5 research outputs found

    Temperature-Independent Singlet Exciton Fission in Tetracene

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    We use transient absorption spectroscopy to demonstrate that the dynamics of singlet exciton fission in tetracene are independent of temperature (10–270 K). Low-intensity, broad-band measurements allow the identification of spectral features while minimizing bimolecular recombination. Hence, by directly observing both species, we find that the time constant for the conversion of singlets to triplet pairs is ∼90 ps. However, in contrast to pentacene, where fission is effectively unidirectional, we confirm that the emissive singlet in tetracene is readily regenerated from spin-correlated “geminate” triplets following fission, leading to equilibrium dynamics. Although free triplets are efficiently generated at room temperature, the interplay of superradiance and frustrated triplet diffusion contributes to a nearly 20-fold increase in the steady-state fluorescence as the sample is cooled. Together, these results require that singlets and triplet pairs in tetracene are effectively degenerate in energy, and begin to reconcile the temperature dependence of many macroscopic observables with a fission process which does not require thermal activation

    Speed Limit for Triplet-Exciton Transfer in Solid-State PbS Nanocrystal-Sensitized Photon Upconversion

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    Hybrid interfaces combining inorganic and organic materials underpin the operation of many optoelectronic and photocatalytic systems and allow for innovative approaches to photon up- and down-conversion. However, the mechanism of exchange-mediated energy transfer of spin-triplet excitons across these interfaces remains obscure, particularly when both the macroscopic donor and acceptor are composed of many separately interacting nanoscopic moieties. Here, we study the transfer of excitons from colloidal lead sulfide (PbS) nanocrystals to the spin-triplet state of rubrene molecules. By reducing the length of the carboxylic acid ligands on the nanocrystal surface from 18 to 4 carbon atoms, thinning the effective ligand shell from 13 to 6 Å, we are able to increase the characteristic transfer rate by an order of magnitude. However, we observe that the energy transfer rate asymptotes for shorter separation distances (≤10 Å) which we attribute to the reduced Dexter coupling brought on by the increased effective dielectric constant of these solid-state devices when the aliphatic ligands are short. This implies that the shortest ligands, which hinder long-term colloidal stability, offer little advantage for energy transfer. Indeed, we find that hexanoic acid ligands are already sufficient for near-unity transfer efficiency. Using nanocrystals with these optimal-length ligands in an improved solid-state device structure, we obtain an upconversion efficiency of (7 ± 1)% with excitation at λ = 808 nm

    Investigation of Bismuth Triiodide (BiI<sub>3</sub>) for Photovoltaic Applications

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    Guided by predictive discovery framework, we investigate bismuth triiodide (BiI<sub>3</sub>) as a candidate thin-film photovoltaic (PV) absorber. BiI<sub>3</sub> was chosen for its optical properties and the potential for “defect-tolerant” charge transport properties, which we test experimentally by measuring optical absorption and recombination lifetimes. We synthesize phase-pure BiI<sub>3</sub> thin films by physical vapor transport and solution processing and single-crystals by an electrodynamic gradient vertical Bridgman method. The bandgap of these materials is ∼1.8 eV, and they demonstrate room-temperature band-edge photoluminescence. We measure monoexponential recombination lifetimes in the range of 180–240 ps for thin films, and longer, multiexponential dynamics for single crystals, with time constants up to 1.3 to 1.5 ns. We discuss the outstanding challenges to developing BiI<sub>3</sub> PVs, including mechanical and electrical properties, which can also inform future selection of candidate PV absorbers

    Searching for “Defect-Tolerant” Photovoltaic Materials: Combined Theoretical and Experimental Screening

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    Recently, we and others have proposed screening criteria for “defect-tolerant” photovoltaic (PV) absorbers, identifying several classes of semiconducting compounds with electronic structures similar to those of hybrid lead–halide perovskites. In this work, we reflect on the accuracy and prospects of these new design criteria through a combined experimental and theoretical approach. We construct a model to extract photoluminescence lifetimes of six of these candidate PV absorbers, including four (InI, SbSI, SbSeI, and BiOI) for which time-resolved photoluminescence has not been previously reported. The lifetimes of all six candidate materials exceed 1 ns, a threshold for promising early stage PV device performance. However, there are variations between these materials, and none achieve lifetimes as high as those of the hybrid lead–halide perovskites, suggesting that the heuristics for defect-tolerant semiconductors are incomplete. We explore this through first-principles point defect calculations and Shockley–Read–Hall recombination models to describe the variation between the measured materials. In light of these insights, we discuss the evolution of screening criteria for defect tolerance and high-performance PV materials