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Tetrapod-shaped CdSe(core)/CdTe(arms) colloidal nanocrystals, capped with alkylphosphonic acids or pyridine, were reacted with various small molecules (acetic acid, hydrazine and chlorosilane) which induced their tip-to-tip assembly into soluble networks. These networks were subsequently processed into films by drop casting and their photoconductive properties were studied. We observed that films prepared from tetrapods coated with phosphonic acids were not photoconductive, but tip-to-tip networks of the same tetrapods exhibited appreciable photocurrents. On the other hand, films prepared from tetrapods coated with pyridine instead of phosphonic acids were already highly photoconductive even if the nanocrystals were not joined tip-to-tip. Based on the current-voltage behavior under light we infer that the tunneling between tetrapods is the dominant charge transport mechanism. In all the samples, chemically-induced assembly into networks tended to reduce the average tunneling barrier. Additionally, pyridine-coated tetrapods and the tip-to-tip networks made out of them were tested as active materials in hybrid photovoltaic devices. Overall, we introduce an approach to chemically-induced tip-to-tip assembly of tetrapods into solution processable networks and demonstrate the enhancement of electronic coupling of tetrapods by various ligand exchange procedures.

We report a phosphine-free synthesis of p-type copper(I) selenide nanocrystals by a colloidal approach in a mixture of oleylamine and 1-octadecene. The nanocrystals had a cuboctahedral shape and cubic berzelianite phase. Films of these nonstoichiometric copper-deficient Cu(2-x)Se nanocrystals were highly conductive and showed high absorption coefficient in the near-infrared region. These nanocrystals could be used as hole-injection layers in optoelectronic devices.

Colloidal semiconductor quantum rods have demonstrated many advantageous properties as light emitters such as high quantum yield, tunable emission wavelength, and polarized emission. This makes them an interesting optical gain material for laser applications. We report room-temperature gain lifetimes in core/shell CdSe/CdS quantum rods exceeding 300 ps, and show that the long gain lifetimes result from the significant reduction of Auger recombination in our quantum rods, even though the electrons are delocalized over the rod volume. We also fabricate devices by deposition of small droplets of quantum rod solution onto flat substrates. The evaporation dynamics of the droplets are governed by the coffee stain effect which leads to the formation of well defined micron-size stripes. These stripes consist of densely packed, laterally aligned quantum rods and provide optical feedback originating from the abrupt changes of refractive index at the stripe borders. We exploit the optical gain and the coffee stain mediated self-assembly and show that we can fabricate novel microlasers solely by deposition of droplets of quantum rod solutions on flat substrates.

We report on photoconduction and optical properties of aligned assemblies of core-shell CdSe/CdS nanorods prepared by a seeded growth approach. We fabricate oriented layers of nanorods by drop casting the nanorods from a solution on substrates with prepatterned, micrometer-spaced electrodes and obtain nanorod alignment due to the coffee stain effect. The photoconductivity of the nanorod layers can be improved significantly by an annealing process under vacuum conditions. The spectral response of the photocurrent shows distinct features that can be assigned to the electronic level structure of the core-shell nanorods and that relate well to the spectra obtained by absorption measurements. We study assemblies of nanorods oriented parallel and perpendicular to the applied electric field by the combined use of photocurrent and photoluminescence spectroscopy. We obtain consistent results which show that charge carrier separation and transport are more efficient for nanorods oriented parallel to the electric field. We also investigate the light polarization sensitivity of the photocurrent for the oriented nanorod layers and observe higher conductivity in the case of perpendicular polarization with respect to the long axis of the nanorods.

An economical nanoarray method to electrically detect hybridization events is demonstrated. As a proof of concept, we fabricated a sensor for DNA sequencing, in which targets are oligonucleotides conjugated to gold nanoparticles. As a consequence of target-probe binding events, a conductive bridge forms between two electrodes, resulting in a quantized change in conductivity. This enables a robust detection of a few (down to single) hybridization events and can be potentially applied also to other binding events (like specific interactions between proteins, antibodies, ligands and receptors). Moreover, target amplification techniques (such as PCR) are no longer necessary.

We deposit droplets of nanorods dispersed in solvents on substrate surfaces and let the solvent evaporate. We find that strong contact line pinning leads to dense nanorod deposition inside coffee stain fringes, where we observe large scale lateral ordering of the nanorods with the long axis of the rods oriented parallel to the contact line. We observe birefringence of these coffee stain fringes by polarized microscopy and we find the direction of the extraordinary refractive index parallel to the long axis of the nanorods.

Key limitations of the colloidal semiconductor nanorods that have been reported so far are a significant distribution of lengths and diameters as well as the presence of irregular shapes produced by the current synthetic routes and, finally, the poor ability to fabricate large areas of oriented nanorod arrays. Here, we report a seeded-growth approach to the synthesis of asymmetric core-shell CdSe/CdS nanorods with regular shapes and narrow distributions of rod diameters and lengths, the latter being easily tunable up to 150 nm. These rods are highly fluorescent and show linearly polarized emission, whereby the emission energy depends mainly on the core diameter. We demonstrate their lateral alignment as well as their vertical self-alignment on substrates up to areas of several square micrometers.

We investigated the optical phonon excitations of laterally aligned nanorod arrays by resonant Raman scattering. We observed a strong suppression of the surface-optical phonon modes in the closely packed aligned arrays and a small asymmetry in the longitudinal-optical phonon peak with respect to the rod alignment orientation. These observations can be explained by the spatial distribution of the potential of the different phonon modes derived from the first principles calculations.

We investigated CdTe nanocrystal tetrapods of different sizes by resonant inelastic light scattering at room temperature and under cryogenic conditions. We observe a strongly resonant behavior of the phonon scattering with the excitonic structure of the tetrapods. Under resonant conditions we detect a set of phonon modes that can be understood as confined longitudinal-optical phonons, surface-optical phonons, and transverse-optical phonons in a nanowire picture.

Electrical conduction through molecules depends critically on the delocalization of the molecular electronic orbitals and their connection to the metallic contacts. Thiolated (- SH) conjugated organic molecules are therefore considered good candidates for molecular conductors: in such molecules, the orbitals are delocalized throughout the molecular backbone, with substantial weight on the sulphur-metal bonds. However, their relatively small size, typically approximately 1 nm, calls for innovative approaches to realize a functioning single-molecule device. Here we report an approach for contacting a single molecule, and use it to study the effect of localizing groups within a conjugated molecule on the electrical conduction. Our method is based on synthesizing a dimer structure, consisting of two colloidal gold particles connected by a dithiolated short organic molecule, and electrostatically trapping it between two metal electrodes. We study the electrical conduction through three short organic molecules: 4,4'-biphenyldithiol (BPD), a fully conjugated molecule; bis-(4-mercaptophenyl)-ether (BPE), in which the conjugation is broken at the centre by an oxygen atom; and 1,4-benzenedimethanethiol (BDMT), in which the conjugation is broken near the contacts by a methylene group. We find that the oxygen in BPE and the methylene groups in BDMT both suppress the electrical conduction relative to that in BPD.