Fluidic flow delay by ionogel passive pumps in microfluidic paper-based analytical devices

[EN] A new concept for fluid flow manipulation in microfluidic paper-based analytical devices (m-PADs) is presented by introducing ionogel materials as passive pumps. m-PADs were fabricated using a new doubleside contact stamping process and ionogels were precisely photopolymerised at the inlet of the m-PADs.The ionogels remain mainly on the surface of the paper and get absorbed in the superficial paper-fibers allowing for the liquid to flow from the ionogel into the paper easily. As a proof of concept the fluid flowand mixing behaviour of two different ionogels mPADs were compared with the non-treated mPADs.It was demonstrated that both ionogels highly affect the fluid flow by delaying the flow due to their different physical and chemical properties and water holding capacities.

From carbon markets to carbon morality: creative compounds as framing devices in online discourses on climate change mitigation

Lexical combinations of at least two roots around "carbon" as the hub, such as "carbon finance" or "carbon footprint," have recently become ubiquitous in English-speaking science, politics, and mass media. They are part of a new language evolving around the issue of climate change that can reveal how it is framed by various stakeholders. In this article, the authors study the role of these "carbon compounds" as tools of communication in different online discourses on climate change mitigation. By combining a quantitative analysis of their occurrences with a qualitative analysis of the contexts in which the compounds were used, the authors identify three clusters of compounds focused on finance, lifestyle, and attitudes and elucidate the communicative purposes to which they were put between the 1990s and the early 21st century. This approach may open up new ways of analyzing the framings of climate change mitigation initiatives in the public sphere.

Mesoscale Optoelectronic Design of Wire-Based Photovoltaic and Photoelectrochemical Devices

The overarching theme of this thesis is mesoscale optical and optoelectronic design of photovoltaic and photoelectrochemical devices. In a photovoltaic device, light absorption and charge carrier transport are coupled together on the mesoscale, and in a photoelectrochemical device, light absorption, charge carrier transport, catalysis, and solution species transport are all coupled together on the mesoscale. The work discussed herein demonstrates that simulation-based mesoscale optical and optoelectronic modeling can lead to detailed understanding of the operation and performance of these complex mesostructured devices, serve as a powerful tool for device optimization, and efficiently guide device design and experimental fabrication efforts. In-depth studies of two mesoscale wire-based device designs illustrate these principles—(i) an optoelectronic study of a tandem Si|WO3 microwire photoelectrochemical device, and (ii) an optical study of III-V nanowire arrays.

The study of the monolithic, tandem, Si|WO3 microwire photoelectrochemical device begins with development and validation of an optoelectronic model with experiment. This study capitalizes on synergy between experiment and simulation to demonstrate the model’s predictive power for extractable device voltage and light-limited current density. The developed model is then used to understand the limiting factors of the device and optimize its optoelectronic performance. The results of this work reveal that high fidelity modeling can facilitate unequivocal identification of limiting phenomena, such as parasitic absorption via excitation of a surface plasmon-polariton mode, and quick design optimization, achieving over a 300% enhancement in optoelectronic performance over a nominal design for this device architecture, which would be time-consuming and challenging to do via experiment.

The work on III-V nanowire arrays also starts as a collaboration of experiment and simulation aimed at gaining understanding of unprecedented, experimentally observed absorption enhancements in sparse arrays of vertically-oriented GaAs nanowires. To explain this resonant absorption in periodic arrays of high index semiconductor nanowires, a unified framework that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes is developed in the context of silicon, using both analytic theory and electromagnetic simulations. This detailed theoretical understanding is then applied to a simulation-based optimization of light absorption in sparse arrays of GaAs nanowires. Near-unity absorption in sparse, 5% fill fraction arrays is demonstrated via tapering of nanowires and multiple wire radii in a single array. Finally, experimental efforts are presented towards fabrication of the optimized array geometries. A hybrid self-catalyzed and selective area MOCVD growth method is used to establish morphology control of GaP nanowire arrays. Similarly, morphology and pattern control of nanowires is demonstrated with ICP-RIE of InP. Optical characterization of the InP nanowire arrays gives proof of principle that tapering and multiple wire radii can lead to near-unity absorption in sparse arrays of InP nanowires.

Interface properties and capacitance-voltage behaviour of diamond devices prepared by microwave-assisted CVD

Free standing diamond films were used to study the effect of diamond surface morphology and microstructure on the electrical properties of Schottky barrier diodes. By using free standing films both the rough top diamond surface and the very smooth bottom surface are available for post-metal deposition. Rectifying electrical contacts were then established either with the smooth or the rough surface. The estimate of doping density from the capacitance-voltage plots shows that the smooth surface has a lower doping density when compared with the top layers of the same film. The results also show that surface roughness does not contribute significantly to the frequency dispersion of the small signal capacitance. The electrical properties of an abrupt asymmetric n(+)(silicon)-p(diamond) junction have also been measured. The I-V curves exhibit at low temperatures a plateau near zero bias, and show inversion of rectification. Capacitance-voltage characteristics show a capacitance minimum with forward bias, which is dependent on the environment conditions. It is proposed that this anomalous effect arises from high level injection of minority carriers into the bulk.

Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

Interface properties and capacitance-voltage behaviour of diamond devices prepared by microwave-assisted CVD

Free standing diamond films were used to study the effect of diamond surface morphology and microstructure on the electrical properties of Schottky barrier diodes. By using free standing films both the rough top diamond surface and the very smooth bottom surface are available for post-metal deposition. Rectifying electrical contacts were then established either with the smooth or the rough surface. The estimate of doping density from the capacitance-voltage plots shows that the smooth surface has a lower doping density when compared with the top layers of the same film. The results also show that surface roughness does not contribute significantly to the frequency dispersion of the small signal capacitance. The electrical properties of an abrupt asymmetric n(+)(silicon)-p(diamond) junction have also been measured. The I-V curves exhibit at low temperatures a plateau near zero bias, and show inversion of rectification. Capacitance-voltage characteristics show a capacitance minimum with forward bias, which is dependent on the environment conditions. It is proposed that this anomalous effect arises from high level injection of minority carriers into the bulk.