Luminescence properties of Ce and Tb co-activated ZnAl2O4 phosphor

In this study, a solution combustion method was used to prepare green emitting Ce³⁺–Tb³⁺ co-activated ZnAl₂O₄ phosphor. The samples were annealed at 700 °C in air or hydrogen atmosphere to improve their crystallinity and optical properties. X-ray diffraction study confirmed that both as-prepared and post-preparation annealed samples crystallized in the well known cubic spinel structure of ZnAl₂O₄. An agglomeration of irregular platelet-like particles whose surfaces were encrusted with smaller spheroidal particles was confirmed by scanning electron microscopy (SEM). The fluorescence data collected from the annealed samples with different concentrations of Ce³⁺ and Tb³⁺ show the enhanced green emission at 543 nm associated with ⁵D₄→⁷F₅ transitions of Tb³⁺. The enhancement was attributed to energy transfer from Ce³⁺ to Tb³⁺. Possible mechanism of energy transfer via a down conversion process is discussed. Furthermore, cathodoluminescence (CL) intensity degradation of this phosphor was also investigated and the degradation data suggest that the material was chemically stable and the CL intensity was also stable after 10 h of irradiation by a beam of high energy electrons.     

Synthesis and optical properties of Er and Eu doped SrAl2O4 phosphor ceramic

We report, for the first time on luminescence from a Er³⁺ doped SrAl₂O₄ phosphor. Effects of Eu³⁺ doping were also studied. The influence of rare-earth doping in crystal structure and its optical properties were analysed by means of X-ray diffraction (XRD), Raman scattering, optical absorption, excitation and emission (PL) spectroscopy, thermally stimulated luminescence (TSL) and scanning electron microscope (SEM). Luminescence spectra and luminescence decay curves for Er³⁺ transitions in the near infrared region were recorded. The PL maximum for Eu doped SrAl₂O₄ is obtained at 620 nm and corresponds to the orange region of the spectrum. Diffraction patterns reveal a dominant phase, characteristic of the monoclinic SrAl₂O₄ compound and the presence of dopants has no effect on the basic crystal structure of SrAl₂O₄. The shapes of the glow curves are different for each dopant irradiated with either a ⁹⁰Sr-⁹⁰Y beta source, or UV light at 311 nm, and in detail the TL signals differ somewhat between Er and Eu dopants.     

Luminescence characterization and electron beam induced chemical changes on the surface of ZnAl2O4:Mn nanocrystalline phosphor

Luminescence characteristics and surface chemical changes of nanocrystalline Mn²⁺ doped ZnAl₂O₄ powder phosphors are presented. Stable green cathodoluminescence (CL) or photoluminescence (PL) with a maximum at ∼512 nm was observed when the powders were irradiated with a beam of high energy electrons or a monochromatic xenon lamp at room temperature. This green emission can be attributed to the ⁴T₁ → ⁶A₁ transitions of the Mn²⁺ ion. Deconvoluted CL spectra resulted in two additional emission peaks at 539 and 573 nm that may be attributed to vibronic sideband and Mn⁴⁺ emission, respectively. The luminescence decay of the Mn²⁺ 512 nm emission under 457 nm excitation is single exponential with a lifetime of 5.20 ± 0.11 ms. Chemical changes on the surface of the ZnAl₂O₄:Mn²⁺ phosphor during prolonged electron beam exposure were monitored using Auger electron spectroscopy. The X-ray photoelectron spectroscopy (XPS) was used to determine the chemical composition of the possible compounds formed on the surface as a result of the prolonged electron beam exposure. The XPS data suggest that the thermodynamically stable Al₂O₃ layer was formed on the surface and is possibly contributing to the CL stability of ZnAl₂O₄:Mn phosphor.     

Tuning magnetic properties of magnetoelectric BiFeO3-NiFe2O4 nanostructures

Multifunctional thin film nanostructures containing soft magnetic materials such as nickel ferrite are interesting for potential applications in microwave signal processing because of the possibility to shrink the size of device architecture and limit device power consumption. An essential prerequisite to future applications of such a system is a firm understanding of its magnetic properties. We show that nanostructures composed of ferrimagnetic NiFe₂O₄ pillars in a multiferroic BiFeO₃ matrix can be tuned magnetically by altering the aspect ratio of the pillars by depositing films of varying thickness. Magnetic anisotropy is studied using ferromagnetic resonance, which shows that the uniaxial magnetic anisotropy in the growth direction changes sign upon increasing the film thickness. The magnitude of this anisotropy contribution can be explained via a combination of shape and magnetostatic effects, using the object-oriented micromagnetic framework (OOMMF). The key factors determining the magnetic properties of the films are shown to be the aspect ratio of individual pillars and magnetostatic interactions between neighboring pillars.     

Magnetodielectric coupling in MnCr2O4 spinel

We have investigated the magnetic and dielectric properties of polycrystalline samples of the spinel MnCr₂O₄. Below the ferrimagnetic ordering temperature at T_N∼43 K, both magnetization and dielectric measurements show signatures of the onset of a conical structure at T_s∼17 K and a lock-in temperature at T_f∼14 K. These values are similar to those previously reported for single-crystal samples, where the spiral structure is short-range ordered (SRO) at low temperatures. The application of magnetic field suppresses the dielectric anomaly at T_f indicating that the coherence length of the ordering increases. MnCr₂O₄ exhibits a symmetrical magnetodielectric response between T_f and T_s that scales with the square of the magnetization. This suggests that the magnetodielectric coupling originates from the P²M² term in the free energy expansion. The magnetodielectric response becomes asymmetric with respect to field below T_f.     

Synthesis and magnetic characterization of Zn0.6Ni0.4Fe2O4 nanoparticles via a polyethylene glycol-assisted hydrothermal route

Zn-doped nickel ferrite nanoparticles (Zn_0.6Ni_0.4Fe₂O₄) have been prepared via a surfactant, polyethylene glycol assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), and vibrating scanning magnetometry (VSM) were used for the structural, morphological, and magnetic characterizations of the product, respectively. TEM analysis revealed that the nanoparticles have a narrow size distribution, with average particle size of 15±1 nm, which agrees well with the XRD based estimate of 14±2 nm. The absence of saturation and remanent magnetization, and coercivity in the high temperature region of the M-H curve and non-zero magnetic moments indicate superparamagnetism of the nanoparticles with a canted spin structure. The appearance of a peak on the temperature-dependent zero-field cooling magnetization curve at ∼190 K indicates the blocking temperature of the sample.     

Synthesis and characterization of CoxZn1−xFe2O4 magnetic nanoparticles via a PEG-assisted route

We present an investigation of properties of Co_xZn_1−xFe₂O₄ (x=0.0-1.0) nanoparticles synthesized by a polyethylene glycol (PEG)-assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and vibrating scanning magnetometry (VSM) were used to characterize the structural, morphological and magnetic properties. The particle size obtained from TEM and XRD are consistent with each other. It was observed that the lattice constant for each composition decreases with increasing Co substitution and follows Vegard's law. Magnetization measurements show that while the materials with high Zn substitution are superparamagnetic at room temperature, they are ferromagnetic at temperatures lower than the blocking temperature. The materials with less Zn substitution are ferromagnetic below room temperature. Magnetizations and the coercivities of the samples decrease with the Zn substitution. The resultant overall magnetic behavior of the superparamagnetic samples are found to be considerably different than that of conventional superparamagnetic systems due to the antiferromagnetic interactions both in intra- and inter-cluster spins, and size (effective moment) distribution of the particles.     

Characterization, EPR and luminescence studies of ZnAl2O4:Mn phosphors

ZnAl₂O₄:Mn green light emitting powder phosphors have been prepared by urea combustion technique involving furnace temperatures about 500 °C in a short time (<5 min). The prepared powders were characterized by X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectrometry and the surface area measurements by a Brunauer-Emmet-Teller (BET) adsorption isotherms. The EPR spectrum exhibits a resonance signal at g≈2.0, which shows a six-line hyperfine structure (hfs). From the EPR spectra the spin-Hamiltonian parameters have been evaluated at room temperature as well as at 110 K. EPR and photoluminescence (PL) studies revealed that manganese ions were present in divalent state and the site symmetry around Mn²⁺ ions is distorted tetrahedral. The spin concentration (N), the paramagnetic susceptibility (χ) and the zero-field splitting parameter (D) have been evaluated and discussed. The green emission at 511 nm in ZnAl₂O₄:Mn phosphor is assigned to a transition from the upper ⁴T₁→⁶A₁ ground state of Mn²⁺ ions.     

Resonance paramagnetique electronique du manganese divalent dans ZnAl2O4

The electron paramagnetic resonance spectrum of a single crystal of ZnAl₂O₄ (spinel structure) doped with manganese displays a fine structure characteristic of a purely cubic crystal field. Contrary to MgAl₂O₄: Mn²⁺, where the degree of inversion is sizable, ZnAl₂O₄ therefore is a normal spinel.     

Magnetic properties of Co2.4Al0.6O4/SiO2 nanocomposite obtained via sol-gel method

Nanocomposite made of 10 wt% of Co_2.4Al_0.6O₄ particles dispersed in an amorphous SiO₂ matrix has been synthesized by a sol-gel method. X-ray diffraction, transmission electron microscopy and magnetic measurements have been used to characterize the properties of nanocomposite. Most of the particles are well crystallized and have an average diameter below 100 nm. Smaller particles with size below 10 nm have also been observed. A large value of the effective magnetic moment per Co²⁺ ion of 5.08 μ_B and negative and the low Curie-Weiss paramagnetic temperature Θ∼−6 K, obtained from the high-temperature susceptibility data, indicate a possible mixing of Co²⁺ and Co³⁺ ions between tetrahedral and octahedral sites of the spinel crystal lattice. The measurements of static and dynamic magnetic susceptibilities have shown that Co_2.4Al_0.6O₄ particles in SiO₂ matrix display a spin glass behavior at low temperatures.     

Effect of temperature on the luminescence processes of SrAl2O4:Eu

The UV excited and persistent luminescence properties as well as thermoluminescence (TL) of Eu²⁺ doped strontium aluminates, SrAl₂O₄:Eu²⁺ were studied at different temperatures. Two luminescence bands peaking at 445 and 520 nm were observed at 20 K but only the latter at 295 K. Both Sr-sites in the lattice are thus occupied by Eu²⁺ but at room temperature efficient energy transfer occurs between the two sites. The UV excited and persistent luminescence spectra were similar at 295 K but the excitation spectra were different. Thus the luminescent centre is the same in both phenomena but excitation processes are different. Two TL peaks were observed between 50 and 250 °C in the glow curve. Multiple traps were, however, observed by preheating and initial rise methods. With longer delay times only the high temperature TL peak was observed. The persistent luminescence is mainly due to slow fading of the low temperature TL peak but the step-wise feeding process from high temperature traps is also probable.     

ZnO nanostructured thin films grown by pulsed laser deposition in mixed O2 / Ar background gas

We report on the properties of ZnO nanostructured thin films grown on either bare or gold patterned a-plane sapphire substrates. The pulsed laser deposition technique was used to deposit all the films at a temperature of 700 C in a mixture of oxygen and argon under a total pressure of 35 Pa. SEM surface characterizations typically showed pyramidal nanostructures with hexagonal symmetry and a coverage density strongly dependent on the O₂ partial pressure. For the patterned samples, wall-like structures of nanoneedles were observed. For all samples, x-ray diffraction results confirmed the high crystalline quality of the nanostructures, with the rocking curve widths of the (0002) reflection as low as 0.09. Similarly, photoluminescence results at room temperature testified to the high optical quality of the material.     

Hydrothermal preparation and photoluminescent properties of MgAl2O4: Eu spinel nanocrystals

Nanoplates of the MgAl₂O₄ spinel doped with Eu³⁺ ions were prepared by a microwave assisted hydrothermal method. Structural properties of the precursor calcined at 700 and 1000 ^oC powders were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to the obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The average spinel particle size was determined to be 11 nm after calcination at 700 °C and it increased up to 14 nm after calcination at 1000 °C. The photoluminescent properties of prepared powders with different Eu³⁺ ion concentrations (0-5% mol) were investigated using excitation and emission spectroscopy at room and low temperatures (77 K).     

Co3O4-ZnO hierarchical nanostructures by electrospinning and hydrothermal methods

A new hierarchical nanostructure that consists of cobalt oxide (Co₃O₄) and zinc oxide (ZnO) was produced by the electrospinning process followed by a hydrothermal technique. First, electrospinning of a colloidal solution that consisted of zinc nanoparticles, cobalt acetate tetrahydrate and poly(vinyl alcohol) was performed to produce polymeric nanofibers embedding solid nanoparticles. Calcination of the obtained electrospun nanofiber mats in air at 600 °C for 1 h, produced Co₃O₄ nanofibers with rough surfaces containing ZnO nanoparticles (i.e., ZnO-doped Co₃O₄ nanofibers). The rough surfaced nanofibers, containing ZnO nanoparticles (ZnNPs), were then exploited as seeds to produce ZnO nanobranches using a specific hydrothermal technique. Scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to characterize the as-spun nanofibers and the calcined product. X-ray powder diffractometery (XRD) analysis was used to study the chemical composition and the crystallographic structure.     

Dynamic magnetic behavior of cluster-glass ZnFe2O4 nanosystem

We present an investigation on the dynamic magnetic behavior of nanosized zinc ferrites with different grain sizes (6–13 nm) and degree of inversion (0.2–0.4). We show that the observed behavior can be interpreted through the progressive blocking and freezing of interacting magnetic clusters formed due to the random non-equilibrium distribution of cations. Furthermore, the glassy character is more pronounced as the ferrite is more inverted, and this coincides with the grain/particle size increment.     

Large reversible magnetocaloric effect in spinel MnV2O4 with minimal Al substitution

Magnetocaloric effect of MnV_1.95Al_0.05O₄ was studied by the magnetization and heat capacity measurements. MnV_1.95Al_0.05O₄ is a cubic spinel structure with ferromagnetism of second order in nature and performs reversible magnetic entropy around the magnetic transition temperature. The large magnetic entropy changes −ΔS_M∼5.2 and 8.2 J/kg K and the adiabatic temperature changes ΔT_ad∼1.5 and 2.6 K are revealed for the magnetic field changes of 2 and 4 T near the Curie temperature (T_C) of 59.6 K, respectively. The relative cooling power (RCP) are about 82.2 and 177.2 J/kg K for magnetic field changes 2 and 4 T, respectively. Compared with the parent compound, although the −ΔS_M and ΔT_ad become smaller, the refrigeration working temperature span and the RCP have been improved.     

First-principles calculations of electronic, optical and elastic properties of ZnAl2S4 and ZnGa2O4

The optimized crystal structures, band structures, partial and total densities of states (DOS), dielectric functions, refractive indexes and elastic constants for ZnAl₂S₄ and ZnGa₂O₄ were calculated using the CASTEP module of Materials Studio package. Pressure effects were modeled by performing these calculations for different values of external hydrostatic pressure up to 50 GPa. Obtained dependencies of the unit cell volume on pressure were fitted by the Murnaghan equation of state, and the relative changes of different chemical bond lengths were approximated by quadratic functions of pressure. Variations of applied pressure were shown to produce considerable re-distribution of the electron densities around ions in both crystals, which is evidenced in different trends for the effective Mulliken charges of the constituting ions and changes of contour plots of the charge densities. The longitudinal and transverse sound velocities and Debye temperatures for both compounds were also estimated using the calculated elastic constants.     

TSL, OSL and ESR studies in ZnAl2O4:Tb phosphor

ZnAl₂O₄:Tb phosphor was prepared by combustion synthesis. ZnAl₂O₄:Tb exhibits three thermally stimulated luminescence (TSL) peaks around 150, 275 and 350 °C. ZnAl₂O₄:Tb exhibits optically stimulated luminescence (OSL) when stimulated with 470 nm light.Electron spin resonance (ESR) studies were carried out to identify defect centres responsible for TSL peaks observed in ZnAl₂O₄:Tb. Two defect centres are identified in irradiated ZnAl₂O₄:Tb phosphor and these centres are assigned to V and F⁺ centres. V centre appears to correlate with the 150 °C TSL peak, while F⁺ centre could not be associated with the observed TSL peaks.     

Novel approach to preparation of LiMn2O4 core/LiNixMn2−xO4 shell composite

Combining two methods, coating and doping, to modify spinel LiMn₂O₄, is a novel approach we used to synthesize active material. First we coated the LiMn₂O₄ particles with the nickel oxide particles by means of homogenous precipitation, and then the nickel oxide-coated LiMn₂O₄ was calcined at 750 °C to form a LiNi_xMn_2−xO₄ shell on the surface of spinel LiMn₂O₄ particles. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cyclic voltammetry (CV) and charge-discharge test were performed to characterize the spinel LiMn₂O₄ before and after modification. The experimental results indicated that a spinel LiMn₂O₄ core is surrounded by a LiNi_xMn_2−xO₄ shell. The resulting composite showed excellent electrochemical cycling performance with an average fading rate of 0.014% per cycle. This improved cycle stability is greatly attributed to the suppression of Jahn-Teller distortion on the surface of spinel LiMn₂O₄ particles during cycling.     

The effect of cation distribution on magnetization of ZnFe2O4 nanoparticles

In this work zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by sol-gel method in two different media, one acidic and another one basic and then annealed at different temperatures from 350 to 800 °C. XRD investigations show that both samples have a single phase spinel structure. Mean crystallite sizes of the samples were calculated, using Scherrer’s formula, which are 13 and 16 nm for the samples prepared in acidic and basic media, respectively. The variation of cation distribution in the samples was estimated by the ratio of (2 2 0) and (2 2 2) intensity diffraction peaks and the results show that as-prepared nanoparticles have different ionic distributions in comparison with that of bulk zinc ferrite. Also the results show that by increasing annealing temperature the ionic distribution of the zinc ferrite nanoparticles tends to that of bulk sample. The magnetic properties of the samples were studied by VSM and the results show that zinc ferrite nanoparticles have a ferrimagnetic behavior. Also the morphology of the powders was examined by TEM.