Tantalum-Titanium Oxynitride Thin Films Deposited by DC Reactive Magnetron Co-Sputtering: Mechanical, Optical, and Electrical Characterization

The possibility to tune the elemental composition and structure of binary Me oxynitride-type compounds (Me1Me2ON) could lead to attractive properties for several applications. For this work, tantalum-titanium oxynitride (TaTiON) thin films were deposited by DC reactive magnetron co-sputtering, with a –50 V bias voltage applied to the substrate holder and a constant substrate temperature of 100 °C. To increase or to decrease in a controlled manner, the Ti and Ta content in the co-sputtered films, the Ti and Ta target currents were varied between 0.00 and 1.00 A, in 0.25 A steps, while keeping the sum of the currents applied to the two targets at 1.00 A. The reactive gases flow, consisting of a nitrogen and oxygen gas mixture with a constant N2/O2 ratio (85%/15%), was also kept constant. The single-metal oxynitrides (TaON and TiON) showed a low degree of crystallinity, while all the other co-sputtered films revealed themselves to be essentially amorphous. These two films also exhibited higher adhesion to the metallic substrate. The TaON film showed the highest hardness value (14.8 GPa) and the TiON film a much lower one (8.8 GPa), while the co-sputtered coatings exhibited intermediary values. One of the most interesting findings was the significant increase in the O content when the Ti concentration surpassed the Ta one. This significantly influenced the optical characteristic of the films, but also their electrical properties. The sheet resistivity of the co-sputtered films is strongly dependent on the O/(Ta + Ti) atomic ratio.

Atmospheric Pressure Catalytic Vapor Deposition of Graphene on Liquid In and Cu-In Alloy Substrates

Liquid substrates are great candidates for the growth of high-quality graphene using chemical vapour deposition (CVD) due to their atomically flat and defect free surfaces. A detailed study of graphene growth using atmospheric pressure CVD (APCVD) on liquid indium (In) was conducted. It was found that the effect of the growth parameters on the quality of the graphene produced is highly dependent on the properties of the substrate used. A short residence time of 6.8 sec for the reactive gases led to a high graphene quality, indicating the good catalytic behaviour of In. The role of hydrogen partial pressure was found to be crucial, with monolayer and bilayer graphene films with a low defect density obtained at low PH2 (38.6 mbar), whilst more defective, thicker graphene films with a partial coverage being obtained at high PH2 (74.3 mbar). The graphene deposition was insensitive to growth time as the graphene growth on liquid In was found to self-limit to bilayer. For further investigation, five compositions of Cu-In alloys were made by arc-melting. Graphene was then grown using the optimum conditions for In and the quality of the graphene was found to degrade with increasing Cu wt.%. This work will aid the future optimisation of the growth conditions based upon the substrate’s properties.

Investigation of Regeneration Mechanisms of Aged Solar Salt

The scope of our study was to examine the potential of regeneration mechanisms of an aged molten Solar Salt (nitrite, oxide impurity) by utilization of reactive gas species (nitrous gases, oxygen). Initially, aging of Solar Salt (60 wt% NaNO3, 40 wt% KNO3) was mimicked by supplementing the decomposition products, sodium nitrite and sodium peroxide, to the nitrate salt mixture. The impact of different reactive purge gas compositions on the regeneration of Solar Salt was elaborated. Purging the molten salt with a synthetic air (p(O2) = 0.2 atm) gas stream containing NO (200 ppm), the oxide ion concentration was effectively reduced. Increasing the oxygen partial pressure (p(O2) = 0.8 atm, 200 ppm NO) resulted in even lower oxide ion equilibrium concentrations. To our knowledge, this investigation is the first to present evidence of the regeneration of an oxide rich molten Solar Salt, and reveals the huge impact of reactive gases on Solar Salt reaction chemistry.

Cr-Based Sputtered Decorative Coatings for Automotive Industry

The present work aims to study the impact of O and N addition on Cr-sputtered coatings on plastic (polycarbonate, PC) used in automobile parts, as a promisor alternative for auto part metallization, while eliminating the usage of toxic hexavalent chromium. The coatings were deposited using DC magnetron sputtering from a single pure Cr target in a reactive atmosphere (N2 and/or O2). The deposition of the coatings was performed maintaining the total pressure constant and close to 1 Pa by tuning Ar pressure while reactive gases were added. The target current density was kept at JW = 20 mA·cm−2. Structural characterization revealed a mixture of α-Cr, δ-Cr, β-Cr2N, and CrN crystalline structures as well as amorphous oxides. The coating hardness ranged from 9 GPa for the CrON coating to 15 GPa for the CrN coating. All deposited coatings showed a particularly good interface adhesion; adjusting the amount of O and N made it possible to tune the optical properties of the Cr-based coatings as desired. The promising results open future industrialization of sputtered Cr-based coatings for automotive industries.

Interaction of Reactive Gases with Platinum Aerosol Particles at Room Temperature: Effects on Morphology and Surface Properties

Nanoparticles produced in technical aerosol processes exhibit often dendritic structures, composed of primary particles. Surprisingly, a small but consistent discrepancy was observed between the results of common aggregation models and in situ measurements of structural parameters, such as fractal dimension or mass-mobility exponent. A phenomenon which has received little attention so far is the interaction of agglomerates with admixed gases, which might be responsible for this discrepancy. In this work, we present an analytical series, which underlines the agglomerate morphology depending on the reducing or oxidizing nature of a carrier gas for platinum particles. When hydrogen is added to openly structured particles, as investigated by tandem differential mobility analysis (DMA) and transmission electron microscopy (TEM) analysis, Pt particles compact already at room temperature, resulting in an increased fractal dimension. Aerosol Photoemission Spectroscopy (APES) was also able to demonstrate the interaction of a gas with a nanoscaled platinum surface, resulting in a changed sintering behavior for reducing and oxidizing atmospheres in comparison to nitrogen. The main message of this work is about the structural change of particles exposed to a new environment after complete particle formation. We suspect significant implications for the interpretation of agglomerate formation, as many aerosol processes involve reactive gases or slightly contaminated gases in terms of trace amounts of unintended species.

Potential Source Regions and Transportation Pathways of Reactive Gases at a Regional Background Site in Northwestern China

Reactive gases (O3, CO, NO2, and SO2) were collected hourly at the Akedala regional background station in northwestern China during September 2017 to August 2018. Wind rose, cluster analysis, potential source contribution function (PSCF), and concentration-weighted trajectory (CWT) methods were adopted for identifying the transport pathways and potential source regions of these atmosphere components at Akedala. The average O3, CO, NO2, and SO2 mixing ratios detected were 29.65 ± 11.44 ppb, 123.78 ± 73.35 ppb, 3.79 ± 0.98 ppb, and 4.59 ± 0.88 ppb during the observation period, and the statistical results of the monthly mean values revealed that there were differences during the highest pollution period, with O3 and CO mainly peaking in February, with mixing ratios of 38.03 ± 7.10 ppb and 208.50 ± 106.50 ppb, respectively. Meanwhile, NO2 peaked in March (4.51 ± 0.54 ppb) and SO2 in January (5.70 ± 1.92 ppb). The most obvious diurnal variation of CO and SO2 was observed in the winter, with maximum levels reaching between 13 : 00 and 14 : 00. The diurnal variations of O3 exhibited low values during the night and maximum values in the afternoon (16 : 00–18 : 00). Diurnal variation was not significant in the case of NO2. Cluster analysis showed that six main paths affected the Akedala atmosphere. In turn, the PSCF and CWT analysis results indicated that the Akedala reactive gas was affected by both local and foreign sources. The high PSCF value of the reactive gas potential source areas appeared in eastern Kazakhstan, northern Xinjiang, Western Mongolia, and Southern Russia. The WCWT (weighted concentration-weight trajectory) values of CO and SO2 in winter were the highest, totaling 180–240 ppb and 5–6.5 ppb, respectively. The WCWT value of O3 in the spring and summer was higher than that in the autumn and winter. The main source area of O3 was about 32–36 ppb in the spring and summer, and the main source area of NO2 in the summer had a low WCWT value of 3–3.5 ppb, whereas the NO2 WCWT value was concentrated at 4–4.5 ppb in the other seasons.

Significant climate benefits from near-term climate forcer mitigation in spite of aerosol reductions

<p>Near-term climate forcers (NTCFs), including aerosols and chemically reactive gases such as tropospheric ozone and methane, offer a potential way to mitigate climate change and improve air quality--so called "win-win" mitigation policies.   Prior studies support improved air quality under NTCF mitigation, but with conflicting climate impacts that range from a significant reduction in the rate of global warming to only a modest impact.  Here, we use state-of-the-art chemistry-climate model simulations conducted as part of the Aerosol and Chemistry Model Intercomparison Project (AerChemMIP) to quantify the 21st-century impact of NTCF reductions, using a realistic future emission scenario with a consistent air quality policy.  Non-methane NTCF (NMNTCF; aerosols and ozone precursors) mitigation improves air quality, but leads to significant increases in global mean precipitation of 1.3% by mid-century and 1.4% by end-of-the-century, and corresponding surface warming of 0.23 and 0.21 K.  NTCF (all-NTCF; including methane) mitigation further improves air quality, with larger reductions of up to 45% for ozone pollution, while offsetting half of the wetting by mid-century (0.7% increase) and all the wetting by end-of-the-century (non-significant 0.1% increase) and leading to surface cooling of -0.15 K by mid-century and -0.50 K by end-of-the-century.  This suggests that methane mitigation offsets warming induced from reductions in NMNTCFs, while also leading to net improvements in air quality.</p>

Recent updates to the atmospheric chemistry modeling of the ECMWF IFS in support to CAMS

<p>The Integrated Forecasting System (IFS) of ECMWF is the core of the Copernicus Atmosphere Monitoring Service (CAMS) which provides global analyses and forecasts of atmospheric composition, namely reactive gases, aerosol and greenhouse gases. With respect to the atmospheric chemistry component, the operational system currently relies on a modified version of the CB05 chemistry scheme for the troposphere, combined with the Cariolle scheme to describe stratospheric ozone. In an alternative, more recent configuration also stratospheric ozone chemistry is included based on the BASCOE chemistry module. Alternative atmospheric chemistry modules which can be employed are based on MOZART and MOCAGE chemistry. <br>Recently, further revisions to the modified CB05 tropospheric chemistry scheme have been developed, focusing both on inorganic and organic chemistry, with the aim of improving the quality of existing air-quality products, and the development of new products. On major update is a revision of the isoprene oxidation scheme based on those employed in existing chemistry transport models, as well as inclusion of the basic chemistry describing C8 and C9 aromatics degradation. <br>An example of a new product derived from these updates include a description of global distribution of glyoxal, while this also resulted in an improved modeling of OH recycling particularly over tropical forests. Also we support improved secondary organic aerosol formation due to gaseous anthropogenic, biogenic and biomass burning sources.<br>In this contribution we provide an overview of these revisions, and provide a first quantification of their uncertainties, by comparing products to observations and to those from alternative chemistry modules.</p>

Emission Monitoring Mobile Experiment (EMME): an overview and first results of the St. Petersburg megacity campaign 2019

Global climate change is one of the most important scientific, societal and economic contemporary challenges. Fundamental understanding of the major processes driving climate change is the key problem which is to be solved not only on a global but also on a regional scale. The accuracy of regional climate modelling depends on a number of factors. One of these factors is the adequate and comprehensive information on the anthropogenic impact which is highest in industrial regions and areas with dense population – modern megacities. Megacities are not only “heat islands”, but also significant sources of emissions of various substances into the atmosphere, including greenhouse and reactive gases. In 2019, the mobile experiment EMME (Emission Monitoring Mobile Experiment) was conducted within the St. Petersburg agglomeration (Russia) aiming to estimate the emission intensity of greenhouse (CO2, CH4) and reactive (CO, NOx) gases for St. Petersburg, which is the largest northern megacity. St. Petersburg State University (Russia), Karlsruhe Institute of Technology (Germany) and the University of Bremen (Germany) jointly ran this experiment. The core instruments of the campaign were two portable Bruker EM27/SUN Fourier transform infrared (FTIR) spectrometers which were used for ground-based remote sensing measurements of the total column amount of CO2, CH4 and CO at upwind and downwind locations on opposite sides of the city. The NO2 tropospheric column amount was observed along a circular highway around the city by continuous mobile measurements of scattered solar visible radiation with an OceanOptics HR4000 spectrometer using the differential optical absorption spectroscopy (DOAS) technique. Simultaneously, air samples were collected in air bags for subsequent laboratory analysis. The air samples were taken at the locations of FTIR observations at the ground level and also at altitudes of about 100 m when air bags were lifted by a kite (in case of suitable landscape and favourable wind conditions). The entire campaign consisted of 11 mostly cloudless days of measurements in March–April 2019. Planning of measurements for each day included the determination of optimal location for FTIR spectrometers based on weather forecasts, combined with the numerical modelling of the pollution transport in the megacity area. The real-time corrections of the FTIR operation sites were performed depending on the actual evolution of the megacity NOx plume as detected by the mobile DOAS observations. The estimates of the St. Petersburg emission intensities for the considered greenhouse and reactive gases were obtained by coupling a box model and the results of the EMME observational campaign using the mass balance approach. The CO2 emission flux for St. Petersburg as an area source was estimated to be 89 ± 28 ktkm-2yr-1, which is 2 times higher than the corresponding value in the EDGAR database. The experiment revealed the CH4 emission flux of 135 ± 68 tkm-2yr-1, which is about 1 order of magnitude greater than the value reported by the official inventories of St. Petersburg emissions (∼ 25 tkm-2yr-1 for 2017). At the same time, for the urban territory of St. Petersburg, both the EMME experiment and the official inventories for 2017 give similar results for the CO anthropogenic flux (251 ± 104 tkm-2yr-1 vs. 410 tkm-2yr-1) and for the NOx anthropogenic flux (66 ± 28 tkm-2yr-1 vs. 69 tkm-2yr-1).