Electrically driven organic laser using integrated OLED pumping.

Organic semiconductors are carbon-based materials that combine optoelectronic properties with simple fabrication and the scope for tuning by changing their chemical structure1-3. They have been successfully used to make organic light-emitting diodes2,4,5 (OLEDs, now widely found in mobile phone displays and televisions), solar cells1, transistors6 and sensors7. However, making electrically driven organic semiconductor lasers is very challenging8,9. It is difficult because organic semiconductors typically support only low current densities, suffer substantial absorption from injected charges and triplets, and have additional losses due to contacts10,11. In short, injecting charges into the gain medium leads to intolerable losses. Here we take an alternative approach in which charge injection and lasing are spatially separated, thereby greatly reducing losses. We achieve this by developing an integrated device structure that efficiently couples an OLED, with exceptionally high internal-light generation, with a polymer distributed feedback laser. Under the electrical driving of the integrated structure, we observe a threshold in light output versus drive current, with a narrow emission spectrum and the formation of a beam above the threshold. These observations confirm lasing. Our results provide an organic electronic device that has not been previously demonstrated, and show that indirect electrical pumping by an OLED is a very effective way of realizing an electrically driven organic semiconductor laser. This provides an approach to visible lasers that could see applications in spectroscopy, metrology and sensing.

The role of the light source in antimicrobial photodynamic therapy.

Antimicrobial photodynamic therapy (APDT) is a promising approach to fight the growing problem of antimicrobial resistance that threatens health care, food security and agriculture. APDT uses light to excite a light-activated chemical (photosensitiser), leading to the generation of reactive oxygen species (ROS). Many APDT studies confirm its efficacy in vitro and in vivo against bacteria, fungi, viruses and parasites. However, the development of the field is focused on exploring potential targets and developing new photosensitisers. The role of light, a crucial element for ROS production, has been neglected. What are the main parameters essential for effective photosensitiser activation? Does an optimal light radiant exposure exist? And finally, which light source is best? Many reports have described the promising antibacterial effects of APDT in vitro, however, its application in vivo, especially in clinical settings remains very limited. The restricted availability may partially be due to a lack of standard conditions or protocols, arising from the diversity of selected photosensitising agents (PS), variable testing conditions including light sources used for PS activation and methods of measuring anti-bacterial activity and their effectiveness in treating bacterial infections. We thus sought to systematically review and examine the evidence from existing studies on APDT associated with the light source used. We show how the reduction of pathogens depends on the light source applied, radiant exposure and irradiance of light used, and type of pathogen, and so critically appraise the current state of development of APDT and areas to be addressed in future studies. We anticipate that further standardisation of the experimental conditions will help the field advance, and suggest key optical and biological parameters that should be reported in all APDT studies. More in vivo and clinical studies are needed and are expected to be facilitated by advances in light sources, leading to APDT becoming a sustainable, alternative therapeutic option for bacterial and other microbial infections in the future.

Dominance of photo over chromatic acclimation strategies by habitat-forming mesophotic red algae.

Red coralline algae are the deepest living macroalgae, capable of creating spatially complex reefs from the intertidal to 100+ m depth with global ecological and biogeochemical significance. How these algae maintain photosynthetic function under increasingly limiting light intensity and spectral availability is key to explaining their large depth distribution. Here, we investigated the photo- and chromatic acclimation and morphological change of free-living red coralline algae towards mesophotic depths in the Fernando do Noronha archipelago, Brazil. From 13 to 86 m depth, thalli tended to become smaller and less complex. We observed a dominance of the photo-acclimatory response, characterized by an increase in photosynthetic efficiency and a decrease in maximum electron transport rate. Chromatic acclimation was generally stable across the euphotic-mesophotic transition with no clear depth trend. Taxonomic comparisons suggest these photosynthetic strategies are conserved to at least the Order level. Light saturation necessitated the use of photoprotection to 65 m depth, while optimal light levels were met at 86 m. Changes to the light environment (e.g. reduced water clarity) due to human activities therefore places these mesophotic algae at risk of light limitation, necessitating the importance of maintaining good water quality for the conservation and protection of mesophotic habitats.

Enhanced Photoluminescence and Reduced Dimensionality via Vacancy Ordering in a 10H Halide Perovskite.

Vacancy-ordered halide perovskites have received great interest in optoelectronic applications. In this work, we report the novel inorganic halide Cs10MnSb6Cl30 with a distinctive 10H (10-layer hexagonal) perovskite polytype structure with (hcccc)2 stacking. Cs10MnSb6Cl30 has 30% B-site vacancies ordered at both corner- and face-sharing sites, resulting in [MnSb6Cl30]10-n columns, i.e., a reduction of octahedral connectivity to 1D. This results in enhanced photoluminescence in comparison to the previously reported 25% vacancy-ordered 3C polytype Cs4MnSb2Cl12 with 2D connectivity. This demonstrates not only the existence of the 10H perovskite structure in halides but also demonstrates the degree of B-site deficiency and stacking sequence variation as a direction to tune the optical properties of perovskite polytypes via vacancy rearrangements.

Red algae acclimate to low light by modifying phycobilisome composition to maintain efficient light harvesting.

BACKGROUND: Despite a global prevalence of photosynthetic organisms in the ocean's mesophotic zone (30-200+ m depth), the mechanisms that enable photosynthesis to proceed in this low light environment are poorly defined. Red coralline algae are the deepest known marine benthic macroalgae - here we investigated the light harvesting mechanism and mesophotic acclimatory response of the red coralline alga Lithothamnion glaciale. RESULTS: Following initial absorption by phycourobilin and phycoerythrobilin in phycoerythrin, energy was transferred from the phycobilisome to photosystems I and II within 120 ps. This enabled delivery of 94% of excitations to reaction centres. Low light intensity, and to a lesser extent a mesophotic spectrum, caused significant acclimatory change in chromophores and biliproteins, including a 10% increase in phycoerythrin light harvesting capacity and a 20% reduction in chlorophyll-a concentration and photon requirements for photosystems I and II. The rate of energy transfer remained consistent across experimental treatments, indicating an acclimatory response that maintains energy transfer. CONCLUSIONS: Our results demonstrate that responsive light harvesting by phycobilisomes and photosystem functional acclimation are key to red algal success in the mesophotic zone.

Merging Boron and Carbonyl based MR-TADF Emitter Designs to Achieve High Performance Pure Blue OLEDs.

Multiresonant thermally activated delayed fluorescence (MR-TADF) compounds are attractive as emitters for organic light-emitting diodes (OLEDs) as they can simultaneously harvest both singlet and triplet excitons to produce light in the device and show very narrow emission spectra, which translates to excellent color purity. Here, we report the first example of an MR-TADF emitter (DOBDiKTa) that fuses together fragments from the two major classes of MR-TADF compounds, those containing boron (DOBNA) and those containing carbonyl groups (DiKTa) as acceptor fragments in the MR-TADF skeleton. The resulting molecular design, this compound shows desirable narrowband pure blue emission and efficient TADF character. The co-host OLED with DOBDiKTa as the emitter showed a maximum external quantum efficiency (EQEmax ) of 17.4 %, an efficiency roll-off of 32 % at 100 cd m-2 , and Commission Internationale de l'Éclairage (CIE) coordinates of (0.14, 0.12). Compared to DOBNA and DiKTa, DOBDiKTa shows higher device efficiency with reduced efficiency roll-off while maintaining a high color purity, which demonstrates the promise of the proposed molecular design.

A Deep-Blue-Emitting Heteroatom-Doped MR-TADF Nonacene for High-Performance Organic Light-Emitting Diodes.

We present a p- and n-doped nonacene compound, NOBNacene, that represents a rare example of a linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emitter. This compound shows efficient narrow deep blue emission, with a λPL of 410 nm, full width at half maximum, FWHM, of 38 nm, photoluminescence quantum yield, ΦPL of 71 %, and a delayed lifetime, τd of 1.18 ms in 1.5 wt % TSPO1 thin film. The organic light-emitting diode (OLED) using this compound as the emitter shows a comparable electroluminescence spectrum peaked at 409 nm (FWHM=37 nm) and a maximum external quantum efficiency (EQEmax ) of 8.5 % at Commission Internationale de l'Éclairage (CIE) coordinates of (0.173, 0.055). The EQEmax values were increased to 11.2 % at 3 wt % doping of the emitter within the emissive layer of the device. At this concentration, the electroluminescence spectrum broadened slightly, leading to CIE coordinates of (0.176, 0.068).

Ecosystem engineer morphological traits and taxon identity shape biodiversity across the euphotic-mesophotic transition.

The euphotic-mesophotic transition is characterized by dramatic changes in environmental conditions, which can significantly alter the functioning of ecosystem engineers and the structure of their associated communities. However, the drivers of biodiversity change across the euphotic-mesophotic transition remain unclear. Here, we investigated the mechanisms affecting the biodiversity-supporting potential of free-living red coralline algae-globally important habitat creators-towards mesophotic depths. Across a 73 m depth gradient, we observed a general decline in macrofaunal biodiversity (fauna abundance, taxon richness and alpha diversity), but an increase in beta-diversity (i.e. variation between assemblages) at the deepest site (86 m depth, where light levels were less than 1% surface irradiance). We identified a gradient in abundance decline rather than distinct ecological shifts, driven by a complex interaction between declining light availability, declining size of the coralline algal host individuals and a changing host taxonomy. However, despite abundance declines, high between-assemblage variability at deeper depths allowed biodiversity-supporting potential to be maintained, highlighting their importance as coastal refugia.

Highly Efficient Green and Red Narrowband Emissive Organic Light-Emitting Diodes Employing Multi-Resonant Thermally Activated Delayed Fluorescence Emitters.

Herein, we demonstrate how judicious selection of the donor decorating a central multi-resonant thermally activated delayed fluorescence (MR-TADF) core based on DiKTa can lead to very high-performance OLEDs. By decorating the DiKTa core with triphenylamine (TPA) and diphenylamine (DPA), 3TPA-DiKTa and 3DPA-DiKTa exhibit bright, narrowband green and red emission in doped films, respectively. The OLEDs based on these emitters showed record-high performance for this family of emitters with maximum external quantum efficiencies (EQEmax ) of 30.8 % for 3TPA-DiKTa at λEL of 551 nm and 16.7 % for 3DPA-DiKTa at λEL =613 nm. The efficiency roll-off in the OLEDs was improved significantly by using 4CzIPN as an assistant dopant in hyperfluorescence (HF) devices. The outstanding device performance has been attributed to preferential horizontal orientation of the transition dipole moments of 3TPA-DiKTa and 3DPA-DiKTa.

Explosives detection by swabbing for improvised explosive devices.

Swabs taken from the surface of a suspicious object are a standard method of identifying a concealed explosive device in security-conscious locations like airports. In this paper we demonstrate a sensitive method to collect and detect trace explosive residues from improvised explosive devices using swabs and an optical sensor element. Swabs coated with a commercial fluoropolymer are used to collect material and are subsequently heated to thermally desorb the explosives, causing the quenching of light emission from a thin film luminescent sensor. We report the sorption and desorption characteristics of swabs loaded with 2,4-DNT tested with Super Yellow fluorescent sensors in a laboratory setting, with detection that is up to three orders of magnitude more sensitive than standard colorimetric tests. The method was then applied in field tests with raw military-grade explosives TNT, PETN and RDX, on various objects containing the explosives, and post-blast craters. We show for the first time results using organic semiconductors to detect sub-milligram amounts of explosive sorbed onto a substrate from real explosives in the field, giving a promising new approach for IED detection.

Exact Solution of Kinetic Analysis for Thermally Activated Delayed Fluorescence Materials.

The photophysical analysis of thermally activated delayed fluorescence (TADF) materials has become instrumental for providing insights into their stability and performance, which is not only relevant for organic light-emitting diodes but also for other applications such as sensing, imaging, and photocatalysis. Thus, a deeper understanding of the photophysics underpinning the TADF mechanism is required to push materials design further. Previously reported analyses in the literature of the kinetics of the various processes occurring in a TADF material rely on several a priori assumptions to estimate the rate constants for forward and reverse intersystem crossing. In this report, we demonstrate a method to determine these rate constants using a three-state model together with a steady-state approximation and, importantly, no additional assumptions. Further, we derive the exact rate equations, greatly facilitating a comparison of the TADF properties of structurally diverse emitters and providing a comprehensive understanding of the photophysics of these systems.

Biogenic Gold Nanoparticles Decrease Methylene Blue Photobleaching and Enhance Antimicrobial Photodynamic Therapy.

Antibiotic resistance is a growing concern that is driving the exploration of alternative ways of killing bacteria. Here we show that gold nanoparticles synthesized by the mycelium of Mucor plumbeus are an effective medium for antimicrobial photodynamic therapy (PDT). These particles are spherical in shape, uniformly distributed without any significant agglomeration, and show a single plasmon band at 522-523 nm. The nanoparticle sizes range from 13 to 25 nm, and possess an average size of 17 ± 4 nm. In PDT, light (from a source consisting of nine LEDs with a peak wavelength of 640 nm and FWMH 20 nm arranged in a 3 × 3 array), a photosensitiser (methylene blue), and oxygen are used to kill undesired cells. We show that the biogenic nanoparticles enhance the effectiveness of the photosensitiser, methylene blue, and so can be used to kill both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria. The enhanced effectiveness means that we could kill these bacteria with a simple, small LED-based light source. We show that the biogenic gold nanoparticles prevent fast photobleaching, thereby enhancing the photoactivity of the methylene blue (MB) molecules and their bactericidal effect.

Using the Mechanical Bond to Tune the Performance of a Thermally Activated Delayed Fluorescence Emitter*.

We report the characterization of rotaxanes based on a carbazole-benzophenone thermally activated delayed fluorescence luminophore. We find that the mechanical bond leads to an improvement in key photophysical properties of the emitter, notably an increase in photoluminescence quantum yield and a decrease in the energy difference between singlet and triplet states, as well as fine tuning of the emission wavelength, a feat that is difficult to achieve when using covalently bound substituents. Computational simulations, supported by X-ray crystallography, suggest that this tuning of properties occurs due to weak interactions between the axle and the macrocycle that are enforced by the mechanical bond. This work highlights the benefits of using the mechanical bond to refine existing luminophores, providing a new avenue for emitter optimization that can ultimately increase the performance of these molecules.

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode.

In this work we showcase the emitter DICzTRZ in which we employed a twin-emitter design of our previously reported material, ICzTRZ. This new system presented a red-shifted emission at 488 nm compared to that of ICzTRZ at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt % CzSi film versus 63.3% for ICzTRZ. The emitter was then incorporated within a solution-processed organic light-emitting diode that showed a maximum external quantum efficiency of 8.4%, with Commission Internationale de l'Éclairage coordinate of (0.22, 0.47), at 1 mA cm-2.

Design of Linear and Star-Shaped Macromolecular Organic Semiconductors for Photonic Applications.

One of the most desirable and advantageous attributes of organic materials chemistry is the ability to tune the molecular structure to achieve targeted physical properties. This can be performed to achieve specific values for the ionization potential or electron affinity of the material, the absorption and emission characteristics, charge transport properties, phase behavior, solubility, processability, and many other properties, which in turn can help push the limits of performance in organic semiconductor devices. A striking example is the ability to make subtle structural changes to a conjugated macromolecule to vary the absorption and emission properties of a generic chemical structure. In this Account, we demonstrate that target properties for specific photonic applications can be achieved from different types of semiconductor structures, namely, monodisperse star-shaped molecules, complex linear macromolecules, and conjugated polymers. The most appropriate material for any single application inevitably demands consideration of a trade-off of various properties; in this Account, we focus on applications such as organic lasers, electrogenerated chemiluminescence, hybrid light emitting diodes, and visible light communications. In terms of synthesis, atom and step economies are also important. The star-shaped structures consist of a core unit with 3 or 4 functional connection points, to which can be attached conjugated oligomers of varying length and composition. This strategy follows a convergent synthetic pathway and allows the isolation of target macromolecules in good yield, high purity, and absolute reproducibility. It is a versatile approach, providing a wide choice of constituent molecular units and therefore varying properties, while the products share many of the desirable attributes of polymers. Constructing linear conjugated macromolecules with multifunctionality can lead to complex synthetic routes and lower atom and step economies, inferior processability, and lower thermal or chemical stability, but these materials can be designed to provide a range of different targeted physical properties. Conventional conjugated polymers, as the third type of structure, often feature so-called "champion" properties. The synthetic challenge is mainly concerned with monomer synthesis, but the final polymerization sequence can be hard to control, leading to variable molecular weights and polydispersities and some degree of inconsistency in the properties of the same material between different synthetic batches. If a champion characteristic persists between samples, then the variation of other properties between batches can be tolerable, depending on the target application. In the case of polymers, we have chosen to study PPV-type polymers with bulky side groups that provide protection of their conjugated backbone from π-π stacking interactions. These polymers exhibit high photoluminescence quantum yields (PLQYs) in films and short radiative lifetimes and are an important benchmark to monodisperse star-shaped systems in terms of different absorption/emission regions. This Account therefore outlines the advantages and special features of monodisperse star-shaped macromolecules for photonic applications but also considers the two alternative classes of materials and highlights the pros and cons of each class of conjugated structure.

Luminescent Dinuclear Copper(I) Complexes Bearing an Imidazolylpyrimidine Bridging Ligand.

The synthesis and photophysical study of two dinuclear copper(I) complexes bearing a 2-(1H-imidazol-2-yl)pyrimidine bridging ligand are described. The tetrahedral coordination sphere of each copper center is completed through the use of a bulky bis(phosphine) ligand, either DPEphos or Xantphos. Temperature-dependent photophysical studies demonstrated emission through a combination of phosphorescence and thermally activated delayed fluorescence for both complexes, and an intense emission (ΦPL = 46%) was observed for a crystalline sample of one of the complexes reported. The photophysics of these two complexes is very sensitive to the environment. Two pseudopolymorphs of one of the dinuclear complexes were isolated, with distinct photophysics. The emission color of the crystals can be changed by grinding, and the differences in their photophysics before and after grinding are discussed.

Organic semiconductors for visible light communications.

Organic semiconductors are an important class of optoelectronic material that are widely studied because of the scope for tuning their properties by tuning their chemical structure, and simple fabrication to make flexible films and devices. Although most effort has focused on developing displays and lighting from these materials, their distinctive properties also make them of interest for visible light communications (VLCs). This article explains how their properties make them suitable for VLC and reviews the main uses that have been explored. On the transmitter side, record white VLC communication has been achieved by using organic semiconductors as colour converters, while direct modulation of organic light-emitting diodes is also possible and could be of interest for display-to-display communication. On the receiver side, organic solar cells can be used to harvest power and data simultaneously, and fluorescent antennas enable fast and sensitive receivers with large field of view. This article is part of the theme issue 'Optical wireless communication'.

Influence of Sulfur Oxidation State and Substituents on Sulfur-Bridged Luminescent Copper(I) Complexes Showing Thermally Activated Delayed Fluorescence.

Copper(I) complexes are seen as more sustainable alternatives to those containing metal ions such as iridium and platinum for emitting devices. Copper(I) complexes have the ability to radiatively decay via a thermally activated delayed fluorescence (TADF) pathway, leading to higher photoluminescent quantum yields. In this work we discuss six new heteroleptic Cu(I) complexes of the diphosphine-diimine motif. The diphosphine ligands employed are (oxidi-2,1-phenylene)bis(diphenylphosphine) (DPEPhos), and the diimine fragments are sulfur-bridged dipyridyl ligands (DPS) which are functionalized at the 6,6'-positions of the pyridyl rings (R = H, Me, Ph) and have varying oxidation states at the bridging sulfur atom (S, SO2). The proton (Cu-DPS, Cu-DPSO2) and phenyl (Cu-Ph-DPS, Cu-Ph-DPSO2) substituted species are found to form monometallic complexes, while those with methyl substitution (Cu-Me-DPS, Cu-Me-DPSO2) are found to have a "Goldilocks" degree of steric bulk leading to bimetallic species. All six Cu(I) complexes show emission in the solid state, with the photophysical properties characterized by low temperature steady-state and time-resolved spectroscopies and variable temperature time-correlated single photon counting. Cu-DPS, Cu-DPSO2, Cu-Me-DPS, Cu-Me-DPSO2, and Cu-Ph-DPSO2 were shown to emit via a TADF mechanism, while Cu-Ph-DPS showed photoluminescence properties consistent with triplet ligand-centered (3LC) emission.

Light Harvesting for Organic Photovoltaics.

The field of organic photovoltaics has developed rapidly over the last 2 decades, and small solar cells with power conversion efficiencies of 13% have been demonstrated. Light absorbed in the organic layers forms tightly bound excitons that are split into free electrons and holes using heterojunctions of electron donor and acceptor materials, which are then extracted at electrodes to give useful electrical power. This review gives a concise description of the fundamental processes in photovoltaic devices, with the main emphasis on the characterization of energy transfer and its role in dictating device architecture, including multilayer planar heterojunctions, and on the factors that impact free carrier generation from dissociated excitons. We briefly discuss harvesting of triplet excitons, which now attracts substantial interest when used in conjunction with singlet fission. Finally, we introduce the techniques used by researchers for characterization and engineering of bulk heterojunctions to realize large photocurrents, and examine the formed morphology in three prototypical blends.

Synthesis and optoelectronic properties of benzoquinone-based donor-acceptor compounds.

Herein, we report a mild and efficient palladium-catalyzed C-H functionalization method to synthesize a series of benzoquinone (BQ)-based charge-transfer (CT) derivatives in good yields. The optoelectronic properties of these compounds were explored both theoretically and experimentally and correlations to their structures were identified as a function of the nature and position of the donor group (meta and para) attached to the benzoquinone acceptor. Compound 3, where benzoquinone is para-conjugated to the diphenylamine donor group, exhibited thermally activated delayed fluorescence (TADF) with a biexponential lifetime characterized by a prompt ns component and a delayed component of 353 µs.