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.     

Remote plasma etching of titanium nitride using NF3/argon and chlorine mixtures for chamber clean applications

To avoid plasma induced erosion of chamber hardware, the application of remote plasma sources to activate the etch gases was introduced. We present results on the etch behaviour of titanium nitride (TiN) using mixtures of NF₃, Cl₂ and argon. The gas mixture was excited in a remote plasma source and then routed through a reaction chamber to study the etch behaviour of TiN samples which simulate the situation at the chamber walls. The dependency of the TiN etch rate on temperature, gas flow, composition and pressure was examined. While the temperature (studied in the range 25-300 °C) turned out to be the most sensitive parameter, the general etch rate was mainly dependent on the availability of atomic fluorine. Etch products and NF₃/Cl₂ dissociation have been monitored by quadrupole mass spectrometry and infrared spectroscopy. While NF₃ showed a high decomposition up to 96%, chlorine decomposition was not observed. However the addition of chlorine increased the etch rates up to 260% in the low pressure/low temperature regime. Surface effects of chlorine addition are indicated by X-Ray Photoelectron Spectrometry and REM surface analysis.     

Demonstration of the monolithic interconnection on CIS solar cells by picosecond laser structuring on 30 by 30 cm2 modules

In this paper, we present the selective structuring of all three patterns (P1, P2 and P3) of a monolithic interconnection of CIS (Cu(In,Ga)(S,Se)₂) thin film solar cells by picosecond laser pulses at a wavelength of 1064 nm. We show results for single pulse ablation threshold values and line scribing of molybdenum films on glass (P1), CIS on molybdenum (P2) and zinc oxide on CIS (P3). The purposes of these processes are the p‐type isolation (P1), cell interconnect (P2) and n‐type isolation (P3), which are required for complete cell architecture. The half micron thick molybdenum back electrode can be structured with a process speed of more than 15 m/s at about 15 W average power without detectable residues and damage by direct induced laser ablation from the back side (P1). The CIS layer can be structured selectively down to the molybdenum at process speeds up to 1 m/s at about 15 W average power, due to the precision of direct laser ablation in the ultrashort pulse regime (P2). The ZnO front electrode layer is separated by clean trenches with straight side walls at process speeds of up to 15 m/s at about 10 W average power, as a result of indirect induced laser ablation (P3). A validation of functionality of all processes is demonstrated on CIS solar cell modules (30 × 30 cm²). By replacing one state‐of‐the‐art process by a picosecond laser process at a time, solar efficiencies could be increased for P1 and P2 and stayed on a similar level for P3. After an optimization of the patterning processes in the R&D pilot line of AVANCIS, we achieved a new record efficiency for an all‐laser‐patterned CIS solar module: 14.7% as best value for the aperture area efficiency of a 30 × 30 cm² sized CIS module was reached. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurement and Calculation of the Absolute Thermoelectric Power of Rhodium and Iridium

The thermoelectric power of Rh and Ir was redetermined between 100 K and 1400 K. It varies almost linearly from +1.7 μV K⁻¹ to −3.8 μV K⁻¹ for Rh and from +1.5 μV K⁻¹ to −2.2 μV K⁻¹ for Ir. The diffusive part of the thermopower could be calculated from the density of states. It is approximately equal to the temperature dependence of the electrochemical potential of the electrons divided by the electronic charge. This is attributed to the approximate establishment of local equilibrium between electrons and lattice atoms above 400 K—a condition not fulfilled in the phonon-drag regime below 300 K.     

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.     

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.     

Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.