Phosphine-free synthesis of CdSe nanocrystals

High quality CdSe nanocrystals have been prepared using elemental selenium as the chalcogenide precursor dispersed in 1-octadecene (ODE). The conditions used to prepare the Se precursor were found to be critical for successful nanocrystal synthesis. Systematic titration of the Se precursor solution with tri-n-octylphosphine (TOP) allowed the Se reactivity to be tuned and the final particle size to be controlled. Band-edge and surface related emission were observed for samples prepared in the presence and absence of added TOP. In the absence of a selenium passivant, the crystal structure of CdSe nanocrystals could be altered from zinc blende to wurtzite by the addition of bis(2,2,4-trimethylpentyl)phosphinic acid (TMPPA).     

Oleic capped CdSe nanocrystals silver-doped in the course of synthesis

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High-temperature microfluidic synthesis of CdSe nanocrystals in nanoliter droplets

The high-temperature synthesis of CdSe nanocrystals in nanoliter-volume droplets flowing in a perfluorinated carrier fluid through a microfabricated reactor is presented. A flow-focusing nanojet structure with a step increase in channel height reproducibly generated octadecene droplets in Fomblin Y 06/6 perfluorinated polyether at capillary numbers up to 0.81 and with a droplet:carrier fluid viscosity ratio of 0.035. Cadmium and selenium precursors flowing in octadecene droplets through a high-temperature (240-300 degrees C) glass microreactor produced high-quality CdSe nanocrystals, as verified by optical spectroscopy and transmission electron microscopy. Isolating the reaction solution in droplets prevented particle deposition and hydrodynamic dispersion, allowing the reproducible synthesis of nanocrystals at three different temperatures and four different residence times in the span of 4 h. Our synthesis of a wide range of nanocrystals at high temperatures, high capillary numbers, and low viscosity ratio illustrates the general utility of droplet-based microfluidic reactors to encapsulate nanoliter volumes of organic or aqueous solutions and to precisely control chemical or biochemical reactions.     

A new route to zinc-blende CdSe nanocrystals: mechanism and synthesis

We report the possible mechanism of forming of CdSe nanocrystals in the high boiling point solvents with long alkane chains and a novel Non-TOP-Based route to zinc-blende CdSe nanocrystals. A new mechanism shows that there exits a redox reaction in the long alkane chain solvents: Se is reduced to H2Se gas; at the same time, the long alkane chains are oxidated to alkene chains; then, the Cd complex reacts with H2Se to form CdSe nanocrystals. Possible chemical reaction equations involved in the process of forming the CdSe nanocrystals have been discussed. The alkene chain and H2Se were detected respectively by a series of experiments to support the new mechanism. Under the guidance of this mechanism, we have developed a much cheaper and greener Non-TOP-Based route for the synthesis of a size series of high-quality zinc-blende (cubic) CdSe nanocrystals. Low-cost, green, and environmentally friendlier reagents are used, without use of expensive solvents such as trioctylphosphine (TOP) or tributylphosphine (TBP). The new route enables us to achieve high-quality CdSe nanocrystals with sharp ultraviolet and visible (UV-vis) absorption peaks, controllable size (2.0-5.0 nm), bright photoluminescence (PL), narrow PL full width of half-maximum (fwhm) (29-48 nm), and high PL quantum yield (up to 60%) without any size sorting.     

Shape evolution of CdSe nanocrystals in vegetable oils: A synergistic effect of selenium precursor

In this contribution, common vegetable oils are used as coordination solvents for synthesis of high quality CdSe nanocrystals. Various shaped nanocrystals (quantum dots, quantum rods, multipods, arc structure, etc.) can be produced free of alkylphosphonic acids. Shape evolution can be induced by three types of selenium precursors: ODE-Se, VO-Se and TOP-Se (ODE, 1-octadecene; VO, vegetable oil; TOP, trio-n-octylphosphine). The quantum yields of NCs are 15–40%. The full width at half-maximum (fwhm) of the photoluminescence spectra are 27 ± 1 nm for quantum dots and 23 ± 1 nm for quantum rods/multipods. The obtained quantum dots are zinc blende structure and stable at high temperature. Wurtzite, zinc blende, twinned and dislocation can coexist in the obtained quantum arc structure, which will provide new physical model to study the subtle optoelectronic properties of NCs.     

Microreactor with integrated temperature control for the synthesis of CdSe nanocrystals

The recent needs in the nanosciences field have promoted the interest towards the development of miniaturized and highly integrated devices able to improve and automate the current processes associated with efficient nanomaterials production. Herein, a green tape based microfluidic system to perform high temperature controlled synthetic reactions of nanocrystals is presented. The device, which integrates both the microfluidics and a thermally controlled platform, was applied to the automated and continuous synthesis of CdSe quantum dots. Since temperature can be accurately regulated as required, size-controlled and reproducible quantum dots could be obtained by regulating this parameter and the molar ratio of precursors. The obtained nanocrystals were characterized by UV-vis and fluorescence spectrophotometry. The band width of the emission peaks obtained indicates a narrow size distribution of the nanocrystals, which confirms the uniform temperature profile applied for each synthetic process, being the optimum temperature at 270 °C (full width at half maximum = 40 nm). This approach allows a temperature controlled, easy, low cost and automated method to produce quantum dots in organic media, enhancing its application from laboratory-scale to pilot-line scale processes.     

Selective synthesis and characterization of CdSe nanorods and fractal nanocrystals

CdSe nanorods and dendritic fractals were synthesized through a novel controllable solution-phase hydrothermal method. Soluble selenite was employed to provide a highly reactive Se source in the synthesis. Both morphologies and phases of the CdSe products could be successfully controlled by choosing appropriate complexing agents to adjust the dynamics of the reaction process. Reaction temperature and Cd/Se ratio in raw materials were also important parameters influencing the morphologies and phases of the products. The phase structures, morphologies, and optical properties of the CdSe products were investigated by XRD, TEM, HRTEM, and UV-vis and photoluminescence spectroscopies. The formation mechanisms of the nanorods and fractals were investigated and discussed on the basis of the experimental results.     

Microwave synthesis of CdSe and CdTe nanocrystals in nonabsorbing alkanes

Controlling nanomaterial growth via the "specific microwave effect" can be achieved by selective heating of the chalcogenide precursor. The high polarizability of the precursor allows instantaneous activation and subsequent nucleation leading to the synthesis of CdSe and CdTe in nonmicrowave absorbing alkane solvents. Regardless of the desired size, narrow dispersity nanocrystals can be isolated in less than 3 min with high quantum efficiencies and elliptical morphologies. The reaction does not require a high temperature injection step, and the alkane solvent can be easily removed. In addition, batch-to-batch variance in size is 4.2 +/- 0.14 nm for 10 repeat experimental runs. The use of a stopped-flow reactor allows near continuous automation of the process leading to potential industrial benefits.     

Comparative study on coating CdSe nanocrystals with surfactants

We have synthesized CdSe nanocrystals (NCs) in sizes from 2.2 to 5.1 nm passivated with hydrophobic trioctylphosphine oxide (TOPO) in combination trioctylphosphine (TOP) or tributylphosphine (TBP) to obtain particles of the type CdSe/TOPO/TOP or CdSe/TOPO/TBP. These NCs were then dispersed in aqueous solution of ionic or non-ionic surfactants (such as stearate, oleic acid, Tween) using a biphase (water and chloroform or hexane) transfer method. It is found that both the structure of the surfactant and the native surface of the ligand govern the coating of the NCs with surfactants. More specifically, the hydrophobicity-hydrophilicity balance of the surfactant regulates the coating efficacy, thereby transferring the NC from the organic to the aqueous phase. The type of ligand on the NCs and the kind of coating surfactant also affect photoluminescence (PL). The ratio of PL and absorbance unit (defined as PL per 0.1 AU) was implemented as a tool to monitor changes in PL intensity and wavelength as a function of size, coatings and surface defects. Finally, the distribution of CdSe nanocrystals between pseudophases in cloud point extraction was discussed based on experimental results. It was concluded that the size of CdSe nanocrystal present in an appropriate pseudophase is correlated with the way in which the non-ionic surfactant coats CdSe nanocrystals.

Visible light excitation of CdSe nanocrystals triggers the release of coumarin from cinnamate surface ligands

The photochemical properties of organic ligands on the surface of nanocrystalline CdSe particles were examined. A number of thiols carrying a substituted cinnamate tail was synthesized. In solution, these cinnamate compounds undergo light-induced (374 nm) E-Z isomerization, followed by a nonphotolytic lactonization to give highly fluorescent coumarin. The cinnamate-thiols were successfully exchanged onto the CdSe nanocrystal, and the photochemical behavior of these conjugates was studied. Upon aerobic photolysis at 374 nm, the surface cinnamates released coumarin accompanied by rapid nanocrystal degradation. This degradation was not observed under similar anaerobic conditions or when the organic ligands did not contain the cinnamate group. Surprisingly, very similar results were obtained upon irradiation at visible wavelengths at which the cinnamate has no absorption. With the aid of UV-visible absorption spectroscopy, fluorescence spectroscopy, and electrochemistry, a unified theory for both the increased photoinstability of the nanocrystal as well as the coumarin release was proposed. It involves cinnamate radical anions on the CdSe surface, formed upon electron transfer from the excited nanocrystal to the surface cinnamate, undergoing E-Z isomerization. Practically, this results in the remarkable ability to release coumarin from nanocrystal ligands simply by exciting the nanocrystal with visible light. This new photorelease protocol not only aids in the understanding of fundamental nanocrystal-ligand interactions but may also offer new opportunities in the areas of drug delivery and imaging.     

Water-soluble CdSe and CdSe/CdS nanocrystals: a greener synthetic route

We report a new green synthetic route of CdSe and core-shell CdSe/CdS nanoparticles (NPs) in aqueous solutions. This route is performed under water-bath temperature, using Se powder as a selenium source to prepare CdSe NPs, and H(2)S generated by the reaction of Na(2)SH(2)SO(4) as a sulfur source to synthesize core-shell CdSe/CdS NPs at 25-35 degrees C. The synthesis time of every step is only 20 min. After illumination with ambient natural light, photoluminescence (PL) intensities of CdSe NPs enhanced up to 100 times. The core-shell CdSe/CdS NPs have stronger photoactive luminescence with quantum yields over 20%. The obtained CdSe NPs exhibit a favorable narrow PL band (FWHM: 50-37 nm) with increasing molar ratio of Cd/Se from 4:1 to 10:1 at pH 9.1 in the crude solution, whereas PL band of corresponding CdSe/CdS NPs is slightly narrower. The emission maxima of nanocrystals can be tuned in a wider range from 492 to 592 nm in water by changing synthesis temperature of CdSe core than those reported previously. The resulting new route is of particular interest as it uses readily-available reagents and simple equipment to synthesize high-quality water-soluble CdSe and CdSe/CdS nanocrystals.     

Oligothiophene-functionalized CdSe nanocrystals: preparation and electrochemical properties

The preparation of new molecular hybrids consisting of CdSe semiconductor nanocrystals, surface-functionalized with conductive and electrochemically active oligothiophene ligands, is described. Specially synthesized aniline-terminated oligoalkylthiophenes containing one, two, or four thiophene units were used for the grafting on CdSe nanocrystals, previously surface-functionalized with 4-formyldithiobenzoate. The electrochemical activity of both the inorganic and the organic parts of the hybrid was investigated by cyclic voltammetry. The oxidative doping of the organic part of the hybrid is irreversible, contrary to the case of the “free” non-grafted ligand which shows reversible doping. Furthermore, the electrochemical doping of the surface ligands, occurring at lower potentials than the oxidation of the nanocrystals, perturbs the latter process via charging of the ligands followed by slow relaxation processes. The first two authors contributed equally to this work Correspondence: Peter Reiss, Adam Pron, DSM/DRFMC/SPrAM (UMR 5819 CEA-CNRS-Université Joseph Fourier 1)/LEMOH CEA Grenoble, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France     

Single-nanocrystal spectroscopy of white-light-emitting CdSe nanocrystals

We report the observation of broad-spectrum fluorescence from single CdSe nanocrystals. Individual semiconductor nanocrystals typically have a narrower emission spectrum than that of an ensemble. However, our experiments show that the ensemble white-light emission observed in ultrasmall CdSe nanocrystals is the result of many single CdSe nanocrystals, each emitting over the entire visible spectrum. These results indicate that each white-light-emitting CdSe nanocrystal contains all the trap states that give rise to the observed white-light emission.     

Amine-assisted facetted etching of CdSe nanocrystals

The treatment of CdSe nanocrystals (NCs) in a 3-amino-1-propanol (APOL)/water (v/v = 10:1) mixture at 80 degrees C in the presence of O(2) causes them to undergo a slow chemical etching process, as evidenced by spectroscopic and structural investigations. Instead of the continuous blue shift expected from a gradual decrease in NC dimensions, a bottleneck behavior was observed with distinct plateaus in the peak position of photoluminescence (PL) and corresponding maxima in PL quantum yield (i.e., 34 +/-7%). It is presently argued that such etching behavior is a result of two competitive processes taking place on the surface of these CdSe NCs: (i) oxidation of the exposed Se-sites to acidic SeO(x)() entities, which are readily solubilized in the basic APOL/H(2)O mixture, and (ii) coordination of the underlying Cd-sites with both amines and hydroxyl moieties to temporally impede NC dissolution. This is consistent with the HRTEM results, which suggest that the etched NCs adopt pyramidal morphologies with Cd-terminated facets (i.e., (0001) bases and either {011} or {21} sides) and account for the apparent resistance to etching at the plateau regions.     

Binary superlattices of PbSe and CdSe nanocrystals

In this paper we show that self-organization of colloidal PbSe and CdSe semiconductor nanocrystals with a size ratio of 0.57 leads to binary structures with a AB2 or a cuboctahedral AB13 lattice. The type of superlattice formed can be regulated by the relative concentration of both nanocrystals in the suspension.     

Preparation of CdSe nanocrystals in a micro-flow-reactor

A micro-reactor was utilized for continuous and controlled CdSe nanocrystal preparation. Effects of reaction conditions on optical properties of the nanocrystals were investigated; in this current system, rapid and exact temperature control of the micro-reactor was beneficial for controlling particle diameter and reproducible preparation of particles; additional effort was made towards narrower particle-size distributions.     

Characterization of CdSe nanocrystals coated with amphiphiles. A capillary electrophoresis study

We have synthesized CdSe nanocrystals (NCs) possessing a trioctylphosphine surface passivation layer and modified with amphiphilic molecules to form a surface bilayer. The NCs covered with single amphiphiles are not stable in aqueous solution, but a mixed amphiphilic system is shown to provide stability in solution over several months. The solutions of the modified NCs were characterized by UV-Vis absorbance, photoluminescence, and transmission electron microscopy. An electrophoretic study revealed two operational modes. The first relies on the enrichment of NCs using a micellar plug as a tool. The accumulation of NCs at the plug-electrolyte buffer interface results in a sharp peak. By controlling the electrophoretic conditions, nanocrystals were forced to exit a micellar plug into an electrolyte buffer. We conclude that a system consisting of modified nanocrystals and a micellar plug can act as a mixed pseudomicellar system, where modified nanocrystals play the role of pseudomicelles.FigureElectrophoretic focusing of amphiphile coated CdSe nanocrystals using a micellar plug. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00604-011-0727-8) contains supplementary material, which is available to authorized users.