Near-forward Raman selection rules of the phonon-polariton created by alloying in (Zn,Be)Se

The Raman selection rules of the (ZnSe, BeSe) mixed phonon polariton created by alloying in the three mode (1ZnSe, 2BeSe) ZnBeSe system, whose dramatic S like dispersion covers the large frequency gap between the ZnSe and BeSe spectral ranges, is studied in its wave vector dependence by near forward scattering. Both the collapse regime away from the Brillouin zone centre and the reinforcement regime near the Brillouin zone centre are addressed, using appropriate laser lines and Be contents. We find that in both regimes the considered phonon polariton, in fact a transverse mode with mixed mechanical and electrical character, obeys the same nominal Raman selection rules as its purely mechanical variant commonly observed in the backscattering geometry. Besides, marked differences in the phonon polariton Raman lineshapes in the two regimes give a hint about how the phonon polariton electrical field E develops while descending the S like dispersion towards the Brillouin zone centre. In the reinforcement regime E is large, leading to intramode on top of intermode transfers of oscillator strength mediated by E between the two BeSe modes, that both exhibit a fine structure on account of the alloy disorder. In contrast, in the collapse regime E remains weak, as testified by the absence of intramode transfer. The discussion is supported by contour modeling of the multi phonon polariton Raman lineshapes in their wave vector dependence within the linear dielectric approach.Comment: 16 pages, 7 figure

Investigation of the thermoelectric response in conducting polymers doped by solid-state diffusion

The thermoelectric effect is a physical phenomenon which intricately relates the thermal energy of charge carriers to their charge transport. Understanding the mechanism of this interaction in different systems lies at the heart of inventing novel materials which can revolutionize thermoelectric power gener- ation technology. Despite a recent surge of interest in organic thermoelectric materials, the community has had difficulties in formulating the charge trans- port mechanism in the presence of a significant degree of disorder. Here, we analyze the thermoelectric properties of various conducting polymers doped by a solid-state diffusion of dopant molecules based on a transport model with a power-law energy-dependence of transport function. A fine control of the degree of doping via post-doping annealing provides an accurate empirical evidence of a strong energy dependence of the carrier mobility in the conducting polymers. A superior thermoelectric power factor of conducting polymers doped by solid-state diffusion to that of other doping methods can be attributed to a resulting higher intrinsic mobility and higher free carrier concentration.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n 610115. Keehoon Kang thanks the for financial support from Samsung Scholarship Foundation and the National Creative Research Laboratory program (Grant No. 2012026372) through the National Research Foundation of Korea, funded by the Korean Ministry of Science and ICT. K.B. acknowledges funding by the German Research Foundation (BR 4869/1-1)

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

Investigation of potential interferences in the detection of atmospheric ROx_{x} radicals by laser-induced fluorescence under dark conditions

Direct detection of highly reactive, atmospheric hydroxyl radicals (OH) is widely accomplished by laser-induced fluorescence (LIF) instruments. The technique is also suitable for the indirect measurement of HO2 and RO2 peroxy radicals by chemical conversion to OH. It requires sampling of ambient air into a low pressure cell, where OH fluorescence is detected after excitation by 308 nm laser radiation. Although the residence time of air inside the fluorescence cell is typically only on the order of milliseconds, there is potential that additional OH is internally produced, which would artificially increase the measured OH concentration. Here, we present experimental studies investigating potential interferences in the detection of OH and peroxy radicals for the LIF instruments of Forschungszentrum Jülich for nighttime conditions. For laboratory experiments, the inlet of the instrument was overflown by excess synthetic air containing one or more reactants. In order to distinguish between OH produced by reactions upstream of the inlet and artificial signals produced inside the instrument, a chemical titration for OH was applied. Additional experiments were performed in the simulation chamber SAPHIR where simultaneous measurements by an open-path differential optical absorption spectrometer (DOAS) served as reference for OH to quantify potential artifacts in the LIF instrument. Experiments included the investigation of potential interferences related to the nitrate radical (NO3, N2O5), related to the ozonolysis of alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene, α-pinene, limonene, isoprene), and the laser photolysis of acetone. Experiments studying the laser photolysis of acetone yield OH signals in the fluorescence cell, which are equivalent to 0.05 × 106 cm−3 OH for a mixing ratio of 5 ppbv acetone. Under most atmospheric conditions, this interference is negligible. No significant interferences were found for atmospheric concentrations of reactants during ozonolysis experiments. Only for α-pinene, limonene, and isoprene at reactant concentrations which are orders of magnitude higher than in the atmosphere artificial OH could be detected. The value of the interference depends on the turnover rate of the ozonolysis reaction. For example, an apparent OH concentration of approximately 1 × 106 cm−3 is observed, if 5.8 ppbv limonene reacts with 600 ppbv ozone. Experiments with the nitrate radical NO3 reveal a small interference signal in the OH, HO2 and RO2 detection. Dependencies on experimental parameters point to artificial OH formation by surface reactions at the chamber walls or in molecular clusters in the gas expansion. The signal scales with the presence of NO3 giving equivalent radical concentrations of 1.1 × 105 cm−3 OH, 1 × 107 cm−3 HO2, and 1.7 × 107 cm−3 RO2 per 10 pptv NO3

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