SANS Study of CdS and CdSe Quantum Dot Crystal Growth in a Silica Matrix by Sol-Gel

Size and size distribution of the semiconductor nanocrystals embedded in a dielectric matrix play a dominant role in line broadening and the exciton quantum confinement level. The results show new aspects of the CdS and CdSe crystal growth as quantum dots using small angle neutron scattering techniques (SANS). Thus, the crystal growth influences the aggregation process of the silica network. The intensity difference of the scattering between the silica matrix and the composite accounts for the crystal size and their volume fraction. Under similar conditions CdS nanocrystals grow faster and bigger than CdSe ones.     

A novel strategy for boosting the photoluminescence quantum efficiency of CdSe nanocrystals at room temperature

Highly luminescent colloidal nanocrystals have wide applications in bioimaging and various optoelectronic devices.Herein we report a facile and mild procedure by combining S2-treatment and binary ligand passivation,which can efficiently enhance the luminescent property of CdSe nanocrystals at room temperature.The photoluminescence quantum yield of as-treated CdSe nanocrystals exhibits drastic enhancement(e.g.,188 times for CdSe nanorods)after this dual-passivation treatment.The methodology proposed here can be applied to various CdSe nanocrystals,regardless of their sizes,shapes,and crystal structures.     

水溶性CdSe/CdS纳米晶合成条件的优化研究

以巯基乙醇为修饰剂,在水溶液中合成了稳定的CdSe/CdS纳米晶,应用单因素法和多目标单纯形法探索合成条件。通过透射电镜观察所合成的纳米晶的形貌和大小,用紫外-可见吸收光谱和荧光光谱对其光学特性进行了表征。并且以L-色氨酸荧光量子产率0.14为标准,测量了合成的CdSe/CdS纳米晶的荧光量子产率为0.37。     

Highly luminescent, stable, and water-soluble CdSe/CdS core-shell dendron nanocrystals with carboxylate anchoring groups

A dendron ligand with two carboxylate anchoring groups at its focal point and eight hydroxyl groups as its terminal groups was found to efficiently convert as-synthesized CdSe/CdS core-shell nanocrystals in toluene to water-soluble dendron-ligand stabilized nanocrystals (dendron nanocrystals). The resulting dendron nanocrystals retained 60% of the photoluminescence value of the original CdSe/CdS core-shell nanocrystals in toluene and were significantly brighter than the similar dendron nanocrystals with thiolate (deprotonated thiol group) as the anchoring group which retained just 10% of the photoluminescence value of the original CdSe/CdS core-shell nanocrystals in toluene. The carboxylate-based dendron nanocrystals survived UV irradiation in air for at least 13 days, about 9 times better than the thiolate-based dendron nanocrystals (35 h) and similar to that of the thiolate-based dendron-box stabilized CdSe/CdS core-shell nanocrystals (box nanocrystals). Upon UV irradiation, the dendron nanocrystals became even 2 times brighter than the original CdSe/CdS core-shell nanocrystals in toluene, and the UV-brightened PL can retain the brightness for at least several months. These stable and bright dendron nanocrystals were soluble in various aqueous media, including all common biological buffer solutions tested, for at least 1.5 years. In addition to their superior performance, the synthetic chemistry of carboxylate dendron ligands and the corresponding dendron nanocrystals is relatively simple and with high yield.     

Planar polarized light emission from CdSe nanoparticle clusters

This paper describes synthesis and optical properties of planar clusters of CdSe nanocrystals. The clusters emit linearly polarized light in the plane of the cluster. The emission wavelength of the clusters can be adjusted between 568 and 639 nm with the size of the CdSe nanocrystals. Planar CdSe microclusters were synthesized by reaction of trioctylphosphine oxide-coated CdSe/CdS nanocrystals with 3-aminopropylsilyl-modified Ca(2)Nb(3)O(10) nanosheets in THF. The clusters are 3.92 +/- 1.18 mum length/width and 91 +/- 37 nm thickness, and they consist of alternating layers of Ca(2)Nb(3)O(10) to which CdSe nanocrystals are attached with densities of 5300 +/-310 particles per side of a single Ca(2)Nb(3)O(10) sheet. The chemical inertness of the clusters in coordinating solvents suggests covalent interactions between the aminopropyl groups and CdSe nanocrystals. Upon excitation at lambda(exc) = 400 nm, the clusters emit green (568 nm), orange (589 nm), or red (639 nm) light, depending on the size of the CdSe crystals. The light is emitted preferentially in the cluster plane and it is linearly polarized along the cluster edges. Combined fluorescence microscopy and atomic force microscopy reveal that the directional emission efficiency depends linearly on the thickness of the clusters, which varies between 70 and 180 nm. The ability to manipulate the direction and polarization of the photoemission of CdSe nanoparticles via assembly into 2D structures is of interest for applications of these and similar structures in advanced optical materials and devices.     

Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction

Successive ion layer adsorption and reaction (SILAR) originally developed for the deposition of thin films on solid substrates from solution baths is introduced as a technique for the growth of high-quality core/shell nanocrystals of compound semiconductors. The growth of the shell was designed to grow one monolayer at a time by alternating injections of air-stable and inexpensive cationic and anionic precursors into the reaction mixture with core nanocrystals. The principles of SILAR were demonstrated by the CdSe/CdS core/shell model system using its shell-thickness-dependent optical spectra as the probes with CdO and elemental S as the precursors. For this reaction system, a relatively high temperature, about 220-240 degrees C, was found to be essential for SILAR to fully occur. The synthesis can be readily performed on a multigram scale. The size distribution of the core/shell nanocrystals was maintained even after five monolayers of CdS shell (equivalent to about 10 times volume increase for a 3.5 nm CdSe nanocrystal) were grown onto the core nanocrystals. The epitaxial growth of the core/shell structures was verified by optical spectroscopy, TEM, XRD, and XPS. The photoluminescence quantum yield (PL QY) of the as-prepared CdSe/CdS core/shell nanocrystals ranged from 20% to 40%, and the PL full-width at half-maximum (fwhm) was maintained between 23 and 26 nm, even for those nanocrystals for which the UV-vis and PL peaks red-shifted by about 50 nm from that of the core nanocrystals. Several types of brightening phenomena were observed, some of which can further boost the PL QY of the core/shell nanocrystals. The CdSe/CdS core/shell nanocrystals were found to be superior in comparison to the highly luminescent CdSe plain core nanocrystals. The SILAR technique reported here can also be used for the growth of complex colloidal semiconductor nanostructures, such as quantum shells and colloidal quantum wells.     

Single-source precursor route for overcoating CdS and ZnS shells around CdSe core nanocrystals

We reported a facile route for overcoating CdS and ZnS shells around colloidal CdSe core nanocrystals. To synthesize such double shelled core/shell nanocrystals, first, CdSe core nanocrystals were prepared in a much “greener” and cheap route, which did not involve the use of hazardous and expensive trioctylphosphine. Then, a low-cost and labor-saving route was adopted for the CdS and ZnS shell growth with the use of thermal decomposition of commercial available air stable single-source precursors cadmium diethyldithio-carbamate and zinc diethyldithiocarbamate in a non-coordinating solvent at intermediate temperatures. Powder X-ray diffraction patterns and transmission electron microscopy images confirm the epitaxial growth of the shell in the core/shell nanocrystals. The photoluminescence quantum yield of the resulting CdSe/CdS/ZnS core/shell nanocrystals can be as high as 90% in organic media and up to 60% after phase transfer into aqueous media. By varying the size of CdSe cores, the emission wavelength of the obtained core/shell nanostructures can span from 554 to 636 nm.     

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.     

Solution-based II-VI core/shell nanowire heterostructures

We demonstrate the solution-phase synthesis of CdS/CdSe, CdSe/CdS, and CdSe/ZnTe core/shell nanowires (NWs). On the basis of bulk band offsets, type-I and type-II heterostructures are made, contributing to the further development of low-dimensional heteroassemblies using solution-phase chemistry. Core/shell wires are prepared by slowly introducing shell precursors into a solution of premade core NWs dispersed in a noncoordinating solvent at moderate temperatures (215-250 degrees C). Resulting heterostructures are characterized through low- and high-resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. From these experiments, initial shell growth appears to occur through either Stranski-Krastanov or Volmer-Weber island growth. However, beyond a critical shell thickness, nucleation of randomly oriented nanocrystals results in a polycrystalline coat. In cases where overcoating has been achieved, corresponding elemental analyses show spatially varying compositions along the NW radial direction in agreement with expected element ratios. Electronic interactions between the core and shell were subsequently probed through optical studies involving UV-vis extinction spectroscopy, photoluminescence experiments, and transient differential absorption spectroscopy. In particular, transient differential absorption studies reveal unexpected shell-induced changes in core NW Auger kinetics at high carrier densities. Previously seen three-carrier Auger kinetics in CdS (bimolecular in CdSe) NWs were suppressed by the presence of a CdSe (CdS) shell. These observations suggest the ability to influence NW optical/electrical properties by coating them with a surrounding shell, a method which could be important for future NW optical studies as well as for NW-based applications.     

Influence of Cd Content and Se Doping on the Formation of CdSe Nanocrystals in Silica Xerogels: A SAXS Study

Small-angle X-ray scattering (SAXS) experiments were carried out to characterize the structure of the composite formed by CdSe nanocrystals embedded in a popous silica matrix (silica xerogels containing Cd with formamide addition and ultrasound treatment). SAXS results from samples before Se diffusion indicate the presence of heterogeneities with a bimodal size distribution which was associated to the existence of mesopores (pores of several hundred Å) immersed in a nanoporous matrix (characteristic pore radii of 20–30 Å). The diffusion of Se induces the nucleation and growth of CdSe nanocrystals. The average size of the nanocrystals increases with Cd content. Higher Se doses promote the formation of larger nanocrystals (radius of gyration of ∼30 to 50 Å). Anomalous scattering results confirm the existence of Se aggregation associated with CdSe nanocrystal formation and suggest that only partial segregation of Cd and Se occurs.     

Inorganic cluster syntheses of TM2+-doped quantum dots (CdSe, CdS, CdSe/CdS): physical property dependence on dopant locale

A series of colloidal transition-metal-doped chalcogenide semiconductor nanocrystals (TM2+:CdSe, TM2+:CdS, etc.) has been prepared by thermal decomposition of inorganic cluster precursors. It is shown through extensive spectroscopic and structural characterization that the nanocrystals prepared following literature procedures for synthesis of TM2+:CdSe nanocrystals actually possess an unintended CdSe/TM2+:CdS core/shell morphology. The conditions required for successful formation of TM2+:CdSe and TM2+:CdS by cluster decomposition have been determined. Magneto-optical and photoluminescence spectroscopic results for this series of doped nanocrystals reveal major physical consequences of dopant localization within the shell and demonstrate the capacity to engineer dopant-carrier exchange interactions via core/shell doping strategies. The results presented here illustrate some of the remarkable and unexpected complexities that can arise in nanocrystal doping chemistries and emphasize the need for meticulous characterization to avoid false positives.     

Catalyst-assisted solution-liquid-solid synthesis of CdS/CdSe nanorod heterostructures

We report the synthesis and characterization of axial nanorod heterostructures composed of cadmium selenide (CdSe) and cadmium sulfide (CdS). The synthesis employs a solution-liquid-solid (SLS) mechanism with the assistance of bismuth nanocrystals adhered to a substrate (silicon or a III-V semiconductor). Transmission electron microscopy (TEM) and diffraction studies show that CdSe and CdS segments exhibit the wurtzite (hexagonal) crystal structure with <5% stacking faults. Both of these segments grow along the [002] direction with an epitaxial interface between them. Energy-dispersive X-ray (EDX) spectrometry using a high-resolution TEM operating in scanning mode confirms the alloy-free composition modulation in the nanorod heterostructures, showing that Se and S are localized in the CdSe and CdS portions of the nanorod heterostructures, respectively. This study demonstrates that SLS synthesis provides an alternate route to prepare axial nanorod heterostructures that have been difficult to generate using either vapor-liquid-solid growth or catalyst-free solution-phase synthesis.     

Controllable Conversion of CdNCN Nanoparticles into Various Chalcogenide Nanostructures for Photo-driven Applications

Semiconductor nanocrystals of tunable shell/core configurations have great potential in photo-driven applications such as photoluminescence and photocatalysis, but few strategies realize a controllable synthesis with respect to both the size of the core and the shell with high crystallinity. Here, a new synthetic method based on cadmium cyanamide (CdNCN) nanoparticle anion exchange reactions was developed to access solid or hollow CdSe nanocrystals with tunable size and CdNCN@CdS heterostructures with modulated shell/core thickness. The gradual shift and narrow width of photoluminescence features demonstrate the high crystallinity and monodispersity of the resulting CdSe nanocrystals. In the CdNCN@CdS heterostructures, synergistic effects of the photocarrier separation is observed between the CdS shell and CdNCN core, which leads to great improvement in photocatalysis with optimized shell/core ratio.     

Preparation and application of L-cysteine-modified CdSe/CdS core/shell nanocrystals as a novel fluorescence probe for detection of nucleic acid

The water-soluble L-cysteine-modified CdSe/CdS core/shell nanocrystals (expressed as CdSe/CdS/Cys nanocrystals) have been synthesized in aqueous by using L-cysteine as stabilizer. The size, shape, component and spectral property of CdSe/CdS/Cys nanocrystals were characterized by high-resolution transmission electron microscope (HRTEM), energy dispersive X-ray fluorescence (EDX), infrared spectrum (IR) and photoluminescence (PL). The results showed that the spherical CdSe/CdS/Cys nanocrystals with an average diameter of 2.3 nm have favorable fluorescent property, theirs photostability and fluorescence intensity are enhanced greatly after overcoating with CdS. The cysteine modified on the surface of core/shell CdSe/CdS nanocrystals renders the nanocrystals water-soluble and biocompatible. Based on the fluorescence quenching of the nanocrystals in the presence of calf thymus deoxyribonucleic acid (ct-DNA), a fluorescence quenching method has been developed for the determination of ct-DNA by using the nanocrystals as a novel fluorescence probe. The pH value of the system was selected at pH 7.4, with excitation and emission wavelength at 380 and 522 nm, respectively. Under the optimal conditions, the fluorescence quenching intensity of the system is linear with the concentration of ct-DNA in the range of 0.1-3.5 microg/mL (r=0.9987). The detection limit is 0.06 microg/mL. And two synthetic samples were analyzed satisfactorily.     

Aqueous synthesis of glutathione-capped CdTe/CdS/ZnS and CdTe/CdSe/ZnS core/shell/shell nanocrystal heterostructures

Here we demonstrate the aqueous synthesis of colloidal nanocrystal heterostructures consisting of the CdTe core encapsulated by CdS/ZnS or CdSe/ZnS shells using glutathione (GSH), a tripeptide, as the capping ligand. The inner CdTe/CdS and CdTe/CdSe heterostructures have type-I, quasi-type-II, or type-II band offsets depending on the core size and shell thickness, and the outer CdS/ZnS and CdSe/ZnS structures have type-I band offsets. The emission maxima of the assembled heterostructures were found to be dependent on the CdTe core size, with a wider range of spectral tunability observed for the smaller cores. Because of encapsulation effects, the formation of successive shells resulted in a considerable increase in the photoluminescence quantum yield; however, identifying optimal shell thicknesses was required to achieve the maximum quantum yield. Photoluminescence lifetime measurements revealed that the decrease in the quantum yield of thick-shell nanocrystals was caused by a substantial decrease in the radiative rate constant. By tuning the diameter of the core and the thickness of each shell, a broad range of high quantum yield (up to 45%) nanocrystal heterostructures with emission ranging from visible to NIR wavelengths (500-730 nm) were obtained. This versatile route to engineering the optical properties of nanocrystal heterostructures will provide new opportunities for applications in bioimaging and biolabeling.     

Size-dependent dissociation pH of thiolate ligands from cadmium chalcogenide nanocrystals

A method, pseudo steady-state titration, is introduced for determining the precipitation pH of nanocrystals coated by electron-donating ligands. CdSe nanocrystals coated with hydrophilic deprotonated thiol (thiolate) ligands were studied systematically. For comparison, CdTe and CdS nanocrystals coated with the same types of ligands were also examined. The results show that the precipitation of the nanocrystals is caused by the dissociation of the nanocrystal-ligand coordinating bonds from the nanocrystal surface. The ligands are removed from the surface due to protonation in a relatively low pH range, between 2 and 7 depending on the size, approximately within the quantum confinement size regime, and chemical composition (band gap) of the nanocrystals. In contrast, the redispersion of the nanocrystals was found to be solely determined by the deprotonation of the ligands. The size-dependent dissociation pH of the ligands was tentatively used as a means for determining the size-dependent free energy associated with the formation of a nanocrystal-ligand coordinating bond.     

Synthesis and Characterization of CdSe Nanocrystals Capped by CdS

CdSe semiconductor nanocrystals capped by CdS were synthesized in the aqueous solution with 2-mercaptoethanol as the stabilizer. The CdS capping with a higher band-gap than that of the core crystallite has successfully eliminated the surface traps. Optical absorption and fluorescence emission spectra were used to probe the effect of CdS passivation on the electronic structure of the nanocrystals. The composite CdSe/CdS nanocrystals exhibit strong, narrow(FWHM≤40 nm) and stable band-edge photoluminescence. X-ray powder diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy were used to analyze the composite nanocrystals and determine their average size, size distribution, shape, internal structure and elemental composition.     

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate

The 1,2,3,4-thiatriazole-5-thiolate anion (TTT(-)) was found to be a strongly binding ligand for CdSe nanocrystals, quantitatively exchanging various long-chain ligands to yield stable colloidal suspensions in common polar solvents. The TTT(-) ligand thermolyzes at <100 °C to produce thiocyanate in situ, resulting in reduced quantum confinement in nanocrystal films. CdSe(TTT) possesses far higher colloidal stability than CdSe(SCN), and that, together with the facile synthesis of TTT(-), implies that this is a useful ligand for nanocrystal applications as a masked thiocyanate.     

Synthesis of monodisperse spherical nanocrystals

Much progress has been made over the past ten years on the synthesis of monodisperse spherical nanocrystals. Mechanistic studies have shown that monodisperse nanocrystals are produced when the burst of nucleation that enables separation of the nucleation and growth processes is combined with the subsequent diffusion-controlled growth process through which the crystal size is determined. Several chemical methods have been used to synthesize uniform nanocrystals of metals, metal oxides, and metal chalcogenides. Monodisperse nanocrystals of CdSe, Co, and other materials have been generated in surfactant solution by nucleation induced at high temperature, and subsequent aging and size selection. Monodisperse nanocrystals of many metals and metal oxides, including magnetic ferrites, have been synthesized directly by thermal decomposition of metal-surfactant complexes prepared from the metal precursors and surfactants. Nonhydrolytic sol-gel reactions have been used to synthesize various transition-metal-oxide nanocrystals. Monodisperse gold nanocrystals have been obtained from polydisperse samples by digestive-ripening processes. Uniform-sized nanocrystals of gold, silver, platinum, and palladium have been synthesized by polyol processes in which metal salts are reduced by alcohols in the presence of appropriate surfactants.     

Shape Control of Colloidal Semiconductor Nanocrystals

Shape control of inorganic nanocrystals is important for understanding basic size- and shape-dependent scaling laws, and may be useful in a wide range of applications. Methods for controlling the shapes of inorganic nanocrystals are evolving rapidly. This paper will focus on how we currently control the shape of semiconductor nanocrystals using CdSe as example.