Size- and shape-controlled synthesis of copper chalcogenide nanocrystals (NCs) is of paramount importance for a careful engineering and understanding of their optoelectronic properties and, thus, for their exploitation in energy- and plasmonic-related applications. From the copper chalcogenide family copper telluride NCs have remained fairly unexplored as a result of a poor size-, shape-, and monodispersity control that is achieved via one-step syntheses approaches. Here we show that copper telluride (namely Cu(2-x)Te) NCs with well-defined morphologies (spheres, rods, tetrapods) can be prepared via cation exchange of preformed CdTe NCs while retaining their original shape. The resulting copper telluride NCs are characterized by pronounced plasmon bands in the near-infrared (NIR), in analogy to other copper-deficient chalcogenides (Cu(2-x)S, Cu(2-x)Se). We demonstrate that the extinction spectra of the as-prepared NCs are in agreement with theoretical calculations based on the discrete dipole approximation and an empirical dielectric function for Cu(2-x)Te. Additionally we show that the Drude model does not appropriately describe the complete set of Cu(2-x)Te NCs with different shapes. In particular, the low-intensity longitudinal plasmon bands for nanorods and tetrapods are better described by a modified Drude model with an increased damping in the long-wavelength interval. Importantly, a Lorentz model of localized quantum oscillators describes reasonably well all three morphologies, suggesting that holes in the valence band of Cu(2-x)Te cannot be described as fully free particles and that the effects of localization of holes are important. A similar behavior for Cu2-xS and Cu(2-x)Se NCs suggests that the effect of localization of holes can be a common property for the whole class of copper chalcogenide NCs. Taken altogether, our results represent a simple route toward copper telluride nanocrystals with well-defined shapes and optical properties and extend the understanding on vacancy-doped copper chalcogenide NCs with NIR optical resonances.

A 3D metal ion assisted assembly of nanoparticles has been developed. The approach relies on the efficient complexation of cadmium ions and 5-mercaptomethyltetrazole employed as the stabilizer of both colloidal CdTe and Au nanoparticles. It enables in a facile way the formation of hybrid metal-semiconductor 3D structures with controllable and tunable composition in aqueous media. By means of critical point drying, these assemblies form highly porous aerogels. The hybrid architectures obtained are characterized by electron microscopy, nitrogen adsorption, and optical spectroscopy methods.

2638www.MaterialsViews.com wileyonlinelibrary.com approaches, [ 15,16 ] effi ciency, [ 17,18 ] extending their spectral range [19][20][21] and environmental friendliness using less toxic materials [22][23][24] sparked industrial applications. Those started with the demonstration of a 40 in. display prototype presented by Samsung [ 25 ] and followed by the foundation of QD Vision, Inc., [ 26 ] whose QDs are now used in the latest series of Sony products. All of the mentioned applications require long-term stability of the QDs under various conditions including high temperatures as well as high intensity illumination. Packaging of the QDs within polymer or inorganic matrices is one way to address these issues, while improving the processability of the QDs at the same time. Commonly used polymers, such as polystyrene and poly(methylmethacrylate) [ 27 ] are relatively less stable and tight in comparison to their inorganic counterparts. Inorganic matrices on the other hand can incorporate the QDs directly from their melt, e.g., using the Czochralski approach, [ 28 ] coated as a thin fi lm directly on their surface [ 29,30 ] or, as recently developed by our group, grown as mixed crystals at ambient temperatures from a saturated salt solution. [ 31 ] Using this method, different types of QDs can be incorporated due to the low thermal stress and, by choosing the proper matrix-QD system, the photoluminescence quantum yields (PL-QYs) are enhanced upon incorporation. [ 32,33 ] Here, a new, fast, and versatile method for the incorporation of colloidal quantum dots (QDs) into ionic matrices enabled by liquid-liquid diffusion is demonstrated. QDs bear a huge potential for numerous applications thanks to their unique chemical and physical properties. However, stability and processability are essential for their successful use in these applications. Incorporating QDs into a tight and chemically robust ionic matrix is one possible approach to increase both their stability and processability. With the proposed liquid-liquid diffusion-assisted crystallization (LLDC), substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process allows to incorporate even the less stable colloids including initially oil-based ligandexchanged QDs into salt matrices. Furthermore, in a modifi ed two-step approach, the seed-mediated LLDC provides the ability to incorporate oilbased QDs directly into ionic matrices without a prior phase transfer. Finally, making use of their processability, a proof-of-concept white light emitting diode with LLDC-based mixed QD-salt fi lms as an excellent color-conversion layer is demonstrated. These fi ndings suggest that the LLDC offers a robust, adaptable, and rapid technique for obtaining high quality QD-salts.

The influence of the chirality of semiconductor nanocrystals, CdSe/ZnS quantum dots (QDs) capped with L- and D-cysteine, on the efficiency of their uptake by living Ehrlich Ascite carcinoma cells is studied by spectral- and time-resolved fluorescence microspectroscopy. We report an evident enantioselective process where cellular uptake of the L-Cys QDs is almost twice as effective as that of the D-Cys QDs. This finding paves the way for the creation of novel approaches to control the biological properties and behavior of nanomaterials in living cells.