Chiral templating of self-assembling nanostructures by circularly polarized light

PMCID: PMC4387888.-- et al.The high optical and chemical activity of nanoparticles (NPs) signifies the possibility of converting the spin angular momenta of photons into structural changes in matter. Here, we demonstrate that illumination of dispersions of racemic CdTe NPs with right- (left-)handed circularly polarized light (CPL) induces the formation of right- (left-)handed twisted nanoribbons with an enantiomeric excess exceeding 30%, which is â 1/410 times higher than that of typical CPL-induced reactions. Linearly polarized light or dark conditions led instead to straight nanoribbons. CPL templating of NP assemblies is based on the enantio-selective photoactivation of chiral NPs and clusters, followed by their photooxidation and self-assembly into nanoribbons with specific helicity as a result of chirality-sensitive interactions between the NPs. The ability of NPs to retain the polarization information of incident photons should open pathways for the synthesis of chiral photonic materials and allow a better understanding of the origins of biomolecular homochirality.This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award number #DE-SC0000957, and by ARO MURI W911NF-12-1-0407 ‘Coherent Effects in Hybrid Nanostructures for Lineshape Engineering of Electromagnetic Media’ (N.A.K. and S.L.). We acknowledge support from the NSF under grant ECS-0601345; CBET 0933384; CBET 0932823; and CBET 1036672. Financial support from the Robert A. Welch Foundation (C-1664) is also acknowledged (S.L.). Support from the NIH grant GM085043 (P.Z.) is gratefully acknowledged. The work of P.K. was supported by the NSF DMR grant No. 1309765 and by the ACS PRF grant No. 53062-ND6.Peer Reviewe

Semiconductor nanowires self-assembled from colloidal CdTe nanocrystal building blocks: optical properties and application perspectives

Solution-based self-assembly of quasi-one-dimensional semiconductor nanostructures (nanowires) from quasi-zero-dimensional (quantum dots) colloidal nanocrystal building blocks has proven itself as a powerful and flexible preparation technique. Polycrystalline CdTe nanowires self-assembled from light-emitting thiol-capped CdTe nanocrystals are the focus of this Feature Article. These nanowires represent an interesting model system for quantum dot solids, where electronic coupling between the individual nanocrystals can be optically accessed and controlled. We provide a literature-based summary of the formation mechanism and the morphology-related aspects of self-assembled CdTe nanowires, and highlight several fundamental and application-related optical properties of these nanostructures. These include fundamental aspects of polarization anisotropies in photoluminescence excitation and emission, the electronic coupling between individual semiconductor nanocrystals constituting the nanowires, and more applied, waveguiding properties of CdTe nanowire bundles and anti-Stokes photoluminescence in a prototypical structure of co-axial nanowires. The optical properties of self-assembled CdTe nanowires considered here render them potential candidates for photonic nanoscale devices

Inorganic–organic nanocomposites of CdSe nanocrystals surface-modified with oligo- and poly(fluorene) moieties

We report a facile grafting-from strategy towards the synthesis of inorganic–organic composites of semiconductor nanocrystals and wide-bandgap polymers. Amino-functional fluorenes have been used as co-ligands for CdSe nanocrystals, thus enabling us to design their surface directly during the synthesis. Highly monodisperse, strongly emitting CdSe nanocrystals have been obtained. Subsequently, a straightforward Yamamoto C–C coupling protocol was used to carry out surface polymerisation, hence modifying CdSe nanocrystals with oligo- and poly(fluorene) moieties. Both amino-fluorene capped CdSe nanocrystals and the resulting nanocrystal–polymer composites were characterized in detail by optical and FT-IR spectroscopy, TEM, AFM, and gel permeation chromatography, showing their potential as novel functional inorganic–organic hybrid materials

Efficient energy transfer in layered hybrid organic/inorganic nanocomposites: A dual function of semiconductor nanocrystals

The efficiency of energy transfer in hybrid organic/inorganic nanocomposites based on conjugated polymers and semiconductor nanocrystals is strongly dependent on both the energy transfer rate and the rate of the nonradiative recombination of the polymer. We demonstrate that the polymer nonradiative recombination can be reduced by the suppression of exciton diffusion via proper morphology engineering of a hybrid structure. In the layer-by-layer assembled nanocomposite of a conjugated polymer and CdTe nanocrystals the latter have a dual role: first, they are efficient exciton acceptors and, second, they reduce nonradiative recombination in the polymer by suppressing exciton diffusion across the layers.Fil: Lutich, Andrey A.. Ludwig Maximilians Universitat; AlemaniaFil: Pöschl, Andreas. Ludwig Maximilians Universitat; AlemaniaFil: Jiang, Guoxin. Ludwig Maximilians Universitat; AlemaniaFil: Stefani, Fernando Daniel. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Susha, Andrei S.. City University of Hong Kong; ChinaFil: Rogach, Andrey L.. City University of Hong Kong; ChinaFil: Feldmann, Jochen. Ludwig Maximilians Universitat; Alemani

Tunable plasmon modes in single silver nanowire optical antennas characterized by far-field microscope polarization spectroscopy

Performing far-field microscope polarization spectroscopy and finite element method simulations, we investigated experimentally and theoretically the surface plasmon modes in single Ag nanowire antennas. Our results show that the surface plasmon resonances in the single Ag nanowire antenna can be tuned from the dipole plasmon mode to a higher order plasmon mode, which would result in the emission with different intensities and polarization states, for the semiconductor quantum dots coupled to the nanowire antenna. The fluorescence polarization is changed with different polarized excitation of the 800 nm light beam, while it remains parallel to the Ag nanowire axis at the 400 nm excitation. The 800 nm incident tight interacts nonresonantly with the dipole plasmon mode with the polarized excitation parallel to the Ag nanowire axis, while it excites a higher order plasmon mode with the perpendicular excitation. Under excitation of 400 nm, either the parallel or perpendicular excitation can only result in a dipole plasmon mode. In addition, we demonstrate that the single Ag nanowire antenna can work as an energy concentrator for enhancing the two-photon excited fluorescence of semiconductor quantum dots

Impact of D₂O/H₂O solvent exchange on the emission of HgTe and CdTe quantum dots: Polaron and energy transfer effects

We have studied light emission kinetics and analyzed carrier recombination channels in HgTe quantum dots that were initially grown in H2O. When the solvent is replaced by D2O, the nonradiative recombination rate changes highlight the role of the vibrational degrees of freedom in the medium surrounding the dots, including both solvent and ligands. The contributing energy loss mechanisms have been evaluated by developing quantitative models for the nonradiative recombination via (i) polaron states formed by strong coupling of ligand vibration modes to a surface trap state (nonresonant channel) and (ii) resonant energy transfer to vibration modes in the solvent. We conclude that channel (i) is more important than (ii) for HgTe dots in either solution. When some of these modes are removed from the relevant spectral range by the H2O to D2O replacement, the polaron effect becomes weaker and the nonradiative lifetime increases. Comparisons with CdTe quantum dots (QDs) served as a reference where the resonant energy loss (ii) a priori was not a factor, also confirmed by our experiments. The solvent exchange (H2O to D2O), however, is found to slightly increase the overall quantum yield of CdTe samples, probably by increasing the fraction of bright dots in the ensemble. The fundamental study reported here can serve as the foundation for the design and optimization principles of narrow bandgap quantum dots aimed at applications in long wavelength colloidal materials forinfrared light emitting diodes and photodetectors.We acknowledge financial support by the grant from the Research Grants Council of the Hong Kong S.A.R., China (project CityU 11302114). MIV acknowledges financial support from the FCT (Portugal)

Cadmium Telluride Quantum Dots as a Fluorescence Marker for Adipose Tissue Grafts

Plastic and reconstructive surgeons increasingly apply adipose tissue grafting in a clinical setting, although the anticipation of graft survival is insecure. There are only few tools for tracking transplanted fat grafts in vivo. Murine adipose tissue clusters were incubated with negatively charged, mercaptoproprionic acid-coated cadmium telluride quantumdots (QDs) emitting in the dark red or near infrared. The intracellular localization of QDs was studied by confocal laser scanning microscopy. As a result, the adipose tissue clusters showed a proportional increase in fluorescence with increasing concentrations (1, 10, 16, 30, 50 nM) of cadmium telluride QDs. Laser scanning microscopy demonstrated a membrane bound localization of QDs. Vacuoles and cell nuclei of adipocytes were spared by QDs. We conclude that QDs were for the first time proven intracellular in adult adipocytes and demonstrate a strong fluorescence signal. Therefore, they may play an essential role for in vivo tracking of fat grafts

Facile solution growth of vertically aligned ZnO nanorods sensitized with aqueous CdS and CdSe quantum dots for photovoltaic applications

Vertically aligned single crystalline ZnO nanorod arrays, approximately 3 μm in length and 50-450 nm in diameter are grown by a simple solution approach on a Zn foil substrate. CdS and CdSe colloidal quantum dots are assembled onto ZnO nanorods array using water-soluble nanocrystals capped as-synthesized with a short-chain bifuncional linker thioglycolic acid. The solar cells co-sensitized with both CdS and CdSe quantum dots demonstrate superior efficiency compared with the cells using only one type of quantum dots. A thin Al2O3 layer deposited prior to quantum dot anchoring successfully acts as a barrier inhibiting electron recombination at the Zn/ZnO/electrolyte interface, resulting in power conversion efficiency of approximately 1% with an improved fill factor of 0.55. The in situ growth of ZnO nanorod arrays in a solution containing CdSe quantum dots provides better contact between two materials resulting in enhanced open circuit voltage

Tunable plasmon modes in single silver nanowire optical antennas characterized by far-field microscope polarization spectroscopy

Performing far-field microscope polarization spectroscopy and finite element method simulations, we investigated experimentally and theoretically the surface plasmon modes in single Ag nanowire antennas. Our results show that the surface plasmon resonances in the single Ag nanowire antenna can be tuned from the dipole plasmon mode to a higher order plasmon mode, which would result in the emission with different intensities and polarization states, for the semiconductor quantum dots coupled to the nanowire antenna. The fluorescence polarization is changed with different polarized excitation of the 800 nm light beam, while it remains parallel to the Ag nanowire axis at the 400 nm excitation. The 800 nm incident tight interacts nonresonantly with the dipole plasmon mode with the polarized excitation parallel to the Ag nanowire axis, while it excites a higher order plasmon mode with the perpendicular excitation. Under excitation of 400 nm, either the parallel or perpendicular excitation can only result in a dipole plasmon mode. In addition, we demonstrate that the single Ag nanowire antenna can work as an energy concentrator for enhancing the two-photon excited fluorescence of semiconductor quantum dots