Tuning Structural and Optical Properties of Porphyrin-based Hydrogen-Bonded Organic Frameworks by Metal Insertion.

Herein, a simple way of tuning the optical and structural properties of porphyrin-based hydrogen-bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB-5 (p-H8 -TPPA (5,10,15,20-Tetrakis[p-phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu-, Ni-, Pd-, and Zn-GTUB-5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal-induced structural changes, viz., changes in the metal-to-nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu-, Zn-, and Pd- GTUB-5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π- orbitals on the porphyrin linkers, while that of Ni-GTUB-5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal-insertion can be used to optimize HOFs for optoelectronics and small-molecule capture applications.

Analysis and optimization of light outcoupling in OLEDs with external hierarchical textures.

Hierarchical textures (combining 2D periodic large and small micro textures) as an external outcoupling solution for OLEDs have been researched, both experimentally and by optical simulations. For the case of a red bottom emitting OLED, different hierarchical textures were fabricated using laser-based methods and a replication step and applied to the OLED substrate, resulting in an increased light outcoupling. Laboratory-size OLED devices with applied textured foils show a smaller increase in efficiency compared to the final large area devices. The results show that the full exploitation of textured foils in laboratory-size samples is mainly limited by the lateral size of the thin film stack area and by limited light collection area of the measuring equipment. Modeling and simulations are used to further evaluate the full prospective of hierarchical textures in large area OLED devices. Optimization of hierarchical textures is done by simultaneously changing the aspect ratios of the small and large textures and a potential of 57% improvement in EQE compared to devices without applied textures is predicted by simulations. Optimized hierarchical textures show similar outcoupling efficiencies compared to optimized single textures, while on the other hand hierarchical textures require less pronounced features, lower aspect ratios, compared to single textures to achieve the same efficiencies. Hierarchical textures also help in eliminating flat parts that limit outcoupling efficiency. Finally, the limiting factors that prevent higher outcoupling are addressed. We show that the dominant factor is non-ideal reflection from the organic thin film stack due to parasitic absorption. In addition, possible ways to further increase the outcoupling from a thick substrate are indicated.

Conjugation-Induced Thermally Activated Delayed Fluorescence: Photophysics of a Carbazole-Benzophenone Monomer-to-Tetramer Molecular Series.

Materials exhibiting thermally activated delayed fluorescence (TADF) have been extensively explored in the last decade. These emitters have great potential of being used in organic light-emitting diodes because they allow for high quantum efficiencies by utilizing triplet states via reverse intersystem crossing. In small molecules, this is done by spatially separating the highest occupied molecular orbital from the lowest unoccupied molecular orbital, forming an intramolecular charge-transfer (iCT) state and leading to a small energy difference between lowest excited singlet and triplet states (ΔEST). However, in polymer emitters, this is harder to achieve, and typical strategies usually include adding known TADF units as sidechains onto a polymer backbone. In a previous work, we proposed an alternative way to achieve a TADF polymer by repeating a non-TADF unit, polymerizing it via electron-donating carbazole moieties. The extended conjugation on the backbone reduced the ΔEST and allowed for an efficient TADF polymer. In this work, we present a more in-depth study of the shift from a non-TADF monomer to TADF oligomers. The monomer shows non-TADF emission, and we find the delayed emission to be of triplet-triplet annihilation origin. An iCT state is formed already in the dimer, leading to a much more efficient TADF emission. This is confirmed by an almost two-fold increase of photoluminescence quantum yield, a decrease in the delayed luminescence lifetime, and the respective spectral lineshapes of the molecules.

Emissive and charge-generating donor-acceptor interfaces for organic optoelectronics with low voltage losses.

Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes1,2. Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range3,4. In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes5-7. Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons8-11.

Dissecting Tetra-N-phenylbenzidine: Biphenyl as the Origin of Room Temperature Phosphorescence.

Amorphous purely organic thin films are able to show efficient phosphorescence under ambient conditions at room temperature. This opens the perspective to a wide range of new applications, which have attracted lots of interest in the field of material science recently. Therefore, an increasing number of different molecules displaying room temperature phosphorescence (RTP) have already been reported. Whereas the efficiency, the lifetime, or the oxygen sensitivity is frequently discussed, the origin of RTP mainly remains vague. Often, material design rules tend to the development of increasingly complex structures. Here, the well-known tetra-N-phenylbenzidine (TPD), an archetypical material showing highly efficient fluorescence and RTP, is broken down to its fragments. As the complexity of the system decreases with the molecule's size, spectroscopic investigation of this molecular family enables a deeper understanding of the appearance of RTP. With spectral and time-resolved measurements, RTP can be detected for all compounds containing a biphenyl core, with lifetimes up to 0.9 s under inert gas conditions. These findings form the basis of a deeper understanding of the appearance of RTP in organic molecules and therefore allow for a more focused investigation of new materials.

Investigation of Thermally Activated Delayed Fluorescence from a Donor-Acceptor Compound with Time-Resolved Fluorescence and Density Functional Theory Applying an Optimally Tuned Range-Separated Hybrid Functional.

Emitters showing thermally activated delayed fluorescence (TADF) in electroluminescent devices rely on efficient reverse intersystem crossing (rISC) arising from small thermal activation barriers between the lowest excited triplet and singlet manifolds. A small donor-acceptor compound consisting of a demethylacridine donor and a methylbenzoate acceptor group is used as a model TADF emitter. The spectroscopic signatures of this system are characterized using a combination of photoluminescence and photoluminescence excitation, and the photoluminescence decay dynamics are recorded between delays of 2 ns and 20 ms. Above T = 200 K, our data provide convincing evidence for TADF at intermediate delays in the microsecond range, whereas triplet-triplet annihilation and slow triplet decay at later times can be observed over the entire temperature range from T = 80 K to room temperature. Moreover, close to room temperature, we find a second and faster up-conversion mechanism, tentatively assigned to reverse internal conversion between different triplet configurations. An interpretation of these experimental findings requires a calculation of the deformation patterns and potential minima of several electronic configurations. This task is performed with a range-separated hybrid functional, outperforming standard density functionals or global hybrids. In particular, the systematic underestimation of the energy of charge transfer (CT) states with respect to local excitations within the constituting chromophores is replaced by more reliable transition energies for both kinds of excitations. Hence, several absorption and emission features can be assigned unambiguously, and the observed activation barriers for rISC and reverse internal conversion correspond to calculated energy differences between the potential surfaces in different electronic configurations.

Synthesis of Vinylene-Linked Two-Dimensional Conjugated Polymers via the Horner-Wadsworth-Emmons Reaction.

In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D-PPQV1 and 2D-PPQV2, via the Horner-Wadsworth-Emmons (HWE) reaction of C2 -symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4'-bis(diethylphosphonomethyl)biphenyl with C3 -symmetric 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino[2,3-a:2',3'-c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C-C single bond formation for the synthesis of crystalline 2D CPs. Powder X-ray diffraction (PXRD) studies and nitrogen adsorption-desorption measurements demonstrate the formation of proclaimed crystalline, dual-pore structures with surface areas of up to 440 m2 g-1 . More importantly, the optoelectronic properties of the obtained 2D-PPQV1 (Eg =2.2 eV) and 2D-PPQV2 (Eg =2.2 eV) are compared with those of cyano-vinylene-linked 2D-CN-PPQV1 (Eg =2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, Eg =2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction.

Thermally Activated Delayed Fluorescence in a Y3 N@C80 Endohedral Fullerene: Time-Resolved Luminescence and EPR Studies.

The endohedral fullerene Y3 N@C80 exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable-temperature steady-state and time-resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y3 N@C80 exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X- and W-band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y3 N@C80 /PFO film is demonstrated opening the possibility for red-emitting fullerene-based organic light-emitting diodes (OLEDs).

Cool white light-emitting three stack OLED structures for AMOLED display applications.

This paper demonstrates 2-stack and 3-stack white organic light-emitting diodes (WOLEDs) with fluorescent blue and phosphorescent yellow emissive units. The 2-stack and 3-stack WOLED comprises blue-yellow and blue-blue-yellow (blue-yellow-blue) combinations. The position of the yellow emitter and possible cavity lengths in different stack architectures are theoretically and experimentally investigated to reach Commission Internationale de L'Eclairage (CIE) coordinates of near (0.333/0.333). Here, a maximum external quantum efficiency (EQE) of 23.6% and current efficiency of 62.2 cd/A at 1000 cd/m2 as well as suitable CIE color coordinates of (0.335/0.313) for the blue-blue-yellow 3-stack hybrid WOLED structure is reported. In addition, the blue-yellow-blue 3-stack architecture exhibits an improved angular dependence compared to the blue-blue-yellow structure at a decreased EQE of 19.1%.

White organic light-emitting diodes with fluorescent tube efficiency.

The development of white organic light-emitting diodes (OLEDs) holds great promise for the production of highly efficient large-area light sources. High internal quantum efficiencies for the conversion of electrical energy to light have been realized. Nevertheless, the overall device power efficiencies are still considerably below the 60-70 lumens per watt of fluorescent tubes, which is the current benchmark for novel light sources. Although some reports about highly power-efficient white OLEDs exist, details about structure and the measurement conditions of these structures have not been fully disclosed: the highest power efficiency reported in the scientific literature is 44 lm W(-1) (ref. 7). Here we report an improved OLED structure which reaches fluorescent tube efficiency. By combining a carefully chosen emitter layer with high-refractive-index substrates, and using a periodic outcoupling structure, we achieve a device power efficiency of 90 lm W(-1) at 1,000 candelas per square metre. This efficiency has the potential to be raised to 124 lm W(-1) if the light outcoupling can be further improved. Besides approaching internal quantum efficiency values of one, we have also focused on reducing energetic and ohmic losses that occur during electron-photon conversion. We anticipate that our results will be a starting point for further research, leading to white OLEDs having efficiencies beyond 100 lm W(-1). This could make white-light OLEDs, with their soft area light and high colour-rendering qualities, the light sources of choice for the future.

In-plane oxygen diffusion measurements in polymer films using time-resolved imaging of programmable luminescent tags.

Oxygen diffusion properties in thin polymer films are key parameters in industrial applications from food packaging, over medical encapsulation to organic semiconductor devices and have been continuously investigated in recent decades. The established methods have in common that they require complex pressure-sensitive setups or vacuum technology and usually do not come without surface effects. In contrast, this work provides a low-cost, precise and reliable method to determine the oxygen diffusion coefficient D in bulk polymer films based on tracking the phosphorescent pattern of a programmable luminescent tag over time. Our method exploits two-dimensional image analysis of oxygen-quenched organic room-temperature phosphors in a host polymer with high spatial accuracy. It avoids interface effects and accounts for the photoconsumption of oxygen. As a role model, the diffusion coefficients of polystyrene glasses with molecular weights between 13k and 350k g/mol are determined to be in the range of (0.8-1.5) × 10-7 cm2/s, which is in good agreement with previously reported values. We finally demonstrate the reduction of the oxygen diffusion coefficient in polystyrene by one quarter upon annealing above its glass transition temperature.

Room Temperature Phosphorescence from Natural, Organic Emitters and Their Application in Industrially Compostable Programmable Luminescent Tags.

Organic semiconductors provide the potential of biodegradable technologies, but prototypes do only rarely exist. Transparent, ultrathin programmable luminescent tags (PLTs) are presented for minimalistic yet efficient information storage that are fully made from biodegradable or at least industrially compostable, ready-to-use materials (bioPLTs). As natural emitters, the quinoline alkaloids show sufficient room temperature phosphorescence when being embedded in polymer matrices with cinchonine exhibiting superior performance. Polylactic acid provides a solution for both the matrix material and the flexible substrate. Room temperature phosphorescence can be locally controlled by the oxygen concentration in the film by using Exceval as additional oxygen blocking layers. These bioPLTs exhibit all function-defining characteristics also found in their regular nonenvironmentally degradable analogs and, additionally, provide a simplified, high-contrast readout under continuous-wave illumination as a consequence of the unique luminescence properties of the natural emitter cinchonine. Limitations for flexible devices arise from limited thermal stability of the polylactic acid foil used as substrate allowing only for one writing cycle and preventing an annealing step during fabrication. Few-cycle reprogramming is possible when using the architecture of the bioPLTs on regular quartz substrates. This work realizes the versatile platform of PLTs with less harmful materials offering more sustainable use in future.

Tuning Charge-Transfer States by Interface Electric Fields.

Intermolecular charge-transfer (CT) states are extended excitons with a charge separation on the nanometer scale. Through absorption and emission processes, they couple to the ground state. This property is employed both in light-emitting and light-absorbing devices. Their conception often relies on donor-acceptor (D-A) interfaces, so-called type-II heterojunctions, which usually generate significant electric fields. Several recent studies claim that these fields alter the energetic configuration of the CT states at the interface, an idea holding prospects like multicolor emission from a single emissive interface or shifting the absorption characteristics of a photodetector. Here, we test this hypothesis and contribute to the discussion by presenting a new model system. Through the fabrication of planar organic p-(i-)n junctions, we generate an ensemble of oriented CT states that allows the systematic assessment of electric field impacts. By increasing the thickness of the intrinsic layer at the D-A interface from 0 to 20 nm and by applying external voltages up to 6 V, we realize two different scenarios that controllably tune the intrinsic and extrinsic electric interface fields. By this, we obtain significant shifts of the CT-state peak emission of about 0.5 eV (170 nm from red to green color) from the same D-A material combination. This effect can be explained in a classical electrostatic picture, as the interface electric field alters the potential energy of the electric CT-state dipole. This study illustrates that CT-state energies can be tuned significantly if their electric dipoles are aligned to the interface electric field.

Molecularly induced order promotes charge separation through delocalized charge-transfer states at donor-acceptor heterojunctions.

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors above 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher structural order of B4PYMPM molecules leads to more delocalized CT states. Furthermore, we find no correlation between the quantum efficiency of FCC radiative recombination and the bound or unbound nature of the CT states. This work highlights the importance of structural ordering at donor-acceptor interfaces for efficient FCC generation and shows that less bound CT states do not preclude efficient radiative recombination.

Selective turn-on ammonia sensing enabled by high-temperature fluorescence in metal-organic frameworks with open metal sites.

We show that fluorescent molecules incorporated as ligands in rigid, porous metal-organic frameworks (MOFs) maintain their fluorescence response to a much higher temperature than in molecular crystals. The remarkable high-temperature ligand-based fluorescence, demonstrated here with tetraphenylethylene- and dihydroxyterephthalate-based linkers, is essential for enabling selective and rapid detection of analytes in the gas phase. Both Zn2(TCPE) (TCPE = tetrakis(4-carboxyphenyl)ethylene) and Mg(H2DHBDC) (H2DHBDC(2-) = 2,5-dihydroxybenzene-1,4-dicarboxylate) function as selective sensors for ammonia at 100 °C, although neither shows NH3 selectivity at room temperature. Variable-temperature diffuse-reflectance infrared spectroscopy, fluorescence spectroscopy, and X-ray crystallography are coupled with density-functional calculations to interrogate the temperature-dependent guest-framework interactions and the preferential analyte binding in each material. These results describe a heretofore unrecognized, yet potentially general property of many rigid, fluorescent MOFs and portend new applications for these materials in selective sensors, with selectivity profiles that can be tuned as a function of temperature.

Highly efficient white top-emitting organic light-emitting diodes comprising laminated microlens films.

White top-emitting organic light-emitting diodes (OLEDs) attract much attention, as they are optically independent from the substrate used. While monochrome top-emitting OLEDs can be designed easily to have high-emission efficiency, white light emission faces obstacles. The commonly used thin metal layers as top electrodes turn the device into a microresonator having detrimental narrow and angular dependent emission characteristics. Here we report on a novel concept to improve the color quality and efficiency of white top-emitting OLEDs. We laminate a refractive index-matched microlens film on the top-emitting device. The microlens film acts both as outcoupling-enhancing film and an integrating element, mixing the optical modes to a broadband spectrum.

Epidemiology and injury morphology of traumatic hip dislocations in children and adolescents in Germany: a multi-centre study.

OBJECTIVE: Traumatic hip dislocations are very rare in childhood and adolescence. The aim of this multi-centre study is to analyse the current epidemiology and injury morphology of a large number of traumatic hip dislocations in children. This can provide a better understanding of childhood hip dislocations and contribute to the development of a therapeutic approach in order to prevent long-term impacts. METHODOLOGY: This retrospective, anonymised multi-centre study included patients, aged up to 17 years, with acute traumatic hip dislocations and open growth plates. The patients came from 16 German hospitals. Exclusion criteria included insufficient data, a positive history of hip dysplasia, or an association with syndromal, neurological or connective tissue diseases predisposing to hip dislocation. An analysis was carried out on the patients' anthropometric data and scans (X-ray, MRI, CT), which were collected between 1979 and 2021. Gender, age at the time of dislocation, associated fractures, mechanism of injury, initial treatment including time between dislocation and reduction, method of reduction, treatment algorithm following reduction and all documented complications and concomitant injuries were evaluated. RESULTS: Seventy-six patients met the inclusion criteria. There were two age peaks at 4-8 years and 11-15 years. There was an increased incidence of girls in the under-eight age group, who had mild trauma, and in the group of over-eights there were more boys, who had moderate and severe trauma. Dorsal dislocation occurred in 89.9% of cases. Mono-injuries dominated across all age groups. Concomitant injuries rarely occurred before the age of eight; however, they increased with increasing ossification of the acetabulum and appeared as avulsion injuries in 32% of 11-15-year-olds. Of the 76 patients, 4 underwent a spontaneous, 67 a closed and 5 a primary open reduction. A reduction was performed within 6 h on 84% of the children; however, in around 10% of cases a reduction was not performed until after 24 h. Concomitant injuries needing intervention were identified in 34 children following reduction. Complications included nerve irritation in the form of sensitivity disorders (n = 6) as well as avascular necrosis (AVN) of the femoral head in 15.8% of the patients (n = 12). CONCLUSIONS: Traumatic hip dislocations are rare in childhood and adolescence and have high complication rates. The most severe complication, femoral head necrosis, occurred in 16% of cases. Minor injuries, especially in younger children, are enough to cause a dislocation. Posterior dislocation was more frequent and primarily occurred as a mono-injury; however, concomitant injuries must be considered with increasing age. Children continue to experience delayed reductions. The length of time until reduction, age and the severity of the concomitant injury play a role in the development of femoral head necrosis; however, this topic requires additional investigation.

Viologen-Immobilized 2D Polymer Film Enabling Highly Efficient Electrochromic Device for Solar-Powered Smart Window.

Electrochromic devices (ECDs) have emerged as a unique class of optoelectronic devices for the development of smart windows. However, current ECDs typically suffer from low coloration efficiency (CE) and high energy consumption, which have thus hindered their practical applications, especially as components in solar-powered EC windows. Here, the high-performance ECDs with a fully crystalline viologen-immobilized 2D polymer (V2DP) thin film as the color-switching layer is demonstrated. The high density of vertically oriented pore channels (pore size ≈ 4.5 nm; pore density ≈ 5.8 × 1016 m-2 ) in the synthetic V2DP film enables high utilization of redox-active viologen moieties and benefits for Li+ ion diffusion/transport. As a result, the as-fabricated ECDs achieve a rapid switching speed (coloration, 2.8 s; bleaching, 1.2 s), and a high CE (989 cm2 C-1 ), and low energy consumption (21.1 µW cm-2 ). Moreover, it is managed to fabricate transmission-tunable, self-sustainable EC window prototypes by vertically integrating the V2DP ECDs with transparent solar cells. This work sheds light on designing electroactive 2D polymers with molecular precision for optoelectronics and paves a practical route toward developing self-powered EC windows to offset the electricity consumption of buildings.

Optical Properties of Perovskite-Organic Multiple Quantum Wells.

A comprehensive study of the optical properties of CsPbBr3 perovskite multiple quantum wells (MQW) with organic barrier layers is presented. Quantum confinement is observed by a blue-shift in absorption and emission spectra with decreasing well width and agrees well with simulations of the confinement energies. A large increase of emission intensity with thinner layers is observed, with a photoluminescence quantum yield up to 32 times higher than that of bulk layers. Amplified spontaneous emission (ASE) measurements show very low thresholds down to 7.3 µJ cm-2 for a perovskite thickness of 8.7 nm, significantly lower than previously observed for CsPbBr3 thin-films. With their increased photoluminescence efficiency and low ASE thresholds, MQW structures with CsPbBr3 are excellent candidates for high-efficiency perovskite-based LEDs and lasers.