Milena De Giorgi

Tetrapod-Shaped Colloidal Nanocrystals of II−VI Semiconductors Prepared by Seeded Growth

We report a general synthetic approach to tetrapod-shaped colloidal nanocrystals made of various combinations of II-VI semiconductors. Uniform tetrapods were prepared using preformed seeds in the sphalerite structure, onto which arms were grown by coinjection of the seeds and chemical precursors into a hot mixture of surfactants. By this approach, a wide variety of core materials could be chosen (in practice, most of the II-VI semiconductors that could be prepared in the sphalerite phase, namely, CdSe, ZnTe, CdTe); in contrast, the best materials for arm growth were CdS and CdTe. The samples were extensively characterized with the aid of several techniques.

Blue-UV-Emitting ZnSe(Dot)/ZnS(Rod) Core/Shell Nanocrystals Prepared from CdSe/CdS Nanocrystals by Sequential Cation Exchange

Great control over size, shape and optical properties is now possible in colloidal Cd-based nanocrystals, which has paved the way for many fundamental studies and applications. One popular example of such class of nanocrystals is represented by CdSe(spherical core)/CdS(rod shell) nanorods. These can be nearly monodisperse in size and shape and have strong and stable photoluminescence that is tunable in the visible range (mainly by varying the size of the CdSe core). The corresponding Zn-based core/shell nanorods would be good candidates for tunable emission in the blue-UV region. However, while the synthesis of ZnS nanocrystals with elongated shapes has been demonstrated based on the oriented-attachment mechanism, elongated ZnS shells are difficult to fabricate because the more common cubic phase of ZnS has a highly symmetric crystal structure. We report here a procedure based on a sequence of two cation exchange reactions, namely, Cd(2+)⇒Cu(+) and then Cu(+)⇒Zn(2+), by which we transform colloidal CdSe(core)/CdS(shell) nanorods first into into Cu(2)Se/Cu(2)S nanorods, which are then converted into blue-UV fluorescent ZnSe(core)/ZnS(shell) nanorods. The procedure transfers the morphological and structural information of the initial Cd-based nanorods to the Zn-based nanorods. Therefore, the final nanoparticles are made by a ZnSe dot embedded in a rod-shaped shell of wurtzite ZnS. Since in the starting Cd-based nanorods the size of the CdSe core and the length of the CdS shell can be well controlled, the same holds for the final Zn-based rods. In the second step of the exchange reaction (Cu(+)⇒Zn(2+)), a large excess of Zn(2+) ions added over the Cu(+) ions present in the Cu(2)Se/Cu(2)S nanorods is the key requisite to obtain bright, band-edge emission (with quantum yields approaching 15%) with narrow line widths (approaching 75 meV). In these ZnSe/ZnS nanorods, photogenerated carriers appear to be more confined in the core region compared to their parent CdSe/CdS nanorods.

Polarized light emitting diode by long-range nanorod self-assembling on a water surface.

We demonstrate a straightforward strategy to fabricate a multilayer inorganic/organic polarized light-emitting diode device based on highly ordered arrays of rod-shaped nanocrystals as the active species. We have developed a simple and effective method that allows colloidal CdSe/CdS core/shell nanorods to be laterally aligned in smectic or nematic phases on the surface of water. A floating film of such ordered nanorods has been collected by a poly(dimethylsiloxane) (PDMS) stamp pad and transferred by contact printing onto previously evaporated organic layers. Thanks to the lateral nanorod alignment the as-prepared film exhibited strong polarized photoluminescence and it has been used as emissive layer in the polarized electroluminescent device.

Fluorescent Asymmetrically Cobalt-Tipped CdSe@CdS Core@Shell Nanorod Heterostructures Exhibiting Room-Temperature Ferromagnetic Behavior

A colloidal two-step seeded-growth approach has been devised to selectively synthesize three-component magnetic/semiconductor hybrid nanocrystals (HNCs) with a matchstick-like profile and tunable geometric parameters. The newly developed heterostructures individually comprise a single metallic Co head connected to either apexes of one rod-shaped section made of a CdSe core eccentrically embedded in a CdS shell. The specific topological arrangement realized arises from the peculiar anisotropic reactivity of the noncentrosymmetric CdSe@CdS core@shell nanorods that have been used as substrates to seed heterogeneous nucleation of Co in a surfactant-free environment from an organometallic precursor. The HNCs retain appreciable fluorescent emission in spite of photoexcited charge transfer from the semiconductor to the metal domain and exhibit unusual ferromagnetic-like behavior at room temperature.

Photoconduction Properties in Aligned Assemblies of Colloidal CdSe/CdS Nanorods

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.

Optical properties of tetrapod-shaped CdTe nanocrystals

We studied the carrier confinement in tetrapod-shaped colloidal CdTe nanocrystals by means of absorption, photoluminescence, and photoluminescence excitation spectroscopy at room and cryogenic temperatures. The spectra show features characteristic of the tetrapod shape together with a clear dependence on the dominant confinement parameter, i.e., the diameter of the tetrapod arm. Theoretical calculations based on an envelope-function approximation and using the exact tetrapod shape have been performed to assign the observed spectral features. Oscillator strength and size dependence of the transitions energy have been calculated showing a direct correlation between the oscillator strength and the nanocrystal shape.

Nonclassical emission from single colloidal nanocrystals in a microcavity: a route towards room temperature single photon sources

Secure quantum communication systems (QCS) based on the transmission of crucial information through single photons are among the most appealing frontiers for telecommunications, though their development is still hindered by the lack of cheap and bright single photon sources (SPSs) operating at room temperature (RT). In this paper, we show the occurrence of photon antibunching at RT from single colloidal CdSe/ZnS nanocrystals (NCs) inserted in a vertical microcavity. Moreover, by using high-resolution lithographic techniques, we conceived a general route for positioning single colloidal quantum dots in the microcavity. The findings and the technique presented here can be considered a first step towards the development of SPS devices operating at RT.

Injection-locked single-mode high-power low-divergence tea CO2 laser using SFUR configuration

Abstract In this communication we report the first experimental results of the SFUR principle applied to a pulse TEA CO 2 laser in which the beam is extracted from the confocal point. This configuration results in low divergence and TEM 00 mode. Injection locking by a cw CO 2 laser is used to achieve single longitudinal mode (SLM) operation. The measured performances of the cavity are: output energy=2.7 J/pulse, pulsewidth (fwhm)-80 ns, divergence=0.65 mrad and gaussian beam propagation, which make it very suitable for a Lidar source.

Room-temperature superfluidity in a polariton condensate

Superfluidity is a phenomenon usually restricted to cryogenic temperatures, but organic microcavities provide the conditions for a superfluid flow of polaritons at room temperature. Superfluidity—the suppression of scattering in a quantum fluid at velocities below a critical value—is one of the most striking manifestations of the collective behaviour typical of Bose–Einstein condensates1. This phenomenon, akin to superconductivity in metals, has until now been observed only at prohibitively low cryogenic temperatures. For atoms, this limit is imposed by the small thermal de Broglie wavelength, which is inversely related to the particle mass. Even in the case of ultralight quasiparticles such as exciton-polaritons, superfluidity has been demonstrated only at liquid helium temperatures2. In this case, the limit is not imposed by the mass, but instead by the small binding energy of Wannier–Mott excitons, which sets the upper temperature limit. Here we demonstrate a transition from supersonic to superfluid flow in a polariton condensate under ambient conditions. This is achieved by using an organic microcavity supporting stable Frenkel exciton-polaritons at room temperature. This result paves the way not only for tabletop studies of quantum hydrodynamics, but also for room-temperature polariton devices that can be robustly protected from scattering.

High-speed flow of interacting organic polaritons

The strong coupling of an excitonic transition with an electromagnetic mode results in composite quasi-particles called exciton polaritons, which have been shown to combine the best properties of their individual components in semiconductor microcavities. However, the physics and applications of polariton flows in organic materials and at room temperature are still unexplored because of the poor photon confinement in such structures. Here, we demonstrate that polaritons formed by the hybridization of organic excitons with a Bloch surface wave are able to propagate for hundreds of microns showing remarkable third-order nonlinear interactions upon high injection density. These findings pave the way for the study of organic nonlinear light–matter fluxes and for a technologically promising route of the realization of dissipation-less on-chip polariton devices operating at room temperature.