Synthesis,biocompatibility and luminescence properties of quantum dots conjugated with amino acid-functionalized β-cyclodextrin

A series of CdSe and CdSe/CdS quantum dots (QDs) labeled with amino acid-modified β-cyclodextrin (β-CD) was prepared by a simple ultrasonic method. These amino acid-modified β-CD-coated QDs are very soluble and stable in biological buffer. They also have high colloidal stability and strong optical emission properties that are similar to those of untreated tri-n-octylphosphine oxide (TOPO)-coated QDs. The quantum yields (QYs) of these amino acid-modified β-CD-coated CdSe and CdSe/CdS QDs in biological buffer were found to be very high. In particular, the QYs of the positively charged l-His-β-CD-coated CdSe/CdS QDs were as high as 33.5±1.8%. In addition, the fluorescence lifetime of these QDs was also very long in PBS solutions as determined by frequency domain spectroscopy. For example, the lifetime of l-His-β-CD-coated CdSe/CdS QDs was 8.6 ns. The in vitro cytotoxicity of these QDs in ECV-304, SH-SY5Y and HeLa cells was found to be lower. l-His-β-CD-coated CdSe/CdS QDs were the least cytotoxic (IC₅₀ 95.6±3.2 mg mL^?1 in ECV-304 cells after 48 h). The flow cytometry results show that the positively charged amino acid led to a considerable increase in biocompatibility of QDs. This may be attributed to the presence of an amino acid-modified β-CD outer layer, which enhanced the biocompatibility.     

CdSe/PMMA: Plastic fiber material containing CdSe quantum dots

An optical gain plastic, CdSe/PMMA, poly-methyl methacrylate doped with CdSe quantum dot (QD), is reported in this study. With a narrow size distribution of the QD prepared by organic synthesis, the measured results show that the photoluminescence (PL) peak intensity is enhanced by ～2.5 times, FWHM broadened by ～10 nm, and the PL peak wavelength blue shifted by ～25 nm in the CdSe/PMMA compared with plain CdSe QD. Under continuous irradiation of 473-nm laser, the PL peak intensity is positively correlated with time within the first hour after the samples are fabricated, but gradually stabilizes afterward. The obtained results suggest that the CdSe/PMMA material reported here is a desirable optical gain plastic. Potential applications include high gain wideband fiber amplifiers or other photonic devices in the future due to its high flexibility, low weight and low cost.     

Sonocatalytic degradation of methylene blue by a novel graphene quantum dots anchored CdSe nanocatalyst

Cadmium selenide/graphene quantum dots (CdSe/GQDs) nanocatalyst with small band gap energy and a large specific surface area was produced via a facile three-step sonochemical-hydrothermal process. The features of the as-prepared CdSe, GQDs and CdSe/GQDs samples were characterized by photoluminescence spectroscopy (PL), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD), Fourier transformed infrared (FT-IR), diffuse-reflectance spectrophotometer (DRS), and Brunauer–Emmett–Teller (BET) analysis. The sonocatalytic activity of the synthesized CdSe/GQDs was effectively accelerated compared with that of pure CdSe nanoparticles in degradation of methylene blue (MB). The influence of the CdSe/GQDs dosage (0.25–1.25 g/L), initial MB concentration (20–30 mg/L), initial solution pH (3–12), and ultrasonic output power (200–600 W/L) were examined on the sonocatalytic treatment of MB aqueous solutions. The degradation efficiency (DE%) of 99% attained at 1 g/L of CdSe/GQDs, 20 mg/L of MB, pH of 9, and an output power of 200 W/L at 90 min of ultrasonic irradiation. Furthermore, DE% increased with addition of K₂S₂O₈ and H₂O₂ as the enhancers via producing more free radicals. However, addition of sulfate, carbonate, and chloride as radical sweeper decreased DE%. Furthermore, well-reusability of the CdSe/GQDs sonocatalyst was demonstrated for 5 successive runs and some of the sonocatalytic generated intermediates were indicated by GC–MS analysis.     

Re-charging the luminescence states in CdSe/ZnS quantum dots at the conjugation to Osteopontin antibodies

The paper presents the original study of photoluminescence (PL) and Raman scattering spectra of core–shell CdSe/ZnS quantum dots (QDs) covered by the amine-derivatized polyethylene glycol (PEG) with luminescence interface states. First commercially available CdSe/ZnS QDs with emission at 640 nm (1.94 eV) covered by PEG polymer have been studied in nonconjugated states. PL spectra of nonconjugated QDs are characterized by a superposition of PL bands related to exciton emission in a CdSe core and to the hot electron–hole recombination via high energy luminescence states. The study of high energy PL bands in QDs at different temperatures has shown that these PL bands are related to luminescence interface states at the CdSe/ZnS or ZnS/polymer interface. Then CdSe/ZnS QDs have been conjugated with biomolecules—the Osteopontin antibodies. It is revealed that the PL spectrum of bioconjugated QDs changed essentially with decreasing hot electron–hole recombination flow via luminescence interface states. It is shown that the QD bioconjugation process to Osteopontin antibodies is complex and includes the covalent and electrostatic interactions between them. The variation of PL spectra due to the bioconjugation is explained on the basis of electrostatic interaction between the QDs and biomolecule dipoles that stimulates re-charging QD interface states. The study of Raman scattering of bioconjugated CdSe/ZnS QDs has confirmed that the antibody molecules have the electric dipoles. It is shown that CdSe/ZnS QDs with luminescence interface states are promising for the study of bioconjugation effects with specific antibodies and can be a powerful technique in biology and medicine.     

Cadmium sulfide quantum dots stabilized by castor oil and ricinoleic acid

Castor oil and ricinoleic acid (an isolate of castor oil) are environmentally friendly bio-based organic surfactants that have been used as capping agents to prepare nearly spherical cadmium sulfide quantum dots (QDs) at 230, 250 and 280 °C. The prepared quantum dots were characterized by Ultra violet–visible (UV–vis), Photoluminescence (PL), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and X-ray diffraction (XRD) giving an overall CdS QDs average size of 5.14±0.39 nm. The broad XRD pattern and crystal lattice fringes in the HRTEM images showed a hexagonal phase composition of the CdS QDs. The calculated/estimated average size of the prepared castor oil capped CdS QDs for various techniques were 4.64 nm (TEM), 4.65 nm (EMA), 5.35 nm (UV–vis) and 6.46 nm (XRD). For ricinoleic acid capped CdS QDs, the average sizes were 5.56 nm (TEM), 4.78 nm (EMA), 5.52 nm (UV–vis) and 8.21 nm (XRD). Optical properties of CdS QDs showed a change of band gap energy from its bulk band gap of 2.42–2.82 eV due to quantum size confinement effect for temperature range of 230–280 °C. Similarly, a blue shift was observed in the photoluminescence spectra. Scanning electron microscope (SEM) observations show that the as-synthesized CdS QDs structures are spherical in shape. Fourier transform infra-red (FTIR) studies confirms the formation of castor oil and ricinoleic acid capped CdS QDs.     

Interface photoluminescence of the SnO2:F/CdS:In/CdTe thin film solar cells prepared partially by the spray pyrolysis technique

CdS/CdTe solar cells were built by depositing a 200 nm layer of SnO₂:F on glass substrates by the spray pyrolysis (SP) technique, a 500 nm CdS:In layer by the same technique and a 1–1.5 μm CdTe layer by vacuum evaporation. The cells were CdCl₂ heat-treated in nitrogen atmosphere for 30 min at 350 °C. The photoluminescence (PL) spectra were measured at the CdS/CdTe interface for two cells with different values of the CdTe layer's thickness at the temperature T=60 K. A deconvolution peak fit was performed from which it is found that the peaks are characteristic of the solid solution CdS_xTe_1?x. The parabolic relation that relates the bandgap energy with the composition was used to estimate x, where x is [S]/([Te]+[S]) and [Te], [S] are the concentrations of Te and S atoms, respectively. The results show that the interface is smooth and the change of the bandgap occurs gradually. The solar cell of the thicker CdTe layer showed more interdiffusion at the CdS/CdTe interface and better photovoltaic characteristics.     

A new and straightforward synthesis route for preparing Cds quantum Dots

In this work, highly stable, soluble and luminescent CdS quantum dots (QDots) with a narrow size distribution were synthesized in ethylene glycol using the polyol process and the solvothermal technique. In this case instead of using a conventional highly toxic sulfur source like H₂S, we use elemental sulfur dissolved in ethylene glycol to perform the reaction. When the solvent reaches its boiling point inside the autoclave, sulfur is reduced to S^?2 and reacts with Cd⁺² ions to form CdS nanocrystals. Analysis of the spectroscopic and TEM measurements showed that 3 nm monodispersed CdS QDots were synthesized and exhibited high photoluminescence (PL) in the blue green region of the spectra when excited with 355 nm.     

Al/CdSe/GaSe/C resonant tunneling thin film transistors

An Al/CdSe/GaSe/C thin film transistor device was prepared by the physical vapor deposition technique at a vacuum pressure of 10⁻⁵ mbar. The x-ray diffraction measurements demonstrated the polycrystalline nature of the surface of the device. The dc current-voltage characteristics recorded for the Al/CdSe/C and Al/CdSe/GaSe/C channels displayed a resonant tunneling diode features during the forward and reverse voltage biasing, respectively. In addition, the switching current ratio of the Al/CdSe/C increased from 18.6 to 9.62×10³ as a result of the GaSe deposition on the CdSe surface. Moreover, the alternating electrical signal analyses in the frequency range of 1.0 MHz to 1.8 GHz, showed some remarkable properties of negative resistance and negative capacitance spectra of the Al/CdSe/GaSe/C thin film transistors. Two distinct resonance-antiresonance phenomena in the resistance spectra and one in the capacitance spectra were observed at 0.53, 1.04 and 1.40 GHz for the Al/CdSe/C channel, respectively. The respective resonating peak positions of the resistance spectra shift to 0.38 and 0.95 GHz when GaSe is interfaced with CdSe. These features of the thin film transistors are promising for use in high quality microwave filtering circuits and also for use as ultrafast switches.     

Second-order non-linear optical studies on CdS microcrystallite-doped alkali borosilicate glasses

CdS microcrystal-doped alkali borosilicate glasses were prepared by conventional fusion and heat-treatment method. Utilizing Maker fringe method, second-harmonic generation (SHG) was both observed from CdS-doped glasses before and after certain thermal/electrical poling. While because the direction of polarization axes of CdS crystals formed in the samples is random or insufficient interferences of generated SH waves occur, the fringe patterns obtained in samples without poling treatments showed no fine structures. For the poled samples, larger SH intensity has been obtained than that of the samples without any poling treatments. It was considered that the increase of an amount of hexagonal CdS in the anode surface layer caused by the applied dc field increased the SH intensity. The second-order non-linearity χ⁽²⁾ was estimated to be 1.23 pm/V for the sample poled with 2.5 kV at 360 °C for 30 min.     

Synthesis of CdS nanostructures using template-assisted ammonia-free chemical bath deposition

CdS micro- and nano-structures (micro/nanotubes and nanostructured films) were obtained by ammonia-free chemical bath deposition using polymer templates (ion track-etched polycarbonate membranes and poly(styrene-hydroxyethyl methacrylate) nanosphere arrays). The semiconductor structures were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), optical absorption, photoluminescence and electrical measurements. The diameters of CdS tubes are between 300 nm and few microns and the lengths are up to tens of micrometers. The SEM images prove that the CdS films are nanostructured due to the deposition on the polymer nanosphere arrays. For both CdS structures (tubes and films) the XRD patterns show a hexagonal phase. The optical studies reveal a band gap value of about 2.5?2.6 eV and a red luminescence at ～1.77 eV. A higher increase of conductivity is observed for illuminating the CdS nanostructured film when compared to the simple semiconductor film. This is a consequence of the periodic patterning induced by the polymer nanosphere array.     

Luminescence properties of InAs quantum dots formed by a modified self-assembled method

The luminescence properties of self-assembled InAs quantum dots (QDs) on GaAs (1 0 0) substrates grown by molecular beam epitaxy have been investigated using temperature-dependent photoluminescence (PL) and time-resolved PL (TRPL). InAs QDs were grown using an In-interruption growth technique, in which the indium flux was periodically interrupted. InAs QDs grown using In-interruption showed reduced PL linewidth, redshifted PL emission energy, increased energy level spacing between the ground state and the first excited state, and reduced decay time, indicating an improvement in the size distribution and size/shape of QDs.     

Temperature-dependent photoluminescence of CuInS2 quantum dots

Temperature-dependent photoluminescence (PL) spectroscopy of CuInS₂ core and CuInS₂/ZnS core–shell quantum dots (QDs) was studied for understanding the influence of a ZnS shell on the PL mechanism. The PL quantum yield and lifetime of CuInS₂ core QDs were significantly enhanced after the QD surface was coated with the ZnS shell. The temperature dependences of the PL energy, linewidth, and intensity for the core and core–shell QDs were studied in the temperature range from 92 to 287 K. The temperature-dependent shifts of 98 meV and 35 meV for the PL energies of the QDs were much larger than those of the excitons in their bulk semiconductors. It was surprisingly found that the core and core–shell QDs exhibited a similar temperature dependence of the PL intensity. The PL in the CuInS₂/ZnS core–shell QDs was suggested to originate from recombination of many kinds of defect-related emission centers in the interior of the cores.     

Tetraalkoxylated-PPV derivative: An efficient and pure green electroluminescent polymer with good solution processability

A new solution-processable tetraalkoxy-substituted poly(1,4-phenylenevinylene) derivative, poly{[2-(3′,7′-dimethyloctyloxy)-3,5,6-trimethoxy]-1,4-phenylenevinylene} (TALK-PPV), was synthesized through a dehydrohalogenation polymerization route, and its light-emitting properties were investigated. The TALK-PPV showed highly blue-shifted UV–visible absorption and PL emission spectra compared to the dialkoxy-substituted PPV derivatives. This is because of the disturbance to the π-conjugation caused by a steric hindered structure. The TALK-PPV thin film exhibited an absorption peak at 446 nm, with an onset at 515 nm. Its PL emission maximum was at 554 nm. Cyclic voltammetric analysis showed the HOMO and LUMO energy levels of the TALK-PPV to be 5.77 and 3.36 eV, respectively. Light-emitting devices were fabricated with an ITO (indium-tin oxide)/PEDOT/polymer/Ca/Al configuration. The TALK-PPV component leads to pure green light emission with a CIE 1931 chromaticity of (0.20, 0.74) at 100 cd/m² brightness, which is very close to the standard green (0.21, 0.71) demanded by the NTSC (National Television System Committee). The maximum brightness of this device was 24,900 cd/m² with an efficiency of 1.45 cd/A.     

Near-white emitting QD-LED based on hydrophilic CdS nanocrystals

In this work we report fabrication of a nanocrystal (NC)-based hybrid organic–inorganic LED with structure of ITO/PEDOT:PSS/PVK/CdS-NCs/(Al or Mg:Ag). The hydrophilic CdS NCs were synthesized using a novel aqueous thermochemical method at 80 °C and sizes (around 2 nm) were controlled by thioglycolic acid (TGA) as the capping agent. The favorite feature of these NCs is their relatively high emission intensity and broad, near-white emission. The hydrophilic CdS NCs were successfully spin coated using Triton X-100 as the wetting agent. The fabricated LEDs demonstrated a turn on voltage about 7 V for Al metallic contact. The electroluminescence was a broad spectrum at 540 and 170 nm width, which was about 50 nm red shifted compared to photoluminescence spectra. The CIE color coordinates of the LED at (0.33, 0.43) demonstrated a near white light LED with an emission on green–yellow boundary of white. Annealing of the device up to 190 °C had a positive effect on the performance, possibly due to better contacts between layers. Replacing Al contacts with Mg:Ag reduced the turn-on voltage to 6 V and changed CIE color coordinate to (0.32, 0.41). The EL peak was also shifted to 525 nm, with a brightness of 15 Cd/m² at working voltage of 15 V. The current efficiency and external quantum efficiency of device were 0.08 Cd/A and 0.03% at current densities higher than 10 mA/cm².     

Stress and morphological development of CdS and ZnS thin films during the SILAR growth on (1 0 0)GaAs

Cadmium sulfide and zinc sulfide films were grown on (1 0 0)GaAs substrate by successive ionic layer adsorption and reaction (SILAR) technique from aqueous precursor solutions at room temperature and normal pressure. The stress development of the thin films was characterized by laser interferometry as a function of the thickness of the films. The morphology and roughness of the films were monitored by atomic force microscopy. Additionally the crystallinity and crystallite size were analyzed by X-ray diffraction and composition by electron spectroscopy for chemical analysis. The CdS thin films had significantly higher stress level and also better crystallinity compared with ZnS thin films. Both films were polycrystalline and cubic, but the CdS thin films followed the substrate (1 0 0) orientation, whereas the ZnS films were (1 1 1) orientated. The roughness vs. film thickness curves of both films followed each other in shape, but the CdS films consisted of smaller particles.     

Midinfrared photoluminescence from SnTe/PbTe/CdTe double quantum wells grown by molecular beam epitaxy

Molecular beam epitaxial growth and photoluminescence (PL) properties of SnTe/PbTe/CdTe double quantum wells (DQWs) on (1 0 0)-oriented GaAs substrates are reported. These DQWs were consisted of a very thin SnTe/PbTe QW nested in a 10-nm-thick PbTe/CdTe QW. Efficient midinfrared PL was observed from the DQWs at 300 K in agreement with the coherent SnTe/PbTe growth on the thick CdTe barrier layer. The PL peak wavelength of the DQWs was found to increase with the SnTe thickness d by covering a wide range of the 3–5 μm atmospheric window with d≤2.5 monolayer.     

Emission of Cu-related complexes in ZnO:Cu nanocrystals

Photoluminescence (PL), its temperature dependence, scanning electronic microscopy (SEM) and X ray diffraction (XRD) have been applied for the comparative study of varying the emission, morphology and crystal structure of ZnO and ZnO:Cu nanocrystals (NCs) versus technological routines, as well as the dependence of ZnO:Cu NC parameters on the Cu concentration. A set of ZnO and ZnO Cu NCs was prepared by the electrochemical (anodization) method at a permanent voltage and different etching durations with follows thermal annealing at 400 °C for 2 h in ambient air. The size of ZnO NCs decreases from 300 nm×540 nm down to 200 nm×320 nm with etching duration increasing. XRD study has confirmed that thermal annealing stimulates the ZnO oxidation and crystallization with the formation of wurtzite ZnO crystal lattice. XRD method has been used for monitoring the lattice parameters and for confirming the Cu doping of ZnO Cu NCs. In ZnO Cu NCs four defect related PL bands are detected with the PL peaks at 1.95–2.00 eV (A), 2.15-2.23  eV (B), 2.43–2.50 eV (C) and 2.61–2.69 eV (D). Highest PL intensities of orange, yellow and green emissions have been obtained in ZnO Cu NCs with the Cu concentration of 2.28 at%. At Cu concentration increasing (≥2.28 at%) the PL intensities of the bands A, B, C decrease and the new PL band peaked at 2.61–2.69 eV at 10 K appears in the PL spectrum. The variation of PL intensities for all PL bands versus temperature has been studied and the corresponding activation energies of PL thermal decay have been estimated. The type of Cu-related complexes is discussed using the correlation between the PL spectrum transformation and the variation of XRD parameters in ZnO Cu NCs.     

The effect of annealing temperature on structural and optical properties of undoped and Cu doped CdS thin films

Cadmium sulphide (CdS) thin films were prepared chemical bath deposition technique. The films were doped with copper using the direct method consisting in the addition of a copper salt in the deposition bath of CdS. The doped films were annealed in air, at 250, 300 and 350 °C, for 1 h. The deposition films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX) and optical properties of CdS thin films before and after Cu doping. XRD analysis shows that the films are polycrystalline in nature with cubic crystalline structure. The various parameters such as crystallite size, micro strain and dislocation density were evaluated. SEM study shows that the total substrate surface is well covered by uniformly distributed spherical shaped grains. Optical transmittance study shows the presence of direct transition with band gap energy decrease 2.5–2.2 eV.     

Influence of argon ambience on the structural,morphological and optical properties of pulsed laser ablated zinc sulfide thin films

Nanostructured zinc suplhide thin films are successfully deposited on quartz substrates using pulsed laser deposition (PLD) under different argon pressures (0, 5, 10, 15 and 20 Pa). The influence of argon ambience on the microstructural, optical and luminescence properties of zinc sulfide (ZnS) thin films is systematically investigated. The GIXRD data suggests rhombohedral structure for ZnS films prepared under different argon ambience. Self-assembly of grains into well-defined patterns along the y direction is observed in the AFM image of the film deposited under argon pressure 20 Pa. All the films show a blue shift in optical band gap. This can be due to the quantum confinement effect and less widening of conduction and valence band for the films with less thickness and smaller grain size. The PL spectra of the different films are recorded at excitation wavelengths 250 nm and 325 nm and the spectra are interpreted. The PL spectra of the films recorded at excitation wavelength 325 nm show intense yellow emission. The film deposited under an argon pressure of 15 Pa shows the highest PL intensity for excitation wavelength 325 nm. For the PL spectra (excitation at 250 nm), the highest PL intensity is observed for the film prepared under argon free ambience. In our study, 15 Pa is the optimum argon pressure for better crystallinity and intense yellow emission when excited at 325 nm.     

Characterization and relative sonocatalytic efficiencies of a new MWCNT and CdS modified TiO2 catalysts and their application in the sonocatalytic degradation of rhodamine B

TiO₂ nanoparticles modified with MWCNTs and CdS were synthesized by the sol–gel method followed by solvothermal treatment at low temperature. The chemical composition and surface structure of the CdS/CNT–TiO₂ composites were investigated by X-ray diffraction, specific surface area measurements, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and scanning electron microscopy. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CNT/TiO₂ and the CdS/CNT–TiO₂ composites. It was found that RhB was quickly and effectively degraded under different ultrasonic conditions. As expected, the nanosized CdS/CNT–TiO₂ photocatalyst showed enhanced activity compared with the non CdS treated CNT/TiO₂ material in the sonocatalytic degradation of RhB. The sonocatalyst CCTb with 34.68% contents of Ti heat treated at 500 °C for 1 h showed the highest sonocatalytic activity. The synergistic effect of the greater surface area and catalytic activities of the composite catalysts was examined in terms of their strong adsorption ability and interphase interaction by comparing the effects of different amounts of MWCNTs and CdS in the catalysts and their roles. The mechanism of sonocatalytic degradation over the CdS/CNT modified TiO₂ composites under different ultrasonic conditions was also discussed.