On the electric conductivity of highly ordered monolayers of monodisperse metal nanoparticles

Monolayers of colloidally synthesized cobalt-platinum nanoparticles of different diameters characterized by TEM (transmission electron microscopy) were deposited on structured silicon oxide substrates and characterized by SEM (scanning electron microscopy), GISAXS (grazing incidence x-ray scattering), and electric transport measurements. The highly ordered nanoparticle films show a thermally activated electron hopping between spatially adjacent particles at room temperature and Coulomb blockade at low temperatures. We present a novel approach to experimentally determine the particles charging energies giving values of 6.7-25.4 meV dependent on the particles size and independent of the interparticle distance. These observations are supported by FEM (finite element method) calculations showing the self-capacitance to be the determining value which only depends on the permittivity constant of the surrounding space and the particles radius.Comment: 6 pages, 5 figure

Oxygen and light sensitive field-effect transistors based on ZnO nanoparticles attached to individual double-wall carbon nanotubes

The attachment of semiconducting nanoparticles to carbon nanotubes is one of the most challenging subjects in nanotechnology. Successful high coverage attachment and control over the charge transfer mechanism and photo-current generation opens a wide field of new applications such as highly effective solar cells and fibre-enhanced polymers. In this work we study the charge transfer in individual double-wall carbon nanotubes highly covered with uniform ZnO nanoparticles. The synthetic colloidal procedure was chosen to avoid long-chained ligands at the nanoparticle-nanotube interface. The resulting composite material was used as conductive channel in a field effect transistor device and the electrical photo-response was analysed under various conditions. By means of the transfer characteristics we could elucidate the mechanism of charge transfer from non-covalently attached semiconducting nanoparticles to carbon nanotubes. The role of positive charges remaining on the nanoparticles is discussed in terms of a gating effect.Comment: 6 pages, 4 figure

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

A common approach to generate tailored materials and nanoparticles (NPs) is the formation of molecular monolayers by chemisorption of bifunctional anchor molecules. This approach depends critically on the choice of a suitable anchor group. Recently, bifunctional catecholates, inspired by mussel-adhesive proteins (MAPs) and bacterial siderophores, have received considerable interest as anchor groups for biomedically relevant metal surfaces and nanoparticles. We report here the synthesis of new tripodal catecholates as multivalent anchor molecules for immobilization on metal surfaces and nanoparticles. The tripodal catecholates have been conjugated to various effector molecules such as PEG, a sulfobetaine and an adamantyl group. The potential of these conjugates has been demonstrated with the immobilization of tripodal catecholates on ZnO NPs. The results confirmed a high loading of tripodal PEG-catecholates on the particles and the formation of stable PEG layers in aqueous solution

Quantum dot attachment and morphology control by carbon nanotubes

Novel applications in nanotechnology rely on the design of tailored nano-architectures. For this purpose, carbon nanotubes and nanoparticles are intensively investigated. In this work we study the influence of non-functionalized carbon nanotubes on the synthesis of CdSe nanoparticles by means of organometallic colloidal routes. This new synthesis methodology does not only provide an effective path to attach nanoparticles non-covalently to carbon nanotubes but represents also a new way to control the shape of nanoparticles.Comment: 6 pages, 6 figure

Growth and reductive transformation of a gold shell around pyramidal cadmium selenide nanocrystals

We report the growth of an unstable shell-like gold structure around dihexagonal pyramidal CdSe nanocrystals in organic solution and the structural transformation to spherical domains by two means: i) electron beam irradiation (in situ) and (ii) addition of a strong reducing agent during synthesis. By varying the conditions of gold deposition, such as ligands present or the geometry of the CdSe nanocrystals, we were able to tune the gold domain size between 1.4 nm to 3.9 nm and gain important information on the role of surface chemistry in hetero nanoparticle synthesis and seed reactivity, both of which are crucial points regarding the chemical design of new materials for photocatalysis and optoelectronic applications.Comment: 5 pages, 4 figure

Hierarchical supercrystalline nanocomposites through the self-assembly of organically-modified ceramic nanoparticles

Biomaterials often display outstanding combinations of mechanical properties thanks to their hierarchical structuring, which occurs through a dynamically and biologically controlled growth and self-assembly of their main constituents, typically mineral and protein. However, it is still challenging to obtain this ordered multiscale structural organization in synthetic 3D-nanocomposite materials. Herein, we report a new bottom-up approach for the synthesis of macroscale hierarchical nanocomposite materials in a single step. By controlling the content of organic phase during the self-assembly of monodisperse organically-modified nanoparticles (iron oxide with oleyl phosphate), either purely supercrystalline or hierarchically structured supercrystalline nanocomposite materials are obtained. Beyond a critical concentration of organic phase, a hierarchical material is consistently formed. In such a hierarchical material, individual organically-modified ceramic nanoparticles (Level 0) self-assemble into supercrystals in face-centered cubic superlattices (Level 1), which in turn form granules of up to hundreds of micrometers (Level 2). These micrometric granules are the constituents of the final mm-sized material. This approach demonstrates that the local concentration of organic phase and nano-building blocks during self-assembly controls the final material's microstructure, and thus enables the fine-tuning of inorganic-organic nanocomposites' mechanical behavior, paving the way towards the design of novel high-performance structural materials.The authors gratefully acknowledge the financial support from the German Research Foundation (DFG) via the SFB 986-M3, projects A1, A6, Z2, and Z3. We thank Dr. F. Beckmann (Helmholtz-Zentrum Geesthacht, Geesthacht, Germany) for scanning the sample with the technique SRµCT and for reconstructing the slices, and Dr. I. Greving (Helmholtz-Zentrum Geesthacht, Geesthacht, Germany) for her inputs on SRµCT. Dr. F. Brun (National Institute of Nuclear Physics, Trieste, Italy) is acknowledged for the discussion regarding quantitative analysis using Pore3d

Determination of the packing fraction in photonic glass using synchrotron radiation nanotomography

Photonic glass is a material class that can be used as photonic broadband reflectors, for example in the infrared regime as thermal barrier coating films. Photonic properties such as the reflectivity depend on the ordering and material packing fraction over the complete film thickness of up to 100 μm. Nanotomography allows acquiring these key parameters throughout the sample volume at the required resolution in a non-destructive way. By performing a nanotomography measurement at the PETRA III beamline P05 on a photonic glass film, the packing fraction throughout the complete sample thickness was analyzed. The results showed a packing fraction significantly smaller than the expected random close packing giving important information for improving the fabrication and processing methods of photonic glass material in the future

Observation of enhanced chiral asymmetries in the inner-shell photoionization of uniaxially oriented methyloxirane enantiomers

Most large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical, it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer - an effect termed Photoelectron Circular Dichroism (PECD). Our comprehensive study demonstrates that the origin of PECD can be found in the molecular frame electron emission pattern connecting PECD to other fundamental photophysical effects as the circular dichroism in angular distributions (CDAD). Accordingly, orienting a chiral molecule in space enhances the PECD by a factor of about 10

Effect of chemical composition on luminescence of thiol-stabilized CdTe nanocrystals

Judicious selection of the amount of surfactant during synthesis enables a drastic increase in the photoluminescence efficiency of aqueous CdTe nanocrystals (NCs) stabilized by thioglycolic acid (TGA). Elemental determination of the NCs was undertaken to identify the origin of this effect. The molar ratio of (Te + S) to Cd approached unity when the optimum amount of TGA was used during synthesis, whereas the number of S atoms originating from TGA molecules in one NC (2.6 nm of diameter) remained unchanged at 90 ± 3. This indicates that the core lattice composition at the beginning of synthesis, rather than the surface conditions, affects the photoluminescence efficiency of the NCs even after prolonged refluxing