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.     

Ultra-broadband near-infrared excitable upconversion core/shell nanocrystals

Monodisperse Er(3+):NaGdF(4)@Ho(3+):NaGdF(4)@NaGdF(4) active-core/active-shell/inert-shell nanocrystals, which can extend the near-infrared wavelength excitable range for upconversion (UC) emissions, were successfully fabricated for the first time. Importantly, doping of Er(3+) and Ho(3+) into the core and shell respectively suppresses adverse energy transfers between them, resulting in intense UC emissions for both Er(3+) and Ho(3+) dopants.     

On doping CdS/ZnS core/shell nanocrystals with Mn

This paper presents a mechanistic study on the doping of CdS/ZnS core/shell semiconductor nanocrystals with Mn based on a three-step synthesis, which includes host-particle synthesis, Mn-dopant growth, and ZnS-shell growth. We used a combination of electron paramagnetic resonance spectroscopy (EPR) and inductively coupled plasma atomic emission spectroscopy (ICP) to monitor Mn-doping level and growth yield during doping synthesis at both the dopant-growth and ZnS-shell-growth steps. First, our kinetic study shows that Mn adsorption onto the nanocrystal surface includes the formation of weakly and strongly bound Mn. The formation of weakly bound Mn is associated with a chemical equilibrium between adsorbed Mn species on the nanocrystal surface and free Mn species in growth solution, while the formation of strongly bound Mn exhibits first-order kinetics with an activation-energy barrier of 211 +/- 13 kJ/mol. Second, our results demonstrate that both weakly and strongly bound Mn can be removed from the surface of nanocrystals during ZnS-shell growth. The replacement of strongly bound Mn requires a higher temperature than that of weakly bound Mn. The yield of the replacement of strongly bound Mn is strongly dependent on the temperature of ZnS-shell growth. Third, our results show that the Mn-growth yield is not dependent on the size and crystal structure of nanocrystals. All together, these results suggest a mechanism in which nanocrystal doping is determined by the chemical kinetics of three activation-controlled processes: dopant adsorption, replacement, and ZnS-shell growth.     

Shaping non-noble metal nanocrystals via colloidal chemistry

Non-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their earth abundance combined with intriguing physical and chemical properties relevant for both fundamental studies and technological applications. Nevertheless, their synthesis is still primitive when compared to noble metals. In this contribution, we focus on third row transition metals Mn, Fe, Co, Ni and Cu that are recently gaining interest because of their catalytic properties. Along with providing an overview on the state-of-the-art, we discuss current synthetic strategies and challenges. Finally, we propose future directions to advance the synthetic development of shape-controlled non-noble metal nanocrystals in the upcoming years.

This minireview describes the state-of-the-art of shape-controlled nanocrystals of third raw transition metals and discusses future directions to advance their synthetic development, which is important for many applications.     

In-vitro cytotoxicity evaluation of surface design luminescent lanthanide core/shell nanocrystals

Lanthanide nanocrystals (NCs) are the most promising luminescent materials for bioapplications, but their use is hindered by difficulties in obtaining biocompatible and photoluminescence lanthanide NCs. To solve this problem, a simple and versatile strategy was developed for improving the luminescence efficiency with the hydrophilicity of the lanthanide NCs. In this study, the effects of shell formation on structural, morphological, and optical properties (optical absorption, band-gap energy, excitation, emission, and luminescent decay time) were evaluated. To improve the luminescence efficiency and aqueous dispersion, luminescent core-NCs were encapsulated with inert NaGdF₄ and amorphous silica layers. These surface coating layers significantly improved the luminescence efficiency and dispersion of the core/shell NCs in which the silica surface provides a negatively charged surface to the NCs at physiological pH. Optical properties of these NCs strongly depend on the external change of NCs, demonstrating the impact of coating in improving the luminescence efficiency. The outcomes can be ascribed to the development of surface chemical bonds between core/shell and noncrystalline SiO₂ shell via GdOSi bridges, activating the ‘dormant’ Ce³⁺ and Tb³⁺ ions on the surface of NCs. An intensive emission and good hydrophilic property from the active functional groups in solutions show a great potential for applications such as multi-analyte fluorescent biolabeling, optical biosensing, staining, display, and other optical technologies. The core/shell/SiO₂ NCs showed higher nontoxicity and biocompatibility with respect to the core NCs because of biocompatible silica surface modification, facilitating entry into the living cells. Therefore, this developed synthesis approach might advance the field of biomolecule-based nanotechnology in near future.     

Solar cells sensitized with type-II ZnSe-CdS core/shell colloidal quantum dots

Type-II quantum dots (QDs) were applied for QDs-sensitized solar cells for the first time and showed prominent absorbed photon to current conversion efficiency.     

Intraband spectroscopy and band offsets of colloidal II-VI core/shell structures

The interband and intraband spectra of colloidal II-VI CdS and CdSe quantum dot cores and CdSZnSe, CdSCdSe, CdSeCdS, and CdSeZnSe core/shell systems are reported. Infrared absorption peaks between 0.5 and 0.2 eV are observed. The slope of the intraband energy versus the first interband absorption feature is characteristic of the relative band alignments of the materials constituting the core and the shell and it is analyzed within an effective mass model. The analysis provides a new estimate of the band gap of zinc blende CdSe as well as the band offsets in zinc blende and wurtzite CdSe, CdS, and ZnSe.     

2D self-organization of core/shell Co(hcp)/Co nanocrystals

In this paper we report the preparation of ordered hexagonal 2D arrays of core/shell Cohcp/CoO nanocrystals. A full structural investigation has been carried out using high-resolution transmission electron microscopy, electron diffraction, and electron energy-loss spectroscopy.     

利用离子型Cd源制备ZnSe/CdSe核-壳结构纳米晶

在有机相体系中利用ZnSe前驱体纳米晶制备过程中的富Se环境,以引入Cd2+的方式在相对温和的环境下通过控制Cd2+离子的加入量及调节反应时间,成功制备了ZnSe/CdSe核-壳复合结构纳米晶.利用X射线衍射(XRD)、透射电镜(TEM)、紫外-可见吸收光谱(UV-vis)和荧光光谱(FL)对其结构形貌以及光学性质进行表征和分析的结果表明,CdSe以外延生长的方式包覆在ZnSe纳米晶表面从而形成具有良好结晶性的核-壳复合结构,其荧光发射始终保持良好单色性,同时实现了在500～620nm可见光范围内的连续可调.     

CoS/N-doped carbon core/shell nanocrystals as an anode material for potassium-ion storage

Journal of Solid State Electrochemistry - Potassium-ion batteries (KIBs) are attracting tremendous attention due to the abundant potassium resources and their low price and high safety. However,...     

Synthesis and characterization of Co/CdSe core/shell nanocomposites: bifunctional magnetic-optical nanocrystals

Nanocomposite materials provide the possibility for multifunctional properties in contrast with their more-limited single-component counterparts. Here, we report the synthesis and characterization of the first all-inorganic core/shell hybrid magnetic-optical nanoparticle, cobalt/cadmium selenide. The core/shell nanocrystals are prepared in a facile one-pot reaction, and their microstructure is analyzed using low- and high-resolution transmission electron microscopy. Using magnetic and optical characterization, we demonstrate bifunctional behavior, whereby the core retains the magnetic properties of the starting Co nanoparticle, and the shell emits similarly to a single-component CdSe nanoparticle. Interestingly, while the coercivity was found to be unchanged by shell formation, the blocking temperature for the composite structure was observed to be substantially lower (Co: >350 K; Co/CdSe: 240 K). In addition, we observed that at low temperatures (20 K) shell CdSe photoluminescence (PL) decay was very rapid (<1 ns). In contrast, nanocrystalline CdSe PL decay is typically much slower at such temperatures (>50 ns). Finally, we propose possible explanations for the unusual magnetic and optical behavior of the core/shell hybrid nanostructures.     

Mn:ZnSe/ZnS核-壳结构纳米晶的无膦法制备和光学性质

以溶于十八烯的Se作为Se前驱体,在无膦条件下制备得到了具有较高量子产率的Mn:ZnSe纳米晶.为了进一步提高纳米晶的稳定性和发光强度,运用外延生长的方法进行ZnS壳层包覆并得到了具有核-壳结构的Mn:ZnSe/ZnS纳米晶.X射线衍射、透射电子显微镜及吸收和荧光光谱测试结果表明,该方法合成的Mn:ZnSe纳米晶以及核-壳结构Mn:ZnSe/ZnS纳米晶均为闪锌矿结构,具有良好的单分散性,包覆ZnS外壳层后量子产率可达到60%以上.此外,对ZnS壳层厚度和Mn2+的掺杂量对Mn:ZnSe/ZnS纳米晶发光强度的影响及发光机制也进行了初步讨论.     

Oscillating fluorescence in an unstable colloidal dispersion of CdSe/ZnS core/shell quantum dots

Fluorescence oscillation is observed in an ensemble of colloidal CdSe/ZnS core/shell quantum dots (QDs) dispersed in nonpolar solvent under continuous irradiation. The QDs dispersed in toluene gradually aggregate and change their fluorescence intensity, even in the dark. During the aggregation, the QD/toluene suspension is unstable, that is, overdispersed. The fluorescence oscillation is found only in this unstable state before the system reaches steady state. In addition, the aggregation rate is promoted by irradiation and strongly correlates with the oscillation amplitude. Our experimental results indicate that the dispersion instability plays an important role in both linear and nonlinear dynamics of the fluorescence. It is inferred from the experimental results and previous studies that the complex time evolution of fluorescence in the QD/toluene dispersion is possibly due to adsorption and desorption of surface ligand molecules over the course of QD aggregation.     

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.     

Water-based route to colloidal Mn-doped ZnSe and core/shell ZnSe/ZnS quantum dots

Relatively monodisperse and highly luminescent Mn(2+)-doped zinc blende ZnSe nanocrystals were synthesized in aqueous solution at 100 °C using the nucleation-doping strategy. The effects of the experimental conditions and of the ligand on the synthesis of nanocrystals were investigated systematically. It was found that there were significant effects of molar ratio of precursors and heating time on the optical properties of ZnSe:Mn nanocrystals. Using 3-mercaptopropionic acid as capping ligand afforded 3.1 nm wide ZnSe:Mn quantum dots (QDs) with very low surface defect density and which exhibited the Mn(2+)-related orange luminescence. The post-preparative introduction of a ZnS shell at the surface of the Mn(2+)-doped ZnSe QDs improved their photoluminescence properties, resulting in stronger emission. A 2.5-fold increase in photoluminescence quantum yield (from 3.5 to 9%) and of Mn(2+) ion emission lifetime (from 0.62 to 1.39 ms) have been observed after surface passivation. The size and the structure of these QDs were also corroborated by using transmission electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction.     

Type-II core/shell CdS/ZnSe nanocrystals: synthesis, electronic structures, and spectroscopic properties

We report a two-step synthesis of highly luminescent CdS/ZnSe core/shell nanocrystals (emission quantum yields up to 50%) that can produce efficient spatial separation of electrons and holes between the core and the shell (type-II localization regime). Our synthesis involves fabrication of cubic-singony CdS core particles that are subsequently overcoated with a layer of ZnSe in the presence of surfactant-ligands in a noncoordinating solvent. Studies of different growth regime of the ZnSe shell indicate that one approach to obtaining high emission efficiencies is through alloying the CdS/ZnSe interface with CdSe, which leads to the formation of an intermediate ZnCdSe layer with a graded composition. We perform theoretical modeling of these core/shell nanocrystals using effective mass approximation and applying first-order perturbation theory for treating both direct electron-hole coupling and the core/shell interface-polarization effects. Using this model we determine the range of geometrical parameters of the core/shell structures that result in a type-II localization regime. We further applied this model to evaluate the degree of electron-hole spatial separation (quantified in terms of the electron-hole overlap integral) based on measured emission wavelengths. We also discuss the potential applicability of these nanocrystals in lasing technologies and specifically the possibility of single-exciton optical gain in type-II nanostructures.     

Amine-induced growth of an In2O3 shell on colloidal InP nanocrystals

A simple and rapid method for the growth of an In2O3 shell on colloidal InP nanocrystals is described, increasing their fluorescence efficiency by one order of magnitude.     

Luminescent CdSe/CdS core/shell nanocrystals in dendron boxes: superior chemical,photochemical and thermal stability

The surface ligands, generation-3 (G3) dendrons, on each semiconductor nanocrystal were globally cross-linked through ring-closing metathesis (RCM). The global cross-linking of the dendron ligands sealed each nanocrystal in a dendron box, which yielded box-nanocrystals. Although the dendron ligands coated CdSe nanocrystals (CdSe dendron-nanocrystals) were already quite stable, the stability of CdSe box-nanocrystals against chemical, photochemical, and thermal treatments were dramatically improved in comparison to that of the original dendron-nanocrystals. Furthermore, the box structure of the ligands monolayer coupled with the stable inorganic CdSe/CdS core/shell nanocrystals resulted in a class of extremely stable nanocrystal/ligands complexes. The band edge photoluminescence of the core/shell dendron-nanocrystals and box-nanocrystals were partially remained, and could be further brightened through controlled chemical oxidation or photooxidation. Practically, the stability of the box-nanocrystals is sufficient for most fundamental studies and technical applications. The box-nanocrystals may represent a general solution for the commonly encountered instability for many types of colloidal nanocrystals. The size distribution of the empty dendron boxes formed by the dissolution of the inorganic nanocrystals in concentrated HCl was very narrow. The empty boxes as new types of polymer capsules are soluble in solution, mesoporous, and with a very thin but stable peripheral. Those nanometer-sized cavities should be of interest for many purposes in the field of solution host-guest chemistry.