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2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film
We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society.
The Anomalous Influence of Polyelectrolyte Concentration on the Deposition and Nanostructure of Poly(ethyleneimine)/Poly(acrylic acid) Multilayers
The deposition and nanostructure of polyelectrolyte (PEL) multilayers (PEMs) of branched poly(ethyleneimine)/poly(acrylic acid) (PEI/PAA) onto silicon substrates was studied in terms of the dependence of pH and the PEL concentration (cPEL) in the individual adsorption steps z. Both a commercial automatic dipping device and a homebuilt automatic stream coating device (flow cell) were used. Gravimetry, SFM, transmission (TRANS) and in situ attenuated total reflection (ATR) FTIR spectroscopy were used for the quantitative determination of the adsorbed amount, thickness, chemical composition and morphology of deposited PEMs, respectively. Firstly, the combination of pH = 10 for PEI and pH = 4 for PAA, where both PEL were predominantly in the neutral state, resulted in an extraordinarily high PEM deposition, while pH combinations, where one PEL component was charged, resulted in a significantly lower PEM deposition. This was attributed to both PEL conformation effects and acid/base interactions between basic PEI and acidic PAA. Secondly, for that pH combination an exponential relationship between PEM thickness and adsorption step z was found. Thirdly, based on the results of three independent methods, the course of the deposited amount of a PEM-10 (z = 10) versus cPEL in the range 0.001 to 0.015 M at pH = 10/4 was non-monotonous showing a pronounced maximum at cPEL = 0.005 M. Analogously, for cPEL = 0.005 M a maximum of roughness and structure size was found. Fourthly, related to that finding, in situ ATR-FTIR measurements gave evidence for the release of outermost located PEI upon PAA immersion (even step) and of outermost PAA upon PEI immersion (odd step) under formation of PEL complexes in solution. These studies help us to prepare PEL-based films with a defined thickness and morphology for interaction with biofluids in the biomedical and food fields. © 2019 by the author.
On the relationship between SiF4plasma species and sample properties in ultra low-k etching processes
The temporal behavior of the molecular etching product SiF4 in fluorocarbon-based plasmas used for the dry etching of ultra low-k (ULK) materials has been brought into connection with the polymer deposition on the surface during plasma treatment within the scope of this work. For this purpose, time-resolved measurements of the density of SiF4 have been performed by quantum cascade laser absorption spectroscopy. A quantification of the non-linear time dependence was achieved by its characterization via a time constant of the decreasing SiF4 density over the process time. The time constant predicts how fast the stationary SiF4 density is reached. The higher the time constant is, the thicker the polymer film on top of the treated ultra low-k surface. A correlation between the time constant and the ULK damage was also found. ULK damage and polymer deposition were proven by Variable Angle Spectroscopic Ellipsometry and X-ray Photoelectron Spectroscopy. In summary, the observed decay of the etching product concentration over process time is caused by the suppressed desorption of the SiF4 molecules due to a more dominant adsorption of polymers. © 2020 Author(s).
Anomalous influence of salt concentration on deposition of poly(L-lysine)/cellulose sulfate multilayers evidenced by in situ ATR-FTIR
The deposition of polyelectrolyte (PEL) multilayers (PEMs) of poly(L-lysine)/cellulose sulfate (PLL/CS) onto germanium (Ge) substrates depending on salt concentration (cS) and deposition step z at constant PEL concentration cPEL = 0.01 M and pH = 7.0 was studied. In situ ATR-FTIR spectroscopy was used for the quantitative determination of alternate PLL/CS deposition profiles (adsorbed amount versus z) and total deposited PEM amount. By varying cS from 0 M to 1.0 M, a maximum of deposited amount was obtained at 0.1 M, so that both no salinity (0 M) and high salinity (1.0 M) revealed deposited amounts that were far lower than for mean salinity (0.1 M). Furthermore, in situ ATR-FTIR allowed to determine the detailed modulation of the PEL composition during the consecutive PEM deposition, which was interpreted as being due to both diffusion of given PEL from the PEM interior towards the outermost region and release of the PEM upon contact with the bulk oppositely charged PEL solution. Finally, ex situ ATR-FTIR measurements on the PEL solutions after deposition of PEM-20 revealed the distinct release of PEL from the PEM solely for cS = 1.0 M, due to the highest mobility of PEL under high salt conditions. These studies help to prepare functional PEM coatings with defined thicknesses and morphologies for the passivation and activation of material surfaces in the biomedical and food field. © 2020 by the author.
Mo-La2O3 multilayer metallization systems for high temperature surface acoustic wave sensor devices
Developing advanced thin film materials is the key challenge in high-temperature applications of surface acoustic wave sensor devices. One hundred nanometer thick (Mo-La2O3) multilayer systems were fabricated at room temperature on thermally oxidized (100) Si substrates (SiO2/Si) to study the effect of lanthanum oxide on the electrical resistivity of molybdenum thin films and their high-temperature stability. The multilayer systems were deposited by the magnetron sputter deposition of extremely thin (≤1 nm) La interlayers in between adjacent Mo layers. After deposition of each La layer the process was interrupted for 25 to 60 min to oxidize the La using the residual oxygen in the high vacuum of the deposition chamber. The samples were annealed at 800 °C in high vacuum for up to 120 h. In case of a 1 nm thick La interlayer in-between the Mo a continuous layer of La2O3 is formed. For thinner La layers an interlayer between adjacent Mo layers is observed consisting of a (La2O3-Mo) mixed structure of molybdenum and nm-sized lanthanum oxide particles. Measurements show that the (Mo-La2O3) multilayer systems on SiO2/Si substrates are stable at least up to 800 °C for 120 h in high vacuum conditions.
Stabilizing the West Antarctic Ice Sheet by surface mass deposition
There is evidence that a self-sustaining ice discharge from the West Antarctic Ice Sheet (WAIS) has started, potentially leading to its disintegration. The associated sea level rise of more than 3m would pose a serious challenge to highly populated areas including metropolises such as Calcutta, Shanghai, New York City, and Tokyo. Here, we show that the WAIS may be stabilized through mass deposition in coastal regions around Pine Island and Thwaites glaciers. In our numerical simulations, a minimum of 7400 Gt of additional snowfall stabilizes the flow if applied over a short period of 10 years onto the region (−2 mm year−1 sea level equivalent). Mass deposition at a lower rate increases the intervention time and the required total amount of snow. We find that the precise conditions of such an operation are crucial, and potential benefits need to be weighed against environmental hazards, future risks, and enormous technical challenges. Copyright © 2019 The Authors,