Synthesis and photoluminescence of ZnS quantum dots

Single-phase zinc sulphide (ZnS) quantum dots were synthesized by a chemical method. The influence of the pH value of the Zn(CH3COO)2 solution on the size and photoluminescence properties of the ZnS quantum dots was evaluated. X-ray power diffraction, transmission electron microscopy, and ultraviolet-visible spectroscopy were used to characterize the structure, size, surface states, and photoluminescence properties of ZnS quantum dots. The results showed that the crystal structure of ZnS quantum dots was a cubic zinc blende structure, and their average diameter was about 3.0 nm. ZnS quantum dots with good distribution and high purity were obtained. A strong broad band centered at about 320 nm was observed in the excitation spectrum of ZnS quantum dots. Their emission spectrum peaking at about 408 nm, was due mostly to the trap-state emission. The relative integrated emission intensity of ZnS quantum dots decreased as the pH value of the Zn(CH3COO)2 solution increased, which could be ascribed to the increase in average diameter of the ZnS quantum dots as the pH value of Zn(CH3COO)2 solution increased.     

A novel route to photoluminescent, water-soluble Mn-doped ZnS quantum dots via photopolymerization initiated by the quantum dots

We design a photopolymerization, in which Mn-doped ZnS quantum dots (ZnS:Mn(2+)) initiate the polymerization of acrylic acid, to convert the non-cytotoxic quantum dots to water-soluble ones for biological chromophores The prepared quantum dots are nearly monodispersed in water and the resulting solution shows long-term stability for months. The water-soluble ZnS:Mn(2+) quantum dots exhibit high quantum efficiency of fluorescence. The polymerization of acrylic acid is ruled by a free-radical mechanism and results in a polymer with a random configuration. Raman scattering shows that, in the water-soluble quantum dots, the vibration modes of surface optical phonons, transverse optical phonons and longitudinal optical phonons are changed in frequencies. Results of model calculations correlate these changes to the polymerization occurring at the surface of QDs.     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

Luminescence properties of Mn and Ni doped ZnS nanoparticles synthesized by capping agent

ZnS and transition metal (Mn and Ni) doped ZnS were synthesized by a simple chemical method using alkyl hydroxyl ethyl dimethyl ammonium chloride (HY) as capping agent. The structural and optical properties were studied using various techniques. FTIR and X-ray diffraction (XRD) can be used to identify the chemical bonding and crystal structure. The XRD analysis show that the particles are in cubic structure. The mean size of the nanoparticles calculated through Scherrer equation is in the range of 5–2.5 nm. Elemental dispersive analysis of doped samples reveals the presence of doping ions. The transmission electron microscopic studies show that the synthesized particles are in spherical shape. Optical characterization of both undoped and doped samples was carried out by ultraviolet–visible and photoluminescence spectroscopy. The absorption spectra of all the samples are blue shifted from the bulk ZnS.     

Shell distribution on colloidal CdSe/ZnS quantum dots

Scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) was used to determine the chemical distribution of semiconductor shell material around colloidal core-shell CdSe/ZnS quantum dots (QDs). EELS signals from positions around the QD indicate a well-defined shell of ZnS surrounding the CdSe core, but the distribution of the shell material is highly anisotropic. This nonuniformity may reflect the differences in chemical activity of the crystal faces of the core QD and implies a nonoptimal QD surface passivation.     

Functionalization and characterization of ZnS quantum dots using biocompatible l-cysteine

In this work, the functionalization of ZnS quantum dots using the thiol group of l-cysteine for different concentrations has been reported. Chemical precipitation method was used for the synthesis of nascent as well as l-cysteine functionalized ZnS quantum dots for optimized values of pH and molar concentrations of the precursors. Morphological studies were done by X-ray diffraction (XRD) and TEM. Optical measurements were done by UV–visible, Fourier transform infrared (FTIR) and energy resolved photoluminescence studies. Particle size was calculated by using Brus equation. Appreciable changes in morphological and optical properties of ZnS quantum dots were observed in few cases. XRD results shows that, the primary crystallite size decreases with increasing the capping concentration, however, the crystal structure remain same for all the used concentrations of l-cysteine. UV–visible analysis shows that band gap and particle size is also tunable with l-cysteine capping. FTIR studies confirmed l-cysteine capping on the surface of quantum dots. As l-cysteine is non toxic and stable compound, the surface modification of ZnS quantum dots with l-cysteine not only prevents the aggregation of quantum dots but also make them available for the interaction with the target materials and make them suitable for specific biomedical applications.     

Identification of mass fractal in chemically synthesized ZnS quantum dots

Zinc sulphide quantum dots chemically capped with thioglycerol having two different sizes have been synthesized. The particles have a disordered sphalerite structure and are slightly contracted by 1% against the bulk. Small angle X-ray scattering investigations reveal that powders of these nanocrystallites are mass fractals that aggregate via a reaction-limited process to form irregular but rather dense networks with a fractal dimensionality of D _f = 2.7 and 2.1, respectively.     

Cytotoxicity tests of water soluble ZnS and CdS quantum dots

Cytotoxicity tests of zinc sulfide (ZnS) and cadmium sulfide (CdS) quantum dots (QDs) synthesized via all-aqueous process with various surface conditions were carried out with human endothelial cells (EA hy926) using two independent viability assays, i.e., by cell counting following Trypan blue staining and by measuring Alamar Blue (AB) fluorescence. The ZnS QDs with all four distinct types of surface conditions were nontoxic at both 1 microM and 10 microM concentrations for at least 6 days. On the other hand, the CdS QDs were nontoxic only at 1 microM, and showed significant cytotoxicity at 10 microM after 3 days in the cell counting assay and after 4 days in the AB fluorescence assay. The CdS QDs with (3-mercaptopropyl)trimethoxysilane (MPS)-replacement plus silica capping were less cytotoxic than those with 3-mercaptopropionic acid (MPA) capping and those with MPS-replacement capping. Comparing the results of ZnS and CdS QDs with the same particle size, surface condition and concentration, it is indicated that the cytotoxicity of CdS QDs and the lack of it in ZnS QDs were probably due to the presence and absence of the toxic Cd element, respectively. The nontoxicity of the aqueous ZnS QDs makes them favorable for in vivo imaging applications.     

Preparation of a ZnS shell on CdSe quantum dots using a single-molecular ZnS precursor

A simple synthetic route to the preparation of a thin ZnS shell on CdSe quantum dot cores from the air-stable, single-molecular precursor zinc diethyldithiocarbamate, Zn(S(2)CNEt(2))(2), in the three-component solvent system octadec-1-ene/oleylamine/tri-n-octylphosphine (ODE/OLA/TOP) is presented. The one-pot synthesis proceeds through heating of the solution of CdSe cores and the amount of crystalline Zn(S(2)CNEt(2))(2) corresponding to a shell thickness of two monolayers of ZnS to 110-120 °C for 1-2 h. The role of the surfactants OLA and TOP and the significance of the temperature and the amount of Zn(S(2)CNEt(2))(2) have been investigated with optical absorption and luminescence spectroscopy. We show that the presence of both OLA and TOP is crucial for the low-temperature growth and that the amount of precursor corresponding to two monolayers of ZnS results in the highest quality of core/shell CdSe/ZnS quantum dots.     

Electronic excited states in bilayer graphene double quantum dots

We report tunneling spectroscopy experiments on a bilayer graphene double quantum dot device that can be tuned by all-graphene lateral gates. The diameter of the two quantum dots are around 50 nm and the constrictions acting as tunneling barriers are 30 nm in width. The double quantum dot features additional energies on the order of 20 meV. Charge stability diagrams allow us to study the tunable interdot coupling energy as well as the spectrum of the electronic excited states on a number of individual triple points over a large energy range. The obtained constant level spacing of 1.75 meV over a wide energy range is in good agreement with the expected single-particle energy spacing in bilayer graphene quantum dots. Finally, we investigate the evolution of the electronic excited states in a parallel magnetic field.     

Radiative interface state study in CdSe/ZnS quantum dots covered by polymer

The paper presents the transformation of photoluminescence (PL) spectra of nonconjugated and bioconjugated core/shell CdSe/ZnS QDs covered by PEG polymer at the aging in ambient air. Studied QDs are characterized by the sizes: (i) 3.6-4.0 nm and color emission with the maxima at 560-565 nm (2.19-2.25 eV) and (ii) 5.2-5.3 nm and with emission at 605-610 nm (2.02-2.08 eV). The part of 565 nm CdSe/ZnS QDs has been bioconjugated to the mouse anti PSA (Prostate-Specific Antigen) antibodies and the part of 605 nm QDs has been bioconjugated to the antihuman IL10 (Interleukin 10) antibodies using the commercially available 565 nm and 605 nm QD conjugation kits. It is revealed that the aging process in ambient air has the very strong impact on PL spectra of nonconjugated core/shell CdSe/ZnS QDs covered with PEG polymer. The aging process relates to the polymer modification in ambient air that is accompanied by the three effects: (i) polymer transparency increasing for the emission of CdSe cores (2.03 or 2.20 eV), (ii) the intensity stimulation of high energy PL bands (2.37, 2.73 and 3.06 eV) related to the interface states at the ZnS/PEG polymer interface and (iii) the elastic strain modification in QD systems. The concentration of interface states at the ZnS/polymer interface increases at the aging of PEG polymer in ambient air.     

Light-controlled bioelectrochemical sensor based on CdSe/ZnS quantum dots

This study reports on the oxygen sensitivity of quantum dot electrodes modified with CdSe/ZnS nanocrystals. The photocurrent behavior is analyzed for dependence on pH and applied potential by potentiostatic and potentiodynamic measurements. On the basis of the influence of the oxygen content in solution on the photocurrent generation, the enzymatic activity of glucose oxidase is evaluated in solution. In order to construct a photobioelectrochemical sensor which can be read out by illuminating the respective electrode area, two different immobilization methods for the fixation of the biocatalyst have been investigated. Both covalent cross-linking and layer-by-layer deposition of GOD by means of the polyelectrolyte polyallylamine hydrochloride show that a sensor construction is possible. The sensing properties of this type of electrode are drastically influenced by the amount and density of the enzyme on top of the quantum dot layer, which can be advantageously adjusted by the layer-by-layer technique. By depositing four bilayers [GOD/PAH](4) on the CdSe/ZnS electrode, a fast-responding sensor for the concentration range of 0.1-5 mM glucose can be prepared. This study opens the door to multianalyte detection with a nonstructured sensing electrode, localized enzymes, and spatial read-out by light.     

Luminescence tuning of amorphous Si quantum dots prepared by plasma-enhanced chemical vapor deposition

Amorphous Si (a-Si) quantum dots (QDs) embedded in a silicon nitride film were prepared by a plasma-enhanced chemical vapor deposition (PECVD) technique using gaseous mixtures of silane, hydrogen and nitrogen. We observed that the Si QDs had an amorphous structure from the Raman spectroscopy measurement. The Fourier transform infrared (FTIR) spectra showed that the relative transmittance of the SiH bands decreased, but that of the NH bands increased, with increasing nitrogen flow rate. During the deposition of SiNx, the number of dangling bonds of silicon acting as nucleation sites increased. As the hydrogen flow rate increased the growth rate decreased, due to the reduction in the hydrogen partial pressure. The hydrogen and nitrogen gas flow rates were found to be important parameters for determining the size of the a-Si QDs. In addition, we observed that the PL peak shifted toward a higher energy with increasing hydrogen and nitrogen gas flow rates, which was attributed to the increase in the quantum confinement effect in the a-Si QDs.     

Photoactivation of CdSe/ZnS quantum dots embedded in silica colloids

A study of the influence of the local environment on the light-induced luminescence enhancement of CdSe/ZnS quantum dots (QD) embedded in silica colloids that are dispersed in various solvents is presented. The photoluminescence of the embedded QD is enhanced up to a factor of ten upon photoactivation by ultraviolet or visible light. This enhancement is strongly dependent on the local environment. The thickness-dependent permeability of the silica shell covering the QD controls the influence of the solvent on the QD. If foreign ions are present the activation state is stabilized after termination of the activation, whereas in their absence the process is partially reversible. A new qualitative model for the photoactivation of QD in various environments is developed. It comprises light-induced passivation and subsequent oxidation processes. The embedded QD also retain their fluorescence quantum yield inside living cells. Moreover, they can be activated for many hours in living cells by laser radiation in the visible regime.     

Photoluminescence of colloidal CdSe/ZnS quantum dots under oxygen atmosphere

The effects of oxygen versus vacuum ambients on colloidal CdSe/ZnS quantum dots (QDs) were studied using both continuous and time-resolved photoluminescence (PL) measurements. The PL intensities were found to be an order of magnitude higher in an oxygen atmosphere, which is explained by the passivation of surface defects by oxygen absorption. The decay of PL intensities can be best fitted by a biexponential function with lifetimes of approximately 1 ns for the fast decay and approximately 10 ns for the slow decay. Based on the emission-energy dependence of carrier lifetimes and of the amplitude ratio of the fast-decay component to the slow-decay component, we suggest that the fast and slow PL decay of colloidal CdSe/ZnS QDs is caused by the recombination of delocalized carriers in the internal core states and the localized carriers in the surface states, respectively.     

Optical nonlinearity and optical limiting of CdSeS/ZnS quantum dots

CdSeS/ZnS quantum dots (QDs) were synthesized through the chemical route. The optical limiting behavior of these QDs was observed. The quantum dots’ nonlinear absorption and nonlinear refraction were investigated by the Z-scan technique using a Nd:YAG laser second-harmonic radiation (λ = 532 nm, t = 35 ps). Based on the absorption and fluorescence spectra, it is reasonable for us to infer that the nonlinear absorption arises from free carrier absorption (FCA). These QDs have average absorption cross-section of 1.26 × 10^?16cm² and nonlinear refractive index in the order of 10^?8esu. The large nonlinear absorption perhaps allows them to be candidate material for the optical limiting devices.     

Enhancement of photoluminescence in ZnS/ZnO quantum dots interfacial heterostructures

ZnS/ZnO quantum dots (QDs) were synthesized by controlled oxidation of ZnS nanoparticles. HRTEM image showed small nanocrystals of size 4 nm and the magnified image of single quantum dot shows interfacial heterostructure formation. The optical absorption spectrum shows a blue shift of 0.19 and 0.23 eV for ZnO and ZnS QDs, respectively. This is due to the confinement of charge carries within the nanostructures. Enormous enhancement in UV emission (10 times) is reported which is attributed to interfacial heterostructure formation. Raman spectrum shows phonons of wurtzite ZnS and ZnO. Phonon confinement effect is seen in the Raman spectrum wherein LO phonon peaks of ZnS and ZnO are shifted towards lower wavenumber side and are broadened.     

Switching in polaritonic-photonic crystal nanofibers doped with quantum dots

We have studied the acousto-optic effect in polaritonic nanofibers made by embedding a cylindrical polaritonic nanowire within a photonic crystal. Here the nanowire consists of either a phonon-polaritonic or an exciton-polaritonic material. The nanowire is doped with ensemble of noninteracting quantum dots. Quantum dots interact with the nanofiber via the exciton-polariton interaction. It is found that for the certain acoustic strain intensity the nanofiber has a localized-to-delocalized polariton transition similar to the metal-to-insulator transitions in doped semiconductors. It is also found that nanofiber has a transparent state due to the exciton-bound polariton coupling. The transparent state can be switched ON or OFF by the external acoustic strain intensity. These are very useful discoveries that can be used to fabricate new types of polaritonic nanoswitches and nanosensors.     

原位聚合法制备聚丙烯酸修饰的ZnS量子点

采用原位聚合法对ZnS量子点表面进行聚丙烯酸(PAA)的修饰。利用XRD、FTIR、TEM、TGA、荧光测试等对ZnS@PAA复合纳米粒子进行系列表征。XRD分析表明,修饰后的ZnS仍为立方晶相。FTIR和TGA结果证明,ZnS纳米粒子表面存在PAA。TEM结果表明,修饰后ZnS@PAA复合纳米粒子在去离子水中分散良好,其直径有所增加,约为28 nm,且呈较明显的核-壳结构。荧光测试发现,修饰PAA前后ZnS@PAA复合纳米粒子的发光特性没有发生明显改变。实验表明,经PAA修饰后,ZnS@PAA复合纳米粒子在水溶液中的分散性和稳定性得到提高,抗氧化性和荧光稳定性也得到了一定的增强。      

Photo-induced suppression of plasmonic emission enhancement of CdSe/ZnS quantum dots

Emission of semiconductor quantum dots can be increased via two fundamentally different processes: (i) surface plasmon resonances (plasmonic emission enhancement) and (ii) irradiation with light (photo-induced fluorescence enhancement). In this paper we theoretically and experimentally study the mutual impacts of these processes on each other in quantum dot solids. We show that when thin films of colloidal quantum dots are placed in the vicinity of Au nano-islands, the plasmonic enhancement of the radiative decay rates of quantum dots and Forster energy transfer can hinder the photo-induced fluorescence enhancement of these films. This in turn leads to significant suppression of their plasmonic emission enhancement when they are irradiated with a laser beam. We investigate the impact of the sizes and shapes of the metallic nanoparticles in this process and theoretically analyze how plasmons and energy transfer can hinder the electrostatic barrier responsible for photo-induced fluorescence enhancement.