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    Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation
    (Cambridge : RSC Publ., 2021) Mendes, Rafael G.; Ta, Huy Q.; Yang, Xiaoqin; Bachmatiuk, Alicja; Praus, Petr; Mamakhel, Aref; Iversen, Bo B.; Su, Ren; Gemming, Thomas; Rümmeli, Mark H.
    Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4.
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    Nanorattles with tailored electric field enhancement
    (Cambridge : RSC Publ., 2017) Schnepf, Max J.; Mayer, Martin; Kuttner, Christian; Tebbe, Moritz; Wolf, Daniel; Dulle, Martin; Altantzis, Thomas; Formanek, Petr; Förster, Stephan; Bals, Sara; König, Tobias A. F.; Fery, Andreas
    Nanorattles are metallic core-shell particles with core and shell separated by a dielectric spacer. These nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions and commensurate variations in enhancement factor. We present a novel synthetic approach for the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy (STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic applications where a defined and robust unit cell is crucial.