Routes for efficiency enhancement in fluorescent TADF exciplex host OLEDs gained from an electro‐optical device model

Fluorescence-based organic light-emitting diodes (OLEDs) using thermally activated delayed fluorescence (TADF) have increasingly attracted attention in research and industry. One method to implement TADF is based on an emitter layer composed of an exciplex host and a fluorescent dopant. Even though the experimental realization of this concept has demonstrated promising external quantum efficiencies, the full potential of this approach has not yet been assessed. To this end, a comprehensive electro-optical device model accounting for the full exciton dynamics including triplet harvesting and exciton quenching is presented. The model parameters are fitted to multiple output characteristics of an OLED comprising a TADF exciplex host with a fluorescent emitter, showing an external quantum efficiency of >10%. With the model at hand, an emission zone analysis and a parameter study are performed, and possible routes for further efficiency enhancement are presented

Aryltriazene photopolymer thin films as sacrificial release layers for laser-assisted forward transfer systems: study of photoablative decomposition and transfer behavior

Thin films of a tailor-made photodecomposible aryltriazene polymer were applied in a modified laser-induced forward transfer (LIFT) process as sacrificial release layers. The photopolymer film acts as an intermediate energy-absorbing dynamic release layer (DRL) that decomposes efficiently into small volatile fragments upon UV laser irradiation. A fast-expanding pressure jet is generated which is used to propel an overlying transfer material from the source target onto a receiver. This DRL-assisted laser direct-write process allows the precise deposition of intact material pixels with micrometer resolution and by single laser pulses. Triazene-based photopolymer DRL donor systems were studied to derive optimum conditions for film thickness and laser fluences necessary for a defined transfer process at the emission wavelength of a XeCl excimer laser (308nm). Photoablation, surface detachment, delamination and transfer behavior of aryltriazene polymer films with a thickness from 25nm to ∼400nm were investigated in order to improve the process control parameters for the fabrication of functional thin-film devices of microdeposited heat- and UV-sensitive material

Improved laser-induced forward transfer of organic semiconductor thin films by reducing the environmental pressure and controlling the substrate-substrate gap width

Laser-induced forward transfer (LIFT) has been investigated for bilayer transfer material systems: silver/organic film (Alq3or PFO). The LIFT process uses an intermediate dynamic release layer of a triazene polymer. This study focuses on the effect of introducing a controlled donor-receiver substrate gap distance and the effect of doing the transfer at reduced air pressures, whilst varying the fluence up to ∼200 mJ/cm2. The gap between ‘in-contact' substrates has been measured to be a minimum of 2-3μm. A linear variation in the gap width from ‘in contact' to 40μm has been achieved by adding a spacer at one side of the substrate-substrate sandwich. At atmospheric pressure, very little transfer is achieved for Alq3, although PFO shows some signs of successful doughnut transfer (with a large hole in the middle) in a narrow fluence range, at gaps greater than 20μm. For the transfer of Ag/PFO bilayers at atmospheric pressure, the addition of a PFO layer onto the receiver substrate improved the transfer enormously at smaller gaps and higher fluences. However, the best transfer results were obtained at reduced pressures where a 100% transfer success rate is obtained within a certain fluence window. The quality of the pixel morphology at less than 100 mbar is much higher than at atmospheric pressure, particularly when the gap width is less than 20μm. These results show the promise of LIFT for industrial deposition processes where a gap between the substrates will improve the throughpu

Ultrafast charge transfer in solid-state films of pristine cyanine borate and blends with fullerene

Photoinduced electron transfer in light-absorbing materials is the first step towards charge separation and extraction in small molecule-based organic solar cells. The excited state dynamics of the cyanine dye cation Cy3 paired with a tetraphenylborate counter-anion (Cy3-B) was studied in pristine solid-state films of the dye and in blends with the electron acceptor material PCBM. Here we show that photoexcited Cy3-B in pure films undergoes intra-ion pair reductive quenching on the picosecond time scale, while in blends with PCBM sub-picosecond formation of the Cy3 oxidized species is observed upon electron injection from the dye excited state into the fullerene. Kinetic competition between light-induced electron- and hole transfer processes strongly depends on the PCBM content in the blends. A high PCBM loading produces a fully intermixed phase, where the cyanine oxidized states appear on ultrashort (<160 fs) time scales. Lower PCBM contents, in contrast, lead to a Cy3-B segregated phase on top of the intermixed phase and slower excited state quenching. These findings show that the phase morphology indeed controls to a large extent the efficiency of primary photoinduced charge separation, on which small molecule-based organic photovoltaic cells rely

Mineralogical characterization of scalings formed in geothermal sites in the Upper Rhine Graben before and after the application of sulfate inhibitors

Scale formation processes in the surface installations of geothermal power plants may have a negative effect on power plant performance. In addition, scales formed within the geothermal water circuit frequently accumulate natural radionuclides. Consequently, scale formation may lead to radiation dose rates, which are of radiological concern, and deposits, which may have to be disposed as radioactive waste. In order to minimize these problems and to foster geothermal power plant availability, it is of major interest to understand scale formation processes and to develop methods for their inhibition. One important pre-requisite towards this goal is a sound mineralogical and geochemical characterization of the formed material. Geothermal brines at sites in the Upper Rhine Graben are in general highly mineralized and become, upon cooling in the heat exchanger, supersaturated with respect to sulfate solid-solutions, e.g. (Ba,Sr)SO4, and other mineral phases. Some geothermal power plants very successfully tested the application of sulfate scaling inhibitors. Here we present mineralogical analyses of scale samples from geothermal power plants in the Upper Rhine Valley deposited in absence and presence of sulfate scaling inhibitors. Solid samples are investigated using wet-chemistry (after digestion), XRPD, SEM-EDX, XPS, EA-IRMS, Raman spectroscopy, and XANES (for explanation of abbreviations, see main text). Samples of scales deposited in the absence of a sulfate scaling inhibitor mainly consist of two phases. The largest part is made up of a barite type (Ba,Sr,Ca)SO4 solid-solution. Traces of Ra occurring in the scaling are assumed to be incorporated in the barite type solid solution. Further minor phases are sulfide phases, either an Xray amorphous nano-particulate phase or galena (PbS). Since the application of the sulfate inhibitor, sulfate minerals are no longer detectable in the scale samples. Subsequent scalings are Pb-dominated and consist mainly of galena (PbS), elemental lead (Pb), arsenic (As) and antimony (Sb). As and Sb are likely present as a nanocrystalline intermetallic mixed compound ((Sb, As) or Pb3(Sb,As)2S3). The absence of barite-type minerals demonstrates the success of the application of the sulfate inhibitor. The precipitation of elemental Pb, As, and Sb, which are more noble than iron, may enhance the corrosion of mild steel pipes in the geothermal water circuit. Elution tests and oxidation of the scalings upon storage at atmospheric conditions demonstrate that proper disposal of the toxic heavy metal and metalloid containing scalings may be challenging

Counterion effects in cyanine heterojunction photovoltaic devices

We investigated cyanine heterojunction photovoltaic devices using carbocyanine dyes as donors and buckminsterfullerene (C60) as acceptor. In particular, we focused on the influence of cyanine counterions on the photovoltaic device characteristics. It was found that counterions can be displaced in the applied electric field and give rise to important hystereses in the current-voltage characteristics, which are related to charge injection processes at electrode and organic heterointerfaces. Mobile counterions have also a drastic effect on the photocurrent spectrum and are responsible for an important C60 contribution at the organic heterojunction between cyanine and C60. If the counterion is covalently linked to the cyanine dye, the C60 contribution in the blue spectral domain can not be observed

On the use of cyanine dyes as low-bandgap materials in bulk heterojunction photovoltaic devices

Cyanine dyes with absorption edges of almost 1000 nm were used in combination with MEH-PPV for the fabrication of organic solar cells. For blended thin films, a pronounced phase separation between the two components occurred and resulted in photocurrents with different signs for bilayer and bulk heterojunction devices. Absorption spectra and selective dissolution experiments were used to illustrate the process of vertical phase segregation, with the preferential wetting of the polar anode by the cyanines while maintaining percolating carrier pathways between the electrodes. For a cyanine with long alkyl side chains, the compatibility with the polymer matrix was increased and the development of the effective inverted bilayer configuration was not observed. The generally low oxidative photocurrents were explained with unfavourable shifts of the highest occupied molecular orbital (HOMO) dye energy levels in the solid state

Dissociation of charge transfer states and carriers separation in bilayer organic solar cells - A time-resolved electroabsorption spectroscopy study

Ultrafast optical probing of the electric field by means of Stark effect in planar heterojunction cyanine dye / fullerene organic solar cells enables to directly monitor the dynamics of free electron formation during the dissociation of interfacial charge transfer (CT) states. Motions of electrons and holes is scrutinized separately by selectively probing the Stark shift dynamics at selected wavelengths. It is shown that only charge pairs with an effective electron-hole separation distance of less than 4 nm are created during the dissociation of Frenkel excitons. Dissociation of the Coulombically bound charge pairs is identified as the major rate-limiting step for charge carriers’ generation. Interfacial CT states split into free charges on the time-scale of tens to hundreds of picoseconds, mainly by electron escape from the Coulomb potential over a barrier that is lowered by the electric field. The motion of holes in the small molecule donor material during the charge separation time is found to be insignificant

Adult height, coronary heart disease and stroke: a multi-locus Mendelian randomization meta-analysis

BACKGROUND: We investigated causal effect of completed growth, measured by adult height, on coronary heart disease (CHD), stroke and cardiovascular traits, using instrumental variable (IV) Mendelian randomization meta-analysis. METHODS: We developed an allele score based on 69 single nucleotide polymorphisms (SNPs) associated with adult height, identified by the IBCCardioChip, and used it for IV analysis against cardiovascular risk factors and events in 21 studies and 60 028 participants. IV analysis on CHD was supplemented by summary data from 180 height-SNPs from the GIANT consortium and their corresponding CHD estimates derived from CARDIoGRAMplusC4D. RESULTS: IV estimates from IBCCardioChip and GIANT-CARDIoGRAMplusC4D showed that a 6.5-cm increase in height reduced the odds of CHD by 10% [odds ratios 0.90; 95% confidence intervals (CIs): 0.78 to 1.03 and 0.85 to 0.95, respectively],which agrees with the estimate from the Emerging Risk Factors Collaboration (hazard ratio 0.93; 95% CI: 0.91 to 0.94). IV analysis revealed no association with stroke (odds ratio 0.97; 95% CI: 0.79 to 1.19). IV analysis showed that a 6.5-cm increase in height resulted in lower levels of body mass index (P < 0.001), triglycerides (P < 0.001), non high-density (non-HDL) cholesterol (P < 0.001), C-reactive protein (P = 0.042), and systolic blood pressure (P = 0.064) and higher levels of forced expiratory volume in 1 s and forced vital capacity (P < 0.001 for both). CONCLUSIONS: Taller individuals have a lower risk of CHD with potential explanations being that taller people have a better lung function and lower levels of body mass index, cholesterol and blood pressure