Enhanced exciton harvesting in a planar heterojunction organic photovoltaic device by solvent vapor annealing

We thank the European Research Council (ERC) for financial support (EXCITON grant 321305). Data supporting this study is available at https://doi.org/10.17630/0e75f92d-6f8a-41be-ad45-ac6d1d890ee2.The singlet exciton diffusion length was measured in a small molecule electron donor material DR3TBDTT using fluorescence quenching at a planar interface with a cross-linked fullerene derivative. The one-dimensional exciton diffusion length was increased from ~16 to ~24 nm by annealing the film in carbon disulfide solvent vapor. Planar heterojunction solar cells were fabricated using bilayers of these materials and it was found that solvent vapor annealing increased the short circuit current density by 46%. This can be explained by improved exciton harvesting in the annealed bilayer.PostprintPeer reviewe

A BODIPY small molecule as hole transporting material for efficient perovskite solar cells

BODIPY-based materials are well known for their outstanding chemical and photo-stability as well as their ease of synthesis and tunability of their frontier molecular orbitals. These are attractive features for hole transporting materials (HTMs) for perovskite solar cells (PSCs) that could help improve device stability and cost. In this paper, we report the straightforward synthesis of a new BODIPY small molecule, PTZ-PTZ-BDP, functionalised with phenothiazine moieties in both the meso and α positions giving rise to a Y-shaped structure. As estimated by DFT calculations, and confirmed by electrochemical and ambient photoemission spectroscopy studies, PTZ-PTZ-BDP presents appropriate energy levels suitable for its use as a HTM in PSCs. Electrochemical measurements also reveal several redox processes with excellent reversibility. Systematic evaluation of its performance as HTM in n–i–p PSC with and without dopants was conducted and the device parameters compared with commonly used HTMs of spiro-OMeTAD and PTAA. The CH3NH3PbI3 based PSCs incorporating simple solution processed PTZ-PTZ-BDP as HTM demonstrated a champion power conversion efficiency of 14.6%, matched in performance and shelf-life stability to complex and expensive state-of-the-art HTMs, showing that BODIPY based HTMs are a promising direction for perovskite solar cells

Electron-withdrawing group modified carbazolophane donors for deep blue thermally activated delayed fluorescence OLEDs

AKG is grateful to the Royal Society for Newton International Fellowship NF171163. We acknowledge support from the Engineering and Physical Sciences Research Council of the UK (grants EP/P010482/1 and EP/L017008/1). The German Research Foundation (formally Deutsche Forschungsgemeinschaft DFG) in the framework of SFB1176 Cooperative Research Centre “Molecular Structuring of Soft Matter” (CRC1176, A4, B3, C2, C6) and the cluster 3D Matter made to order all funded under Germany's Excellence Strategy 2082/1-390761711 are acknowledged for financial contributions.We report two blue-emitting thermally activated delayed fluorescence (TADF) compounds employing a substituted carbazolophane (Czp) donor (indolo[2.2]paracyclophane). The compounds CNCzpPhTRZ and CF3CzpPhTRZ show emission maxima of 426 nm and 432 nm, respectively, with high photoluminescence quantum yields (ΦPL) of 73% and 80%, respectively. The singlet–triplet energy gap (ΔEST) of both emitters is 0.22 eV, resulting in long-delayed lifetimes of 132 μs for CNCzpPhTRZ and 158 μs for CF3CzpPhTRZ in PPT as the host matrix. Blue organic light-emitting diodes (OLEDs) showed maximum external quantum efficiencies (EQEs) of 7.4% for CNCzpPhTRZ and 11.6% for CF3CzpPhTRZ with electroluminescence maxima of ca. 460 nm.Publisher PDFPeer reviewe

Design of linear and star-shaped macromolecular organic semiconductors for photonic applications

P.J.S. and A.L.K. thank the EPSRC for funding under Grants EP/R03480X/1, EP/P02744X/2, and EP/N009908/2.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.Publisher PDFPeer reviewe

Исследование желаемого образа семьи молодежи, проживающей в больших, средних и малых городах

Funding: EPSRC EP/J01771X, Royal Society Wolfson Research Merit AwardBackground Topical Photodynamic therapy (PDT) is an effective treatment for superficial non-melanoma skin cancers (NMSC) and dysplasia. During PDT light activates the photosensitiser (PpIX), metabolised from a topical pro-drug. A combination of PpIX, light and molecular oxygen results in inflammation and cell death. However, the outcomes of the treatment could be better. Insufficient biosynthesis of PpIX may be one of the causes of incomplete response or recurrence. Measuring surface fluorescence is usually employed as a means of studying PpIX formation. The aim of this work was to develop a device and a method for convenient fluorescence imaging in clinical settings to gather information on PpIX metabolism in healthy skin and NMSC with a view to improving PDT regimes. Methods A handheld fluorescence camera and a time course imaging method was developed and used in healthy volunteers and patients diagnosed with basal cell carcinoma (BCC) and actinic keratosis (AK). The photosensitiser (precursor) creams used were 5-aminolaevulinic acid (ALA; Ameluz®) and methyl aminolevulinate (MAL; Metvix®). Pain was assessed using a visual analogue score immediately after the PDT. Results Fluorescence due to PpIX increases over three hours incubation in healthy skin and in lesional BCC and AK. Distribution of PpIX fluorescence varies between the lesion types and between subjects. There was no significant correlation between PpIX fluorescence characteristics and pro-drug, diagnosis or pain experienced. However, there was a clear dependence on body site. Conclusion The device and the method developed can be used to assess the characteristics of PpIX fluorescence, quantitative analysis and time course. Our findings show that body site influences PpIX fluorescence which we suggest may be due to the difference in skin temperature at different body sites.PostprintPeer reviewe

Ultra-wide coverage VLC system with alignment-free receiver

In this work we present an ultra-wide coverage visible light communication (VLC) system based on a mechanical beam steering system at the transmitter terminal and a fluorescent optical concentrator at the receiver. The transmitter and receiver full field of view (FFOV) are 100° and 120°, respectively. The coverage area of the transmitter system at 2m is 12.5m2 and a data link of 300Mbps has been achieved at this range.Postprin

Non-radiative decay mechanisms in blue phosphorescent iridium(III)complexes

By using phosphorescent emitters, organic light emitting displays can be up to four times more efficient than those of fluorescent materials. Full colour displays based on phosphorescent materials have not been achieved thus far due to the poor efficiency of blue phosphorescent emitters. We show that there is a correlation between non-radiative decay of phosphorescence and vibrational coupling for related blue emissive materials containing similar iridium(III) complex chromophores. The materials had solution photoluminescence quantum yields (PLQYs) of up to 55% at room temperature with Commission Internationale de l’Eclairage co-ordinates of (0.155, 0.16). Stronger vibrational coupling was found to lead to an increased non-radiative decay rate and decreased PLQY. The activation energy for non-radiative decay was found to depend on the environment with the non-radiative decay rate being decreased when the emissive materials were placed in a solid host