Role of surface coating in ZrO2/Eu3+ nanocrystals

The sol-emulsion-gel method is used for the preparation of Eu3+ ion-doped and coated ZrO2 nanocrystals. Here, we report the role of surface coating, dopant concentration, and temperature of heating in the modification of their crystal structure and photoluminescence properties. It is found that the volume fraction of the tetragonal phase increases from 28.08 to 91.56% because of surface coating. This is a significant modification of the crystal phase in ZrO2 nanocrystals due to surface coating by Eu2O3. It is found that the photoluminescence properties are sensitive to the crystal structure, which is again controlled by surface coating, concentration, and heating temperature. It is found that the decay time (tau) of Eu-doped ZrO2 nanocrystals increases with increasing the concentration of dopant and with increasing the temperature of heating because of changes in their crystal phase. The emission intensity of the peak at 611-617 nm (5D0 --> 7F2) of the Eu3+ ion-activated ZrO2 nanocrystals (doped and coated) is also found to be sensitive to the nanoenvironment. The average decay times are 770 and 488 mus for 1100 degrees C-heated 1.0 mol % Eu2O3-doped and coated ZrO2 nanocrystals, respectively. Our analysis suggests that the site symmetry of the ions plays the most important role in the modifications of the radiative and nonradiative relaxation mechanisms as a result of the overall photoluminescence properties.     

Effect of particle size and dopant concentration on photophysical properties of Eu3+-doped rare earth oxysulphide phosphor coatings

Europium-doped rare-earth oxysulphides (red phosphors) are often used as reference luminophore in pyrene-based pressure sensor coatings for aerodynamic applications. Different red phosphor samples were characterized for their particle size, chemical composition, photoluminescent properties and temperature sensitivity. The red phosphor samples were characterized using energy-dispersive X-ray spectroscopy (EDX) for elemental analysis and scanning electron microscopy (SEM) for morphology and particle size measurement. The particle size was in the range of 1.5-5.7 μm with morphology of hexagonal or spherical shape. It was found that phosphor with higher europium content exhibited higher luminescent emission intensity. The phosphor coatings were prepared by spraying a dispersion of the material in silicone resin. Smooth coatings were obtained by using phosphor samples with smaller particle size. Upon 334 nm excitation, the coatings showed characteristic luminescence 5D0→7FJ (J=0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 626 nm (5D0→7F2) of Eu3+ ions was stronger than the magnetic dipole transition located at 595 nm (5D0→7F1). Luminescence decay curves obeyed double exponential behaviour. The phosphor samples showed temperature sensitivity of -0.012 to -0.168%/°C in the temperature range of 25-50 °C.     

Eu3+ concentration dependent optical properties and energy transfer from host Gd3+ to Eu3+ in GdF3 nanocrystals

By using a hydrothermal method, a series of Eu³⁺ concentration dependent GdF₃ nanocrystals have been synthesized. The crystalline structures of samples are characterized by XRD patterns, the morphology and size of the samples are illustrated by FE-SEM images, and the optical properties of the samples are presented by PL excitation and emission spectra. The energy transfer from host Gd³⁺ to Eu³⁺ is observed in the Eu³⁺ doped GdF₃ nanocrystals. The optical properties of Eu³⁺ and the energy transfer efficiency from host Gd³⁺ to Eu³⁺ are discussed on the basis of the Eu³⁺ concentration dependent integrated PL excitation and emission spectra of Gd³⁺ and Eu³⁺. The discussion on optical properties of Eu³⁺ and the energy transfer from Gd³⁺ to Eu³⁺ is meaningful to design and synthesize Gd³⁺ based compounds.     

Novel dumbbell-like LaVO4:Eu3+ nanocrystals and effect of Ba2+ codoping on luminescence properties of LaVO4:Eu3+ nanocrystals

Journal of Sol-Gel Science and Technology - LaVO4:Eu3+ nanocrystals with different morphologies were synthesized via a simple hydrothermal method in a wide pH range. The as-synthesized samples were...     

Chemically binding Eu^3＋ onto CdS semiconductor nanoparticle surface

Europium ions were chemically bound to CdS nanoparticles surface by diethylenetri-aminepentaacetate (DTPA, 1) in a two-step synthetic route. First 1 was applied to chelate with cadmium on the surface of cadmium-rich CdS nanoparticles and act as a capping agent. Further, the purified 1-capped particles were used to bind with Eu~3 . The purified and redispersed particles were characterized by photoluminescence spectroscopy, TEM and SEM. It was observed that Eu~3 on the nanoparticle surface significantly increased the band gap emission and decreased the surface emission intensity of the CdS nanoparticles.     

Preparation and photoluminescence properties of Y2SiO5:Eu3+ nanocrystals

The sol-emulsion-gel method is used for the preparation of about 5-7 nm size Eu2O3 doped and coated Y2SiO5 nanoparticles at 1300 degrees C. Here, we report the role of surface coating, dopant concentration and temperature of heating on the modification of crystal structure and the photoluminescence properties of Y2SiO5:Eu3+ nanocrystals. It is found that photoluminescence properties are sensitive to the crystal structure which is again controlled by surface coating, concentration and heating temperature. The decay times are 0.76, 1.14, 1.23 and 1.40 ms for 0.25, 0.5, 1.0 and 2.5 mol% Eu2O3 doped Y2SiO5 nanocrystals prepared at 1100 degrees C (X1-Y2SiO5). However, in X2-Y2SiO5 crystal phase (at 1300 degrees C) the average decay times are 1.05, 1.35, 1.55 and 1.60 ms for 0.25, 0.5, 1.0 and 2.5 mol% Eu2O3 doped Y2SiO5 nanocrystals, indicating the photoluminescence properties depend on both the crystal structure and the concentration of ions. The emission intensity of the peak at 612 nm (5D0-->7F2) of the Eu3+-ions is found to be sensitive to the doping and surface coating of Y2SiO5 nanocrystals. The decay times are 1.55 and 1.70 ms for 1300 degrees C heated 1.0 mol% Eu2O3 doped and coated Y2SiO5 nanocrystals, respectively. Our analysis suggests that the site symmetry of ions plays a most important role in the modification of radiative relaxation mechanisms and as a result on the overall photoluminescence properties.     

Judd-Ofelt intensity parameters and spectral properties of Gd2O3:Eu3+ nanocrystals

Three nonequivalent centers of Cs (A, B, and C) in monoclinic phase and C2 and S6 centers in cubic phase were identified in the Gd2O3:Eu3+ nanocrystals with spectral techniques. Size dependence in the spectra indicated that the excitations from both host and charge-transfer band (CTB) for the 5D0 --> 7F2 transition of Eu3+ ions were nearly equal for a larger size of 135 nm of the cubic phase; however, with decreasing the size to or less than 23 nm, the excitations by the CTB dominated. The variation of excitation leading to the symmetry and energy change in the C2 and S6 sites was also observed for larger particle sizes. The Judd-Ofelt intensity parameters Omega(lambda) (lambda = 2, 4) for Gd2O3:Eu3+ nanoparticles were experimentally determined. The parameters Omega(lambda) were found to significantly change with the sizes of Gd2O3:Eu3+ from nanoparticles to bulk material. With decreasing the size from 135 to 15 nm, the quantum efficiencies for 5D0 reduced from 23.6% to 4.6% due to the increasing ratio of surface to volume.     

LaOF:Eu3+ nanocrystals: hydrothermal synthesis, white and color-tuning emission properties

Uniform LaOF and LaOF : Eu(3+) nanocrystals of the γ-form have been successfully synthesized under mild conditions via a facile hydrothermal method followed a heat treatment of their bastnaesite-type precursor (LaCO(3)F). The synthetic details, investigations into the phase purity and the presence of the oxocarbonate anion CO(3)(2-) proven by IR measurements and EDX, as well as X-ray powder diffraction data, are given. Photoluminescence (PL) and cathodoluminescence (CL) spectra were utilized to characterize the luminescence properties of the LaCO(3)F : Eu(3+) and LaOF : Eu(3+) samples. Under ultraviolet light excitation, the LaCO(3)F : Eu(3+) precursor shows an orange emission of Eu(3+) (dominated by (5)D(0)→(7)F(1)), while the product of heat treatment, LaOF : Eu(3+), shows the characteristic emissions of Eu(3+) ((5)D(J)→(7)F(J')J, J' = 0, 1, 2, 3 transitions). Under the excitation of UV and low-voltage electron beams, the emission color (including white) of LaOF : Eu(3+) can be tuned by adjusting the doping concentration of Eu(3+). The corresponding luminescence mechanisms have been discussed in detail.     

Energy Transfer Between Eu3+ Ions and CdS Quantum Dots in Sol-Gel Derived CdS/SiO2 : Eu3+ Gel

We have investigated the energetic correlation between rare-earth ions and semiconductor nanocrystals, using europium ion (Eu³⁺) doped silica (SiO₂) gel with adsorbed cadmium sulfide (CdS) particles. Samples were prepared by a sol-gel technique, in which several methods for the precipitation of CdS colloids were attempted. The fluorescence intensities were compared for different gels, with and without CdS particles. The intrinsic emission lines due to ⁵D₀ ⁷F_J(J = 0–4) transitions of Eu³⁺ were observed, which were enhanced for 24 h-immersed gel (dried at 50°C). From the results on the decay dynamics of fluorescence, we proposed the model that surface-trapped electrons on CdS particles nonradiatively excited 4f electrons in Eu³⁺ ions due to an energy transfer process.     

Structural and spectroscopic properties of LaOF:Eu3+ nanocrystals prepared by the sol-gel Pechini method

A new method was used to obtain Eu(3+)-doped LaOF nanocrystals. The obtained nanocrystals were synthesized for the first time using a modified Pechini sol-gel method. The products were analyzed by X-ray powder diffraction and the Rietveld method. Optimal conditions for the synthesis were found. Luminescent properties of the tetragonal and rhombohedral LaOF:Eu(3+) nanocrystals were investigated by collecting excitation and luminescence spectra. The most effective dopant concentrations in both hosts were found. Luminescent lifetimes were also measured. The time-resolved luminescent traces showed both a growth and a decay, which pointed to energy transfer processes between Eu(3+) ions in the LaOF host. In order to explain these phenomena, an adequate mechanism has been proposed. Intensity parameters Ω(2), Ω(4) and quantum efficiencies were calculated using the Judd-Ofelt theory, allowing for an extensive study of the luminescent properties of Eu(3+) ion in the LaOF matrix.     

Thermal annealing of LaF3:Eu3+ nanocrystals synthesized by a solvothermal method and their luminescence properties

In this work, we used a low temperature solvothermal method to synthesize Eu³⁺-doped LaF₃ (LaF₃:Eu³⁺) nanocrystals. The effect of thermal annealing on their phase structures and luminescence properties was studied. Transformation from LaF₃ to LaOF was observed after the annealing, and the initial transformation process was studied using a rapid thermal annealing technique. It was found that a sufficiently high annealing temperature is required for the transformation of LaF₃ to LaOF. LaOF phase started to be formed after annealing at 500 °C for as short as 5 min, and higher annealing temperatures and longer annealing time led to a larger amount of LaOF formed. With the increase of the formation of LaOF, the luminescence was greatly enhanced. Strong O^2? → Eu³⁺ charge transfer band was present in these samples annealed at 500 °C and higher temperatures, and greatly enhanced ⁷F₀ → ⁵D₂ transition of Eu³⁺ was also observed.     

The critical concentration for quenching of the Eu3+ luminescence in some Gd3+ : Eu3+ systems

The critical concentration for quenching of the Eu³⁺ luminescence is calculated theoretically for several Gd³⁺ : Eu³⁺ systems. A comparison is made with the experimental values. The results are discussed in terms of energy migration.     

Growth and optical properties of wurtzite-type CdS nanocrystals

This paper reports wurtzite-type CdS nanostructures synthesized via a hydrothermal reaction route using dithiol glycol as the sulfur source. The reaction time was found to play an important role in the shape of the CdS nanocrystals: from dots to wires via an oriented attachment mechanism. This work has enabled us to generate nanostructures with controllable geometric shapes and structures and thus optical properties. The CdS nanostructures show a hexagonal wurtzite phase confirmed by X-ray diffraction and show no evidence for a mixed phase of cubic symmetry. The Raman peak position of the characteristic first-order longitudinal optical phonon mode does not change greatly, and the corresponding full width at half-maximum is found to decrease with the CdS shape, changing from nanoparticles to nanowires because of crystalline quality improvement. The photoluminescence measurements indicate tunable optical properties just through a change in the shape of the CdS nanocrystals; i.e., CdS nanoparticles show a band-edge emission at approximately 426 nm in wavelength, while the CdS nanowires show a band-edge emission at approximately 426 nm as well as a weaker trap-state green emission at approximately 530 nm in wavelength. These samples provide an opportunity for the study of the evolution of crystal growth and optical properties, with the shape of the nanocrystals varying from nearly spherical particles to wires.     

CdS aerogels: Effect of concentration and primary particle size on surface area and opto-electronic properties

Porous aerogels of CdS that exhibit quantum confined optical properties have been prepared by supercritical drying of wet CdS gels prepared by oxidative stripping of nanoparticle capping groups. The water-to-surfactant ratio (W) employed in the preparation of the nanoparticles is found to have a large impact on the surface areas of resultant aerogels, with W=5 samples producing mesoporous samples with the highest surface areas and cumulative pore volumes. In contrast, the concentration of the CdS sol employed in the gelation has only a small effect on the porosity characteristics, but a large impact on the apparent crystallite and chromophore sizes in as-prepared aerogels. Higher concentrations of the sol result in larger crystallite sizes and lower degrees of quantum confinement, as evidenced by a red shift in the absorbance spectra.     

Ordered alignment of CdS nanocrystals on MWCNTs without surface modification

This paper describes a facile hydrothermal procedure capable of aligning CdS nanocrystals on multiwalled carbon nanotubes (MWCNTs) without the use of organic bridging molecules such as cysteamine and carboxylates. The direct placement of CdS on MWCNTs allows good mixing and better interfacing between the two nanophases. The synthesis conditions can in principle be tuned to produce modulations in compositions, phases, and crystal orientations to the need of optoelectronic and photonic applications.     

Photophysical properties of spherical aggregations of CdS nanocrystals capped with a chromophoric surface agent

A novel sulfur-terminal Cd(II) complex, CdS(2)L (L = N-hexyl-3-{2-[4-(2,2':6',2'-terpyridin-4'-yl)phenyl]ethenyl}-carbazole), was successfully synthesized from CdS nanocrystals and the organic chromophores (L), which was confirmed by single-crystal X-ray diffraction analysis. Its photophysical properties have been investigated both experimentally and theoretically. The novel hybrid nanoparticles (CdS/L) were then obtained using the L as surface capped agent, which aggregate into large spheres, exhibiting novel luminescent properties, strong two photon absorption (TPA) and obvious prolonged fluorescence lifetime, which differ from those of the pure CdS nanocrystals and free L.     

GdPO4:Eu3+和GdBO3:Eu3+中"Gd-Eu"间的能量传递

利用同步辐射光源(德国HASYLAB实验室的SUPERLUMI实验站)对高温固相法制备的GdPO4 Eu3+和GdBO3Eu3+的发射谱与激发谱进行了研究, 并从量子剪裁的角度对"Gd3+-Eu3+"之间的能量传递作了讨论. 在两种样品监测Eu3+红光发射的激发谱上, 都显著观察到了对应Gd3+离子4f-4f跃迁的谱线, 说明从基质中Gd3+离子向掺杂的Eu3+离子之间存在非常有效的能量传递, 这有利于量子剪裁的发生. 在激发谱上还观察到了对应Eu3+-O2-电荷迁移态的宽激发带(180～270 nm), 而对应Gd3+离子8S7/2→6GJ跃迁的谱线(196 nm, 203 nm)叠加在这个宽带之上, 微弱可辨, 这不利于Gd3+-Eu3+间交叉弛豫的能量传递过程, 从而不利于量子剪裁的发生. 结合Eu3+-O2-电荷迁移态位置变化的规律, 提出了如何避开其干扰以增强量子剪裁效应的材料设计方案.     

Effect of thermal annealing on the kinetics of rehydroxylation of Eu3+:La2O3 nanocrystals

Europium-doped lanthanum oxide (5 mol % Eu(3+):La(2)O(3)) was prepared by calcining europium-doped lanthanum hydroxide (5 mol % Eu(3+):La(OH)(3)) previously synthesized by a simple hydrothermal method. Interestingly, we observed different emission Eu(3+) signatures depending on the phase of the host (lanthanum oxide or hydroxide) by cathodoluminescence. Taking into account that lanthanum oxide easily rehydroxylates in air, for the first time, we report the use of cathodoluminiscence as a novel characterization technique to follow the lanthanum oxide rehydroxylation reaction versus time according to different annealing procedures. Additionally, differential thermal-thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction techniques were used to identify the phases formed from the Eu(3+):La(OH)(3) depending on temperature and to study the evolution of La(2)O(3) to La(OH)(3) versus time. The results showed that the higher the temperature and the longer the annealing time, the higher the resistance to rehydroxylation of the Eu(3+):La(2)O(3) sample.     

CdS:Mn nanocrystals passivated by ZnS: synthesis and luminescent properties

Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO(4)) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed.     

Morphological control and luminescent properties of YVO4:Eu nanocrystals

Rodlike, olivelike, pineapplelike, and particlelike nanocrystals of theYVO4:Eu (5 at. % Eu) were synthesized by a hydrothermal reaction with different conditions, respectively. The rodlike nanocrystal has a rectangular cross-section with about 35 x 60 nm2 and a length of about 220 nm. The olivelike nanocrystal has an equatorial diameter of approximately 40 nm and a length of approximately 200 nm. The pineapplelike nanocrystal with an equatorial diameter of approximately 200 nm and a length of approximately 300 nm, is a superstructure consisting of self-organized nanorods with a diameter of approximately 20 nm and a length of approximately 50 nm. The particlelike nanocrystals show globular and polyhedral shape with a diameter of approximately 50 nm. Their UV-vis absorption peaks are at 305, 308, 285, and 280 nm, respectively, and there is such a trend that the absorption peaks shift to higher energy as the size of the particles decreases. Compared with other-shape nanocrystals, the luminescence intensity of the olivelike nanocrystals is obviously enhanced. It suggests that we could obtain the function-improved materials by tailoring the size and shape of theYVO4:Eu nanostructures.