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Light-Generating CdSe/CdS Colloidal Quantum Dot-Doped Plastic Optical Fibers

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 Publication date 2020
  fields Physics
and research's language is English




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Colloidal quantum dots (cQDs) are now a mature nanomaterial with optical properties customizable through varying size and composition. However, their use in optical devices is limited as they are not widely available in convenient forms such as optical fibers. With advances in polymerization methods incorporating nanocrystals, nanocomposite materials suitable for processing into high quality hybrid active fibers can be achieved. We demonstrate a plastic optical fiber fabrication method which ensures homogeneous dispersion of cQDs within a polymer core matrix. Loading concentrations between 10$^{11}$-10$^{13}$ CdSe/CdS cQDs per cm$^{3}$ in polystyrene were electronically imaged, confirming only sporadic sub-wavelength aggregates. Rayleigh scattering losses are therefore dominant at energies below the semiconductors band gap, but are overtaken by a sharp CdS-related absorption onset around 525 nm facilitating cQD excitation. The redshifted photoluminescence emission is then minimally reabsorbed along the fiber with a spectrum barely affected by the polymerization and a quantum yield staying at $sim$65$%$ of its initial value. The latter, along with the glass transition temperature and refractive index, is independent of the cQD concentration hence yielding a proportionally increasing light output. Our cQD-doped fibers are photostable to within 5$%$ over days showing great promise for functional material applications.



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Luminescent colloidal CdSe nanorings are a new type of semiconductor structure that have attracted interest due to the potential for unique physics arising from their non-trivial toroidal shape. However, the exciton properties and dynamics of these materials with complex topology are not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and single particle measurements to study these materials. We find that on transformation of CdSe nanoplatelets to nanorings, by perforating the center of platelets, the emission lifetime decreases and the emission spectrum broadens due to ensemble variations in the ring size and thickness. The reduced PL quantum yield of nanorings (~10%) compared to platelets (~30%) is attributed to an enhanced coupling between: (i) excitons and CdSe LO-phonons at 200 cm-1 and (ii) negatively charged selenium-rich traps which give nanorings a high surface charge (~-50 mV). Population of these weakly emissive trap sites dominates the emission properties with an increased trap emission at low temperatures relative to excitonic emission. Our results provide a detailed picture of the nature of excitons in nanorings and the influence of phonons and surface charge in explaining the broad shape of the PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that the excitonic properties of nanorings are not solely a consequence of the toroidal shape but are also a result of traps introduced by puncturing the platelet center.
Atomically thin transition metal dichalcogenides are highly promising for integrated optoelectronic and photonic systems due to their exciton-driven linear and nonlinear interaction with light. Integrating them into optical fibers yields novel opportunities in optical communication, remote sensing, and all-fiber optoelectronics. However, scalable and reproducible deposition of high quality monolayers on optical fibers is a challenge. Here, we report the chemical vapor deposition of monolayer MoS2 and WS2 crystals on the core of microstructured exposed core optical fibers and their interaction with the fibers guided modes. We demonstrate two distinct application possibilities of 2D-functionalized waveguides to exemplify their potential. First, we simultaneously excite and collect excitonic 2D material photoluminescence with the fiber modes, opening a novel route to remote sensing. Then we show that third harmonic generation is modified by the highly localized nonlinear polarization of the monolayers, yielding a new avenue to tailor nonlinear optical processes in fibers. We anticipate that our results may lead to significant advances in optical fiber based technologies.
We prove experimentally, upon polarization analysis performed on a large statistic of single nanoemitters, that high quality core/shell CdSe/CdS dot-in-rods behave as linear dipoles. Moreover, the dipole in-plane and out-of-plane orientations could be assessed. We demonstrate in particular that, contrary to expectations, the emitting dipole is not aligned with the elongated axis of the dot-in-rod. Besides, the polarimetric measurements prove that the excitation transition cannot be approximated by a single linear dipole, contrary to the emission transition. Finally, we highlight that non-radiative channels of charge carrier recombination do not affect the dipolar nature of the radiative transitions.
221 - M. Manceau , S. , Vezzoli 2015
The photon statistics of CdSe/CdS dot-in-rods nanocrystals is studied with a method involving post-selection of the photon detection events based on the photoluminescence count rate. We show that flickering between two states needs to be taken into account to interpret the single-photon emission properties. With post-selection we are able to identify two emitting states: the exciton and the charged exciton (trion), characterized by different lifetimes and different second order correlation functions. Measurements of the second order autocorrelation function at zero delay with post- selection shows a degradation of the single photon emission for CdSe/CdS dot-in-rods in a charged state that we explain by deriving the neutral and charged biexciton quantum yields.
The blinking dynamics of colloidal core-shell CdSe/CdS dot-in-rods is studied in detail at the single particle level. Analyzing the autocorrelation function of the fluorescence intensity, we demonstrate that these nanoemitters are characterized by a short value of the mean duration of bright periods (ten to a few hundreds of microseconds). The comparison of the results obtained for samples with different geometries shows that not only the shell thickness is crucial but also the shape of the dot- in-rods. Increasing the shell aspect ratio results in shorter bright periods suggesting that surface traps impact the stability of the fluorescence intensity.
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