Reconstructing the 3D Coordinates of Guest:Host OLED Blends with Single Atom Resolution.

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light-emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high-end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)-based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac-tris(2-phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20 wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film-forming process and are also consistent with the experimentally measured charge transport and photophysical properties.

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.

Understanding plasticiser leaching from polystyrene microplastics.

Plastic pollution in our oceans is of growing concern particularly due to the presence of toxic additives, such as plasticisers. Therefore, this work aims to develop a comprehensive understanding of the leaching properties of plasticisers from microplastics. This work investigates the leaching of phthalate acid ester (dioctyl terephthalate (DEHT) and diethylhexyl phthalate (DEHP)) and diphenol (bisphenol A (BPA) and bisphenol S (BPS)) plasticisers from polystyrene (PS) microplastics (mean diameter = 136 µm to 1.4 mm) under controlled aqueous conditions (temperature, agitation, pH and salinity). The leaching behaviours of plasticised polymers were quantified using gel permeation chromatography, high performance liquid chromatography and thermal gravimetric analysis, and the particle's plasticisation characterised using differential scanning calorimetry. Leaching rates of phthalate acid ester and diphenol plasticisers were modelled using a diffusion and boundary layer model, whereby these behaviours varied depending on their plasticisation efficiency of PS, the size of the microplastic particle and the surrounding abiotic conditions. Leaching behaviours of DEHT and DEHP were strongly influenced by the microplastic-surface water boundary layer properties, thus wave action (i.e., water agitation) increased the leaching rate of these plasticiser up to 66 % over 21-days, whereas BPA and BPS plasticisers displayed temperature- and size-dependent leaching and were limited by molecular diffusion throughout the bulk polymer (i.e., the microplastic). This information will improve predictions of plasticiser concentration (both that remain in the plastic and released into the surrounding water) at specific time points during the lifetime of a plastic, ultimately ensuring greater accuracy in the assessment of toxicity responses and environmental water quality.

Understanding the performance differences between solution and vacuum deposited OLEDs: A computational approach.

Solution-processing of organic light-emitting diode films has potential advantages in terms of cost and scalability over vacuum-deposition for large area applications. However, solution processed small molecule films can have lower overall device performance. Here, novel molecular dynamics techniques are developed to enable faster simulation of solvent evaporation that occurs during solution processing and give films of thicknesses relevant to real devices. All-atom molecular dynamics simulations are then used in combination with kinetic Monte Carlo transport modeling to examine how differences in morphology stemming from solution or vacuum film deposition affect charge transport and exciton dynamics in films consisting of light-emitting bis(2-phenylpyridine)(acetylacetonate)iridium(III) [Ir(ppy)2(acac)] guest molecules in a 4,4'-bis(N-carbazolyl)biphenyl host. While the structures of the films deposited from vacuum and solution were found to differ, critically, only minor variations in the transport properties were predicted by the simulations even if trapped solvent was present.

The validity of using inertial measurement units to monitor the torso and pelvis sagittal plane motion of elite rowers.

In elite sport, inertial measurement units (IMUs) are being used increasingly to measure movement in-field. IMU data commonly sought are body segment angles as this gives insights into how technique can be altered to improve performance and reduce injury risk. The purpose of this was to assess the validity of IMU use in rowing and identify if IMUs are capable of detecting differences in sagittal torso and pelvis angles that result from changes in stroke rates. Eight elite female rowers participated. Four IMUs were positioned along the torso and over the pelvis of each athlete. Reflective markers surrounded each IMU which were used to compute gold-standard data. Maxima, minima, angle range and waveforms for ten strokes at rates of 20, 24, 28 and 32 strokes per minute were analysed. Root mean square errors as a percentage of angle range fell between 1.44% and 8.43%. In most cases when significant differences (p < 0.05) in the angles were detected between stroke rates, this was observed in both IMU and gold-standard angle data. These findings suggest that IMUs are valid for measuring torso and pelvis angles when rowing and are capable of detecting differences that result from changes in stroke rate.

Unraveling exciton processes in Ir(ppy)3:CBP OLED films upon photoexcitation.

Emissive layers in phosphorescent organic light-emitting diodes commonly make use of guest-host blends such as Ir(ppy)3:CBP to achieve high external quantum efficiencies. However, while the Ir(ppy)3:CBP blend has been studied experimentally, crucial questions remain regarding how exciton diffusion is dependent on the distribution of the guest in the host, which can currently only be addressed at the atomic level via computational modeling. In this work, kinetic Monte Carlo simulations are utilized to gain insight into exciton diffusion in Ir(ppy)3:CBP blend films. The effects of both guest concentration and exciton density on various system properties are analyzed, including the probability of singlet excitons being converted to triplets, and the probability of those triplets decaying radiatively. Significantly, these simulations suggest that triplet diffusion occurs almost exclusively via guest-guest Dexter transfer and that concentration quenching of triplets induced by guest-guest intermolecular dipole-dipole interactions has a negligible effect at high exciton densities due to the prevalence of triplet-triplet annihilation. Furthermore, results for vacuum deposited morphologies derived from molecular dynamics simulations are compared to the results obtained using a simple cubic lattice approximation with randomly distributed guest molecules. We show that while differences in host-based processes such as singlet diffusion are observed, overall, the results on the fate of the excitons are in good agreement for the two morphology types, particularly for guest-based processes at low guest concentrations where guest clustering is limited.

Charge and exciton dynamics of OLEDs under high voltage nanosecond pulse: towards injection lasing.

Electrical pumping of organic semiconductor devices involves charge injection, transport, device on/off dynamics, exciton formation and annihilation processes. A comprehensive model analysing those entwined processes together is most helpful in determining the dominating loss pathways. In this paper, we report experimental and theoretical results of Super Yellow (Poly(p-phenylene vinylene) co-polymer) organic light emitting diodes operating at high current density under high voltage nanosecond pulses. We demonstrate complete exciton and charge carrier dynamics of devices, starting from charge injection to light emission, in a time scale spanning from the sub-ns to microsecond region, and compare results with optical pumping. The experimental data is accurately replicated by simulation, which provides a robust test platform for any organic materials. The universality of our model is successfully demonstrated by its application to three other laser active materials. The findings provide a tool to narrow the search for material and device designs for injection lasing.

Comparing inertial measurement units and marker-based biomechanical models during dynamic rotation of the torso.

Inertial measurement units (IMUs) enable human movements to be captured in the field and are being used increasingly in high performance sport. One key metric that can be derived from IMUs are relative angles of body segments which are important for monitoring form in many sports. The purpose of this study was to (a) examine the validity of relative angles derived from IMUs placed on the torso and pelvis; and (b) determine optimal positioning for torso mounted sensors such that the IMU relative angles match closely with gold standard torso-pelvis and thorax-pelvis relative angle data derived from an optoelectronic camera system. Seventeen adult participants undertook a variety of motion tasks. Four IMUs were positioned on the torso and one was positioned on the pelvis between the posterior superior iliac spines. Reflective markers were positioned around each IMU and over torso and pelvis landmarks. Results showed that the IMUs are valid with the root mean square errors expressed as a percentage of the angle range (RMSE%) ranging between 1% and 7%. Comparison between the IMU relative angles and the torso-pelvis and thorax-pelvis relative angles showed there were moderate to large differences with RMSE% values ranging between 4% and 57%. IMUs are highly accurate at measuring orientation data; however, further work is needed to optimise positioning and modelling approaches so IMU relative angles align more closely with relative angles derived using traditional motion capture methods.

Understanding charge transport in Ir(ppy)3:CBP OLED films.

Ir(ppy)3:CBP blends have been widely studied as the emissive layer in organic light emitting diodes (OLEDs), yet crucial questions about charge transport within the layer remain unaddressed. Recent molecular dynamics simulations show that the Ir(ppy)3 molecules are not isolated from each other, but at concentrations of as low as 5 wt. % can be part of connected pathways. Such connectivity raises the question of how the iridium(iii) complexes contribute to long-range charge transport in the blend. We implement a kinetic Monte Carlo transport model to probe the guest concentration dependence of charge mobility and show that distinct minima appear at approximately 10 wt. % Ir(ppy)3 due to an increased number of trap states that can include interconnected complexes within the blend film. The depth of the minima is shown to be dependent on the electric field and to vary between electrons and holes due to their different trapping depths arising from the different ionization potentials and electron affinities of the guest and host molecules. Typical guest-host OLEDs use a guest concentration below 10 wt. % to avoid triplet-triplet annihilation, so these results suggest that optimal device performance is achieved when there is significant charge trapping on the iridium(iii) complex guest molecules and minimum interactions of the emissive chromophores that can lead to triplet-triplet annihilation.

DeepWeeds: A Multiclass Weed Species Image Dataset for Deep Learning.

Robotic weed control has seen increased research of late with its potential for boosting productivity in agriculture. Majority of works focus on developing robotics for croplands, ignoring the weed management problems facing rangeland stock farmers. Perhaps the greatest obstacle to widespread uptake of robotic weed control is the robust classification of weed species in their natural environment. The unparalleled successes of deep learning make it an ideal candidate for recognising various weed species in the complex rangeland environment. This work contributes the first large, public, multiclass image dataset of weed species from the Australian rangelands; allowing for the development of robust classification methods to make robotic weed control viable. The DeepWeeds dataset consists of 17,509 labelled images of eight nationally significant weed species native to eight locations across northern Australia. This paper presents a baseline for classification performance on the dataset using the benchmark deep learning models, Inception-v3 and ResNet-50. These models achieved an average classification accuracy of 95.1% and 95.7%, respectively. We also demonstrate real time performance of the ResNet-50 architecture, with an average inference time of 53.4 ms per image. These strong results bode well for future field implementation of robotic weed control methods in the Australian rangelands.

Third-order transport coefficients for localised and delocalised charged-particle transport.

We derive third-order transport coefficients of skewness for a phase-space kinetic model that considers the processes of scattering collisions, trapping, detrapping and recombination losses. The resulting expression for the skewness tensor provides an extension to Fick's law which is in turn applied to yield a corresponding generalised advection-diffusion-skewness equation. A physical interpretation of trap-induced skewness is presented and used to describe an observed negative skewness due to traps. A relationship between skewness, diffusion, mobility and temperature is formed by analogy with Einstein's relation. Fractional transport is explored and its effects on the flux transport coefficients are also outlined.

Generalized balance equations for charged particle transport via localized and delocalized states: Mobility, generalized Einstein relations, and fractional transport.

A generalized phase-space kinetic Boltzmann equation for highly nonequilibrium charged particle transport via localized and delocalized states is used to develop continuity, momentum, and energy balance equations, accounting explicitly for scattering, trapping and detrapping, and recombination loss processes. Analytic expressions detail the effect of these microscopic processes on mobility and diffusivity. Generalized Einstein relations (GER) are developed that enable the anisotropic nature of diffusion to be determined in terms of the measured field dependence of the mobility. Interesting phenomena such as negative differential conductivity and recombination heating and cooling are shown to arise from recombination loss processes and the localized and delocalized nature of transport. Fractional transport emerges naturally within this framework through the appropriate choice of divergent mean waiting time distributions for localized states, and fractional generalizations of the GER and mobility are presented. Signature impacts on time-of-flight current transients of recombination loss processes via both localized and delocalized states are presented.

The Role of Space Charge Effects on the Competition between Recombination and Extraction in Solar Cells with Low-Mobility Photoactive Layers.

The competition between charge extraction and nongeminate recombination critically determines the current-voltage characteristics of organic solar cells (OSCs) and their fill factor. As a measure of this competition, several figures of merit (FOMs) have been put forward; however, the impact of space charge effects has been either neglected, or not specifically addressed. Here we revisit recently reported FOMs and discuss the role of space charge effects on the interplay between recombination and extraction. We find that space charge effects are the primary cause for the onset of recombination in so-called non-Langevin systems, which also depends on the slower carrier mobility and recombination coefficient. The conclusions are supported with numerical calculations and experimental results of 25 different donor/acceptor OSCs with different charge transport parameters, active layer thicknesses or composition ratios. The findings represent a conclusive understanding of bimolecular recombination for drift dominated photocurrents and allow one to minimize these losses for given device parameters.

Solution of a generalized Boltzmann's equation for nonequilibrium charged-particle transport via localized and delocalized states.

We present a general phase-space kinetic model for charged-particle transport through combined localized and delocalized states, capable of describing scattering collisions, trapping, detrapping, and losses. The model is described by a generalized Boltzmann equation, for which an analytical solution is found in Fourier-Laplace space. The velocity of the center of mass and the diffusivity about it are determined analytically, together with the flux transport coefficients. Transient negative values of the free particle center-of-mass transport coefficients can be observed due to the trapping to, and detrapping from, localized states. A Chapman-Enskog-type perturbative solution technique is applied, confirming the analytical results and highlighting the emergence of a density gradient representation in the weak-gradient hydrodynamic regime. A generalized diffusion equation with a unique global time operator is shown to arise, reducing to the standard diffusion equation and a Caputo fractional diffusion equation in the normal and dispersive limits. A subordination transformation is used to solve the generalized diffusion equation by mapping from the solution of a corresponding standard diffusion equation.

Photocarrier drift distance in organic solar cells and photodetectors.

Light harvesting systems based upon disordered materials are not only widespread in nature, but are also increasingly prevalent in solar cells and photodetectors. Examples include organic semiconductors, which typically possess low charge carrier mobilities and Langevin-type recombination dynamics--both of which negatively impact the device performance. It is accepted wisdom that the "drift distance" (i.e., the distance a photocarrier drifts before recombination) is defined by the mobility-lifetime product in solar cells. We demonstrate that this traditional figure of merit is inadequate for describing the charge transport physics of organic light harvesting systems. It is experimentally shown that the onset of the photocarrier recombination is determined by the electrode charge and we propose the mobility-recombination coefficient product as an alternative figure of merit. The implications of these findings are relevant to a wide range of light harvesting systems and will necessitate a rethink of the critical parameters of charge transport.

Molecular weight dependent bimolecular recombination in organic solar cells.

Charge carrier recombination is studied in operational organic solar cells made from the polymer:fullerene system PCDTBT:PC71BM (poly[N-9''-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]: [6,6]-phenyl-C70-butyric acid methyl ester). A newly developed technique High Intensity Resistance dependent PhotoVoltage is presented for reliably quantifying the bimolecular recombination coefficient independently of variations in experimental conditions, thereby resolving key limitations of previous experimental approaches. Experiments are performed on solar cells of varying thicknesses and varying polymeric molecular weights. It is shown that solar cells made from low molecular weight PCDTBT exhibit Langevin recombination, whereas suppressed (non-Langevin) recombination is found in solar cells made with high molecular weight PCDTBT.

The impact of hot charge carrier mobility on photocurrent losses in polymer-based solar cells.

A typical signature of charge extraction in disordered organic systems is dispersive transport, which implies a distribution of charge carrier mobilities that negatively impact on device performance. Dispersive transport has been commonly understood to originate from a time-dependent mobility of hot charge carriers that reduces as excess energy is lost during relaxation in the density of states. In contrast, we show via photon energy, electric field and film thickness independence of carrier mobilities that the dispersive photocurrent in organic solar cells originates not from the loss of excess energy during hot carrier thermalization, but rather from the loss of carrier density to trap states during transport. Our results emphasize that further efforts should be directed to minimizing the density of trap states, rather than controlling energetic relaxation of hot carriers within the density of states.