Plasmon-enhanced luminescence of CdSe quantum dots on the porous silicon with silver nanoparticles

Russian Chemical Bulletin -     

Preparation of colloidal CdSe and CdS/CdSe nanoparticles from sodium selenosulfate in aqueous polymers solutions

Cadmium selenide nanoparticles formation at the interaction between CdCl2 and Na2SeSO3 in aqueous solutions of sodium polyphosphate and gelatin has been studied. Structural and optical properties of CdSe nanoparticles have been characterized. It has been shown that the temperature and the ratio of reagents concentrations are the basic parameters, controlling the size of CdSe nanoparticles. Photocatalytic activity of CdS nanoparticles in Na2SeSO3 reduction has been found and investigated; structural and optical properties of binary CdS/CdSe nanoparticles have been characterized. This photoreaction, when carried out in the presence of CdCl2, results in the formation of composite CdS/CdSe nanoparticles. It has been shown that slow interaction of adsorbed selenosulfate with surface-trapped CdS conduction band electrons is the limiting stage of the photocatalytic reaction.     

Subsecond luminescence intensity fluctuations of single CdSe quantum dots

Photoluminescence (PL) intermittency characteristics are examined for single quantum dots (QDs) in a CdSe QD sample synthesized at a slow rate at 75 degrees C. Although the PL quantum efficiency was relatively low ( approximately 0.25), we noticed that the PL intensity of single CdSe QDs fluctuated on a subsecond time scale with short-lived "on" and "off" states. The subsecond PL intensity fluctuations of CdSe QDs are different from "on" and "off" PL blinking generally observed for QDs fluctuating on a millisecond to minute time scale. We characterized single QDs by identifying polarized excitations, topographic imaging using atomic force microscopy (AFM), and transmission electron microscopy (TEM). From analysis of the PL intensity trajectories from >100 single CdSe QDs, the average intermittency time was 213 ms. From the PL quantum efficiency, slow growth of QDs, intensity trajectory analyses, and previous reports relating surface trap states and PL properties of QDs, we attribute the subsecond PL intensity fluctuations of single CdSe QDs and short-lived "on" and "off" states to a high-density distribution of homogeneous surface trap states.     

Upconversion multicolor fine-tuning: visible to near-infrared emission from lanthanide-doped NaYF4 nanoparticles

A general approach to fine-tuning the upconversion emission colors, based upon a single host source of NaYF4 nanoparticles doped with Yb3+, Tm3+, and Er3+, is presented. The emission intensity balance can be precisely controlled using different host-activator systems and dopant concentrations. The approach allows access to a wide range of luminescence emission from visible to near-infrared by single-wavelength excitation.     

Electrical bistability in electrostatic assemblies of CdSe nanoparticles

We report electrical bistability in electrostatic assembly of CdSe nanoparticles. We obtained thin films of the nanoparticles via layer-by-layer electrostatic assembly technique, which provided a nanoscale control to tune the thickness. Devices based on such thin films exhibit electrical bistability along with memory phenomenon. The bistability is due to charge confinement in the nanoparticles. Conduction mechanism changes from an injection-dominated to a bulk one during switching from a low- to a high-conducting state. Additionally, results from impedance spectroscopy show that the dielectric constant of the material increases during the transition. Both random-access and read-only memory applications are observed in these systems.     

Synthesis and characterization of photoluminescent In-doped CdSe nanoparticles

Indium-doped CdSe nanoparticles have been synthesized and characterized. Their light absorption, photoluminescence, and structure are similar to undoped CdSe nanoparticles. The greater part of the In associated with the nanoparticles is removed when the nanoparticles undergo ligand exchange by pyridine. As observed with undoped nanoparticles, a ZnS capping layer on the indium-doped nanoparticles results in enhanced nanocrystal photoluminescence. Also, the ZnS cap enhances the retention of In by the nanoparticles. Elemental analysis shows ligand exchange causes CdSe to be lost and capping with ZnS results in the loss of Se. We conclude that In-doped nanoparticles have most of the In on their surface, capping helps the nanoparticles retain the In, and they do not have altered electronic properties.     

The effects of chemisorption on the luminescence of CdSe quantum dots

We report on the effects of Lewis bases and other ligands on radiative recombination in CdSe quantum dots (QDs) in several solvents. Long-chain primary amines are found to be the most efficacious capping agents for CdSe QDs in nonpolar solvents. Primary alkylamines are superior to secondary and tertiary alkylamines. The kinetics of chemisorption and desorption in less polar solvents, such as hexane or chloroform, are temperature controlled and obey a Langmuir isotherm. Mercaptan adsorption also obeys a Langmuir isotherm, and alkylmercaptans rapidly displace amines, leading to luminescence quenching. In more polar solvents, such as toluene, ligands desorb, leading to luminescence quenching. It is proposed that surface Cd vacancies function as nonradiative recombination centers. The adsorption of a Lewis base to the QD raises the surface vacancy energy close to, or above, the conduction band edge and eliminates electron capture by the surface vacancies. Solvent polarity has a strong effect on luminescence since the solvent determines the extent of ligand adsorption to the QD surface.     

Tuning the properties of CdSe nanoparticles in reverse micelles

A new and simple approach of synthesizing size-quantized CdSe colloids in reverse micellar suspension is described. The room temperature reaction between Cd²⁺ and selenosulfate is carried out within the water pool of di-octyl sulphosuccinate (Aerosol-OT) reverse micelles. The size dependent absorption and emission properties of these small CdSe particles (3—5 nm) are described. The Q-sized CdSe nanoparticles exhibit an emission yield of 0.13. Up to a factor of two enhancement in the emission efficiency can be achieved following the surface functionalization of CdSe colloids with triethyl amine.     

Sol-Gel assembly of CdSe nanoparticles to form porous aerogel networks

A detailed study of CdSe aerogels prepared by oxidative aggregation of primary nanoparticles (prepared at room temperature and high temperature conditions, >250 degrees C), followed by CO2 supercritical drying, is described. The resultant materials are mesoporous, with an interconnected network of colloidal nanoparticles, and exhibit BET surface areas up to 224 m2/g and BJH average pore diameters in the range of 16-32 nm. Powder X-ray diffraction studies indicate that these materials retain the crystal structure of the primary nanoparticles, with a slight increase in primary particle size upon gelation and aerogel formation. Optical band gap measurements and photoluminescence studies show that the as-prepared aerogels retain the quantum-confined optical properties of the nanoparticle building blocks despite being connected into a 3-D network. The specific optical characteristics of the aerogel can be further modified by surface ligand exchange at the wet-gel stage, without destroying the gel network.     

Capping ligand effects on the amorphous-to-crystalline transition of CdSe nanoparticles

Amorphous CdSe nanoparticles were prepared by a base-catalyzed room-temperature reaction between cadmium nitrate and selenourea, with dodecanethiol as a capping ligand. The nanoparticle size could be controlled from 1.9 to 3.6 nm by increasing the water concentration in the reaction. When the nanoparticles were heated in a pyridine suspension, excitonic peaks appeared in the initially featureless optical absorption spectra. By changing the suspension solvent and the capping ligand and its concentration, it was shown that the dynamic surface exchange between the ligand and pyridine controls the crystallization process. This phenomenon was interpreted as a surface rigidity effect imposed by the ligand, whose importance was separately evidenced on the dried nanoparticles by the evolution of X-ray diffraction patterns and Raman spectra. In particular, both techniques showed that a threshold temperature is needed before crystallization occurs, and such a threshold was related to ligand desorption. The surface effect was directly visualized by high-resolution transmission electron microscopy observations of the amorphous particles, where crystallization under the electron beam was observed to start by the formation of a crystalline nucleus in the nanoparticle interior and then to extend to the whole structure.     

Ordered CdSe nanoparticles within self-assembled block copolymer domains on surfaces

Hierarchical, high-density, ordered patterns were fabricated on Si substrates by self-assembly of CdSe nanoparticles within approximately 20-nm-thick diblock copolymer films in a controlled manner. Surface-modified CdSe nanoparticles formed well-defined structures within microphase-separated polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) domains. Trioctylphosphine oxide (TOPO)-coated CdSe nanoparticles were incorporated into PS domains and polyethylene glycol-coated CdSe nanoparticles were located primarily in the P2VP domains. Nearly close-packed CdSe nanoparticles were clearly identified within the highly ordered patterns on Si substrates by scanning electron microscopy (SEM). Contact angle measurements together with SEM results indicate that TOPO-CdSe nanoparticles were partially placed at the air/copolymer interface.     

High-quality ZnS shells for CdSe nanoparticles: rapid microwave synthesis

Using a domestic microwave oven and new, inexpensive precursors, a rapid and reliable synthesis of highly luminescent CdSe/ZnS NPs was developed. To evaluate the quality of our core/shell particles for varying shell thickness in comparison to that of CdSe/ZnS nanoparticles obtained commercially, the parameter fluorescence quantum yield is been used as well as a new, straightforward, thiophenol-based shell-quality test as a tool to ensure a dense ZnS shell without holes and cracks, which is a prerequisite for high luminescence and stability.     

Bioconjugation of CdSe/ZnS nanoparticles with SNAP tagged proteins

A method for protein immobilization onto modified CdSe/ZnS quantum dot surfaces was developed using simple SNAP tag methodology.     

Fingerprint detection and using intercalated CdSe nanoparticles on non-porous surfaces

A fluorescent nanocomposite based on the inclusion of CdSe quantum dots in porous phosphate heterostructures, functionalized with amino groups (PPH-NH₂@CdSe), was synthesized, characterized and used for fingerprint detection. The main scopes of this work were first to develop a friendly chemical powder for detecting latent fingerprints, especially in non-porous surfaces; their further intercalation in PPH structure enables not to spread the fluorescent nanoparticles, for that reason very good fluorescent images can be obtained. The fingerprints, obtained on different non-porous surfaces such as iron tweezers, mobile telephone screen and magnetic band of a credit card, treated with this powder emit a pale orange luminescence under ultraviolet excitation. A further image processing consists of contrast enhancement that allows obtaining positive matches according to the information supplied from a police database, and showed to be more effective than that obtained with the non-processed images. Experimental results illustrate the effectiveness of proposed methods.     

Synthesis and characterization of water-soluble CdSe nanoparticles capped by AOT

Water-soluble CdSe nanoparticles were synthesized using AOT (sodium bis(2-ethylehexyl)-sulfosuccinate) as stabilizer, cadmium acetate and Na2SeSO3 as precursors in aqueous phase. The influence of some key factors, such as reaction time, temperature, concentration and molar ratio of precursors on the optical properties of CdSe nanoparticles was systematically investigated through UV-Vis and PL spectra. Powder X-ray diffraction (XRD) was used to characterize the crystalline structure of synthesized CdSe nanoparticles. As-prepared CdSe nanoparticles exhibit an apparent quantum confinement effect and typical hexagonal wurtzite structures. Finally, the optimal experimental conditions were obtained.     

A one-step aqueous synthetic route to extremely small CdSe nanoparticles

By employing Na2Se as a selenium source, we demonstrate that extremely small ( approximately 1 nm) mercapto acid-stabilized CdSe nanoparticles can be conveniently prepared in water. The as-prepared nanoparticles start to show dominant near band-gap photoluminescence in the blue spectral range and show high photoluminescence in the green spectral range.     

Controlled placement of polystyrene-grafted CdSe nanoparticles in self-assembled block copolymers

Surface functionalization of semiconductor CdSe nanoparticles has been achieved with polystyrene (PS) brushes by “grafting from” technique for further addition to a polystyrene-b-polybutadiene-b-polystyrene (SBS) block copolymer in order to obtain self-assembled composites. For modification of nanoparticle surface 3-glycidoxypropyltrimethoxysilane (GPS) was used at first for the later attachment of the 4,4′-azobis(4-cyanopentanoic acid) azo initiator. Fourier-transform infrared spectroscopy confirmed the presence of GPS and PS on the surface of nanoparticles. Atomic force microscopy was used for morphological characterization of SBS/CdSe nanocomposites. Modification of nanoparticles with PS brushes by radical polymerization improved their affinity with PS block and the dispersion of nanoparticles avoiding agglomeration. CdSe nanoparticle size was measured to be around 2 nm by the use of X-ray diffraction and UV–Vis techniques. Optical properties were characterized using fluorescence measurements.