ZnS Outer Shell Research Articles

Increased shell thickness in indium phosphide multishell quantum dots leading to efficiency and stability enhancement in light-emitting diodes

We report efficient indium phosphide (InP) quantum dot-based light-emitting diodes (QD-LEDs). The current efficiency and the device stability of QD-LEDs were enhanced by increasing the thickness of ZnS outer shell of InP/ZnSe/ZnS multishell QDs. Reversible luminance degradation was observed in operation of QD-LEDs, which was hypothesized to result from QD charging. QDs having thicker ZnS shell with strong confinement suppressed the luminescence quenching as well as QD charging. Our findings about the reversible QD charging and the developed performance by the thick ZnS outer shell would help to rationalize the luminance quenching issue in QD-LED operation.

Over 40 cd/A efficient green quantum dot electroluminescent device comprising uniquely large-sized quantum dots.

Green CdSe@ZnS quantum dots (QDs) of 9.5 nm size with a composition gradient shell are first prepared by a single-step synthetic approach, and then 12.7 nm CdSe@ZnS/ZnS QDs, the largest among ZnS-shelled visible-emitting QDs available to date, are obtained through the overcoating of an additional 1.6 nm thick ZnS shell. Two QDs of CdSe@ZnS and CdSe@ZnS/ZnS are incorporated into the solution-processed hybrid QD-based light-emitting diode (QLED) structure, where the QD emissive layer (EML) is sandwiched by poly(9-vinlycarbazole) and ZnO nanoparticles as hole and electron-transport layers, respectively. We find that the presence of an additional ZnS shell makes a profound impact on device performances such as luminance and efficiencies. Compared to CdSe@ZnS QD-based devices the efficiencies of CdSe@ZnS/ZnS QD-based devices are overwhelmingly higher, specifically showing unprecedented values of peak current efficiency of 46.4 cd/A and external quantum efficiency of 12.6%. Such excellent results are likely attributable to a unique structure in CdSe@ZnS/ZnS QDs with a relatively thick ZnS outer shell as well as a well-positioned intermediate alloyed shell, enabling the effective suppression of nonradiative energy transfer between closely packed EML QDs and Auger recombination at charged QDs.

Probing the Quenching of Quantum Dot Photoluminescence by Peptide-Labeled Ruthenium(II) Complexes.

Charge transfer processes with semiconductor quantum dots (QDs) have generated much interest for potential utility in energy conversion. Such configurations are generally nonbiological; however, recent studies have shown that a redox-active ruthenium(II)–phenanthroline complex (Ru2+-phen) is particularly efficient at quenching the photoluminescence (PL) of QDs, and this mechanism demonstrates good potential for application as a generalized biosensing detection modality since it is aqueous compatible. Multiple possibilities for charge transfer and/or energy transfer mechanisms exist within this type of assembly, and there is currently a limited understanding of the underlying photophysical processes in such biocomposite systems where nanomaterials are directly interfaced with biomolecules such as proteins. Here, we utilize redox reactions, steady-state absorption, PL spectroscopy, time-resolved PL spectroscopy, and femtosecond transient absorption spectroscopy (FSTA) to investigate PL quenching in biological assemblies of CdSe/ZnS QDs formed with peptide-linked Ru2+-phen. The results reveal that QD quenching requires the Ru2+ oxidation state and is not consistent with Förster resonance energy transfer, strongly supporting a charge transfer mechanism. Further, two colors of CdSe/ZnS core/shell QDs with similar macroscopic optical properties were found to have very different rates of charge transfer quenching, by Ru2+-phen with the key difference between them appearing to be the thickness of their ZnS outer shell. The effect of shell thickness was found to be larger than the effect of increasing distance between the QD and Ru2+-phen when using peptides of increasing persistence length. FSTA and time-resolved upconversion PL results further show that exciton quenching is a rather slow process consistent with other QD conjugate materials that undergo hole transfer. An improved understanding of the QD–Ru2+-phen system can allow for the design of more sophisticated charge-transfer-based biosensors using QD platforms.

Magnetically engineered Cd-free quantum dots as dual-modality probes for fluorescence/magnetic resonance imaging of tumors

Magnetically engineered Cd-free CuInS2@ZnS:Mn quantum dots (QDs) were designed, synthesized, and evaluated as potential dual-modality probes for fluorescence and magnetic resonance imaging (MRI) of tumors in vivo. The synthesis of Mn-doped core–shell structured CuInS2@ZnS mainly comprised three steps, i.e., the preparation of fluorescent CuInS2 seeds, the particle surface coating of ZnS, and the Mn-doping of the ZnS shells. Systematic spectroscopy studies were carried out to illustrate the impacts of ZnS coating and the following Mn-doping on the optical properties of the QDs. In combination with conventional fluorescence, fluorescence excitation, and time-resolved fluorescence measurements, the structure of CuInS2@ZnS:Mn QDs prepared under optimized conditions presented a Zn gradient CuInS2 core and a ZnS outer shell, while Mn ions were mainly located in the ZnS shell, which well balanced the optical and magnetic properties of the resultant QDs. For the following in vivo imaging experiments, the hydrophobic CuInS2@ZnS:Mn QDs were transferred into water upon ligand exchange reactions by replacing the 1-dodecanethiol ligand with dihydrolipoic acid-poly(ethylene glycol) (DHLA-PEG) ligand. The MTT assays based on HeLa cells were carried out to evaluate the cytotoxicity of the current Cd-free CuInS2@ZnS:Mn QDs for comparing with that of water soluble CdTe QDs. Further in vivo fluorescence and MR imaging experiments suggested that the PEGylated CuInS2@ZnS:Mn QDs could well target both subcutaneous and intraperitoneal tumors in vivo.

Synthesis and characterization of Fe3O4@ZnS and Fe3O4@Au@ZnS core–shell nanoparticles

In the present work we report new assets on the synthesis and characterization of magnetite based core–shell nanoparticles such as Fe3O4@ZnS and Fe3O4@Au@ZnS. The composites were prepared by seed mediated growth which consist in a sequential growth of a second or third component on a preformed magnetite seeds in the presence of sodium laurylsulphate additives with essential role in growth and aggregation of nanoparticles. Evolved gas analysis (EGA) coupled with FT-IR was used in order to evidence the stages of ZnS shell formation. XRD studies were used for the structural characterization while high resolution transmission electron microscopy gave information concerning morphology and size distributions of nanoparticles. Qualitative and quantitative compositional analysis of samples was made by X-ray photoelectron spectroscopy (XPS). All the samples showed magnetic response due to the superparamagnetic behavior of magnetite cores. Increased saturation magnetization was determined for Fe3O4@ZnS samples. A significant photoluminescence (PL) enhancement was also observed as a result of Fe3O4:Zn2+ molar ratio decrease. Additional PL increased response was realized by inserting a gold shell between the magnetite core and ZnS outer shell. Considerations regarding both PL and magnetization enhancements are also presented.

Facile Synthesis of near-Infrared-Emitting Water-Dispersed CdHgTe/CdS/ZnS Core/Shell/Shell Quantum Dots

We report the synthesis and characterization of highly luminescent quantum dots consisting of CdHgTe cores protected with double inorganic shells (core−shell−shell quantum dots). The outer ZnS shell provides efficient confinement of electron and hole wave functions inside the quantum dots as well as high photochemical stability. Introducing the middle shell sandwiched between CdHgTe core and ZnS outer shell allows considerable reducing strain inside nanocrystals because CdS had the lattice parameter intermediate to those of CdHgTe and ZnS. Preferential growth of the middle CdS shell in one crystallographic direction allows engineering the shape and luminescence polarization of the core−shell−shell quantum dots.

Utilizing Quantum Dots to Enhance Solar Spectrum Conversion Efficiencies for Photovoltaics

AbstractSilicon-based photovoltaics typically convert less than 30% of the solar spectrum into usable electric power. This study explores the utilization of CdSe based quantum dots as spectral converters that absorb the under utilized UV portion of the solar spectrum and fluoresce at wavelengths near the band-gap of silicon-based solar cells. A flexible 1 mm thick thin-film structure that contains an array of microfluidic channels is designed and fabricated in polydimethylsiloxane (PDMS) using soft-lithographic techniques. The channels are approximately 85 microns wide by 37 microns tall and are filled with a solution containing the quantum dots. The thin-film structure can easily be attached to the surface of a single-junction solar cell. As a result, solar energy striking the coated solar cell with wavelengths less than 450 nm, which would normally experience low conversion efficiency, are absorbed by the quantum dots which fluoresce at 620nm. The high energy photons are converted to photons near the band-gap which increase the overall conversion efficiency of the solar cell. The quantum dots employed in this study are fabricated with a CdSe core (5.2 nm) and a ZnS outer shell and they exhibit a 25 nm hydrodynamic diameter. The UV-VIS spectral transmission properties of PDMS, along with its refractive index, are determined in order to characterize the spectral conversion efficiency of the thin-film structure. A model is developed to predict the optimum path length and concentration of quantum dots required to improve the power output of an amorphous silicon solar cell by 10%.

PH-Sensitive Photoluminescence of CdSe/ZnSe/ZnS Quantum Dots in Human Ovarian Cancer Cells

The photoluminescence of mercaptoacetic acid (MAA)-capped CdSe/ZnSe/ZnS semiconductor nanocrystal quantum dots (QDs) in SKOV-3 human ovarian cancer cells is pH-dependent, suggesting applications in which QDs serve as intracellular pH sensors. In both fixed and living cells the fluorescence intensity of intracellular MAA-capped QDs (MAA QDs) increases monotonically with increasing pH. The electrophoretic mobility of MAA QDs also increases with pH, indicating an association between surface charging and fluorescence emission. MAA dissociates from the ZnS outer shell at low pH, resulting in aggregation and loss of solubility, and this may also contribute to the MAA QD fluorescence changes observed in the intracellular environment.

CdSe/CdS/ZnS and CdSe/ZnSe/ZnS Core−Shell−Shell Nanocrystals

We report the synthesis and characterization of highly luminescent colloidal nanocrystals consisting of CdSe cores protected with double inorganic shells (core−shell−shell nanocrystals). The outer ZnS shell provides efficient confinement of electron and hole wave functions inside the nanocrystal as well as high photochemical stability. Introducing the middle shell (CdS or ZnSe) sandwiched between CdSe core and ZnS outer shell allows considerable reducing strain inside nanocrystals because CdS and ZnSe have the lattice parameter intermediate to those of CdSe and ZnS. In contrast to CdSe/ZnS core−shells, in the core−shell−shell nanocrystals ZnS shell grows nearly defect free. Due to high quality of the ZnS shell, the core−shell−shell nanocrystals exhibit PL efficiency and photostability exceeding those of CdSe/ZnS nanocrystals. Preferential growth of the middle CdS shell in one crystallographic direction allows engineering the shape and luminescence polarization of the core−shell−shell nanocrystals.

Optical properties of core/multishell CdSe/Zn(S,Se) nanocrystals

CdSe nanocrystals are now known as highly efficient fluorescent light sources. Their efficiency is however strongly dependent on the quality of the passivation layers. We show here that using a ZnSe/ZnS bi-layer shell leads to a larger photoluminescence yield than both ZnSe and ZnS simple shells. The intermediate ZnSe layer acts as a lattice parameter adaptation layer to improve on the core/shell interface quality, while the ZnS outer shell maximizes the exciton confinement.