A facile and fast approach for the synthesis of doped nanoparticles using a microfluidic device

The microfluidic approach emerges as a new and promising technology for the synthesis of nanomaterials. A microreactor allows a variety of reaction conditions to be quickly scanned without consuming large amounts of raw material. In this study, we investigated the synthesis of water soluble 1-thioglycerol-capped Mn-doped ZnS nanocrystalline semiconductor nanoparticles (TG-capped ZnS:Mn) via a microfluidic approach. This is the first report for the successful doping of Mn in a ZnS semiconductor at room temperature as well as at 80?°C using a microreactor. Transmission electron microscopy and x-ray diffraction analysis show that the average particle size of Mn-doped ZnS nanoparticles is ～3.0?nm with a zinc-blende structure. Photoluminescence, x-ray photoelectron spectroscopy, atomic absorption spectroscopy and electron paramagnetic resonance studies were carried out to confirm that the Mn(2+) dopants are present in the ZnS nanoparticles.     

Luminescence in Mn-doped CdS nanocrystals

We have synthesized Mn-doped CdS nanocrystals (NCs) with size ranging from 1.8–3 nm. Photoluminescence (PL) spectra of the doped NCs differ from that of the undoped NCs with an additional peak due to Mn d-d transitions. Electron paramagnetic resonance spectra along with X-ray absorption spectroscopy and PL spectra confirm the incorporation of Mn in the CdS lattice. The fact that emissions from surface states and the Mn d levels occur at two different energies, allowed us to study the PL lifetime decay behaviour of both kinds of emissions.     

Optical and magnetic properties of manganese-doped zinc sulfide nanoclusters

We report the synthesis of fixed-size ZnS nanoclusters approximately 24 A in diameter with varying manganese concentrations. Various samples of Zn1-x MnxS, with x = 0, 0.02, 0.055, 0.09, and 0.13, have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-rays, UV absorption, fluorescence emission and excitation, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements. The manganese ions are found to substitute Zn randomly without giving rise to any clustering of Mn sites, as seen from EPR and magnetic susceptibility results. Our studies reveal that the band gap of the doped nanoclusters passes through a maximum as the manganese concentration is varied. Also, we observe orange emission from Mn2+ ions in the doped ZnS nanoclusters, apart from the blue emission characteristic of the ZnS defect states. The relative intensity of the orange emission compared with the blue varies with the manganese concentration in a nonmonotonic way. The inverse of susceptibility temperature plots can be plotted onto a universal curve by simple multiplicative constants, thus showing that the magnetic interactions between Mn2+ ions are weak.     

Syntheses and applications of Mn-doped II-VI semiconductor nanocrystals

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.     

Structural, Optical and Magnetic Properties of Mn-doped CdS Diluted Magnetic Semiconductor Nanoparticles

Diluted magnetic CdS:Mn nanoparticles were synthesized by the aqueous solution method with different manganese (Mn²⁺) concentrations (x=7?C10?atom?%) at room temperature in nitrogen atmosphere and capped with Thiogelycerol. The X-ray diffraction patterns of CdS nanoparticles with different Mn doping concentration indicated that samples have hexagonal structure at room temperature. Energy dispersive X-ray spectroscopy confirmed incorporative of Mn ions in CdS nanoparticles. UV-Visible spectroscopy is used to investigate optical absorption of Mn-doped CdS. From photoluminescence measurement it was found that the intensity of the luminescence spectra decreases by increasing Mn²⁺ dopant ions at high precursor concentration. Also, the room temperature ferromagnetic behavior of Mn-doped CdS nanoparticles is discussed by using hysteresis measurement results.     

EPR study of ZnS: Mn2+ nanocrystals in Pyrex glasses

ZnS: Mn2+ nanocrystals embedded in Pyrex glasses were spectrally studied using EPR and photoluminescence techniques. Photoluminescence (PL) and excitation (PLE) spectra revealed that manganese impurities can be classified as two types of luminescent centers, i.e., occupying substitutional sites (Mn2+)sub or interstitial sites (Mn2+)int. Three types of manganese sites of (Mn2+)sub, (Mn2+)int, and Mn clusters were identified by the EPR spectra. An increase of the g1 factor and hyperfine structure (HFS) constant with decreasing sizes of nanocrystals was observed. The increase was attributed to a hybridization of the s-p state of ZnS and the d state of manganese ions enhanced by quantum confinement effects or surface states.     

Ferromagnetic GaN--Cr Nanowires

Using first-principles theory, we predict ferromagnetism in Cr-doped GaN nanowires irrespective of the sites that the Cr atoms occupy. This is in contrast to Mn-doped GaN nanowires in which the magnetic coupling between the Mn atoms is sensitive to the Mn--Mn and Mn--N distances, although the ground state of Mn-doped GaN nanowires is ferromagnetic. Each Cr atom carries a magnetic moment of about 2.5 micro(B). The magnetic moment at the N site, however, is small and is aligned antiferromagnetically to the moments at the Cr atom. The magnetization axis is perpendicular to the axis of the wire, but the anisotropy energy is rather small. The easy solubility of Cr in GaN and the lack of sensitivity of ferromagnetic coupling to Cr distribution suggest that Cr-doped GaN nanowires may be a more suitable system for applications in spintronics than Mn-doped GaN nanowires.     

Structural, optical and magnetic properties of Zn1 − xMnxO micro-rod arrays synthesized by spray pyrolysis method

Undoped and Mn-doped ZnO micro-rod arrays were fabricated by the spray pyrolysis method on glass substrates. X-ray diffraction and scanning electron microscopy showed that these micro-rod arrays had a polycrystalline wurtzite structure and high c-axis preferred orientation. Photoluminescence studies at 10 K show that the increase of manganese content leads to a relative decrease in deep level band intensity with respect to undoped ZnO. Magnetic measurements indicated that undoped ZnO was diamagnetic in nature whereas Mn-doped ZnO samples exhibited ferromagnetic behavior at room temperature, which is possibly related to the substitution of Mn ions (Mn^2 +) for Zn ions in the ZnO lattice.     

Structure and elemental distribution of (Ga,Mn)N nanowires

(Ga,Mn)N nanowires were grown by plasma-assisted molecular beam epitaxy on p-type Si(111) substrates. Chemical composition and elemental distribution of single nanowires were analyzed by energy dispersive X-ray spectroscopy revealing an inhomogeneous Mn distribution decreasing from the surface of the nanowires toward the inner core region. The average Mn concentration within the nanowires is found to be below 1%. High-resolution transmission electron microscopy shows the presence of planar defects perpendicular to the growth direction in undoped and Mn-doped GaN nanowires. The density of planar defects dramatically increases under Mn supply.     

Synthesis and optoelectrochemical properties of ZnS:Mn nanocrystals

Mn2+ ions doped ZnS semiconductor nanocrystals (ZnS:Mn NCs) were synthesized using colloidal chemical method at 70 degrees C without any capping agents. The as-prepared undoped ZnS and ZnS:Mn NCs were characterized by UV-Vis absorption spectra, fluorescent emission spectra, X-ray powder diffraction (XRD), inductively coupled plasma analysis (ICP), X-ray photoelectron spectroscopy (XPS), Dynamic light scattering (DLS), cyclic voltammogram and electronic transmission microscopy (TEM). The dependence of photoluminescence of ZnS:Mn NCs on dopant concentration was studied. The results show that Mn2+ ions mainly stay at ZnS nanocystal surface, and Mn2+-surface defect state complex was formed, as a result of which, surface defect emission of ZnS nanocrystals was substituted with Mn2+-related PL emission. The strongest fluorescent emission intensity was obtain at 1.85 at% Mn2+ doped ZnS:Mn NCs. The Mn2+ doped ZnS:Mn NCs are of 5 nm in diameter. The emission peak at 575 nm is attributed to d-d (4T1 --> 6A1) transition of Mn2+ ions. The existence of Mn2+-related photoluminescence could be well correlated with cyclic voltammogram of Mn2+-doped NCs, where pair of oxidation and reduction peaks were clearly observed due to the doped Mn2+ ions. The adsorbed Mn2+ ions on ZnS NCs produced neither Mn2+ emission nor redox peaks. For heavily doped ZnS:Mn NCs (4.87 at%), redox peaks gap in cyclic voltammogram became larger and new oxidation peak appeared. Correspondingly, when the Mn2+ doping concentration reached 4.87 at%, the Mn2+-related emission totally disappears due to the Mn-Mn interactions. This work implys that electrochemical technique is possibly an useful tool to probe the local structure of doped Mn2+ ions.     

Hydrothermal synthesis and luminescent properties of microtubes constructed by fluffy Zns:Mn2+ with nanostructures

Tubular micrometer-sized ZnS:Mn2+ constructed by fluffy nanostructures were fabricated in the mixed solutions of water and ethanol in a fixed volume ratio with the aid of ethylenediamine. In the X-ray diffraction pattern, the products obtained in the presence and absence of ethylenediamine show the wurtzite and sphalerite phases, respectively. Field-emission scanning electron microscopic images reveal the evolution process from nanowires to fluffy ZnS:Mn2+ to microtubes with the reaction times of 2, 4, and 8 hours at 100 degrees C, and the basal nanowires are below 10 nm in diameter. Photoluminescence and photoluminescence excitation spectra were investigated. The results suggest that the wurtzite phase, instead of the sphalerite phase ZnS:Mn2+ is luminescence-active for the 4T1 -6A1 transition of the Mn2+ in the ZnS host. The excitation spectra monitored at orange emission bands exhibit sharp peaks at 320, 326 and 327 nm with increasing reaction times of 2, 4, and 8 hours, respectively, indicating the energy transfer from ZnS host to Mn2+ ions, and the blue-shifts compared with the band gap absorption of the bulk counterpart (344 nm) are also observed due to the quantum confinement effects. The formation mechanism of the wurtzite one-dimensional nanostructures at such a low temperature is proposed based on a molecular template mechanism involving the bidentate coordinating ligand, ethylenediamine, and the possible formation mechanism of novel tubular structure are also discussed.     

One-step,solvothermal synthesis of graphene-CdS and graphene-ZnS quantum dot nanocomposites and their interesting photovoltaic properties

The synthesis of graphene-semiconductor nanocomposites has attracted increasing attention due to their interesting optoelectronic properties. However the synthesis of such nanocomposites, with decorated particles well dispersed on graphene, is still a great challenge. This work reports a facile, one-step, solvothermal method for the synthesis of graphene-CdS and graphene-ZnS quantum dot nanocomposites directly from graphene oxide, with CdS and ZnS very well dispersed on the graphene nanosheets. Photoluminescence measurements showed that the integration of CdS and ZnS with graphene significantly decreases their photoluminescence. Transient photovoltage studies revealed that the graphene-CdS nanocomposite exhibits a very unexpected strong positive photovoltaic response, while separate samples of graphene and CdS quantum dots (QDs) of a similar size do not show any photovoltaic response.     

General control of transition-metal-doped GaN nanowire growth: toward understanding the mechanism of dopant incorporation

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.     

Synthesis and photoluminescent properties of doped ZnS nanocrystals capped by poly(vinylpyrrolidone)

Zinc sulfide semiconductor nanocrystals doped with selected transition metal ions (Mn²⁺, Cu²⁺, and Ni²⁺) have been synthesized via a solution-based method utilizing low dopant concentrations (0–1%) and employing poly(vinylpyrrolidone) (PVP) as a capping agent. UV/Vis absorbance spectra for all of the synthesized nanocrystals show an exitonic peak at around 310 nm, indicating that the introduction of the dopant does not influence the particle size. Calculated particle sizes for undoped and doped nanocrystals are in the 4.3 nm size range. Photoluminescence spectra recorded for undoped ZnS nanocrystals, using an excitation wavelength of 310 nm, exhibit an emission peak centered at around 460 nm. When a dopant ion is included in the synthesis, peaks in the corresponding photoluminescence spectra are red-shifted. For Mn-doped nanocrystals, an intense peak centered at approximately 590 nm is found and is seen to increase in photoluminescence intensity with an increase in dopant concentration. In contrast, for Cu-doped and Ni-doped nanocrystals, weaker peaks centered at around 520 and 500 nm, respectively, are observed and are noticed to decrease in photoluminescence intensity with an increase in dopant concentration. These results clearly show that careful control of synthetic conditions must be employed in the synthesis of doped semiconductor nanocrystals in order to obtain materials with optimized properties.     

Photoluminescence decay kinetics of doped ZnS nanophosphors

Doped nanophosphor samples of ZnS:Mn, ZnS:Mn, Co and ZnS:Mn, Fe were prepared using a chemical precipitation method. Photoluminescence (PL) spectra were obtained and lifetime studies of the nanophosphors were carried out at room temperature. To the best of our knowledge, there are very few reports on the photoluminescence investigations of Co-doped or Fe-doped ZnS:Mn nanoparticles in the literature. Furthermore, there is no report on luminescence lifetime shortening of ZnS:Mn nanoparticles doped with Co or Fe impurity. Experimental results showed that there is considerable change in the photoluminescence spectra of ZnS:Mn nanoparticles doped with X (X = Co, Fe). The PL spectra of the ZnS:Mn, Co nanoparticle sample show three peaks at 410, 432 and 594?nm, while in the case of the ZnS:Mn, Fe nanoparticle sample the peaks are considerably different. The lifetimes are found to be in microsecond time domain for 594?nm emission, while nanosecond order lifetimes are obtained for 432 and 411?nm emission in ZnS:Mn, X nanophosphor samples. These lifetimes suggest a new additional decay channel of the carrier in the host material.     

Study of electrical and optical properties of Mn doped ZnS clusters

A simple, easy approach to the synthesis of manganese Mn doped zinc sulphide (ZnS) clusters is reported. The synthesis of Mn–ZnS clusters involved mixing and drying of zinc acetate, sodium sulphide and acrylic acid in appropriate ratio and adding Mn at proper conditions. These clusters were trapped in polyacrylic acid (PAA) to form PAA capping to provide stability. The clusters were characterized using high resolution SEM for morphological investigation; XRD for its crystalline nature; photoluminescence (PL) for optical characterization and electrical conductivity measurement. Clusters of Mn–ZnS were formed of the size ~ 10 nm.     

One-pot fabrication and magnetic studies of Mn-doped TiO(2) nanocrystals with an encapsulating carbon layer

Mn-doped TiO(2) nanocrystals encapsulated in a carbon layer (Ti(1-x)Mn(x)O(2)@C) were synthesized by the one-pot RAPET (reaction under autogenic pressure at elevated temperature) technique. Manganese was doped into the body-centered tetragonal TiO(2) anatase phase to give a Mn:Ti atomic ratio of 1%, 5% and 10%. The surface modification by carbon was achieved in order to make the cubic/tetragonal nanocrystals non-toxic and biocompatible. Electron paramagnetic resonance (EPR) studies revealed a broad resonance (centered at g = 1.9977 due to the interacting spins in the oxide matrix) with increased dopant concentration and the resonance due to carbon. Manganese is mainly present as +II or +III oxidation states. The magnetic behavior was found to be very dependent on the manganese concentration with a ferromagnetic behavior of the 1% doped sample due to the coupling between carriers and manganese spins. A predominant paramagnetic behavior was observed for the higher Mn-doped samples. This study opens up a new dimension for the carbon encapsulation of room-temperature ferromagnetic diluted magnetic semiconductor (DMS) nanomaterials.     

The light emission properties of ZnS:Mn nanoparticles

ZnS and Mn-doped ZnS nanoparticles were synthesized via a simple hydrothermal synthesis method. The former emits super bright blue fluorescence light while the latter exhibits super-bright yellow light under a fluorescence microscope. Accordingly, their photoluminescence peaks are located at 420 nm and 580 nm in the spectra excited with 281 nm and 335 nm wavelengths, respectively. The super-bright ZnS:Mn nanoparticles can be used as a yellow fluorescence powder in making LED and plat display, and can be used as biological fluorescence probe to replace CdSe, CdS quantum dos without any damage to mankind and environment.     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

MS(M=Cd或Zn)纳米粒子负载TiO_2纳米线的制备及可见光催化性能

以具有层状结构的钛酸盐纳米线、CdCl2或ZnSO4及硫代乙酰胺为原料,采用两步水热合成法制备了高温稳定的六方相CdS或低温稳定的立方相ZnS纳米粒子负载的TiO2纳米线复合材料。首先,CdCl2或ZnSO4与钛酸盐纳米线在水热条件下进行离子交换制得含Cd2+或Zn2+的钛酸盐纳米线;然后,在硫代乙酰胺溶液中于160℃下直接处理含Cd2+或Zn2+的钛酸盐纳米线就可获得负载有硫化物纳米粒子的TiO2复合纳米线。它们在酸浸后,TiO2纳米线的表面仍存在少量硫化物纳米粒子。通过测试酸浸后样品、纯TiO2纳米线和商用P25对亚甲基蓝水溶液的可见光催化降解实验结果证实,含CdS纳米粒子样品的光催化活性最高。