Distance dependence of excitation energy transfer between spacer-separated conjugated polymer films

We report a systematic study of the scaling with distance of electronic energy transfer between thin films of conjugated polymers separated by a silica spacer. The energy-transfer kinetics were obtained directly from time-resolved photoluminescence measurements and show a 1/ z3 distance dependence of the transfer rate between the excited donor and the acceptor film for z≥8 nm. This is consistent with Förster theory; but at shorter separations the energy transfer is slower than predicted and can be explained by the breakdown of the point-dipole approximation at z∼5 nm. The results are relevant for organic photovoltaics and light-emitting devices, where energy transfer can provide a means of increasing performance

Improving the uniformity of top emitting organic light emitting diodes using a hybrid electrode structure

Funding: The authors are grateful to the Engineering and Physical Sciences Research Council (grant EP/R035164/1) for financial support.Some applications of organic light-emitting diodes (OLEDs) require large area, high light output, and high uniformity. It is difficult to achieve these attributes simultaneously because of voltage drops in the contacts, which cannot easily satisfy high optical transparency and electrical conductivity simultaneously. In large area OLEDs, thin electrodes with high sheet resistance induce voltage drops across the devices, leading to non-uniform distribution of light. However, thick electrodes with low sheet resistance decrease the light output due to low transmittance. To overcome this trade-off, a multilayer hybrid electrode based on Ag (20 nm)/WO3/Ag (20 nm)/WO3 is designed to obtain high electrical conductance with low optical loss. Compared to conventional devices using a single Ag (40 nm) top electrode, there is a considerable increase in the external quantum efficiency (EQE) of the device using this electrode (from 11.5% to 25.5% at 1000 cd m−2), while maintaining similar sheet resistance. In addition, a large area (≈57 cm2) OLED with the hybrid electrode demonstrates a luminance uniformity of 77% as compared to a device using single silver electrode with uniformity of 66%. Therefore, the proposed Ag/WO3/Ag/WO3 hybrid electrode is a promising choice for the fabrication of efficient and uniform large-area OLEDs.Publisher PDFPeer reviewe

The role of the light source in antimicrobial photodynamic therapy

This work was financially supported by the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant (agreement no. 764837) and NCN Opus grant no. 2019/35/B/ST4/03280. We are also grateful to the Engineering and Physical Sciences Research Council of the UK for financial support from grants EP/R511778/1 and EP/L015110/1.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.Publisher PDFPeer reviewe

Exciton-polaron interactions in polyfluorene films with β phase

The authors acknowledge financial support from the European Research Council (grant 321305), Spanish Ministry of Economy Explora Ciencia Project MAT2013-49534-EXP and the Engineering and Physical Sciences Research Council (grants EP/L017008/1 and EP/J009016/1). I.D.W.S. also acknowledges support from a Royal Society Wolfson Research Merit Award.Fluorescence quenching by electric charges is an important loss mechanism in high-brightness organic light emitting diodes (OLEDs) but its effect is difficult to quantify in working devices. Here we combine an electrochemical technique to control the charge density with time-resolved photoluminescence to distinguish between different quenching mechanisms. The material studied was the blue electroluminescent polymer poly(9,9-dioctylfluorenene) with β phase. Our results show that quenching occurs by Förster resonance energy transfer and is mediated by exciton diffusion. We determine the quenching parameters over a wide range of charge concentrations and estimate their impact on the OLED efficiency roll-off at high current density. We find that fluorescence quenching by charges and singlet-triplet exciton annihilation are the two main mechanisms leading to the efficiency roll-off. Our results suggest that hole polarons are not very effective quenchers of singlet excitons which is important for understanding current devices and encouraging for the development of high-brightness OLEDs and lasers.PostprintPeer reviewe

Ultrafast electronic energy transfer beyond the weak coupling limit in a proximal but orthogonal molecular dyad

Electronic energy transfer (EET) from a donor to an acceptor is an important mechanism that controls the light harvesting efficiency in a wide variety of systems, including artificial and natural photosynthesis and contemporary photovoltaic technologies. The detailed mechanism of BET at short distances or large angles between the donor and acceptor is poorly understood. Here the influence of the orientation between the donor and acceptor on EET is explored using a molecule with two nearly perpendicular chromophores. Very fast EET with a time constant of 120 fs is observed, which is at least 40 times faster than the time predicted by Coulombic coupling calculations. Depolarization of the emission signal indicates that the transition dipole rotates through ca. 64 degrees, indicating the near orthogonal nature of the EET event. The rate of EET is found to be similar to structural relaxation rates in the photoexcited oligothiophene donor alone, which suggests that this initial relaxation brings the dyad to a conical intersection where the excitation jumps to the acceptor.PostprintPeer reviewe

Correlating photovoltaic properties of PTB7-Th:PC71BM blend to photophysics and microstructure as a function of thermal annealing

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I.D.W.S. also acknowledges a Royal Society Wolfson Research Merit Award. VS acknowledges support from the Office of Naval Research NDSEG fellowship. Research data supporting this paper is available at doi http://dx.doi.org/10.17630/eadf56f3-8c70-47da-ac6d-67f2d78b3f74Selective optimisation of light harvesting materials and interface properties has brought breakthroughs in power conversion efficiency (11-12 %) of organic photovoltaics (OPVs). However to translate this promising efficiency to economically viable applications, long term stability is a fundamental requirement. A number of degradation pathways, both extrinsic and intrinsic, reduce the long term stability of OPVs. Here, the photovoltaic properties of a highly efficient bulk heterojunction PTB7-Th:PC71BM blend were investigated as a function of thermal annealing. The changes in charge generation, separation, and transport due to thermal annealing were measured and related to changes in the microstructure and photovoltaic performance. A 30 % drop in power conversion efficiency of PTB7-Th:PC71BM blends upon thermal annealing at 150 oC was identified as mainly due to morphological instability induced by strong phase separation of donor and acceptor molecules of the blend films. Based on the insight gained from these investigations, enhanced thermal stability was demonstrated by replacing the PC71BM fullerene acceptor with the non-fullerene acceptor ITIC, for which power conversion efficiency dropped only by 9 % upon thermal annealing at 150 oC.PostprintPeer reviewe

Low-threshold organic laser based on an oligofluorene truxene with low optical losses

A blue-emitting distributed feedback laser based on a star-shaped oligofluorene truxene molecule is presented. The gain, loss, refractive index, and (lack of) anisotropy are measured by amplified spontaneous emission and variable-angle ellipsometry. The waveguide losses are very low for an organic semiconductor gain medium, particularly for a neat film. The results suggest that truxenes are promising for reducing loss, a key parameter in the operation of organic semiconductor lasers. Distributed feedback lasers fabricated from solution by spin-coating show a low lasing threshold of 270 W/cm(2) and broad tunability across 25 nm in the blue part of the spectrum

Efficient indoor p-i-n hybrid perovskite solar cells using low temperature solution processed NiO as hole extraction layers

We are grateful to the European Commission for financial support through the grant, EXCITON 321305. Dr. L.K.Jagadamma acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (European Commission) (MCIF: No. 745776). We are also grateful to EPSRC for an equipment grant (EP/L017008/1).Hybrid perovskites have received tremendous attention due to their exceptional photovoltaic and optoelectronic properties. Among the two widely used perovskite solar cell device architectures of n-i-p and p-i-n, the latter is interesting in terms of its simplicity of fabrication and lower energy input. However this structure mostly uses PEDOT:PSS as a hole transporting layer which can accelerate the perovskite solar cell degradation. Hence the development of stable, inorganic hole extraction layers (HEL), without compromising the simplicity of device fabrication is crucial in this fast-growing photovoltaic field. Here we demonstrate a low temperature (~100 °C) solution - processed and ultrathin (~6 nm) NiO nanoparticle thin films as an efficient HEL for CH3NH3PbI3 based perovskite solar cells. We measure a power conversion efficiency (PCE) of 13.3% on rigid glass substrates and 8.5% on flexible substrates. A comparison with PEDOT:PSS based MAPbI3 solar cells (PCE ~ 7.9%) shows that NiO based solar cells have higher short circuit current density and improved open circuit voltage (1.03 V). Apart from the photovoltaic performance under 1 Sun, the efficient hole extraction property of NiO is demonstrated for indoor lighting as well with a PCE of 23.0% for NiO based CH3NH3PbI2.9Cl0.1 p-i-n solar cells under compact fluorescent lighting. Compared to the perovskite solar cells fabricated on PEDOT:PSS HEL, better shelf-life stability is observed for perovskite solar cells fabricated on NiO HEL. Detailed microstructural and photophysical investigations imply uniform morphology, lower recombination losses, and improved charge transfer properties for CH3NH3PbI3 grown on NiO HEL.PostprintPeer reviewe

A low-cost, portable optical explosive-vapour sensor

This project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under agreement no 284747. IDWS acknowledges a Royal Society Wolfson Research Merit Award. Data supporting this research can be found at http://dx.doi.org/10.17630/5868c89a-7019-4897-9c54-24ccc551a6e6.Humanitarian demining requires a broad range of methodologies and instrumentation for reliable identification of landmines, antipersonnel mines, and other explosive remnants of war (ERWs). Optical sensing methods are ideal for this purpose due to advantages in sensitivity, time-of-response and small form factor. In this work we present a portable photoluminescence-based sensor for nitroaromatic vapours based on the conjugated polymer Super Yellow integrated into an instrument comprising an excitation LED, photodiode, Arduino microprocessor and pumping mechanics for vapour delivery. The instrument was shown to be sensitive to few-ppb concentrations of explosive vapours under laboratory conditions, and responds to simulated buried landmine vapour. The results indicate that a lightweight, easy-to-operate, lowcost and highly-sensitive optical sensor can be readily constructed for landmine and ERW detection in the field, with potential to aid worldwide efforts in landmine mitigation.PostprintPeer reviewe

Patterning multicolor hybrid perovskite films via top-down lithography

This work was (partially) supported by the European Commission under the European Union’s Horizon 2020 research and innovation programme, project MILEDI (grant agreement no. 779373), and by the Engineering and Physical Sciences Research Council (EPSRC) of the UK Grants EP/M025330/1, EP/L017008/1, and EP/M508214/1.Lead-halide perovskites have attracted great attention due to their excellent optoelectronic properties, with rapid progress being made in their performance as light-emitting diodes (LEDs), photodiodes, and solar cells. Demonstrating large scale, high-resolution patterning of perovskites is a key enabling step to unlock their full potential for a range of optoelectronic applications. However, the development of a successful top-down lithography fabrication procedure has so far been hampered by the incompatibility of perovskite films with the solvents used during lithographic processes. Here, we perform a study on the effect of different lithographic solvents on perovskite films and use this insight to develop photolithography and electron-beam lithography procedures for patterning perovskite films. This procedure uses standard resists at low temperatures and achieves micron-scale features with flat tops. Furthermore, we expand this platform to produce arrays of multicolor pixels for potential commercial perovskite LED display applications.PostprintPeer reviewe