Chalcogenide Thermoelectrics Empowered by an Unconventional Bonding Mechanism

Thermoelectric materials have attracted significant research interest in recent decades due to their promising application potential in interconverting heat and electricity. Unfortunately, the strong coupling between the material parameters that determine thermoelectric efficiency, i.e., the Seebeck coefficient, electrical conductivity, and thermal conductivity, complicates the optimization of thermoelectric energy converters. Main‐group chalcogenides provide a rich playground to alleviate the interdependence of these parameters. Interestingly, only a subgroup of octahedrally coordinated chalcogenides possesses good thermoelectric properties. This subgroup is also characterized by other outstanding characteristics suggestive of an exceptional bonding mechanism, which has been coined metavalent bonding. This conclusion is further supported by a map that separates different bonding mechanisms. In this map, all octahedrally coordinated chalcogenides with good performance as thermoelectrics are located in a well‐defined region, implying that the map can be utilized to identify novel thermoelectrics. To unravel the correlation between chemical bonding mechanism and good thermoelectric properties, the consequences of this unusual bonding mechanism on the band structure are analyzed. It is shown that features such as band degeneracy and band anisotropy are typical for this bonding mechanism, as is the low lattice thermal conductivity. This fundamental understanding, in turn, guides the rational materials design for improved thermoelectric performance by tailoring the chemical bonding mechanism.     

The Dynamic Emission Zone in Sandwich Polymer Light‐Emitting Electrochemical Cells

In light‐emitting electrochemical cells (LECs), the position of the emission zone (EZ) is not predefined via a multilayer architecture design, but governed by a complex motion of electrical and ionic charges. As a result of the evolution of doped charge transport layers that enclose a dynamic intrinsic region until steady state is reached, the EZ is often dynamic during turn‐on. For thick sandwich polymer LECs, a continuous change of the emission color provides a direct visual indication of a moving EZ. Results from an optical and electrical analysis indicate that the intrinsic zone is narrow at early times, but starts to widen during operation, notably well before the electrical device optimum is reached. Results from numerical simulations demonstrate that the only precondition for this event to occur is that the mobilities of anions (μ_a) and cations (μ_c) are not equal, and the direction of the EZ shift dictates μ_c > μ_a. Quantitative ion profiles reveal that the displacement of ions stops when the intrinsic zone stabilizes, confirming the relation between ion movement and EZ shift. Finally, simulations indicate that the experimental current peak for constant‐voltage operation is intrinsic and the subsequent decay does not result from degradation, as commonly stated.     

Structure–Thermodynamic‐Property Relationships in Cyanovinyl‐Based Microporous Polymer Networks for the Future Design of Advanced Carbon Capture Materials

Nitrogen‐rich solid absorbents, which have been immensely tested for carbon dioxide capture, seem until this date to be without decisive molecular engineering or design rules. Here, a family of cyanovinylene‐based microporous polymers synthesized under metal‐catalyzed conditions is reported as a promising candidate for advanced carbon capture materials. These networks reveal that isosteric heats of CO₂ adsorption are directly proportional to the amount of their functional group. Motivated by this finding, polymers produced under base‐catalyzed conditions with tailored quantities of cyanovinyl content confirm the systematical tuning of their sorption enthalpies to reach 40 kJ mol^?1. This value is among the highest reported to date in carbonaceous networks undergoing physisorption. A six‐point‐plot reveals that the structure–thermodynamic‐property relationship is linearly proportional and can thus be perfectly fitted to tailor‐made values prior to experimental measurements. Dynamic simulations show a bowl‐shaped region within which CO₂ is able to sit and interact with its conjugated surrounding, while theoretical calculations confirm the increase of binding sites with the increase of Ph? C?C(CN)? Ph functionality in a network. This concept presents a distinct method for the future design of carbon dioxide capturing materials.     

The Twitterization of News Making: Transparency and Journalistic Professionalism

Twitter makes visible some of the most fundamental divides in professional journalism today. It reveals tensions about what constitutes news, the norms guiding journalists providing it, professional identity, and public service. This article argues that these tensions result from a clash between the institutional logic of professional control (Lewis, 2012)) and an ethic of transparency. Drawing from extensive research on a political press corps, involving observation, interviews, and analysis of tweets, this study witnesses the adoption of Twitter in the everyday working practices of reporters. It thereby also provides reasons why Twitter has been so successful in journalism. Tensions between professional control and transparency in journalism may, furthermore, be emblematic for divides in other professions today.     

Characterization of Micro-Powders for the Fabrication of Compression Molded THz Lenses

We investigate different micro-powders that can be used as base materials for THz lenses fabricated by compression molding. For this application materials with a very weak THz absorbance and low dispersion are required. By measuring the THz absorption coefficient and refractive index of pellets pressed from the different micro-powders, we identify several materials that are well suited for the fabrication of compression molded THz lenses (CMLs). In addition, a considerable range of the refractive index is covered by the samples, which will allow for the fabrication of CMLs with different focal lengths for one and the same lens design.     

Potentials and challenges of peer-to-peer based content distribution

Multimedia content currently accounts for over three quarters of all Internet traffic. This increase in traffic volume and content availability derives from a paradigm shift from the traditional text and picture based Web, to more resource demanding audio and video content. A controversial driver for this development is content distribution systems based on peer-to-peer overlay networks. Flooding the Internet with often illegal content, these networks now pose challenges to all actors in the value chain. However, if viewed as surmountable challenges in an evolutionary path, peer-to-peer technology has the potential of increasing efficiency in content distribution and unleashing resources to form scalable and resilient overlay networks of unprecedented dimensions.

In this paper we examine the potentials and challenges of peer-to-peer technology in content distribution, and analyse how, and under which circumstances, peer-to-peer technology can be used to increase the efficiency of multimedia services. The paper provides an up-to-date overview of the development of peer-to-peer networks as well as describing the economics laws governing their use. To conclude the study, the paper analyses Skype, a well known telecommunications service utilising the peer-to-peer technology, as well as demonstrating the benefits of peer-to-peer based content distribution using empirical data from the Danish Broadcasting Corporation.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Linearisation of asymmetrical Doherty amplifier by the even-order non-linear signals

This paper considers the linearisation of an asymmetrical two-way Doherty amplifier by the method that uses the second harmonics and fourth-order non-linear signals for linearisation. These even-order signals for linearisation are extracted at the output of the peaking amplifier, adjusted in amplitude and phase and injected at the input and output of the carrier amplifier transistor in the Doherty configuration. The effect of linearisation has been experimentally confirmed on a fabricated asymmetrical Doherty amplifier with the additional circuit for linearisation. The suppression of the third-order intermodulation products has been carried out for two-tone test, 64QAM and WCDMA digitally modulated signals in a range of signal power.     

Core‐Brominated Tetraazaperopyrenes as n‐Channel Semiconductors for Organic Complementary Circuits on Flexible Substrates

Organic thin‐film transistors (TFTs) are prepared by vacuum deposition and solution shearing of 2,9‐bis(perfluoroalkyl)‐substituted tetraazaperopyrenes (TAPPs) with bromine substituents at the aromatic core. The TAPP derivatives are synthesized by reacting known unsubstituted TAPPs with bromine in fuming sulphuric acid, and their electrochemical properties are studied in detail by cyclic voltammetry and modelled with density functional theory (DFT) methods. Lowest unoccupied molecular orbital (LUMO) energies and electron affinities indicate that the core‐brominated TAPPs should exhibit n‐channel semiconducting properties. Current‐voltage characteristics of the TFTs established electron mobilities of up to μ_n = 0.032 cm² V^?1 s^?1 for a derivative which was subsequently processed in the fabrication of a complementary ring oscillator on a flexible plastic substrate (PEN).