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.     

纳晶的制备及其光谱的尺寸依赖性

用再沉淀法制备了纳米晶体,向体系中加入水溶性高分子聚乙烯醇（PVA）可有效地抑制纳晶的生长,从而制得了稳定的具有不同粒径的纳晶.光谱研究表明,随着纳晶粒径增加,由于纳晶中分子间相互作用的变化,其吸收峰和激发峰位置都发生了红移,同时纳晶中激基缔合物的荧光发射峰强度减弱,荧光寿命有所延长.     

Heterostructured Tin oxide-pillared tetratitanate with enhanced photocatalytic activity

Here we point out that the nanocrystals well ordered in compact hexagonal networks are highly stable compared to the same nanocrystals either isolated on a substrate or ordered in a less compact manner. The emergence of unexpected collective physical intrinsic properties results in the nanocrystals being ordered over a long distance in colloidal crystals called supracrystals. Some morphologies of nanocrystals ordered, at the micrometer scale, in 3D superlattices called supracrystals are similar to those obtained with atoms in nanocrystals. From a comparison between vibrational and magnetic properties of supracrystals and aggregates composed of the same nanocrystals, it is proposed that nanocrystals in a supracrystal could behave as atoms in a nanocrystal. From these data a possible analogy between nanocrystals in a supracrystal and atoms in nanocrystals is proposed.     

Solventless nanoparticles synthesis under low pressure

In the present study, metal nanocrystals were obtained by the very easy, economical, and nontoxic thermal decomposition method and stabilized by coating oleate without any solvent. These nanocrystals have a highly crystalline structure due to a high decomposition temperature (~563-573 K) at low pressure and very narrow distribution. The prepared Fe3O4 nanocrystals were controlled by the annealing time and vacuum pressure. A TEM image of monodispersed Fe3O4 nanocrystals showed the 2D assembly of nanocrystals, demonstrating their uniformity. The particle size is 10.6 +/- 1.2 nm. TEM images of silver nanocrystals a showed 2D assembly with 9.5 +/- 0.7 nm. An electron diffraction image and X-ray diffraction of the nanocrystals showed the highly crystalline nature of metal nanocrystals.     

Passivation of GaAs nanocrystals by chemical functionalization

The effective use of nanocrystalline semiconductors requires control of the chemical and electrical properties of their surfaces. We describe herein a chemical functionalization procedure to passivate surface states on GaAs nanocrystals. Cl-terminated GaAs nanocrystals have been produced by anisotropic etching of oxide-covered GaAs nanocrystals with 6 M HCl(aq). The Cl-terminated GaAs nanocrystals were then functionalized by reaction with hydrazine or sodium hydrosulfide. X-ray photoelectron spectroscopic measurements revealed that the surfaces of the Cl-, hydrazine-, and sulfide-treated nanocrystals were As-rich, due to significant amounts of As0. However, no As0 was observed in the photoelectron spectra after the hydrazine-terminated nanocrystals were annealed at 350 degrees C under vacuum. After the anneal, the N 1s peak of hydrazine-exposed GaAs nanocrystals shifted to 3.2 eV lower binding energy. This shift was accompanied by the appearance of a Ga 3d peak shifted 1.4 eV from the bulk value, consistent with the hypothesis that a gallium oxynitride capping layer had been formed on the nanocrystals during the annealing process. The band gap photoluminescence (PL) was weak from the Cl- and hydrazine- or sulfide-terminated nanocrystals, but the annealed nanocrystals displayed strongly enhanced band-edge PL, indicating that the surface states of GaAs nanocrystals were effectively passivated by this two-step, wet chemical treatment.     

Electron transfer between colloidal ZnO nanocrystals

Colloidal ZnO nanocrystals capped with dodecylamine and dissolved in toluene can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction-band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals (e(-)(CB):ZnO-S) with a solution of uncharged large nanocrystals (ZnO-L) caused changes in the EPR spectrum indicative of quantitative electron transfer from small to large nanocrystals. EPR spectra of the reverse reaction, e(-)(CB):ZnO-L + ZnO-S, showed that electrons do not transfer from large to small nanocrystals. Stopped-flow kinetics studies monitoring the change in the UV band-edge absorption showed that reactions of 50 μM nanocrystals were complete within the 5 ms mixing time of the instrument. Similar results were obtained for the reaction of charged nanocrystals with methyl viologen (MV(2+)). These and related results indicate that the electron-transfer reactions of these colloidal nanocrystals are quantitative and very rapid, despite the presence of ~1.5 nm long dodecylamine capping ligands. These soluble ZnO nanocrystals are thus well-defined redox reagents suitable for studies of electron transfer involving semiconductor nanostructures.     

单源前体合成水溶性的CdS和ZnS纳米晶

0引言量子点(QuantumDots)一般指半径小于或接近玻尔激子半径的半导体纳米晶颗粒。和有机染料分子相比,无机半导体纳米晶的带隙宽度可通过简单     

Template-assisted synthesis of shape-controlled Rh2P nanocrystals

When reacted with trioctylphosphine at approximately 360 degrees C, rhodium nanocrystals convert to rhodium phosphide Rh(2)P nanocrystals. Careful control over synthetic variables, such as temperature, stabilizing ligands, and cosolvents, can result in Rh(2)P nanocrystals with shapes that reflect the Rh nanocrystal templates. Accordingly, Rh nanocrystals with multipod, cube- and triangle-derived shapes convert to Rh(2)P nanocrystals that maintain the shape of their Rh precursors. Both dense and hollow Rh(2)P nanocrystals can be generated using a single unified chemical conversion strategy. These empirical guidelines for generating a morphologically diverse library of Rh(2)P nanocrystals provide important insights into shape conservation using nanocrystal templates and will likely be portable to other multielement systems for which rigorous shape-controlled synthesis remains challenging.     

Directing the self-assembly of nanocrystals beyond colloidal crystallization

This article gives an overview of recent progress in the self-assembly of nanocrystals. Classic self-assembly of nanocrystals, so-called colloidal crystallization driven by van der Waals interactions, is highlighted first with an emphasis on the recent realization of binary colloidal crystals. Next, new developments in the integration of nanocrystals into clusters based on electrostatic interactions, hydrogen bonding and dipole-dipole interactions are summarized, shedding light on the defined control of the interactions between the nanocrystals. Finally, the fabrication of heterogenous nanocrystals, obtained via either phase selective modification at the water/oil interface or facet-selective crystal growth on non-spherical nanocrystals is discussed. These last materials may provide significant building blocks for mimicking molecular self-assembly.     

Stabilization of inorganic nanocrystals by organic dendrons

A series of hydrophilic organic dendron ligands was designed and synthesized for stabilizing high-quality semiconductor and noble metal nanocrystals. The focal point of the dendron ligands is chosen to be a thiol group which is a universal coordinating site for compound semiconductor and noble metal nanocrystals. The methods for binding these dendron ligands onto the surface of the nanocrystals are simple and straightforward. The thin, about 1-2 nm, but closely packed and tangled ligand shell provides sufficient stability for the "dendron-protected nanocrystals" to withstand the rigors of the coupling chemistry and the standard separation/purification techniques. The chemistry presented can be immediately applied for the development of a new generation of biomedical labeling reagents based on high-quality semiconductor nanocrystals. It also provides an alternative path to apply noble metal nanocrystals for developing sensitive detection schemes for chemical and biochemical purposes. The concept may further provide an optimal solution for many other problems encountered in nanocrystal-related research and development, for which the stability of the nanocrystals is a critical issue. Furthermore, the experimental results confirmed that the photochemical stability of colloidal semiconductor and noble metal nanocrystals is the key for developing reliable and reproducible processing chemistry for these nanocrystals.     

One-step facile surface engineering of hydrophobic nanocrystals with designer molecular recognition

High quality nanocrystals have demonstrated substantial potential for biomedical applications. However, being generally hydrophobic, their use has been greatly limited by complicated and inefficient surface engineering that often fails to yield biocompatible nanocrystals with minimal aggregation in biological fluids and active targeting toward specific biomolecules. Using chimeric DNA molecules, we developed a one-step facile surface engineering method for hydrophobic nanocrystals. The procedure is simple and versatile, generating individual nanocrystals with multiple ligands. In addition, the resulting nanocrystals can actively and specifically target various molecular addresses, varying from nucleic acids to cancer cells. Together, the strategy developed here holds great promise in generating critical technologies needed for biomedical applications of nanocrystals.     

Tuning of the structure and emission spectra of upconversion nanocrystals by alkali ion doping

Recently, lanthanide based nanocrystals with upconversion fluorescence emission have attracted a lot of interest and the nanocrystals have been used for bioimaging, biodetection, and therapeutic applications. Use of the nanocrystals for multiplexed detection has also been explored; however, nanocrystals with multicolor emission are required. Some efforts have been made to tune the emission spectra of the nanocrystals based on manipulation of upconverting lanthanide ions doped in the crystals or creation of core/shell structures. In this work, alkali ions with an ionic radius slightly larger or smaller than Na such as Li and K were doped into NaYF(4):Yb,Er nanocrystals and their effect on the crystal structure and subsequently the upconversion emission spectra were studied. It was found that the phase transition occurs in the nanocrystals when a different amount of Li and K was doped. Furthermore, the intensity ratios between the blue, green, and red emission peaks changed accordingly, and make it possible to tune the upconversion fluorescence of the nanocrystals by Li and K doping.     

Seed-mediated growth method for high-quality noble metal nanocrystals

This review highlights work from the authors’ laboratory on the recent development of seed-mediated growth method for noble metal nanocrystals. The seed-mediated growth method has become one of the most efficient and versatile methods for synthe-sizing high-quality noble metal nanocrystals. The seed-mediated growth method can separate the nucleation and growth stages of metal nanocrystals, and thus provide better control over the size, size distribution, and crystallographic evolution of metal nanocrystals. Because of its high controllability, the seed-mediated growth method is especially promising in providing mechanistic insights into the growth mechanisms of noble metal nanocrystals. In this review, the thermodynamic and kinetic parameters for the nucleation and growth of noble metal nanocrystals are systematically summarized. Mechanistic understanding of these parameters is provided. These studies provide useful guidelines for the rational design and synthesis of novel noble metal nanocrystals with high quality.     

Large-scale cubic InN nanocrystals by a combined solution- and vapor-phase method under silica confinement

Large-scale cubic InN nanocrystals were synthesized by a combined solution- and vapor-phase method under silica confinement. Nearly monodisperse cubic InN nanocrystals with uniform spherical shape were dispersed stably in various organic solvents after removal of the silica shells. The average size of InN nanocrystals is 5.7 ± 0.6 nm. Powder X-ray diffraction results indicate that the InN nanocrystals are of high crystallinity with a cubic phase. X-ray photoelectron spectroscopy and energy-dispersive spectroscopy confirm that the nanocrystals are composed of In and N elements. The InN nanocrystals exhibit infrared photoluminescence at room temperature, with a peak energy of ~0.62 eV, which is smaller than that of high-quality wurtzite InN (~0.65-0.7 eV) and is in agreement with theoretical calculations. The small emission peak energy of InN nanocrystals, as compared to other low-cost solution or vapor methods, reveals the superior crystalline quality of our samples, with low or negligible defect density. This work will significantly promote InN-based applications in IR optoelectronic device and biology.     

Shape-dependent electrocatalytic activity of monodispersed gold nanocrystals toward glucose oxidation

We systematically explore the shape-dependent catalytic activities of Au nanocrystals toward glucose oxidation in alkaline electrolytes, which is strongly dependent on the shape of the Au nanocrystals. The {100}-bounded cubic Au nanocrystals are significantly more active than the {110}-bounded rhombic dodecahedral and {111}-bounded octahedral Au nanocrystals.     

Surface morphology dependent photoluminescence from colloidal silicon nanocrystals

Monodisperse 1-2 nm silicon nanocrystals are synthesized in reverse micelles and have their surfaces capped with either allylamine or 1-heptene to produce either hydrophilic or hydrophobic silicon nanocrystals. Optical characterization (absorption, PL, and time-resolved PL) is performed on colloidal solutions with the two types of surface-capped silicon nanocrystals with identical size distributions. Direct evidence is obtained for the modification of the optical properties of silicon nanocrystals by the surface-capping molecule. The two different surface-capped silicon nanocrystals show remarkably different optical properties.     

Microwave-assisted aqueous synthesis: a rapid approach to prepare highly luminescent ZnSe(S) alloyed quantum dots

In this paper, we present a new procedure for the rapid synthesis of luminescent ZnSe nanocrystals in aqueous phase by microwave irradiation with controllable temperature. The effects of microwave irradiation and experimental conditions on the synthesis of nanocrystals were investigated systematically. It was found that there were significant effects of pH value of reaction solutions, molar ratio of precursors, and heating time of microwave irradiation on the optical properties of the ZnSe nanocrystals. A series of nanocrystals with different size was prepared in 1 h, and the photoluminescence quantum yield reached up to 17% at the optimal reaction condition. The results of HRTEM and XRD showed that the as-prepared nanocrystals had high crystallinity. The characterizations of EDS spectra and elemental analysis showed that the sulfur content of nanocrystals increased with the growth of nanocrystals. We speculated that the structure of nanocrystals was an alloy ZnSe(S) shell on the surface of the ZnSe particles core. Furthermore, we found that the oxygen from air in the reaction vessel played an important role in the decomposition of the thiol group under microwave irradiation.     

Generalized and facile synthesis of semiconducting metal sulfide nanocrystals

We report on the synthesis of semiconductor nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive synthetic process. Metal-oleylamine complexes, which were obtained from the reaction of metal chloride and oleylamine, were mixed with sulfur. The reaction mixture was heated under appropriate experimental conditions to produce metal sulfide nanocrystals. Uniform cube-shaped PbS nanocrystals with particle sizes of 6, 8, 9, and 13 nm were synthesized. The particle size was controlled by changing the relative amount of PbCl(2) and sulfur. Uniform 11 nm sized spherical ZnS nanocrystals were synthesized from the reaction of zinc chloride and sulfur, followed by one cycle of size-selective precipitation. CdS nanocrystals that consist of rods, bipods, and tripods were synthesized from a reaction mixture containing a 1:6 molar ratio of cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained from a reaction mixture with a cadmium to sulfur molar ratio of 2:1. MnS nanocrystals with various sizes and shapes were synthesized from the reaction of MnCl(2) and sulfur in oleylamine. Rod-shaped MnS nanocrystals with an average size of 20 nm (thickness) x 37 nm (length) were synthesized from a 1:1 molar ratio of MnCl(2) and sulfur at 240 degrees C. Novel bullet-shaped MnS nanocrystals with an average size of 17 nm (thickness) x 44 nm (length) were synthesized from the reaction of 4 mmol of MnCl(2) and 2 mmol of sulfur at 280 degrees C for 2 h. Shorter bullet-shaped MnS nanocrystals were synthesized from a 3:1 molar ratio of MnCl(2) and sulfur. Hexagon-shaped MnS nanocrystals were also obtained. All of the synthesized nanocrystals were highly crystalline.     

Controllable synthesis of Cu2S nanocrystals and their assembly into a superlattice

Highly uniform Cu2S nanocrystals with controllable sizes and shapes (circular and elongated) have been synthesized through a novel water-oil interface confined reaction. They can self-assemble into highly ordered multilayer superlattices. By controlling the size and shape of building block nanocrystals, the packing symmetry of the superlattice can be engineered. For circular nanocrystals, both fcc and hcp multilayer superlattices are found in the sample. For elongated nanocrystals, they can also generate a close-packed layer and further stack into a multilayer superlattice. The dipole moment of the inner nanocrystals is useful for their stacking. This work provides a simple bottom-up approach to integrate nanocrystals, as well as to adjust the packing symmetry of the final superlattice, which may have potential applications for nanomaterials and nanodevices in the future.     

Radial-position-controlled doping in CdS/ZnS core/shell nanocrystals

In this paper, we report a new doping approach using a three-step synthesis to make high-quality Mn-doped CdS/ZnS core/shell nanocrystals. This approach allows precise control of the Mn radial position and doping level in the core/shell nanocrystals. On the basis of this synthetic advance, we have demonstrated the first example in which optical properties of Mn-doped nanocrystals strongly depend on Mn radial positions inside the nanocrystals. In addition, we have synthesized nanocrystals with a room-temperature Mn-emission quantum yield of 56%, which is nearly twice as high as that of the best Mn-doped nanocrystals reported previously. Nanocrystals with such a high-emission quantum yield are very important to applications such as nanocrystal-based biomedical diagnosis.