Fluorescence and Judd-Ofelt analysis of Nd ions in oxyfluoride glass ceramics containing CaF2 nanocrystals

Judd-Ofelt analyses of Nd³⁺ ions in the oxyfluoride glasses and glass ceramics containing CaF₂ nanocrystals are performed to evaluate the intensity parameters Ω_2,4,6, spontaneous emission probability, radiative lifetime, quantum efficiency, as well as stimulated emission cross-section. The influences of Nd³⁺-doping level and heating temperature on these parameters for the ⁴F_3/2→⁴I_J (J=9/2, 11/2, and 13/2) transitions are systematically discussed. The decrease of intensity parameter Ω₂ evidences the incorporation of Nd³⁺ ions into CaF₂ nanocrystals after crystallization. With increasing of Nd³⁺-doping level, the measured lifetime and quantum efficiency gradually decrease, while the stimulated emission cross-section keeps almost unchanged. For 1.0 mol% Nd³⁺-doped sample, both the emission intensity and the measured lifetime enhance with increasing of heating temperature up to 650 °C. The results indicate that the investigated glass ceramics are potentially applicable as the 1.06 um laser host.     

Synthesis and VUV spectral properties of nanoscaled Zn2SiO4:Mn green phosphor

Nanoscaled Zn₂SiO₄:Mn²⁺ green phosphor with regular and uniform morphology was synthesized by hydrothermal method at a low temperature of 140 °C. The structure and morphology of the phosphor was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of the hydrothermal temperature and the time on the crystallite structure and the vacuum ultraviolet (VUV) photoluminescence (PL) properties were evaluated. The as-synthesized nanoscaled Zn₂SiO₄:Mn²⁺ phosphor exhibited intensive broad emission around 523 nm, which was attributed to the ⁴T₁→⁶A₁ transition of Mn²⁺. The PL intensity increased along with the increasing hydrothermal temperature and time. The heat-treated phosphors exhibited higher PL intensity than the corresponding samples prepared using the conventional solid-state reaction.     

EPR and photoluminescence properties of Mn-activated zinc gallate phosphor prepared by urea combustion route and post heat treatment

Mn²⁺ activated ZnGa₂O₄ powder phosphors have been prepared by urea combustion route. Powder X-ray diffraction and scanning electron microscopy (SEM) techniques have been used to characterize the as-prepared and post-treated (900 °C, 3 h) phosphors. The morphology shows small particles, voids and pores, with non-uniform shapes and sizes. The EPR spectrum exhibits an intense resonance signal at g≈1.985 with a sextet hyperfine structure (hfs) besides a weak broad signal at g≈4.05 and a hump near g≈2.27. The g≈1.985 resonance is due to Mn²⁺ ions in an environment close to tetrahedral symmetry. The resonances at g≈4.05 and 2.27 are attributed to the rhombic surroundings of the Mn²⁺ ions. The spin concentration (N) and the paramagnetic susceptibility (χ) are evaluated and discussed. It is observed that the intensity of the resonance signal at g≈1.985 increases with decrease in temperature obeying the Boltzmann law. Upon post treatment the intensity of the green emission (λ_em=528 nm,⁴T₁→⁶A₁ transition of Mn²⁺ ions) has been increased to 3.35 times and a red shift has been observed.     

EPR and photoluminescence properties of green light emitting LaAl11O18:Mn phosphors

The LaAl₁₁O₁₈:Mn²⁺ powder phosphor has been prepared using a self-propagating synthesis. Formation and homogeneity of the LaAl₁₁O₁₈:Mn²⁺ phosphor has been verified by X-ray diffraction and energy dispersive X-ray analysis respectively. The EPR spectra of Mn²⁺ ions exhibit resonance signals with effective g values at g≈4.8 and g≈1.978. The signal at g≈1.978 exhibits six-line hyperfine structure and is due to Mn²⁺ ions in an environment close to tetrahedral symmetry, whereas the resonance at g≈4.8 is attributed to the rhombic surroundings of the Mn²⁺ ions. It is observed that the number of spins participating in resonance for g≈1.978 increases with decreasing temperature obeying the Boltzmann law. Upon 451 nm excitation, the photoluminescence spectrum exhibits a green emission peak at 514 nm due to ⁴T₁ (G)→⁶A₁ (S) transition of Mn²⁺ ions. The crystal field parameter Dq and Racah inter-electronic repulsion parameters B and C have been evaluated from the excitation spectrum.     

Some studies about the green and red light emitting structures in NaCl1−xBrx:Mn

In this work we present the results obtained from the luminescence spectra and X-ray diffraction as well as transmission electron microscopy, at room temperature on crystals of NaCl_1−xNaBr_x:MnCl₂:0.3% (x=0.00, 0.05, 0.25, and 0.50). The results suggest the existence of structures between the crystal planes (1 1 1) and (2 0 0), which may be associated with different types of Mn²⁺ arrangements, such as dipole complexes, octahedral and rhombohedral structures as well as other possible nanostructures that include mixtures of bromine/chlorine ions. These are responsible for the emission spectra of “as grown” crystals consisting of maxima around 500 nm and 600 nm. The green emission has been usually attributed to rhombohedral/tetrahedral symmetry sites; the present results point out that this is due to Mn–Cl/Br nanostructures with rhombohedral structure. On the other hand when the crystals are thermally quenched from 500 °C to room temperature the structures previously detected present changes. Only a red band appears around 620 nm if the samples are later annealed at 80 °C.     

Synthesis, characterization and optical properties of water-soluble ZnS:Mn nanoparticles

ZnS nanoparticles with Mn²⁺ doping (0.5-20%) have been prepared through a simple chemical method, namely the chemical precipitation method. The structure of the nanoparticles has been analyzed using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV-vis spectrometer. The size of the particles is found to be 3-5 nm range. Photoluminescence spectra were recorded for undoped ZnS nanoparticles using an excitation wavelength of 320 nm, exhibiting an emission peak centered at around 445 nm. However, from the Mn²⁺-doped samples, a yellow-orange emission from the Mn²⁺⁴T₁-⁶A₁ transition is observed along with the blue emission. The prepared Mn²⁺-doped sample shows efficient emission of yellow-orange light with the peak emission 580 nm with the blue emission suppressed. The maximum PL intensity is observed only at the excitation energy of 3.88 eV (320 nm). Increase in stabilizing time up to 48 h in de-ionized water yields the enhancement of emission intensity of doped (4% Mn²⁺) ZnS. The correlation made through the concentration of Mn²⁺ versus PL intensity resulted in opposite trend (mirror image) of blue and yellow emissions.     

Observation of green emission from Ce-doped gadolinium oxide nanoparticles

Green emission at around 500 nm is observed in Gd₂O₃:Ce³⁺ nanoparticles and the intensity is highly dependent on the concentration of Ce³⁺ in the nanoparticles. The luminescence of this emission displays both picosecond (ps) and millisecond (ms) lifetimes. The ms lifetime is over four orders of magnitude longer than typical luminescence lifetimes (10-40 ns) of Ce³⁺ in traditional Ce³⁺ doped phosphors and therefore likely originates from defect states. The picosecond lifetime is shorter than the typical Ce³⁺ value and is also likely due to defect or surface states. When the samples are annealed at 700 °C, this emission disappears possibly due to changes in the defect moieties or concentration. In addition, a blue emission at around 430 nm is observed in freshly prepared Gd₂O₃ undoped nanoparticles, which is attributed to the stabilizer, polyethylene glycol biscarboxymethyl ether. On aging, the undoped particles show similar emission to the doped particles with similar luminescence lifetimes. When Eu³⁺ ions are co-doped in Gd₂O₃:Ce nanoparticles, both the green emission and the emission at 612 nm from Eu³⁺ are observed.     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Study of magnetotransport in double-layered La1.4Ca1.6Mn2O7 manganite: Presence of nano-ferromagnetic domains in paramagnetic matrix

Double-layered manganite La_1.4Ca_1.6Mn₂O₇ has been synthesized using the solid-state reaction method. It had a metal-to-insulator transition at temperature T_M1≈127 K. The temperature dependence of ac susceptibility showed a broad ferromagnetic transition. The two-dimensional (2D)-ferromagnetic ordering temperature (T_C2) was observed as ≈245 K. The temperature dependence of its low-field magnetoresistance has been studied. The low-field magnetoresistance of double-layered manganite, in the temperature regions between T_M1 and T_C2, has been found to follow 1/T⁵. The observed behaviour of temperature dependence of resistivity and low-field magnetoresistance has been explained in terms of two-phase model where ferromagnetic domains exist in the matrix of paramagnetic regions in which spin-dependent tunneling of charge carriers occurs between the ferromagnetic correlated regions. Based on the two-phase model, the dimension of these ferromagnetic domains inside the paramagnetic matrix has been estimated as ∼12 Å.     

Characterization and luminescent properties of SiO2:ZnS:Mn and ZnS:Mn nanophosphors synthesized by a sol-gel method

ZnS and SiO₂-ZnS nanophosphors, with or without different concentration of Mn²⁺ activator ions, were synthesized by using a sol-gel method. Dried gels were annealed at 600 °C for 2 h. Structure, morphology and particle sizes of the samples were determined by using X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM) and field emission scanning electron microscopy (FESEM). The diffraction peaks associated with the zincblende and the wurtzite structures of ZnS were detected from as prepared ZnS powders and additional diffraction peaks associated with ZnO were detected from the annealed powders. The particle sizes of the ZnS powders were shown to increase from 3 to 50 nm when the powders were annealed at 600 °C. An UV-Vis spectrophotometer and a 325 nm He-Cd laser were used to investigate luminescent properties of the samples in air at room temperature. The bandgap of ZnS nanoparticles estimated from the UV-Vis data was 4.1 eV. Enhanced orange photoluminescence (PL) associated with ⁴T₁→⁶A₁ transitions of Mn²⁺ was observed from as prepared ZnS:Mn²⁺and SiO₂-ZnS:Mn²⁺ powders at 600 nm when the concentration of Mn²⁺ was varied from 2-20 mol%. This emission was suppressed when the powders were annealed at 600 °C resulting in two emission peaks at 450 and 560 nm, which can be ascribed to defects emission in SiO₂ and ZnO respectively. The mechanism of light emission from Mn²⁺, the effect of varying the concentration on the PL intensity, and the effect of annealing are discussed.     

Blue and red long lasting phosphorescence (LLP) in β-Zn3(PO4)2:Mn,Zr

Multi-color long lasting phosphorescent (LLP) phenomenon in β-Zn₃(PO₄)₂:Mn²⁺,Zr⁴⁺ was systematically investigated. It is found that the red (λ_Em=616 nm) LLP performance of Mn²⁺ such as brightness and duration is largely improved, and that the blue (λ_Em=475 nm) LLP of Zr⁴⁺ with lower intensity appears when Zr⁴⁺ ions are co-doped into the matrix. The fluorescence, phosphorescence and thermoluminescence (TL) spectra show that Mn²⁺ ion is solely expected as a luminescent center, while Zr⁴⁺ ion not only acts as a luminescent center, but also induces an electron trap (Trap_Zr) associated with a TL peak at 344 K. The trap depth for Trap_Zr is 0.25 eV, while that for the intrinsic trap is 0.38 eV, associated with a dominant peak at 385 K for Zn₃(PO₄)₂:Mn²⁺. The Zr⁴⁺-induced trap with suitable depth is responsible for the improvement of the red LLP of Mn²⁺ ion and the appearance of the blue LLP of Zr⁴⁺ ion. The LLP mechanism is also investigated.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Sol-gel synthesis and photoluminescence of CaSiO3:Eu nanophosphors using novel silicate sources

In this paper, seven kinds of silane coupling reagents were employed as silicate sources to prepare CaSiO₃:Eu³⁺ phosphors by the sol-gel method. The different silicate precursors were used to adjust the microstructure and size of the resulting phosphors. The crystallite size of phosphors is in the range of 30-35 nm and some of them show regular microstructure after high-temperature thermolysis. The photoluminescence properties show that all of them exhibit the characteristic fluorescence ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) of the Eu³⁺ ion and the strongest one is the red emission at 610 nm. Furthermore, the emission quantum efficiency (η) of the ⁵D₀ Eu³⁺ excited state has been calculated to be around 33% from the emission spectrum and the lifetime of the Eu³⁺ first excited level (τ, ⁵D₀).     

Synthesis and luminous characteristics of Ba2MgSi2−xAlxO7: 0.1Eu, 0.1Mn phosphor for WLED

The shift of the emission band to longer wavelength (yellow-orange) of the Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺ phosphor under the 350-450 nm excitation range has been achieved by adding the codoping element (Mn²⁺) in the host. The single-host silicate phosphor for WLED, Ba₂MgSi_2−xAl_xO₇: 0.1Eu²⁺, 0.1Mn²⁺ was prepared by high-temperature solid-state reaction. It was found experimentally that, its three-color emission peaks are situated at 623, 501 and 438 nm, respectively, under excitation of 350-450 nm irradiation. The emission peaks at 438 and 501 nm originate from the transition 5d to 4f of Eu²⁺ ions that occupy the two Ba²⁺ sites in the crystal of Ba₂MgSi_2−x Al_xO₇, while the 623 nm emission is attributed to the energy transfer from Eu²⁺ ions to Mn²⁺ ions. The white light can be obtained by mixing the three emission colors of blue (438 nm), green (501 nm) and red (623 nm) in the single host. When the concentrations of the Al³⁺, Eu²⁺ and Mn²⁺ ions were 0.4, 0.1 and 0.1 mol, respectively, the sample presented intense white emission. The addition of Al ion to the host leads to a substantial change of intensity ratio between blue and green emissions. White light could be obtained by combining this phosphor with 405 nm light-emitting diodes. The near-ultraviolet GaN-based Ba₂MgSi_1.7 Al_0.3O₇: 0.1Eu²⁺, 0.1Mn²⁺ LED achieves good color rendering of over 85.     

On the spectra luminescence properties of charoite silicate

Charoite is a hydrous alkali calcium silicate mineral [K₄NaCa₇Ba_0.75Mn_0.2Fe_0.05(Si₆O₁₅)₂(Si₂O₇)Si₄O₉(OH)·3(H₂O)] exhibiting an intense lilac colour related to Mn²⁺ and Fe³⁺ colour centres. These ions also contribute to a strong luminescence at ∼585 and 705 nm. This work studies the thermal dependence of these luminescent centres by (i) thermoluminescence (TL) of pre-heated and pre-irradiated charoite aliquots, (ii) by time-resolved cathodoluminescence (TRS-CL) at room and cryogenic temperatures (RT and CT), (iii) by spatially resolved spectra CL under scanning electron microscopy (SRS-CL-SEM) and (iv) by ion beam spectra luminescence (IBL) with H⁺, H₂⁺ and ⁴He⁺ ions at RT and LT. The main peak, ∼585 nm, is linked to a transition ⁴T_1,2 (G)→⁶A₇(S) in Mn²⁺ ions in distorted six-fold coordination and the emission at ∼705 nm with Fe²⁺→Fe³⁺ oxidation in Si⁴⁺ lattice sites. Less intense UV-blue emissions at 340 and 390 nm show multi-order kinetic TL glow curves involving continuous processes of electron trapping and de-trapping along with an irreversible phase transition of charoite by de-hydroxylation and lattice shortening of Δa=0.219 Å, Δb=0.182 Å; Δc=0.739 Å. The Si-O stressed lattice of charoite has non-bridging oxygen or silicon vacancy-hole centres, and Si-O bonding defects which seem to be responsible for the 340 nm emission. Extrinsic defects such as the alkali (or hydrogen)—compensated [AlO₄/M⁺] centres could be linked with the 390 nm emission. Large variations in 585 and 705 nm intensities are strongly temperature dependent, modifying local Fe-O and Mn-O bond distances, short-range-order luminescence centres being very resistant under the action of the heavy ion beam of ⁴He⁺. The SRS-CL demonstrates strong spatial heterogeneity in the luminescence of the charoite.     

Luminescence and EPR studies of Mn-activated SrAl12O19 phosphor prepared by facile combustion approach

Manganese-activated strontium hexa-aluminate (SrAl₁₂O₁₉) phosphor has been prepared at low temperature (500 °C) and in a very short time (<5 min) by urea combustion route. Powder X-ray diffraction pattern showed the presence of hexagonal SrAl₁₂O₁₉ phase. Scanning electron microscopy (SEM) indicated the presence of several particles with sizes of 200 nm. The luminescence of Mn²⁺ activated SrAl₁₂O₁₉ exhibits a strong green emission peak around 515 nm from the synthesized phosphor particles under excitation (451 nm). The luminescence is assigned to a transition from the upper ⁴T₁→⁶A₁ ground state of Mn²⁺ ions. EPR investigations also indicated the presence of Mn²⁺ ions in the prepared material. From the observed EPR spectrum, the spin-Hamiltonian parameters have been evaluated. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between Mn²⁺ ions and the surrounding ligands. The variation of zero-field splitting parameter (D) with temperature is measured and discussed. The mechanism involved in the generation of a green emission has been explained in detail.     

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.     

Energy transfer among three luminescent centers in full-color emitting ZnGa2O4:Mn, Cr phosphors

The ZnGa₂O₄:Mn²⁺, Cr³⁺ phosphors show three colors; the blue band of 380 nm from the charge transfer between Ga-O, the green band of 505 nm from Mn²⁺ and the red band of 705 nm from Cr³⁺. As a variation of Mn²⁺ or Cr³⁺ concentrations in ZnGa₂O₄:Mn²⁺, Cr³⁺, the relative emission intensity can be tuned. This phenomenon is explained in terms of the energy transfer based on four factors: the spectral overlap between the energy donors (Ga-O) and the energy accepters of Mn²⁺ or Cr³⁺, the absorption cross section of the energy accepters, the distance between them, and the decay time of the energy donors. ZnGa₂O₄:0.0025Mn²⁺, 0.010Cr³⁺ shows the CIE coordinates of x=0.4014, y=0.3368, which is a pure white light. The single-phased full-color emitting ZnGa₂O₄:Mn²⁺, Cr³⁺ phosphors can be applied to illumination devices.     

Thermomagnetic transitions and coercivity mechanism in bulk composite Nd60Fe30Al10 alloys

The thermomagnetic behaviour (within the temperature range 553-300 K) for the bulk composite Nd₆₀Fe₃₀Al₁₀ alloy is described in terms of a transition from paramagnetic to superferromagnetic state at T=553 K, followed by a ferromagnetic ordering for T<473 K. For the superferromagnetic regime, the alloy thermomagnetic response was associated to a homogeneous distribution of magnetic clusters with mean magnetic moment and size of 1072 μ_B and 2.5 nm, respectively. For T<473 K, a pinning model of domain walls described properly the alloy coercivity dependence with temperature, from which the domain wall width and the magnetic anisotropy constant were estimated as being of ≈8 nm and ≈10⁵ J/m³, typical values of hard magnetic phases. Results are supported by microstructural and magnetic domain observations.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.