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- ItemColloidal PbS nanoplatelets synthesized via cation exchange for electronic applications(Cambridge : RSC Publ., 2019) Sonntag, Luisa; Shamraienko, Volodymyr; Fan, Xuelin; Samadi Khoshkhoo, Mahdi; Kneppe, David; Koitzsch, Andreas; Gemming, Thomas; Hiekel, Karl; Leo, Karl; Lesnyak, Vladimir; Eychmüller, AlexanderIn this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 V−1 s−1.
- ItemMixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom(Cambridge : RSC Publ., 2019) Schlesier, C.; Liu, F.; Dubrovin, V.; Spree, L.; Büchner, B.; Avdoshenko, S.M.; Popov, A.A.Systematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.
- ItemSERS and plasmonic heating efficiency from anisotropic core/satellite superstructures(Cambridge : RSC Publ., 2019) Kuttner, Christian; Höller, Roland P. M.; Quintanilla, Marta; Schnepf, Max J.; Dulle, Martin; Fery, Andreas; Liz-Marzán, Luis M.The optical properties of nanoparticle assemblies can be tailored via hybridization of plasmon modes. Isotropic core/satellite superstructures made of spherical nanoparticles are known to exhibit coupled modes with a strongly scattering (radiative) character, and provide hot spots yielding high activity in surface-enhanced Raman scattering (SERS). However, to complement this functionality with plasmonic heating, additional absorbing (non-radiative) modes are required. We introduce herein anisotropic superstructures formed by decorating a central nanorod with spherical satellite nanoparticles, which feature two coupled modes that allow application for both SERS and heating. On the basis of diffuse reflectance spectroscopy, small-angle X-ray scattering (SAXS), and electromagnetic simulations, the origin of the coupled modes is disclosed and thus serves as a basis toward alternative designs of functional superstructures. This work represents a proof-of-principle for the combination of high SERS efficiency with efficient plasmonic heating by near-infrared irradiation.
- ItemSpatial resolution of tip-enhanced Raman spectroscopy – DFT assessment of the chemical effect(Cambridge : RSC Publ., 2016) Latorre, Federico; Kupfer, Stephan; Bocklitz, Thomas; Kinzel, Daniel; Trautmann, Steffen; Gräfe, Stefanie; Deckert, VolkerExperimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle–substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range.
- ItemHigh-rate amorphous SnO2 nanomembrane anodes for Li-ion batteries with a long cycling life(Cambridge : RSC Publ., 2014) Liu, Xianghong; Zhang, Jun; Si, Wenping; Xi, Lixia; Oswald, Steffen; Yan, Chenglin; Schmidt, Oliver G.Amorphous SnO2 nanomembranes as anodes for lithium ion batteries demonstrate a long cycling life of 1000 cycles at 1600 mA g−1 with a high reversible capacity of 854 mA h g−1 and high rate capability up to 40 A g−1. The superior performance is because of the structural features of the amorphous SnO2 nanomembranes. The nanoscale thickness provides considerably reduced diffusion paths for Li+. The amorphous structure can accommodate the strain of lithiation/delithiation, especially during the initial lithiation. More importantly, the mechanical feature of deformation can buffer the strain of repeated lithiation/delithiation, thus putting off pulverization. In addition, the two-dimensional transport pathways in between nanomembranes make the pseudo-capacitance more prominent. The encouraging results demonstrate the significant potential of nanomembranes for high power batteries.
- ItemSurface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticles(Cambridge : RSC Publ., 2015) Rodriguez, Raul D.; Sheremet, Evgeniya; Deckert-Gaudig, Tanja; Chaneac, Corinne; Hietschold, Michael; Deckert, Volker; Zahn, Dietrich R. T.Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm−1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal–nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced.
- ItemA manual and an automatic TERS based virus discrimination(Cambridge : RSC Publ., 2015) Olschewski, Konstanze; Kämmer, Evelyn; Stöckel, Stephan; Bocklitz, Thomas; Deckert-Gaudig, Tanja; Zell, Roland; Cialla-May, Dana; Weber, Karina; Deckert, Volker; Popp, JürgenRapid techniques for virus identification are more relevant today than ever. Conventional virus detection and identification strategies generally rest upon various microbiological methods and genomic approaches, which are not suited for the analysis of single virus particles. In contrast, the highly sensitive spectroscopic technique tip-enhanced Raman spectroscopy (TERS) allows the characterisation of biological nano-structures like virions on a single-particle level. In this study, the feasibility of TERS in combination with chemometrics to discriminate two pathogenic viruses, Varicella-zoster virus (VZV) and Porcine teschovirus (PTV), was investigated. In a first step, chemometric methods transformed the spectral data in such a way that a rapid visual discrimination of the two examined viruses was enabled. In a further step, these methods were utilised to perform an automatic quality rating of the measured spectra. Spectra that passed this test were eventually used to calculate a classification model, through which a successful discrimination of the two viral species based on TERS spectra of single virus particles was also realised with a classification accuracy of 91%.