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2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film
2020, Molodtsova, Olga V., Aristova, Irina M., Potorochin, Dmitrii V., Babenkov, Sergey V., Khodos, Igor I., Molodtsov, Serguei L., Makarova, Anna A., Smirnov, Dmitry A., Aristov, Victor Yu.
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.
One-Pot Synthesis of Copper Iodide-Polypyrrole Nanocomposites
2021, Konakov, Artem O., Dremova, Nadejda N., Khodos, Igor I., Koch, Marcus, Zolotukhina, Ekaterina V., Silina, Yuliya
A novel one-pot chemical synthesis of functional copper iodide-polypyrrole composites, CuI-PPy, has been proposed. The fabrication process allows the formation of nanodimensional metal salt/polymer hybrid structures in a fully controlled time- and concentration-dependent manner. The impact of certain experimental conditions, viz., duration of synthesis, sequence of component addition and concentrations of the intact reagents on the structure, dimensionality and yield of the end-product was evaluated in detail. More specifically, the amount of marshite CuI within the hybrid composite can be ranged from 60 to 90 wt.%, depending on synthetic conditions (type and concentration of components, process duration). In addition, the conditions allowing the synthesis of nano-sized CuI distributed inside the polypyrrole matrix were found. A high morphological stability and reproducibility of the synthesized nanodimensional metal-polymer hybrid materials were approved. Finally, the electrochemical activity of the formed composites was verified by cyclic voltammetry studies. The stability of CuI-PPy composite deposited on the electrodes was strongly affected by the applied anodic limit. The proposed one-pot synthesis of the hybrid nanodimensional copper iodide-polypyrrole composites is highly innovative, meets the requirements of Green Chemistry and is potentially useful for future biosensor development. In addition, this study is expected to generally contribute to the knowledge on the hybrid nano-based composites with tailored properties.