OLEDs with enhanced high temperature operational stability

Temperature dependence of electroluminescence degradation is studied in organic light emitting devices containing an emitting layer composed of a mixture of different hole transport molecules and tris(8-hydroxyquinoline)aluminum (AlQ(3)) electron transport and emitter molecule. The emitting layer is sandwiched between hole and electron transport layers. Devices containing the hole transport molecule N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPB), doped with quinacridone (DMQ) green emitter showed remarkable temperature stability. For these devices, a half-life of about 78,500 hours, 18,700 hours, and 8,600 hours can be projected for operating temperatures of 22degreesC, 700degreesC and 100degreesC, respectively, at an initial device luminance of 100 cd/m(2). Activation energies for device degradation were determined for devices with different hole transport molecules and it was found that devices with higher activation energy show better high temperature stability. These results are consistent with the recently proposed degradation mechanism based on the unstable cationic AlQ(3) species

Modulating electron injection from an organic dye to a titania nanoparticle with a photochromic energy transfer acceptor

We have prepared titania nanoparticles with an organic dye sensitiser and diarylethene molecular switch attached to the surface. Spectroscopic investigations show that the dye sensitiser's electron injection efficiency is reduced when the diarylethene is switched from its colourless, ring-open isomer to its coloured, ring-closed isomer, due to the introduction of a competing energy transfer pathway

Plasticiser leaching from polyvinyl chloride microplastics and the implications for environmental risk assessment

Microplastics in aquatic environments is a growing concern, particularly due to the leaching of chemical additives such as plasticisers. To develop comprehensive environmental risk assessments (ERAs) of high-concern polymers and plasticisers, an understanding of their leachability is required. This work investigated diethylhexyl phthalate (DEHP) and bisphenol A (BPA) leaching from polyvinyl chloride (PVC) microplastics (average diameter = 191 μm) under simulated marine conditions. Leaching behaviours were quantified using gel permeation chromatography (GPC) and thermal gravimetric analysis (TGA), and the polymer's physiochemical properties analysed using differential scanning calorimetry (DSC), Fourier Transform-Infrared Spectroscopy (FT-IR) and optical microscopy. Experimental data were fitted to a diffusion and boundary layer model, which found that BPA leaching was temperature-dependent (diffusion-limited), whereas DEHP leaching was controlled by surface rinsing. Model predictions also highlighted the importance of microplastic size on leaching dynamics. These data contribute towards greater accuracy in ERAs of microplastics, with implications for water quality and waste management, including decommissioning of plastic infrastructure

A modeling approach to understanding OLED performance improvements arising from spatial variations in guest:host blend ratio

Phosphorescent organic light emitting diodes (OLEDs) suffer from efficiency roll off, where device efficiency rapidly decays at higher luminance. One strategy to minimize this loss of efficiency at higher luminance is the use of non-uniform or graded guest:host blend ratios within the emissive layer. This work applies a multi-scale modeling framework to elucidate the mechanisms by which a non-uniform blend ratio can change the performance of an OLED. Mobility and exciton data are extracted from a kinetic Monte–Carlo model, which is then coupled to a drift diffusion model for fast sampling of the parameter space. The model is applied to OLEDs with uniform, linear, and stepwise graduations in the blend ratio in the emissive layer. The distribution of the guests in the film was found to affect the mobility of the charge carriers, and it was determined that having a graduated guest profile broadened the recombination zone, leading to a reduction in second order annihilation rates. That is, there was a reduction in triplet–triplet and triplet-polaron annihilation. Reducing triplet–triplet and triplet-polaron annihilation would lead to an improvement in device efficiency

Noise and charge transport in polymer thin-film structures

The low frequency noise (LFN) properties of. the field-effect transistors (FETs) using polymers as the semiconducting material in thin-film transistor (TFT) structures are investigated and discussed in terms of the charge carrier transport. Results obtained from several research groups are summarized. Injection-drift limited model (IDLM) for charge transport in amorphous PFETs is discussed. IDLM has some advantages in comparison to the commonly used metal-oxide-semiconductor (MOS) transistor models. A general trend of proportionality between noise power density and the DC power applied to the polymer FET's (PFET's), channel is observed in the data from several research groups. This trend implies mobility fluctuation in PFET as the dominant noise source

Photochrome-doped organic films for photonic key-pad locks and multi-state fluorescence

The spectroscopic properties of poly(methyl methacrylate) polymer films doped with two kinds of photochromic molecular switches are investigated. A green-fluorescent sulfonyl diarylethene (P1) is combined with either a non-fluorescent diarylethene (P2) or red-fluorescent spiropyran (P3). Photoswitching between the colorless and colored isomers (P1: o-BTFO4 ↔ c-BTFO4, P2: o-DTE ↔ c-DTE, P3: SP ↔ MC) enables the P1+P2 and P1+P3 films to be cycled through three distinct states. From the initial state (o-BTFO4 + o-DTE/SP), irradiation with UV light generates the second state (c-BTFO4 + c-DTE/MC), where c-BTFO4 → c-DTE/MC energy transfer is established. Irradiation with green light then generates the third state (c-BTFO4 + o-DTE/SP), where the energy transfer acceptor is no longer present. Finally, irradiation with blue light regenerates the initial state. For the P1+P2 film, only one state is fluorescent, with the irradiation inputs required to be entered in the correct order to access this state, acting as a keypad lock. For the P1+P3 film, the states emit either no fluorescence, red fluorescence, or green fluorescence, all using a common excitation wavelength. Additionally, once the fluorescence is activated with UV light, it undergoes a time-dependent color transition from red to green, due to the pairing of P-type and T-type photochromes. These multi-photochromic systems may be useful for security ink or imaging applications

Oil spill source identification using colorimetric detection

The colorimetric detection of polycyclic aromatic hydrocarbons (PAHs) was investigated for the quick and easy identification of likely oil spill offenders. In this new technology, photochromic compounds were used to sense PAHs by varying their photoswitching capacity. To that end, three photochromes were designed and showed varying degrees of photoswitching inhibition depending on PAH analyte, photochrome and excitation wavelength. PAH mixtures that mimic oil spills showed the same varying response and demonstrated the accuracy of this technology. To prove the applicability of this technology, an array was assembled using the three photochromes at three excitation wavelengths and tested against authentic crude oil samples. Not only could these samples be differentiated, weathering of two distinctly different oil samples showed limited variation in response, demonstrating that this may be a viable technique for in situ oil identification

The effect of the phenylene linkage in poly(fluorene-alt-phenylene)s on the thermodynamics and kinetics of nitroaromatic and nitroaliphatic sensing

The preparation, photophysical characterization and sensing of a series of highly luminescent poly(fluorene-alt-phenylene)s (PFP) were studied. These PFP polymers varied the phenylene linkage in the 1,4 (PFP-p), 1,3 (PFP-m) and 1,2 (PFP-o) positions. The photoluminescence of these polymers ranged from ultraviolet to blue in color in both solution and film states by simply varying the linkage of the phenylene moiety. Photon Electron Spectroscopy in Air (PESA) revealed that the change in the emission was primarily attributed to the difference of the electron affinity of the polymer. Stern-Volmer quenching studies indicated that these poly(fluorene-alt-phenylene) polymers are highly sensitive towards nitroaromatic materials in solution, particularly in comparison to the reference poly(9,9-di-n-hexylflourene) (PDHF). These PFP polymers were found to be four to ten times more sensitive towards dinitrobenzene as compared to PDHF. In addition, PFP-o displayed the highest polymer-based Stern-Volmer quenching towards the taggant DMNB. The solid-state fluorescence quenching of the PFP-p and PFP-m films using DMNB was enhanced (up to 71.5%) compared to the reference PDHF (59.6%) and was attributed to both thermodynamic and diffusion kinetic factors

Evaluating the Effect of Chemical Digestion Treatments on Polystyrene Microplastics: Recommended Updates to Chemical Digestion Protocols

Establishing the toxicity and exposure consequences of microplastics (MPs) on marine organisms relies on the nondestructive isolation of plastics from biological matrices. MPs are commonly extracted from these matrices by chemical digestion using alkali (e.g., potassium hydroxide (KOH) and sodium hydroxide (NaOH)), oxidative (e.g., hydrogen peroxide (H2O2)) and/or acidic (e.g., nitric acid (HNO3)) reagents. Although these digestion conditions can be highly effective for MP extraction, they can also react with the plastics. This can attribute an inaccurate representation of plastic contamination by altering MP visual characteristics (size, shape, color), thereby impeding identification and potentially returning erroneous numbers of ingested particles. In this study, the degradative impacts are assessed of the routinely applied digestion reagents (i) KOH, (ii) NaOH, (iii) H2O2, and (iv)HNO3 on polystyrene (PS) based MPs sized between 200 μm and 5 mm. Degradation of the PS MPs is evaluated using FT-IR, gel permeation chromatography, NMR, photoluminescence spectroscopy, and microscopy. These studies reveal HNO3 to be the most destructive for PS MPs, while the alkali and oxidative reagents result in negligible changes in plastic properties. These results are recommended to be used as a guideline to update current protocols to ensure the nondestructive treatment of MPs