A Novel Mitigation Mechanism for Photo-Induced Trapping in an Anthradithiophene Derivative Using Additives

© 2020 Wiley-VCH GmbH A novel trap mitigation mechanism using molecular additives, which relieves a characteristic early turn-on voltage in a high-mobility p-type acene-based small-molecule organic semiconductor, when processed from hydrous solvents, is reported. The early turn-on voltage is attributed to photo-induced trapping, and additive incorporation is found to be very effective in suppressing this effect. Remarkably, the molecular additive does not disturb the charge transport properties of the small-molecule semiconductor, but rather intercalates in the crystal structure. This novel technique allows for the solution-processing of small molecular semiconductors from hydrous solvents, greatly simplifying manufacturing processes for large-area electronics. Along with various electric and spectroscopic characterization techniques, simulations have given a deeper insight into the trap mitigation effect induced by the additive

Strong Suppression of Thermal Conductivity in the Presence of Long Terminal Alkyl Chains in Low-Disorder Molecular Semiconductors

While the charge transport properties of organic semiconductors have been extensively studied over the recent years, the field of organics-based thermoelectrics is still limited by a lack of experimental data on thermal transport and of understanding of the associated structure–property relationships. To fill this gap, a comprehensive experimental and theoretical investigation of the lattice thermal conductivity in polycrystalline thin films of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (Cn-DNTT-Cn with n = 0, 8) semiconductors is reported. Strikingly, thermal conductivity appears to be much more isotropic than charge transport, which is confined to the 2D molecular layers. A direct comparison between experimental measurements (3ω–Völklein method) and theoretical estimations (approach-to-equilibrium molecular dynamics (AEMD) method) indicates that the in-plane thermal conductivity is strongly reduced in the presence of the long terminal alkyl chains. This evolution can be rationalized by the strong localization of the intermolecular vibrational modes in C8-DNTT-C8 in comparison to unsubstituted DNTT cores, as evidenced by a vibrational mode analysis. Combined with the enhanced charge transport properties of alkylated DNTT systems, this opens the possibility to decouple electron and phonon transport in these materials, which provides great potential for enhancing the thermoelectric figure of merit ZT

Global Diversity of the Stylasteridae (Cnidaria: Hydrozoa: Athecatae)

The history and rate of discovery of the 247 valid Recent stylasterid species are discussed and graphed, with emphasis on five historical pulses of species descriptions. A table listing all genera, their species numbers, and their bathymetric ranges are presented. The number of species in 19 oceanographic regions is mapped, the southwestern temperate Pacific (region including New Zealand) having the most species; species are cosmopolitan from the Arctic Circle to the Antarctic at depths from 0 to 2789 m. The current phylogenetic classification of the genera is briefly discussed. An illustrated glossary of 53 morphological characters is presented. Biological and ecological information pertaining to reproduction, development, commensals, and distribution is discussed. Aspects of stylasterid mineralogy and taxa of commercial value are discussed, concluding with suggestions for future work

Chasing the ‘Killer’ Phonon Mode for the Rational Design of Low Disorder, High Mobility Molecular Semiconductors

Molecular vibrations play a critical role in the charge transport properties of weakly van der Waals bonded organic semiconductors. To understand which specific phonon modes contribute most strongly to the electron – phonon coupling and ensuing thermal energetic disorder in some of the most widely studied high mobility molecular semiconductors, we have combined state-of-the-art quantum mechanical simulations of the vibrational modes and the ensuing electron phonon coupling constants with experimental measurements of the low-frequency vibrations using inelastic neutron scattering and terahertz time-domain spectroscopy. In this way we have been able to identify the long-axis sliding motion as a ‘killer’ phonon mode, which in some molecules contributes more than 80% to the total thermal disorder. Based on this insight, we propose a way to rationalize mobility trends between different materials and derive important molecular design guidelines for new high mobility molecular semiconductors.Royal Society German Research Foundation European Research Council Engineering and Physical Sciences Research Council ARCHER UK National Supercomputing Service Belgian National Fund for Scientific Research Leverhulme Trust Wiener-Anspach Foundation Belgian Walloon Region GENCI-CINES/IDRI

Robust singlet fission in pentacene thin films with tuned charge transfer interactions

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings

Quantum Field Kinetics of QCD: Quark-Gluon Transport Theory for Lightcone Dominated Processes

A quantum kinetic formalism is developed to study the dynamical interplay of quantum and statistical-kinetic properties of non-equilibrium multi-parton systems produced in high-energy QCD processes. The approach provides the means to follow the quantum dynamics in both space-time and energy-momentum, starting from an arbitrary initial configuration of high-momentum quarks and gluons. Using a generalized functional integral representation and adopting the `closed-time-path' Green function techniques, a self-consistent set of equations of motions is obtained: a Ginzburg-Landau equation for a possible color background field, and Dyson-Schwinger equations for the 2-point functions of the gluon and quark fields. By exploiting the `two-scale nature' of light-cone dominated QCD processes, i.e. the separation between the quantum scale that specifies the range of short-distance quantum fluctuations, and the kinetic scale that characterizes the range of statistical binary inter- actions, the quantum-field equations of motion are converted into a correspon- ding set of `renormalization equations' and `transport equations'. The former describe renormalization and dissipation effects through the evolution of the spectral density of individual, dressed partons, whereas the latter determine the statistical occurrence of scattering processes among these dressed partons. The renormalization equations and the transport equations are coupled, and hence must be solved self-consistently. This amounts to evolving the multi-parton system, from a specified initial configuration, in time and full 7-dimensional phase-space. This description provides a proba- bilistic interpretation and is therefore of important practical value for the solution of the dynamical equations of motion, e.g. by Monte Carlo simulation.Comment: 70 pages, latex, 12 figures as uu-encoded postscript fil

Less invasive methods of advanced hemodynamic monitoring: principles, devices, and their role in the perioperative hemodynamic optimization.

The monitoring of the cardiac output (CO) and other hemodynamic parameters, traditionally performed with the thermodilution method via a pulmonary artery catheter (PAC), is now increasingly done with the aid of less invasive and much easier to use devices. When used within the context of a hemodynamic optimization protocol, they can positively influence the outcome in both surgical and non-surgical patient populations. While these monitoring tools have simplified the hemodynamic calculations, they are subject to limitations and can lead to erroneous results if not used properly. In this article we will review the commercially available minimally invasive CO monitoring devices, explore their technical characteristics and describe the limitations that should be taken into consideration when clinical decisions are made

Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations