Influence of alkanethiols on fluorescence blinking of InP@ZnS colloidal quantum dots

Luminescence decay curves have been measured for InP@ZnS colloidal quantum dots (CQDs) synthesized at different ratios between 1-octanethiol and 1-dodecanethiol. The luminescence lifetime distributions reflecting the ratios between the on, off, and grey states of CQDs have been calculated. With an increase in the portion of 1-octanethiol, the distribution is shifted toward the on states, which almost completely suppresses fluorescence blinking at all detection wavelengths.     

Specifics of the spectral and luminescent properties of ensembles of colloidal quantum dots

Using colloidal solutions of ZnS-shell indium phosphide quantum dots with two average sizes of 2.1 and 3.0 nm and a size distribution variance of 10%, it has been shown that the luminescence and the luminescence excitation spectra of the colloidal quantum dots substantially depend on the wavelength of exciting light and the detection wavelength, respectively, with both the relationships being nonlinear in character, which may indicate the bimodal type of the size distribution function. Similar measurements for CdSe colloidal quantum dots with an average particle size of d_av = 2.5 nm and a variance of 6% have shown that the effect of dependence of the luminescence peak position on the excitation wavelength is manifested to a much lesser extent.     

Influence of gold nanoparticles on nonradiative energy transfer in nanoclusters of colloidal quantum dots InP@ZnS

The influence of gold nanoparticles on the efficiency of nonradiative resonance energy transfer between InP@ZnS quantum dots composed of nanoclusters, a new type of organized structures consisting of hydrophobic quantum dots and gold nanoparticles, has been experimentally studied.     

Preparation and spectral properties of high-efficiency luminescent polyethylenimine-stabilized CdS quantum dots

Feasibility was demonstrated for obtaining ultrasmall colloidal CdS nanoparticles (with diameter about 2 nm) stabilized in aqueous solution by polyethylenimine with a narrow size distribution (~10%) and luminescing at 400-600 nm (quantum yield about 10%). Complexation between Cd^II and polyethylenimine is a necessary condition for formation of such nanoparticles.     

Specifics of luminescence of nanoclusters consisting of InP@ZnS colloidal quantum dots stabilized by oleylamine

Spectral, luminescent, and kinetic characteristics of nanoclusters of hydrophobic colloidal quantum dots (CQDs) of the core@shell type InP@ZnS stabilized by oleylamine have been studied, with the nanoclusters consisting of CQDs of two average sizes: with core diameters of 2.1 and 3.0 nm. For the nanoclusters consisting of the particles of any of these kinds, the experimental data indicate the occurrence of Förster resonance energy transfer with an efficiency of about 50%. For the mixed nanoclusters, energy transfer has not been observed within the experimental error.     

Optical and dynamic properties of water-soluble highly luminescent CdTe quantum dots

CdTe quantum dots (QDs) were synthesized in aqueous solution using thioglycolic acid (HS-CH2COOH, TGA) as a stabilizer. The phenomenon of "on" and "off" luminescence intermittency (blinking) of CdTe QDs in PVA and trehalose was investigated by single-molecule optical microscopy, and we identified that the intermittencies of single QDs were correlated with the interaction of water molecules absorbed on the QD surface. The "off" times, the interval between adjacent "on" states, remained essentially unaffected with an increase in excitation intensity. Every QD showed a similar power law behavior for the "off" time distribution regardless of the excitation intensity and aqueous environment of the QDs. In the case of "on" time distribution, power law behavior with an exponential cutoff tail is observed at longer time scales. The time traces indicated that the "on" time was inversely proportional to the excitation intensity; the duration of "on" time became shorter with increasing excitation intensity. An increase in the duration of "on" time was observed in trehalose with respect to that in PVA. We obtained a clear decrease in the power law exponent when PVA was replaced with trehalose. These observations indicate that the luminescence blinking statistics of water-soluble single CdTe QDs is significantly dependent on the aqueous environment, which is interpreted in terms of passivation of the surface trap states of QDs.     

Colloidal quantum dots InP@ZnS: Inhomogeneous broadening and distribution of luminescence lifetimes

Indium phosphide colloidal quantum dots with a zinc sulfide shell, an average core diameter of 3 nm, a luminescence peak position of 600 nm, and a luminescence quantum yield up to 50% have been synthesized. By analyzing the stationary absorption and luminescence spectra in terms of the Kennard—Stepanov relationship, the values of homogeneous width and inhomogeneous broadening have been obtained, which determine the resulting width of the spectra: the corresponding full widths at half maximum (FWHM) were 31, 63, and 70 nm. From the value of inhomogeneous broadening and the sizing curve of indium phosphide, polydispersity of the synthesized particles has been estimated as 11%. Analysis of the luminescence decay kinetics has revealed three reproducible peaks with maxima near 4.35, 35 (main) and 200 ns in the lifetime distribution. It has been found that although repeated washing of the synthesized particles with methanol can decrease the quantum yield, the lifetime distribution observed remains constant, which in the context of the “blinking” effect indicates a very short luminescence decay time of the particles in the OFF-state.     

Absorption cross-section and related optical properties of colloidal InAs quantum dots

We report the absorption cross-section of colloidal InAs quantum dots of mean radii from 1.6 to 3.45 nm. We find excellent agreement between the measured results and calculated values based on a model of small-particle light absorption. The absorption cross-section per dot is 6.2 x 10(-16)R(3) cm(2) at 2.76 eV and 3.15 x 10(-16)R(1.28) cm(2) at the first-exciton absorption peak, with the dot radius R in nm. We find that the per-quantum-dot particle oscillator strength of the first-exciton transition is constant for all sizes studied. The radiative lifetime of the first exciton calculated from the oscillator strength increases with dot size and ranges from 4 ns for the smallest dots to 14 ns for the largest ones.     

Synthesis and luminescent properties of polymer-silica multilayer-encapsulated perovskite quantum dots for optoelectronics

Hydrophobic all-inorganic perovskite quantum dots (IPQDs) CsPbX₃ (X = Cl, Br, and I) were synthesized using conventional solution methods. IPQDs are potential materials for lasers, solar cells, and displays because of their narrow full width at half-maximum, optically tunable wavelength, and great photoluminescence quantum yield. Their shortcomings are structurally unstable and moisture sensitive. To overcome the poor stability, we have developed a chemical modification to form GQD + PMAO@SiO₂ that enhances their photoluminescence quantum yield (from 60 to ~90%), thermal stability (from 60 to ~90°C), and photochemical stability. The combination of the green-emitting GQD + PMAO@SiO₂ and red-emitting RQD + PMAO with a 450 nm blue InGaN-based LED chip was used to fabricate a white light emitting diode with the correlated color temperature (CCT) value of 6,943 K and Commission Internationale del'Eclairage of (0.312, 0.290).     

Synthesis and luminescent properties of water-soluble nanobiocomposite CdSe/polysaccharide quantum dots

Water-soluble nanobiocomposite CdSe quantum dots were obtained using the stabilizing potential of natural biologically active polysaccharides galactomannan and κ-carrageenan. A complex of physicochemical methods was used to investigate the biphasic amorphous-crystalline structure of the obtained nanocomposites, the size range (4.8—6.9 nm) of the formed CdSe particles was determined, and, additionally, it was shown that aqueous solutions of the nanocomposites in question were characterized by the presence of photoluminescence in two spectral regions, namely, 410—450 and 510—580 nm.     

pH-sensitive ligand for luminescent quantum dots

We developed a strategy to switch the luminescence of semiconductor quantum dots with chemical stimulations. It is based on the photoinduced transfer of either energy from CdSe-ZnS core-shell quantum dots to [1,3]oxazine ligands or electrons from the organic to the inorganic components. The organic ligands incorporate a dithiolane anchoring group, an electron-rich indole, and a 4-nitrophenylazophenoxy chromophore in their molecular skeleton. Their adsorption on the surface of the quantum dots results in partial luminescence quenching. Electron transfer from the indole fragment to the nanoparticles is mainly responsible for the decrease in luminescence intensity. Upon addition of base, the [1,3]oxazine ring of the ligands opens to generate a 4-nitrophenylazophenolate chromophore, which absorbs in the range of wavelengths where the quantum dots emit. This transformation activates an energy-transfer pathway from the excited nanoparticles to the ligands. In addition, the oxidation potential of the ligand shifts in the negative direction, improving the efficiency of electron transfer. The overall result is a decrease in the luminescence quantum yield of 83%. Addition of acid also opens the [1,3]oxazine ring of the ligands. However, the resulting 4-nitrophenylazophenol does not absorb in the visible region and cannot accept energy from the excited nanoparticles. Furthermore, the oxidation potential shifts in the positive direction, lowering the electron-transfer efficiency. In fact, the luminescence quantum yield increases by 33% as a result of this transformation. These changes are fully reversible and can be exploited to probe the pH of aqueous solutions from 3 to 11. Indeed, our sensitive quantum dots adjust their luminescence in response to variations in pH within this particular range of values. Thus, our general design strategy can eventually lead to the development of pH-sensitive luminescent probes for biomedical applications based on the unique photophysical properties of semiconductor quantum dots.     

Chiral highly luminescent CdS quantum dots

Strongly white-emitting (lambda(max) = 495 +/- 10 nm) D- and L- penicillamine capped CdS nanoparticles, which show strong circular dichroism in the range 200-390 nm, have been prepared.     

Multicarrier recombination in colloidal quantum dots

The rates of multicarrier recombination are measured in colloidal quantum dots with and without hole surface trapping and with hole extraction in type II core/shell systems. We report that hole trapping or the physical separation of electronic and hole wavefunctions into different semiconductor domains of a type II system have an insignificant effect on the multicarrier recombination dynamics. These observations are inconsistent with the accepted Auger transition mechanism.     

Features of the influence of stabilizing ligands on luminescence properties of cadmium selenide colloidal quantum dots

It has been shown that immediately after the synthesis, the luminescence efficiency of CdSe quantum dots stabilized by n-octadecylphosphonic acid together with one of the auxiliary ligands decreases in the order: oleylamine, hexadecylamine, trioctylphosphine oxide, 1-octadecene, and stearic acid, which is due to combination of the energy of their binding with surface atoms of the nanoparticles and the packing density of the ligands in the shell. In the course of post-synthetic ripening of the quantum dots in a solution, changes in their luminescence quantum yield occur, depending on the solvent polarity and due to rearrangement of the ligands in the shells. The effect of dark recovery of trap luminescence from UV-irradiated quantum dots stabilized by octadecylphosphonic acid and a long-chain amine has been found.     

Oligomeric ligands for luminescent and stable nanocrystal quantum dots

We report a new family of oligomeric alkyl phosphine ligands for nanocrystal quantum dots. These oligomeric phosphines show effective binding affinity to quantum dot surfaces. They form thin and secure organic shells that stabilize quantum dots in diverse environments including serum and polymer matrices. They maintain the initial as-grown photoluminescence quantum yield of the quantum dots and enable homogeneous incorporation into various matrices. They present a chemically flexible structure that can be used for further chemistry, such as cross-linking, copolymerization, and conjugation to biomolecules.     

Synthesis of cadmium arsenide quantum dots luminescent in the infrared

We present the synthesis of Cd(3)As(2) colloidal quantum dots luminescent from 530 to 2000 nm. Previous reports on quantum dots emitting in the infrared are primarily limited to the lead chalcogenides and indium arsenide. This work expands the availability of high quality infrared emitters.     

Surface passivation of luminescent colloidal quantum dots with poly(dimethylaminoethyl methacrylate) through a ligand exchange process

Polydimethylaminoethyl methacrylate (PDMAEMA) was used as a multidentate ligand to modify the surface of CdSe/ZnS core-shell colloidal quantum dots in toluene with trioctylphosphine oxide (TOPO) as the surface ligand. Adsorption of PDMAEMA was accompanied by release of TOPO. The process is free of agglomeration, and the modified nanocrystals become soluble in methanol. The photoluminescence properties are well-preserved in either toluene or methanol.     

Rational hydrothermal synthesis of graphene quantum dots with optimized luminescent properties for sensing applications

Hydrothermal synthesis using graphene oxide (GO) as a precursor has been used to produce luminescent graphene quantum dots (GQDs). However, such a method usually requires many reagents and multistep pretreatments, while can give rise to GQDs with low quantum yield (QY). Here, we investigated the concentration, the temperature of synthesis, and the pH of the GO solution used in the hydrothermal method through factorial design experiments aiming to optimize the QY of GQDs to reach a better control of their luminescent properties. The best synthesis condition (2 mg/mL, 175 °C, and pH = 8.0) yielded GQDs with a relatively high QY (8.9%) without the need of using laborious steps or dopants. GQDs synthesized under different conditions were characterized to understand the role of each synthesis parameter in the materials' structure and luminescence properties. It was found that the control of the synthesis parameters enables the tailoring of the amount of specific oxygen functionalities onto the surface of the GQDs. By changing the synthesis' conditions, it was possible to prioritize the production of GQDs with more hydroxyl or carboxyl groups, which influence their luminescent properties. The as-developed GQDs with tailored composition were used as luminescent probes to detect Fe³⁺. The lowest limit of detection (0.136 μM) was achieved using GQDs with higher amounts of carboxylic groups, while wider linear range was obtained by GQDs with superior QY. Thus, our findings contribute to rationally produce GQDs with tailored properties for varied applications by simply adjusting the synthesis conditions and suggest a pathway to understand the mechanism of detection of GQDs-based optical sensors.