Tetrazole and Oxadiazole Derivatives as Thermally Activated Delayed Fluorescence Emitters.

Organic light-emitting diodes (OLEDs) are promising lighting solutions for sustainability and energy efficiency. Incorporating thermally activated delayed fluorescence (TADF) molecules enables OLEDs to achieve internal quantum efficiency (IQE), in principle, up to 100 %; therefore, new classes of promising TADF emitters and modifications of existing ones are sought after. This study explores the TADF emission properties of six designed TADF emitters, examining their photophysical responses using experimental and theoretical methods. The design strategy involves creating six distinct types of a donor-acceptor (D-A) system, where tert-butylcarbazoles are used as donors, while the acceptor component incorporates three different functional groups: nitrile, tetrazole and oxadiazole, with varying electron-withdrawing character. Additionally, the donor-acceptor distance is adjusted using a phenylene spacer, and its influence on TADF functionality is examined. The clear dependency of an additional spacer, inhibiting TADF, could be revealed. Emitters with a direct donor-acceptor connection are demonstrated to exhibit TADF moderate emissive behavior. The analysis emphasizes the impact of charge transfer, singlet-triplet energy gaps (ΔEST), and other microscopic parameters on photophysical rates, permitting TADF. Among the emitters, TCz-CN shows optimal performance as a blue-green emitter with an 88 % photoluminescence quantum yield (PLQY) and fast rate of reversible intersystem crossing of 2×106 s-1 and 1×107 s-1, obtained from time-resolved photoluminescence (TRPL) experiment in PMMA matrix and quantum mechanical calculations, respectively. This comprehensive exploration identifies molecular bases of superior TADF emitters and provides insights for future designs, advancing the optimization of TADF properties in OLEDs.

Enhancement of Amplified Spontaneous Emission by Electric Field in CsPbBr3 Perovskites.

Perovskite gain materials can sustain continuous-wave lasing at room-temperature. A first step toward the unachieved goal of electrically excited lasing would be an improvement in gain when electrical stimulation is added to the optical. However, to date, electrical stimulation supplementing optical has reduced gain performance. We find that amplified spontaneous emission (ASE) in a CsPbBr3 perovskite light-emitting diode (LED) held under invariant subthreshold optical excitation can be turned on/off by the addition/removal of an electric field. A positive bias voltage leads to a factor of 3 reduction in the optical ASE threshold, the cause of which can be attributed to an enhancement of the radiative rate. The slow components (10 s time scale) of the modulation in the photoluminescence and ASE when the voltage is changed suggest that the relocation of mobile ions trigger the increased radiative rate and observed lowering of ASE thresholds.

Annual energy yield of mono- and bifacial silicon heterojunction solar modules with high-index dielectric nanodisk arrays as anti-reflective and light trapping structures.

While various nanophotonic structures applicable to relatively thin crystalline silicon-based solar cells were proposed to ensure effective light in-coupling and light trapping in the absorber, it is of great importance to evaluate their performance on the solar module level under realistic irradiation conditions. Here, we analyze the annual energy yield of relatively thin (crystalline silicon (c-Si) wafer thickness between 5 µm and 80 µm) heterojunction (HJT) solar module architectures when optimized anti-reflective and light trapping titanium dioxide (TiO2) nanodisk square arrays are applied on the front and rear cell interfaces, respectively. Our numerical study shows that upon reducing c-Si wafer thickness down to 5 µm, the relative increase of the annual energy yield can go up to 23.3 %rel and 43.0 %rel for mono- and bifacial solar modules, respectively, when compared to the reference modules with flat optimized anti-reflective coatings of HJT solar cells.

Numerical study on the angular light trapping of the energy yield of organic solar cells with an optical cavity.

A limiting factor in organic solar cells (OSCs) is the incomplete absorption in the thin absorber layer. One concept to enhance absorption is to apply an optical cavity design. In this study, the performance of an OSC with cavity is evaluated. By means of a comprehensive energy yield (EY) model, the improvement is demonstrated by applying realistic sky irradiance, covering a wide range of incidence angles. The relative enhancement in EY for different locations is found to be 11-14% compared to the reference device with an indium tin oxide front electrode. The study highlights the improved angular light absorption as well as the angular robustness of an OSC with cavity.

Tuning Optical Properties by Controlled Aggregation: Electroluminescence Assisted by Thermally-Activated Delayed Fluorescence from Thin Films of Crystalline Chromophores.

Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally-activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal-organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA-TPE (diphenylamine-tetraphenylethylene) chromophore, which is non-emissive in its solvated state due to vibrational quenching. Turning this DPA-TPE into a ditopic linker makes it possible to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, this work reports that the layer-by-layer process used for MOF thin film deposition allows the integration of the TADF-DPA-TPE in a functioning LED device.

Horsefly reactions to black surfaces: attractiveness to male and female tabanids versus surface tilt angle and temperature.

Tabanid flies (Diptera: Tabanidae) are attracted to shiny black targets, prefer warmer hosts against colder ones and generally attack them in sunshine. Horizontally polarised light reflected from surfaces means water for water-seeking male and female tabanids. A shiny black target above the ground, reflecting light with high degrees and various directions of linear polarisation is recognised as a host animal by female tabanids seeking for blood. Since the body of host animals has differently oriented surface parts, the following question arises: How does the attractiveness of a tilted shiny black surface to male and female tabanids depend on the tilt angle δ? Another question relates to the reaction of horseflies to horizontal black test surfaces with respect to their surface temperature. Solar panels, for example, can induce horizontally polarised light and can reach temperatures above 55 °C. How long times would horseflies stay on such hot solar panels? The answer of these questions is important not only in tabanid control, but also in the reduction of polarised light pollution caused by solar panels. To study these questions, we performed field experiments in Hungary in the summer of 2019 with horseflies and black sticky and dry test surfaces. We found that the total number of trapped (male and female) tabanids is highest if the surface is horizontal (δ = 0°), and it is minimal at δ = 75°. The number of trapped males decreases monotonously to zero with increasing δ, while the female catch has a primary maximum and minimum at δ = 0° and δ = 75°, respectively, and a further secondary peak at δ = 90°. Both sexes are strongly attracted to nearly horizontal (0° ≤ δ ≤ 15°) surfaces, and the vertical surface is also very attractive but only for females. The numbers of touchdowns and landings of tabanids are practically independent of the surface temperature T. The time period of tabanids spent on the shiny black horizontal surface decreases with increasing T so that above 58 °C tabanids spent no longer than 1 s on the surface. The horizontally polarised light reflected from solar panels attracts aquatic insects. This attraction is adverse, if the lured insects lay their eggs onto the black surface and/or cannot escape from the polarised signal and perish due to dehydration. Using polarotactic horseflies as indicator insects in our field experiment, we determined the magnitude of polarised light pollution (being proportional to the visual attractiveness to tabanids) of smooth black oblique surfaces as functions of δ and T.

Microlens arrays with adjustable aspect ratio fabricated by electrowetting and their application to correlated color temperature tunable light-emitting diodes.

We develop a facile, fast, and cost-effective method based on the electrowetting effect to fabricate concave microlens arrays (MLA) with a tunable height-to-radius ratio, namely aspect ratio (AR). The electric parameters including voltage and frequency are demonstrated to play an important role in the MLA forming process. With the optimized frequency of 5 Hz, the AR of MLA are tuned from 0.057 to 0.693 for an increasing voltage from 0 V to 180 V. The optical properties of the MLA, including their transmittance and light diffusion capability, are investigated by spectroscopic measurements and ray-tracing simulations. We show that the overall transmittance can be maintained above around 90% over the whole visible range, and that an AR exceeding 0.366 is required to sufficiently broaden the transmitted light angular distribution. These properties enable to apply the developed MLA films to correlated-color-temperature (CCT)-tunable light-emitting-diodes (LEDs) to enhance their angular color uniformity (ACU). Our results show that the ACU of CCT-tunable LEDs is significantly improved while preserving almost the same lumen output, and that the MLA with the highest AR exhibits the best ACU performance.

Methodology of energy yield modelling of perovskite-based multi-junction photovoltaics.

Energy yield (EY) modelling is an indispensable tool to minimize payback time of emerging perovskite-based multi-junction photovoltaics (PV) but it relies on many assumptions about device architecture and environmental conditions. Here, we propose a comprehensive framework that enables rapid simulation of complex architectures of perovskite-based multi-junction PV and detailed calculation of their power output under realistic irradiation conditions in various climatic zones. Applying the framework to perovskite/silicon multi-junction solar modules, we showcase the impact of tracking on energy losses arising from spectral variations. Moreover, we demonstrate the strong dependency of the EY of bifacial multi-junction solar modules on the albedo.

Inkjet-printed perovskite distributed feedback lasers.

We report on digitally printed distributed feedback lasers on flexible polyethylene terephthalate substrates based on methylammonium lead iodide perovskite gain material. The perovskite lasers are printed with a digital drop-on-demand inkjet printer, providing full freedom in the shape and design of the gain layer. We show that adjusting the perovskite ink increases the potential processing window and decreases the surface roughness of the active layer to less than 7 nm, which is essential for low lasing thresholds. Prototype inkjet-printed perovskite lasers processed on top of nanopatterned rigid as well as flexible substrates are demonstrated. Optimized perovskite gain layers printed on PET substrates demonstrated lasing and showed a linewidth of 0.4 nm and a lasing threshold of 270 kW/cm2. In addition, printing of a distinct shape shows a high level of uniformity, demonstrated by a low spatial resolved full width half maximum variation over the whole printing area. These results reveal the possibilities of digital printed perovskite layers towards large-scale and low-cost laser applications of arbitrary shape.

Cloaking of metal grid electrodes on Lambertian emitters by free-form refractive surfaces.

We discuss invisibility cloaking of metal grid electrodes on Lambertian light emitters by using dielectric free-form surfaces. We show that cloaking can be ideal in geometrical optics for all viewing directions if reflections at the dielectric-air interface are negligible. We also present corresponding white-light proof-of-principle experiments that demonstrate close-to-ideal cloaking for a wide range of viewing angles. Remaining imperfections are analyzed by ray-tracing calculations. The concept can potentially be used to enhance the luminance homogeneity of large-area organic light-emitting diodes.

Substrate-Independent Surface Energy Tuning via Siloxane Treatment for Printed Electronics.

Digital printing enables solution processing of functional materials and opens a new route to fabricate low-cost electronic devices. One crucial parameter that affects the wettability of inks for all printing techniques is the surface free energy (SFE) of the substrate. Siloxanes, with their huge variety of side chains and their ability to form self-assembled monolayers, offer exhaustive control of the substrate SFE from hydrophilic to hydrophobic. Thus, siloxane treatment is a suitable approach to adjust the substrate conditions to the desired ink, instead of optimizing the ink to an arbitrary substrate. In this work, the influence of different fluorinated and nonfluorinated siloxanes on the SFE of different substrates, such as polymers, glasses, and metals, are examined. By mixing several siloxanes, we demonstrate the fine tuning of the surface energy. The polar and dispersive components of the SFE are determined by the Owens-Wendt-Rabel-Kaelble (OWRK) method. Furthermore, the impact of the siloxanes and therefore the SFE on the pinning of droplets and wet films are assessed via dynamic contact angle measurements. SFE-optimized substrates enable tailoring the resolution of inkjet printed silver structures. A nanoparticulate silver ink was used for printing single drops, lines, and source-drain electrodes for transistors. These were examined in terms of diameter, edge quality, and functionality. We show that by adjusting the SFE of an arbitrary substrate, the printed resolution is substantially increased by minimizing the printed drop size by up to 70%.

3D whispering-gallery-mode microlasers by direct laser writing and subsequent soft nanoimprint lithography.

We demonstrate the realization of 3D whispering-gallery-mode (WGM) microlasers by direct laser writing (DLW) and their replication by nanoimprint lithography using a soft mold technique ("soft NIL"). The combination of DLW as a method for rapid prototyping and soft NIL offers a fast track towards large scale fabrication of 3D passive and active optical components applicable to a wide variety of materials. A performance analysis shows that surface-scattering-limited Q-factors of replicated resonators as high as 1×105 at 635 nm can be achieved with this process combination. Lasing in the replicated WGM resonators is demonstrated by the incorporation of laser dyes in the target material. Low lasing thresholds in the order of 15 kW/cm2 are obtained under ns-pulsed excitation.

Lab-on-Chip, Surface-Enhanced Raman Analysis by Aerosol Jet Printing and Roll-to-Roll Hot Embossing.

Surface-enhanced Raman spectroscopy (SERS) combines the high specificity of Raman scattering with high sensitivity due to an enhancement of the electromagnetic field by metallic nanostructures. However, the tyical fabrication methods of SERS substrates suffer from low throughput and therefore high costs. Furthermore, point-of-care applications require the investigation of liquid solutions and thus the integration of the SERS substrate in a microfluidic chip. We present a roll-to-roll fabrication approach for microfluidics with integrated, highly efficient, surface-enhanced Raman scattering structures. Microfluidic channels are formed using roll-to-roll hot embossing in polystyrene foil. Aerosol jet printing of a gold nanoparticle ink is utilized to manufacture highly efficient, homogeneous, and reproducible SERS structures. The modified channels are sealed with a solvent-free, roll-to-roll, thermal bonding process. In continuous flow measurements, these chips overcome time-consuming incubation protocols and the poor reproducibility of SERS experiments often caused by inhomogeneous drying of the analyte. In the present study, we explore the influence of the printing process on the homogeneity and the enhancement of the SERS structures. The feasibility of aerosol-jet-modified microfluidic channels for highly sensitive SERS detection is demonstrated by using solutions with different concentrations of Rhodamine 6G and adenosine. The printed areas provide homogeneous enhancement factors of ~4 × 106. Our work shows a way towards the low-cost production of tailor-made, SERS-enabled, label-free, lab-on- chip systems for bioanalysis.

Light scattering by oblate particles near planar interfaces: on the validity of the T-matrix approach.

We investigate the T-matrix approach for the simulation of light scattering by an oblate particle near a planar interface. Its validity has been in question if the interface intersects the particle's circumscribing sphere, where the spherical wave expansion of the scattered field can diverge. However, the plane wave expansion of the scattered field converges everywhere below the particle, and in particular at the planar interface. We demonstrate that the particle-interface scattering interaction is correctly accounted for through a plane wave expansion in combination with Fresnel reflection at the planar interface. We present an in-depth analysis of the involved convergence mechanisms, which are governed by the transformation properties between spherical and plane waves. The method is illustrated with the cases of spherical and oblate spheroidal nanoparticles near a perfectly conducting interface, and its accuracy is demonstrated for different scatterer arrangements and materials.

Efficient evaluation of Sommerfeld integrals for the optical simulation of many scattering particles in planarly layered media.

A strategy for the efficient numerical evaluation of Sommerfeld integrals in the context of electromagnetic scattering at particles embedded in a plane parallel layer system is presented. The scheme relies on a lookup-table approach in combination with an asymptotic approximation of the Bessel function in order to enable the use of fast Fourier transformation. Accuracy of the algorithm is enhanced by means of singularity extraction and a novel technique to treat the integrand at small arguments. For short particle distances, this method is accomplished by a slower but more robust direct integration along a deflected contour. As an example, we investigate enhanced light extraction from an organic light-emitting diode by optical scattering particles. The calculations are discussed with respect to accuracy and computing time. By means of the present strategy, an accurate evaluation of the scattered field for several thousand wavelength scale particles can be achieved within a few hours on a conventional workstation computer.

Single-pass and omniangle light extraction from light-emitting diodes using transformation optics.

We present a light-extraction approach allowing for single-pass and omniangle outcoupling of light from light-emitting diodes (LED). By using transformation optics, we perceive a feasible graded-index structure that is a transition from the LED exit facet to a low refractive index region with expanded space that represents air. Apart from the material dispersion of the constituents, our approach is wavelength independent. The suggested extractor is geometrically compact with size parameters comparable to the width of an LED and therefore well adapted for pixelated LEDs. A beam-expanding functionality is possible while fully preserving the outcoupling efficiency by applying index and geometry truncation.

A biphasic mercury-ion sensor: exploiting microfluidics to make simple anilines competitive ligands.

Combining the molecular wire effect with a biphasic sensing approach (analyte in water, sensor-dye in 2-methyltetrahydrofuran) and a microfluidic flow setup leads to the construction of a mercury-sensitive module. We so instantaneously detect Hg(2+) ions in water at a 500 µM concentration. The sensor, conjugated non-water soluble polymer 1 (XFPF), merely supports dibutylaniline substituents as binding units. Yet, selective and sensitive detection of Hg(2+) -ions is achieved in water. The enhancement in sensory response, when comparing the reference compound 2 to that of 1 in a biphasic system in a microfluidic chip is >10(3) . By manipulation of the structure of 1, further powerful sensor systems should be easily achieved.

Dipolar SAMs Reduce Charge Carrier Injection Barriers in n-Channel Organic Field Effect Transistors.

In this work we examine small conjugated molecules bearing a thiol headgroup as self assembled monolayers (SAM). Functional groups in the SAM-active molecule shift the work function of gold to n-channel semiconductor regimes and improve the wettability of the surface. We examine the effect of the presence of methylene linkers on the orientation of the molecule within the SAM. 3,4,5-Trimethoxythiophenol (TMP-SH) and 3,4,5-trimethoxybenzylthiol (TMP-CH2-SH) were first subjected to computational analysis, predicting work function shifts of -430 and -310 meV. Contact angle measurements show an increase in the wetting envelope compared to that of pristine gold. Infrared (IR) measurements show tilt angles of 22 and 63°, with the methylene-linked molecule (TMP-CH2-SH) attaining a flatter orientation. The actual work function shift as measured with photoemission spectroscopy (XPS/UPS) is even larger, -600 and -430 meV, respectively. The contact resistance between gold electrodes and poly[N,N'-bis(2-octyldodecyl)-naphthalene-1,4:5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) (Polyera Aktive Ink, N2200) in n-type OFETs is demonstrated to decrease by 3 orders of magnitude due to the use of TMP-SH and TMP-CH2-SH. The effective mobility was enhanced by two orders of magnitude, significantly decreasing the contact resistance to match the mobilities reported for N2200 with optimized electrodes.

Soluble diazaiptycenes: materials for solution-processed organic electronics.

The synthesis and characterization of soluble azaiptycenes is reported. Optical and physical properties were studied and compared with those of the structurally consanguine azaacenes. Electrochemical experiments and quantum-chemical calculations revealed the electronic structure of the iptycene derivatives. Their crystallization behavior was examined. A highly fluorescent amorphous diazatetracene derivative was integrated into a simple organic light-emitting diode, showing enhanced performance compared with that of previously reported, structurally similar tetracenes.

Light emission, light detection and strain sensing with nanocrystalline graphene.

Graphene is of increasing interest for optoelectronic applications exploiting light detection, light emission and light modulation. Intrinsically, the light-matter interaction in graphene is of a broadband type. However, by integrating graphene into optical micro-cavities narrow-band light emitters and detectors have also been demonstrated. These devices benefit from the transparency, conductivity and processability of the atomically thin material. To this end, we explore in this work the feasibility of replacing graphene with nanocrystalline graphene, a material which can be grown on dielectric surfaces without catalyst by graphitization of polymeric films. We have studied the formation of nanocrystalline graphene on various substrates and under different graphitization conditions. The samples were characterized by resistance, optical transmission, Raman and x-ray photoelectron spectroscopy, atomic force microscopy and electron microscopy measurements. The conducting and transparent wafer-scale material with nanometer grain size was also patterned and integrated into devices for studying light-matter interaction. The measurements show that nanocrystalline graphene can be exploited as an incandescent emitter and bolometric detector similar to crystalline graphene. Moreover the material exhibits piezoresistive behavior which makes nanocrystalline graphene interesting for transparent strain sensors.