Spatially Resolved Optical Efficiency Measurements of Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) are able to concentrate both direct and diffuse solar radiation, and this ability has led to great interest in using them to improve solar energy capture when coupled to traditional photovoltaics (PV). In principle, a large-area LSC could concentrate light onto a much smaller area of PV, thus reducing costs or enabling new architectures. However, LSCs suffer from various optical losses which are hard to quantify using simple measurements of power conversion efficiency. Here, we show that spatially resolved photoluminescence quantum efficiency measurements on large-area LSCs can be used to resolve various loss processes such as out-coupling, self-absorption via emitters, and self-absorption from the LSC matrix. Further, these measurements allow for the extrapolation of device performance to arbitrarily large LSCs. Our results provide insight into the optimization of optical properties and guide the design of future LSCs for improved solar energy capture.

Photosynthesis re-wired on the pico-second timescale.

Photosystems II and I (PSII, PSI) are the reaction centre-containing complexes driving the light reactions of photosynthesis; PSII performs light-driven water oxidation and PSI further photo-energizes harvested electrons. The impressive efficiencies of the photosystems have motivated extensive biological, artificial and biohybrid approaches to 're-wire' photosynthesis for higher biomass-conversion efficiencies and new reaction pathways, such as H2 evolution or CO2 fixation1,2. Previous approaches focused on charge extraction at terminal electron acceptors of the photosystems3. Electron extraction at earlier steps, perhaps immediately from photoexcited reaction centres, would enable greater thermodynamic gains; however, this was believed impossible with reaction centres buried at least 4 nm within the photosystems4,5. Here, we demonstrate, using in vivo ultrafast transient absorption (TA) spectroscopy, extraction of electrons directly from photoexcited PSI and PSII at early points (several picoseconds post-photo-excitation) with live cyanobacterial cells or isolated photosystems, and exogenous electron mediators such as 2,6-dichloro-1,4-benzoquinone (DCBQ) and methyl viologen. We postulate that these mediators oxidize peripheral chlorophyll pigments participating in highly delocalized charge-transfer states after initial photo-excitation. Our results challenge previous models that the photoexcited reaction centres are insulated within the photosystem protein scaffold, opening new avenues to study and re-wire photosynthesis for biotechnologies and semi-artificial photosynthesis.

Microcavity-like exciton-polaritons can be the primary photoexcitation in bare organic semiconductors.

Strong-coupling between excitons and confined photonic modes can lead to the formation of new quasi-particles termed exciton-polaritons which can display a range of interesting properties such as super-fluidity, ultrafast transport and Bose-Einstein condensation. Strong-coupling typically occurs when an excitonic material is confided in a dielectric or plasmonic microcavity. Here, we show polaritons can form at room temperature in a range of chemically diverse, organic semiconductor thin films, despite the absence of an external cavity. We find evidence of strong light-matter coupling via angle-dependent peak splittings in the reflectivity spectra of the materials and emission from collective polariton states. We additionally show exciton-polaritons are the primary photoexcitation in these organic materials by directly imaging their ultrafast (5 × 106 m s-1), ultralong (~270 nm) transport. These results open-up new fundamental physics and could enable a new generation of organic optoelectronic and light harvesting devices based on cavity-free exciton-polaritons.

Optical and Electronic Properties of Colloidal CdSe Quantum Rings.

Luminescent colloidal CdSe nanorings are a recently developed type of semiconductor structure that have attracted interest due to the potential for rich physics arising from their nontrivial toroidal shape. However, the exciton properties and dynamics of these materials with complex topology are not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and single-particle measurements to study these materials. We find that on transformation of CdSe nanoplatelets to nanorings, by perforating the center of platelets, the emission lifetime decreases and the emission spectrum broadens due to ensemble variations in the ring size and thickness. The reduced PL quantum yield of nanorings (∼10%) compared to platelets (∼30%) is attributed to an enhanced coupling between (i) excitons and CdSe LO-phonons at 200 cm-1 and (ii) negatively charged selenium-rich traps, which give nanorings a high surface charge (∼-50 mV). Population of these weakly emissive trap sites dominates the emission properties with an increased trap emission at low temperatures relative to excitonic emission. Our results provide a detailed picture of the nature of excitons in nanorings and the influence of phonons and surface charge in explaining the broad shape of the PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that the excitonic properties of nanorings are not solely a consequence of the toroidal shape but also a result of traps introduced by puncturing the platelet center.