Efficient charge transfer in solution-processed PbS quantum dot–reduced graphene oxide hybrid materials

We developed a general approach to couple silane-functionalized rGO with colloidal semiconductor nanocrystals, which show efficient and tunable charge transfer

Broadband amplified spontaneous emission and random lasing from wurtzite CdSe/CdS 'giant-shell' nanocrystals

Colloidal nanocrystals (NCs) are attractive materials for light-emitting applications thanks to their flexible synthesis, size-dependent properties, and bright emission. Yet, colloidal NCs still present a narrow gain band (full-width half maximum around 10 nm), which limits their application to single-color lasers. Widening of the gain band by specifically engineered NCs can further improve the prospect of this class of materials toward the fabrication of solution-processed white-emitting or color-tunable lasers. Here, we report broadband amplified spontaneous emission (ASE) from wurtzite CdSe/CdS "giant-shell" nanocrystals (g-NCs) with an unprecedented large core up to 7.5 nm in diameter that were synthesized through a continuous injection route. The combination of large core and shell enables ASE from different CdSe optical transitions as well as from the CdS. Importantly, thin films of g-NCs with a large CdSe core (7.5 and 5.1 nm in diameter) show ASE at different colors with a similar threshold, indicating that light emission amplification can be achieved from different optical transitions simultaneously. Tuning of the core diameter allows obtaining ASE in a wide spectral range, and blending of g-NCs with different core sizes gives rise to a continuous amplified spontaneous emission band from green to red (510 to 650 nm). Drop-cast films of CdSe/CdS g-NCs demonstrate simultaneous dual-color random lasing under nanosecond-pulsed excitation

shape control of zincblende cdse nanoplatelets

Water matters: the aspect ratio of CdSe nanoplatelets can be precisely tuned by adjusting the fraction of hydrated cadmium acetate in the synthesis

Piezoelectric Control of the Exciton Wave Function in Colloidal CdSe/CdS Nanocrystals

Using multiband k·p calculations, we show that strain-engineered piezoelectricity is a powerful tool to modulate the electron−hole spatial separation in a wide class of wurtzite CdSe/CdS nanocrystals. The inherent anisotropy of the hexagonal crystal structure leads to anisotropic strain and, consequently, to a pronounced piezoelectric field along the c axis, which can be amplified or quenched through a proper design of the core−shell structure. The use of large cores and thick shells promotes a gradual departure from quantum confined nanocrystals to a regime dominated by piezoelectric confinement. This allows excitons to evolve from the usual type-I and quasi-type-II behavior to a type-II behavior in dot-in-dots, dot-in-rods, rod-in-rods, and dot-in-plates. Piezoelectric fields explain experimental observations for giant-shell nanocrystals, whose time-resolved photoluminescence reveals long exciton lifetimes for large cores, contrary to the expectations of standard quantum confinement models. They also explain the large differences in exciton lifetimes reported for different classes of CdSe/CdS nanocrystals.Support from MINECO project CTQ2014-60178-P, UJI project P1-1B2014-24 and a FPU grant (C.S.) is acknowledged. The present publication is further realized with the support of the Ministero degli Affari Esteri e della Cooperazione Internazionale (IONX-NC4SOL, I.M.)

Near-infrared emitting colloidal PbS nanoplatelets : lateral size control and optical spectroscopy

Two dimensional (2D) colloidal PbS nano platelets (NPLs) with a thickness of 1.8-2.8 nm have been synthesized using a single-molecule precursor approach with lead octadecylxanthate. The lateral dimensions were tuned by varying the reaction temperature, growth time, and capping ligands. Transmission electron microscopy and X-ray diffraction reveal that the NPLs have an orthorhombic crystal structure rather than the rocksalt phase usually reported for bulk and nanostructured PbS. The 1.8 nm thickness, in combination with the tunable lateral dimensions, results in a blue-shifted absorption peak at 71S-730 nm and a 48-68 nm narrow emission spectrum with a surprisingly small, 18 nm Stokes shift at room temperature. The fluorescence lifetime of these PbS NPLs is 2 orders of magnitude shorter than the typical lifetime in OD colloidal PbS quantum dots, highlighting the advantageous properties of colloidal 2D nanostructures that combine strong transversal with weak lateral confinement

Surface spin magnetism controls the polarized exciton emission from CdSe nanoplatelets

The surface of nominally diamagnetic colloidal CdSe nanoplatelets can demonstrate paramagnetism owing to the uncompensated spins of dangling bonds (DBSs). We reveal that by optical spectroscopy in high magnetic fields up to 15 Tesla using the exciton spin as probe of the surface magnetism. The strongly nonlinear magnetic field dependence of the circular polarization of the exciton emission is determined by the DBS and exciton spin polarization as well as by the spin-dependent recombination of dark excitons. The sign of the exciton-DBS exchange interaction can be adjusted by the nanoplatelet growth conditions

Giant-Shell CdSe/CdS Nanocrystals: Exciton Coupling to Shell Phonons Investigated by Resonant Raman Spectroscopy

The interaction between excitons and phonons in semiconductor nanocrystals plays a crucial role in the exciton energy spectrum and dynamics, and thus in their optical properties. We investigate the exciton2 phonon coupling in giant-shell CdSe/CdS core-shell nanocrystals via resonant Raman spectroscopy. The Huang-Rhys parameter is evaluated by the intensity ratio of the longitudinal-optical (LO) phonon of CdS with its first multiscattering (2LO) replica. We used four different excitation wavelengths in the range from the onset of the CdS shell absorption to well above the CdS shell band edge to get insight into resonance effects of the CdS LO phonon with high energy excitonic transitions. The isotropic spherical giant-shell nanocrystals show consistently stronger exciton-phonon coupling as compared to the anisotropic rod-shaped dot-in-rod (DiR) architecture, and the 2LO/LO intensity ratio decreases for excitation wavelengths approaching the CdS band edge. The strong exciton-phonon coupling in the spherical giant-shell nanocrystals can be related to the delocalization of the electronic wave functions. Furthermore, we observe the radial breathing modes of the GS nanocrystals and their overtones by ultralow frequency Raman spectroscopy with nonresonant excitation, using laser energies well below the band gap of the heteronanocrystals, and highlight the differences between higher orderComment: 16 pages, 3 figure

Electrical control of single-photon emission in highly charged individual colloidal quantum dots

Electron transfer to an individual quantum dot promotes the formation of charged excitons with enhanced recombination pathways and reduced lifetimes. Excitons with only one or two extra charges have been observed and exploited for very efficient lasing or single-quantum dot light-emitting diodes. Here, by room-temperature time-resolved experiments on individual giant-shell CdSe/CdS quantum dots, we show the electrochemical formation of highly charged excitons containing more than 12 electrons and 1 hole. We report the control over intensity blinking, along with a deterministic manipulation of quantum dot photodynamics, with an observed 210-fold increase in the decay rate, accompanied by 12-fold decrease in the emission intensity, while preserving single-photon emission characteristics. These results pave the way for deterministic control over the charge state, and room-temperature decay rate engineering for colloidal quantum dot-based classical and quantum communication technologies

Two-photon based pulse autocorrelation with CdSe nanoplatelets

We investigate broadband two-photon absorption autocorrelators based on II–VI semiconductor nanoplatelets as an alternative to common second harmonic generation based techniques. As compared to bulk materials the exceptionally high enhancement of two-photon absorption in these 2D structures results in very efficient two-photon absorption based autocorrelation detected via PL emission. We compare the results with TPA autocorrelation in CdS bulk as well as SHG based autocorrelation in β-barium borate. We show that CdSe nanoplatelet based autocorrelation can exceed the efficiency of conventional methods by two orders in magnitude, especially for short interaction length, and allows a precise pulse-width determination. We demonstrate that very high two-photon absorption cross sections of the nanoplatelets are the basis for this effective TPA autocorrelation. Based on our results with II–VI nanoplatelets efficient broadband autocorrelation with more than ∼100 nm bandwidth and very high sensitivity seems feasible.EC/H2020/714876/EU/Photonics in Flatland: Band Structure Engineering of 2D Excitons in Fluorescent Colloidal Nanomaterials/PHOCONATU Berlin, Open-Access-Mittel - 201

Synthesis of Air-Stable CdSe/ZnS Core–Shell Nanoplatelets with Tunable Emission Wavelength

In the past few years, several protocols have been reported on the synthesis of CdSe nanoplatelets with narrow photoluminescence (PL) spectrum, high PL quantum efficiency, and short exciton lifetime. The corresponding core/shell nanoplatelets are however still mostly based on CdSe/CdS, which possess an extended lifetime and a strong red shift of the band-edge absorption and emission, in accordance with a quasi-type-II band alignment. Here we report on a robust synthesis procedure to grow a ZnS shell around CdSe nanoplatelets at moderate temperatures of 100–150 °C, to improve the optical properties of CdSe nanoplatelets via a type-I core/shell heterostructure. The shell growth is performed under ambient atmosphere, in either toluene or 1,2-dichlorobenzene. The variation of the shell thickness induces a continuous red shift of the PL peak, eventually reaching 611 nm. The PL quantum efficiency is increased compared to the original CdSe cores, with values up to 60% depending on the shell thickness. High-resolution transmission electron microscopy reveals a bending of the nanoplatelets caused by strain due to 12% lattice mismatch between CdSe and ZnS. The present procedure can easily be translated to other core/shell nanocrystals, such as CdSe/CdS and CdSe/CdZnS nanoplatelets.The present publication is realized with the support of the Ministero degli Affari Esteri e della Cooperazione Internazionale (IONX-NC4SOL). This project has also received funding from the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 696656 (GrapheneCore1). J.L.M. acknowledges support from UJI project P1-1B2014-24 and MINECO project CTQ2014-60178-P