Study of Gallium-Doped Zinc Oxide Thin Films Processed by Atomic Layer Deposition and RF Magnetron Sputtering for Transparent Antenna Applications.

Gallium-doped zinc oxide (GZO) films were fabricated using RF magnetron sputtering and atomic layer deposition (ALD). The latter ones demonstrate higher electrical conductivities (up to 2700 S cm-1) and enhanced charge mobilities (18 cm2 V-1 s-1). The morphological analysis reveals differences mostly due to the very different nature of the deposition processes. The film deposited via ALD shows an increased transmittance in the visible range and a very small one in the infrared range that leads to a figure of merit of 0.009 Ω-1 (10 times higher than for the films deposited via sputtering). A benchmarking is made with an RF sputtered indium-doped tin oxide (ITO) film used conventionally in the industry. Another comparison between ZnO, Al:ZnO (AZO), and Ga:ZnO (GZO) films fabricated by ALD is presented, and the evolution of physical properties with doping is evidenced. Finally, we processed GZO thin films on a glass substrate into patterned transparent patch antennas to demonstrate an application case of short-range communication by means of the Bluetooth Low Energy (BLE) protocol. The GZO transparent antennas' performances are compared to a reference ITO antenna on a glass substrate and a conventional copper antenna on FR4 PCB. The results highlight the possibility to use the transparent GZO antenna for reliable short-range communication and the achievability of an antenna entirely processed by ALD.

Low-Temperature Growth of AlN Films on Magnetostrictive Foils for High-Magnetoelectric-Response Thin-Film Composites.

This study reports a strong ME effect in thin-film composites consisting of nickel, iron, or cobalt foils and 550 nm thick AlN films grown by PE-ALD at a (low) temperature of 250 °C and ensuring isotropic and highly conformal coating profiles. The AlN film quality and the interface between the film and the foils are meticulously investigated by means of high-resolution transmission electron microscopy and the adhesion test. An interface (transition) layer of partially amorphous AlxOy/AlOxNy with thicknesses of 10 and 20 nm, corresponding to the films grown on Ni, Fe, and Co foils, is revealed. The AlN film is found to be composed of a mixture of amorphous and nanocrystalline grains at the interface. However, its crystallinity is improved as the film grew and shows a highly preferred (002) orientation. High self-biased ME coefficients (αME at a zero-bias magnetic field) of 3.3, 2.7, and 3.1 V·cm-1·Oe-1 are achieved at an off-resonance frequency of 46 Hz in AlN/Ni thin-film composites with different Ni foil thicknesses of 7.5, 15, and 30 µm, respectively. In addition, magnetoelectric measurements have also been carried out in composites made of 550 nm thick films grown on 12.5 µm thick Fe and 15 µm thick Co foils. The maximum magnetoelectric coefficients of AlN/Fe and AlN/Co composites are 0.32 and 0.12 V·cm-1·Oe-1, measured at 46 Hz at a bias magnetic field (Hdc) of 6 and 200 Oe, respectively. The difference of magnetoelectric transducing responses of each composite is discussed according to interface analysis. We report a maximum delivered power density of 75 nW/cm3 for the AlN/Ni composite with a load resistance of 200 kΩ to address potential energy harvesting and electromagnetic sensor applications.

Waste- and Cd-Free Inkjet-Printed Zn(O,S) Buffer for Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells.

Thin film semiconductors grown using chemical bath methods produce large amounts of waste solvent and chemicals that then require costly waste processing. We replace the toxic chemical bath deposited CdS buffer layer from our Cu(In,Ga)(S,Se)2 (CIGS)-based solar cells with a benign inkjet-printed and annealed Zn(O,S) layer using 230 000 times less solvent and 64 000 times less chemicals. The wetting and final thickness of the Zn(O,S) layer on the CIGS is controlled by a UV ozone treatment and the drop spacing, whereas the annealing temperature and atmosphere determine the final chemical composition and band gap. The best solar cell using a Zn(O,S) air-annealed layer had an efficiency of 11%, which is similar to the best conventional CdS buffer layer device fabricated in the same batch. Improving the Zn(O,S) wetting and annealing conditions resulted in the best device efficiency of 13.5%, showing the potential of this method.

Chemical instability at chalcogenide surfaces impacts chalcopyrite devices well beyond the surface.

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe2 solar cells.

Visualising Silicon in Plants: Histochemistry, Silica Sculptures and Elemental Imaging.

Silicon is a non-essential element for plants and is available in biota as silicic acid. Its presence has been associated with a general improvement of plant vigour and response to exogenous stresses. Plants accumulate silicon in their tissues as amorphous silica and cell walls are preferential sites. While several papers have been published on the mitigatory effects that silicon has on plants under stress, there has been less research on imaging silicon in plant tissues. Imaging offers important complementary results to molecular data, since it provides spatial information. Herein, the focus is on histochemistry coupled to optical microscopy, fluorescence and scanning electron microscopy of microwave acid extracted plant silica, techniques based on particle-induced X-ray emission, X-ray fluorescence spectrometry and mass spectrometry imaging (NanoSIMS). Sample preparation procedures will not be discussed in detail, as several reviews have already treated this subject extensively. We focus instead on the information that each technique provides by offering, for each imaging approach, examples from both silicifiers (giant horsetail and rice) and non-accumulators (Cannabis sativa L.).

Identification of the aquaporin gene family in Cannabis sativa and evidence for the accumulation of silicon in its tissues.

Cannabis sativa is an economically important crop providing bast fibres for the textile and biocomposite sector. Length is a fundamental characteristic determining the properties of bast fibres. Aquaporins, channel-forming proteins facilitating the passage of water, urea, as well as elements such as boron and silicon, are known to play a role in the control of fibre length in other species, like cotton. By mining the available genome, we here identify, for the first time, the aquaporin gene family of C. sativa. The analysis of published RNA-Seq data and targeted qPCR on a textile variety reveal an organ-specific expression of aquaporin genes. Computational analyses, including homology-based search, phylogeny and protein modelling, identify two NOD26-like intrinsic proteins harbouring the Gly-Ser-Gly-Arg (GSGR) aromatic/Arg selectivity filter and 108 amino acid NPA (Asn-Pro-Ala) spacing, features reported to be associated with silicon permeability. SIMS nano-analysis and silica extraction coupled to fluorescence microscopy performed on hemp plantlets reveal the presence of silicon in the bast fibres of the hypocotyl and in leaves. The accumulation of silica in the distal cell walls of bast fibres and in the basal cells of leaf trichomes is indicative of a mechanical role.

Do the pristine physico-chemical properties of silver and gold nanoparticles influence uptake and molecular effects on Gammarus fossarum (Crustacea Amphipoda)?

The specific and unique properties of silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs), make them of high interest for different scientific and industrial applications. Their increasing use will inevitably lead to their release in the environment and aquatic ecosystems where they may represent a threat to aquatic organisms. Being a widespread and important component of the aquatic macroinvertebrate assemblage, amphipods and more specifically Gammarus fossarum will certainly be exposed to AgNPs and AuNPs. For these reasons, G. fossarum was selected as model organism for this study. The aim of the present work was the evaluation of the influence of both size (20, 40 and 80 nm) and surface coating (citrate CIT, polyethylene glycol PEG) on the acute toxicity of AgNPs and AuNPs on G. fossarum. We investigated the effects of AgNPs and AuNPs on the uptake by G. fossarum, NP tissue distribution and the expression of stress related genes by the use of ICP-MS, NanoSIMS50, Cytoviva®, and Rt-qPCR, respectively. Ag and Au bioaccumulation revealed a significant surface-coating dependence, with CIT-AgNPs and CIT-AuNPs showing the higher bio-accumulation potential in G. fossarum as compared to PEG-NPs. Opposite to that, no size-dependent effects on the bioaccumulation potential was observed. SIMS imaging and CytoViva® revealed an influence of the type of metal on the tissue distribution after uptake, with AgNPs detected in the cuticle and the gills of G. fossarum, while AuNPs were detected in the gut area. Furthermore, AgNPs were found to up-regulate CuZnSOD gene expression while AuNPs led to its down-regulation. Modulation of SOD may indicate generation of reactive species of oxygen and a possible activation of antioxidant defence in order to prevent and defend the organism from oxidative stress. However, further investigations are still needed to better define the mechanisms underlying the observed AgNPs and AuNPs effects.

Sodium enhances indium-gallium interdiffusion in copper indium gallium diselenide photovoltaic absorbers.

Copper indium gallium diselenide-based technology provides the most efficient solar energy conversion among all thin-film photovoltaic devices. This is possible due to engineered gallium depth gradients and alkali extrinsic doping. Sodium is well known to impede interdiffusion of indium and gallium in polycrystalline Cu(In,Ga)Se2 films, thus influencing the gallium depth distribution. Here, however, sodium is shown to have the opposite effect in monocrystalline gallium-free CuInSe2 grown on GaAs substrates. Gallium in-diffusion from the substrates is enhanced when sodium is incorporated into the film, leading to Cu(In,Ga)Se2 and Cu(In,Ga)3Se5 phase formation. These results show that sodium does not decrease per se indium and gallium interdiffusion. Instead, it is suggested that sodium promotes indium and gallium intragrain diffusion, while it hinders intergrain diffusion by segregating at grain boundaries. The deeper understanding of dopant-mediated atomic diffusion mechanisms should lead to more effective chemical and electrical passivation strategies, and more efficient solar cells.

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

Temperature-dependent wear mechanisms for magnetron-sputtered AlTiTaN hard coatings.

AlTiTaN coatings have been demonstrated to have high thermal stability at temperatures up to 900 °C. It has been speculated that the high oxidation resistance promotes an improved wear resistance, specifically for dry machining applications. This work reports on the influence of temperature up to 900 °C on the wear mechanisms of AlTiTaN hard coatings. DC magnetron-sputtered coatings were obtained from an Al(46)Ti(42)Ta(12) target, keeping the substrate bias at -100 V and the substrate temperature at 265 °C. The coatings exhibited a single-phase face-centered cubic AlTiTaN structure. The dry sliding tests revealed predominant abrasion and tribo-oxidation as wear mechanisms, depending on the wear debris formed. At room temperature, abrasion leading to surface polishing was observed. At 700 and 800 °C, slow tribo-oxidation and an amorphous oxide formed reduced the wear rate of the coating compared to room temperature. Further, an increase in temperature to 900 °C increased the wear rate significantly due to fast tribo-oxidation accompanied by grooving. The friction coefficient was found to decrease with temperature increasing from 700 to 900 °C due to the formation of oxide scales, which reduce adhesion of asperity contacts. A relationship between the oxidation and wear mechanisms was established using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, surface profilometry, confocal microscopy, and dynamic secondary ion mass spectrometry.

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.