Improved photoluminescence of ZnS:Mn nanocrystals by microwave assisted growth of ZnS shell

The photoluminescence (PL) of ZnS:Mn nanocrystals was improved greatly by microwave assisted growth of ZnS shell. Under optimized conditions, the luminescence quantum yield of ZnS:Mn nanocrystals increased from 2.8% to 12.1% after the growth of the ZnS shell. Time-resolved fluorescence spectroscopic and electron paramagnetic resonance measurements indicate that the improvement of the dispersivity of the doped Mn ions is responsible for the PL enhancement. Growth of the ZnS shell not only facilitated the diffusion of Mn ions during microwave irradiation but also prohibited the segregation of Mn ions on the particle surface. As a result, more isolated Mn²⁺ ions were produced after the growth of the ZnS shell, and thus the orange luminescence of ZnS:Mn nanocrystals was enhanced greatly.     

Photoluminescence of colloidal YVO4:Eu/SiO2 core/shell nanocrystals

YVO₄:Eu, and YVO₄:Eu/SiO₂ nanocrystals (NCs) were prepared by hydrothermal method with citrate as capping ligands. Their morphologies, structures, components, and photoluminescence properties were investigated and presented in this paper. A remarkable fluorescence enhancement up to 2.17 times was observed in colloidal YVO₄:Eu/SiO₂ NCs, compared to that of colloidal YVO₄:Eu NCs. This is mainly attributed to the formation of the outer protecting layers of biocompatible SiO₂ shells; which shield the Eu³⁺ ions effectively from water and thus reduces the deleterious effects of water on the luminescence. Meanwhile, on the basis of laser selective excitation, two kinds of luminescent centers were confirmed in the NCs, namely, inner Eu³⁺ ions and surface Eu³⁺ ions. The surface modifications for YVO₄:Eu NCs effectively reduced the surface defects and accordingly enhanced the luminescence. The core/shell NCs exhibited long fluorescence lifetime and high photostability under ultraviolet radiation.     

Fast two-step microwave-activated synthesis of Mn doped ZnS nanocrystals: Comparison of the luminescence and doping process with thermochemical approach

In this work we report a fast two-step microwave activated synthesis of the ZnS:Mn nanocrystals. Zn(NO₃)₂ and Na₂S₂O₃ were used as the precursors and Mn(NO₃)₂ was employed as the source of the impurity. The aqueous synthesis was based on the heat sensitivity of Na₂S₂O₃, which releases some S species on heating. Consequently, the reaction was well activated under microwave irradiation resulting in formation of ZnS:Mn nanocrystals. Thioglycerol (TG) was also used as the capping agent and the catalyst of the reaction. The synthesis process was done in two steps, i.e. 1 min irradiation without TG and then injection of TG and continuation of irradiation. ZnS:Mn nanocrystals were quickly formed in the solution and luminescence was emerged in a few minutes. Optical transmission spectroscopy and X-ray diffraction analysis demonstrated formation of ZnS:Mn nanocrystals with a cubic crystalline structure and 3.0 nm average size. Photoluminescence measurements also showed some spectra with a Mn related peak located at 585 nm. The mentioned peak corresponds to ⁴T₁→⁶A₁ transition in Mn impurities and revealed the effective incorporation of Mn ions inside the nanocrystals. Evolution of the PL was also investigated and showed an increase in longer irradiation times. A qualitative model is also used to justify the necessity of using a two-step method as well as the PL emergence and increase in longer irradiation times. The model is based on separation between the nucleation and growth steps and significant role of TG in these stages. Finally, we present a comparison between the results of microwave activated method and two-step thermochemical approach. Although the synthesis time in microwave activated method was considerably short (less than 5 min), the luminescence properties were quite comparable with long time thermochemical approach. The doping process was also investigated for different Mn/Zn concentrations in two approaches. The results demonstrated that the doping occurred more effectively in the microwave activated synthesis.     

Synthesis and characterization of Mn-doped Zn2SiO4/SiO2 phosphor particles in core-shell structure

Manganese-doped zinc silicate (Zn₂SiO₄:Mn) is a kind of phosphor material that has a photo-luminescent (PL) and cathode-luminescent (CL) properties with intensive green light emission at 520 nm. The particles consisting of SiO₂@Zn₂SiO₄:Mn (SiO₂ core-Zn₂SiO₄:Mn shell) were synthesized via colloidal process and forced precipitation. After drying, the Zn/Mn precipitates were coated on the surface of SiO₂ particles. The Zn/Mn precipitates reacted with SiO₂ and transformed to Zn₂SiO₄:Mn by suitable calcination. The microstructure, crystalline phase, and luminescent characteristics of the products were studied. Besides, a CL device consisting of the core-shell powder was characterized.     

核/壳结构ZnS : Mn/CdS纳米粒子的制备及发光

利用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS : Mn),利用沉淀法对ZnS ∶ Mn纳米粒子进行了不同厚度的CdS无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及光致发光(PL)光谱等手段对样品进行了表征。TEM显示粒子为球形,直径大约在14~18 nm之间。由XRD结果可以看出CdS壳层的形成过程受到了ZnS ∶ Mn核的影响,导致其结晶较差。XRD和XPS测量证明了ZnS : Mn/CdS的核壳结构。随着CdS壳层的增厚,样品的发光强度呈现一直减弱的现象。     

Functionalized CdS nanospheres and nanorods

Functionalized nanoparticles are discussed. Surfaces of CdS:Mn/ZnS core/shell nanospheres (Qdots) were converted from hydrophobic to hydrophilic by growth of a SiO₂ shell. The colloidal dispersion was stabilize by adding a surfactant with a negative surface charge, and a cell-penetrating-peptide, TAT, was attached through a primary amine group. The TAT functionalized Qdots were shown to pass the blood-brain-barrier and luminescence in the infused half of the brain.In addition, nanorods of S²⁻ rich CdS were synthesized by reaction of excess S with Cd precursors in the presence of ethylene diamine. The photoluminescence (PL) peak from the S²⁻ rich CdS nanorods was broad with a maximum at ∼710 nm, which was 40 nm longer in wavelength than the PL peak from Cd²⁺ rich CdS (∼670 nm) nanorods. The influence of surface electron or hole trap states on the luminescent pathway of CdS nanorods were used to explain these shifts in wavelength. Nanocrystals of Au with ∼2 nm diameters were grown on S²⁻ rich surfaces of CdS nanorods. Significant quenching of photoluminescence was observed from Au nanocrystals on CdS nanorods due to interfacial charge separation. Charge separation by Au nanocrystals on CdS resulted in enhanced UV photocatalytic degradation of Procion red mix-5B (PRB) dye in aqueous solution.     

Hydrothermal synthesis and optical characteristics of Eu in Zn2SnO4 nanocrystals

Zn₂SnO₄:Eu³⁺ nanocrystals were one-step synthesized by hydrothermal method for the first time. All the products were systematically characterized by powder X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), electron probe X-ray microanalyzer (EPMA), photoluminescence (PL) and photoluminescent excitation (PLE). The characteristic peak of Eu³⁺-doped in Zn₂SnO₄ nanocrystals was also detected. The luminescent properties of blank and Eu³⁺-doped Zn₂SnO₄ nanocrystals were reported.     

核/壳结构的ZnS:Mn/SiO_2纳米粒子的制备及发光性质研究

采用溶剂热法制备了Mn离子掺杂的ZnS纳米粒子(ZnS∶Mn),然后利用正硅酸乙酯(TEOS)的水解反应对其进行了不同厚度的SiO2无机壳层包覆。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及荧光发射光谱(PL)对样品的结构及光学性质进行了表征和研究。包覆SiO2壳层后,粒子的粒径明显增大并且在ZnS∶Mn纳米粒子表面可以观察到明显的SiO2壳层。XPS测试印证了ZnS∶Mn/SiO2的核壳结构。随着SiO2壳层的增厚,ZnS∶Mn/SiO2的Mn离子的发光先增强后减弱,这是因为SiO2壳层同时具有表面修饰和降低发光中心浓度这两种相反的作用。当壳层厚度(壳与核的物质的量的比)达到5时,发光效果达到最好,其强度达到未包覆样品的7.5倍。     

Preparation and photoluminescence characteristics of Eu-doped MgAl1.8Y0.2O4 nanocrystals

A simple combustion route was employed for the preparation of Eu³⁺-doped MgAl_1.8Y_0.2−xO₄ nanocrystals using metal nitrates as precursors and urea as a fuel in a preheated furnace at 500 °C. The powders thus obtained were then fired at 1000 °C for 3 h to get better luminescent properties. The incorporation of Eu³⁺ activator in these nanocrystals was checked by luminescence characteristics. These nanocrystals displayed bright red color on excitation under 254 nm UV source. The main emission peak was assigned to the transition [⁵D₀→⁷F₂] at 615 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were carried out to understand surface morphological features and the particle size. Crystal structures of the nanocrystals were investigated by the X-ray diffraction (XRD) technique. The crystallite size of the as-prepared nanocrystals was around 29 nm, which was evaluated from the broad XRD peaks. The crystallite size increased to ∼45 nm on further heat treatment at 1000 °C.     

Preparation and luminescence of water soluble poly (N-vinyl-2-pyrrolidone)/LaF3:Eu nanocrystals

Lanthanide-doped luminescent nanocrystals have great potential as biological luminescent labels, but their use has been limited because of most of these nanocrystals are hydrophobic. In this work, water soluble LaF₃:Eu³⁺ down-conversion nanocrystals were prepared by encapsulated individual nanocrystals with polyvinylpyrrolidone (PVP). Their morphology, surface structure and luminescence properties were explored in detail. The results indicate that these nanocrystals can be readily dispersed in water, forming a stable and transparent colloidal solution. The colloidal solution displayed unique red luminescence with high emission intensity under ultraviolet excitation. These results suggest that these nanocrystals have great potential as luminescent labeling materials for biological applications.     

Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles

Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO₂ core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.     

Photoluminescence properties of impurity-doped ZnS nanocrystals fabricated by sequential ion implantation

We have studied photoluminescence (PL) spectrum and dynamics of Cu- and Al-doped ZnS (ZnS:Cu,Al) nanocrystals fabricated by sequential implantation of Zn⁺, S⁺, Cu⁺, and Al⁺ ions into Al₂O₃ matrices. These samples exhibit intense green PL under UV light excitation. The space- and time-resolved PL measurements show that the broad green PL is due to the donor–acceptor (DA) pair luminescence of single ZnS:Cu,Al nanocrystals.     

Enhancement of luminescence properties of Eu:YVO4 in polymeric nanocomposites upon UV excitation

Highly emissive Eu³⁺:YVO₄ nanocrystals were successfully prepared by the hydrothermal method. The average diameter of grains was determined to be 15 nm. Transparent polymer nanocomposites composed of PMMA and well dispersed Eu³⁺:YVO₄ nanocrystals were fabricated by in situ polymerization. The nanocrystalline powders and nanocomposites were characterized by scanning and transmission electron microscopy (TEM) and X-ray diffraction (XRD). The luminescence properties of the obtained nanocomposites were investigated and compared with the starting powders and Eu³⁺:YVO₄ single crystal. The effect of the polymeric host on the luminescence properties of Eu³⁺:YVO₄ is presented and discussed.     

Luminescence kinetics in silica gel doped with Tb3+ ions and ZnS:Mn2+ nanocrystals

Luminescence kinetics and time-resolved luminescence spectra of SiO₂, SiO₂ doped with ZnS:Mn²⁺ nanocrystals and SiO₂ doped with ZnS:Mn²⁺, and additionally co-doped with Tb³⁺, are presented. The purposes of the paper are the analysis of the kinetics of the Tb³⁺ and Mn²⁺ intra-shell luminescence and the elucidation of the energy-transfer mechanism between the ZnS:Mn²⁺ nanocrystals and the Tb³⁺ ions. We have found a blue luminescence related to defects in the ZnS nanocrystals and an intrinsic luminescence of the SiO₂ lattice, which decays in few ns. A yellow luminescence related to the Mn^{2+ 4}T₁(G)→⁶A₁ transition and yellow sharp lines related to the ⁵D₄→⁷F₆, ⁷F₅, ⁷F₄ and ⁷F₃ transitions in Tb³⁺ are found to decay in ms. A very effective energy transfer between ZnS:Mn²⁺ nanoparticles and Tb³⁺ ions has been observed.     

Self-assembled one-pot synthesis of red luminescent CdS:Mn/Mn(OH)2 nanoparticles

We report a novel method of growing red luminescent (635 nm) Mn-doped CdS (CdS:Mn) nanoparticles capped by an inorganic shell of Mn(OH)₂. CdSO₄, Na₂S₂O₃ and Mn(NO₃)₂ were used as the precursors, and thioglycerol (C₃H₈O₂S) was employed as the capping agent and also the catalyst of the reaction. Using these materials resulted in very slow rate of the reaction and particles growth. The self-assembled one-pot process was performed at pH of 8 and Mn:Cd ratio of 10, and took about 10 days for completion. CdS:Mn nanoparticles are slowly formed in the first day of the process; however, the luminescence is weak. After 7 days, the solution turns white turbid through the formation of additional particles, which precipitate on the walls on the next day. At this stage, a relatively strong red luminescence at 635 nm appears from transparent solution of the CdS:Mn nanoparticles. The white deposit on the walls turns to dark-brown color and luminescence increases on the 9th day. Finally, the CdS:Mn nanoparticles agglomerate and precipitate out of the solution on 10th day. X-ray diffraction and optical spectroscopy showed crystalline phase CdS nanoparticles with an average size of 3.6 nm. We explain the luminescence enhancement based on the formation of a Mn(OH)₂ shell on the surface of the CdS:Mn nanoparticles during the precipitation stage. This can passivate the S dangling bonds located on the particles surface. As the surface Cd sites are previously capped with thioglycerol molecules, a complete surface passivation is achieved and results in emergence of high-intensity luminescence.     

Structural and photoluminescence properties of ZrO2:Eu @ SiO2 nanophosphors as a function of annealing temperature

The synthesis, morphology and luminescence properties of two systems comprising luminescent Eu³⁺-doped zirconium oxide nanocrystals embedded in an amorphous silica matrix are reported. The two systems, prepared with the same overall wt% composition of silica (75%) and Eu_xZr_(1−x)O_(2−x/2) solid solution (25%), have been annealed in the range 135–1000 °C and subsequently functionalized with (3-aminopropyl)triethoxysilane. Detailed X-ray diffraction analyses and transmission electron micrographs, combined with infrared spectroscopy and luminescence spectroscopy data, have been used to demonstrate the influence of annealing temperature on the: (i) nanostructure, (ii) luminescence properties and (iii) availability of superficial –OH groups for efficient surface functionalization. The optimum calcination temperature was found to be 700 °C for each series in terms of luminescence lifetime efficiency and post-functionalization efficiency with (3-aminopropyl)triethoxysilane.     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

Synthesis and photoluminescence characteristics of doped ZnS nanoparticles

Free-standing powders of doped ZnS nanoparticles have been synthesized by using a chemical co-precipitation of Zn²⁺, Mn²⁺, Cu²⁺ and Cd²⁺ with sulfur ions in aqueous solution. X-ray diffraction analysis shows that the diameter of the particles is ∼2–3 nm. The unique luminescence properties, such as the strength (its intensity is about 12 times that of ZnS nanoparticles) and stability of the visible-light emission, were observed from ZnS nanoparticles co-doped with Cu²⁺ and Mn²⁺. The nanoparticles could be doped with copper and manganese during the synthesis without altering the X-ray diffraction pattern. However, doping shifts the luminescence to 520–540 nm in the case of co-doping with Cu²⁺ and Mn²⁺. Doping also results in a blue shift on the excitation wavelength. In Cd²⁺-doped ZnS nanometer-scale particles, the fluorescence spectra show a red shift in the emission wavelength (ranging from 450 nm to 620 nm). Also a relatively broad emission (ranging from blue to yellow) has been observed. The results strongly suggest that doped ZnS nanocrystals, especially two kinds of transition metal-activated ZnS nanoparticles, form a new class of luminescent materials. Received: 16 October 2000 / Accepted: 17 October 2000 / Published online: 23 May 2001     

Combustion synthesis and photoluminescence of ZnS:Mn particles

An efficient process based on a solid-state combustion technique has been developed to produce high crystalline and micrometer sized particles of ZnS:Mn⁺² phosphor with sphalerite structure. The precursor mixture of 0.915Zn+S+0.05Mn+0.035ZnCl₂+kNaCl composition (where k is the mole number of NaCl) was combusted under the argon atmosphere followed by post-heat treatment procedure at 700 °C. It was shown that photoluminescence (PL) intensity of ZnS sample can be easily controlled through adjusting NaCl concentration. In the optimized reaction conditions ZnS samples have showed PL intensity almost comparable to that of a commercial one, despite the relatively low purity of precursor materials used. Many interesting phenomena such as high luminescent efficiency, pure cubic ZnS formation after the post-heat treatment and strong influence of Cl⁻ ion on PL intensity have been observed and discussed.     

Tb ions in presence of ZnS:Mn nanocrystals immobilized on silica: Energy transfer ZnS→Tb and coordination state of Mn ions

Three-component luminescent material consisting of silica xerogel as a support with immobilized ZnS:Mn²⁺ nanocrystals and Tb³⁺ ions was compared with such two-component materials as the silica support with ZnS:Mn²⁺ as well as the support with Tb³⁺. In each case the nanocrystals and the lanthanide ions were immobilized at silica surface by impregnation procedure. Size of the ZnS quantum dots doped with Mn²⁺ were estimated by Scherrer method from the X-ray diffraction (XRD) pattern. The materials have been characterized by EPR and optical spectroscopy techniques. EPR spectra allow to distinguish two different Mn²⁺ sites: the first is assigned to isolated Mn²⁺ substitutionally and incorporated into cubic ZnS lattice and the second is ascribed to the Mn²⁺ situated near the nanocrystal surface. From the optical spectra we have found that in the three-component material, energy transfer from excited ZnS:Mn²⁺ nanocrystals to Tb³⁺ ions takes place. The different mechanisms of such transfer are discussed.