available and developing new organic materials that undergo singlet fission is a significant challenge. Using a new strategy based on conjugating strong donor and acceptor building blocks, the small molecule (BDT(DPP)2) and polymer (p‐BDT‐DPP) systems are designed and synthesized knowing that bisthiophene‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione (DPP) has a low lying triplet energy level, which is further confirmed by time‐dependent density functional theory (TD‐DFT) calculations. TD‐DFT and natural transition orbital (NTO) analysis are conducted to gain insight into the photophysical properties and features of excited states in BDT(DPP)2, respectively. Femtosecond and nanosecond transient absorption spectroscopies are used to investigate the excited state kinetics in the synthesized compounds. Fast formation of triplet pairs in thin film of p‐BDT‐DPP and BDT(DPP)2 and the equilibrium formation of correlated triplet pairs and S1 from triplet–triplet annihilation in solution of BDT(DPP)2 are further evidence of SF in these compounds. The short triplet lifetime, as a result of fast biexcitonic recombination, provides additional support for triplet pair formation through singlet fission.
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ItemNo Preview AvailableReduced Recombination and Capacitor-like Charge Buildup in an Organic Heterojunction(American Chemical Society, 2020-02-05)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 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 buildup of electric charge in donor and acceptor domains—away from the interface—resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced 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.
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ItemEnergy Migration in Organic Solar Concentrators with a Molecularly Insulated Perylene Diimide(AMER CHEMICAL SOC, 2016-06-23)
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ItemHighly Fluorescent Molecularly Insulated Perylene Diimides: Effect of Concentration on Photophysical Properties(AMER CHEMICAL SOC, 2017-10-10)