Fluorescence emission spectrum and energy transfer in Eu and Mn co-doped Ba2Ca(BO3)2 phosphors

Eu²⁺ and Mn²⁺ co-doped Ba₂Ca(BO₃)₂ phosphors yield two emission bands consisting of green and red components under the excitation of 360 nm, which shows a great potential for white LEDs. Effective energy transfer occurs in Eu²⁺/Mn²⁺ co-doped Ba₂Ca(BO₃)₂ host due to the large spectral overlap between the emission of Eu²⁺ and the excitation of Mn²⁺. The energy transfer from Eu²⁺ to Mn²⁺ is thoroughly investigated by their excitation, emission and photoluminescence decay behaviors, and is demonstrated to be via the dipole–quadrupole interaction.     

Localized magnon gap modes in the 2-d Ising antiferromagnets K2CoF4 and Rb2CoF4

The defect (Mn²⁺,Ni²⁺,Fe²⁺) induced magnon gap modes in the layered antiferromagnets K₂CoF₄ and Rb₂CoF₄ were investigated with the methods of FIR absorption-and IR emission spectroscopy. The anisotropic exchange-parameters describing the strongly localized Mn²⁺ spin excitations far below the host lattice magnon band and the Ni²⁺ excitations in the vacinity of this band are presented. In the diluted system K₂Co_1-cMn_cF₄ localized Mn²⁺ cluster modes up to about C≈0.1 were observed. The excitation energy of these modes can only be explained by assuming an anisotropic Mn²⁺-Mn²⁺ exchange which is in contrast to the pure isomorphous system K₂MnF₄. In the spin mismatch system K₂CoF₄: Fe the magnetic moments of the isolated Fe²⁺ impurities are pulled from the plane perpendicular to the c-axis and aligned parallel to the easy axis of the magnetic crystal.     

Band gap and electronic structure of MgSiN2 determined using soft X‐ray spectroscopy and density functional theory

We present a study of MgSiN₂ using soft X‐ray absorption and emission spectroscopy which directly probe the partial density of states. MgSiN₂ is new as a host lattice for luminescence materials and used in phosphor‐converted light‐emitting diodes. We compare our measurements to our full potential, all electron density funtional theory calculations. We find excellent agreement between experiment and theory and the band gap of MgSiN₂ is measured to be 5.6 ± 0.2 eV in agreement with our calculated value of 5.72 eV. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Photoluminescence properties of color-tunable SrMgAl10O17:Eu2+,Mn2+ phosphors for UV LEDs

Aluminate phosphors SrMgAl₁₀O₁₇ codoped with Eu²⁺ and Mn²⁺ ions were prepared by solid-state reaction. The phase structure and photoluminescence properties of the as-prepared phosphors were characterized by powder X-ray diffraction, photoluminescence excitation and emission spectra. Upon excitation of UV light, two broad emission bands centered at 470 and 515 nm were observed, and they were assigned to Eu²⁺ and Mn²⁺ emissions, respectively. The emission color of the phosphors can be tuned from blue to cyan and finally to green by adjusting the concentration ratios of Eu²⁺ and Mn²⁺. Effective energy transfer occurs from Eu²⁺ to Mn²⁺ in the host due to the spectral overlap between the emission band of Eu²⁺ and the excitation bands of Mn²⁺. The energy transfer mechanism was demonstrated to be electric dipole–quadrupole interaction. The energy transfer efficiency and critical distance were also calculated. The phosphors exhibit strong absorption in near UV spectral region and therefore they are potentially useful as UV-convertible phosphors for white LEDs.     

Luminescent properties of SrMg<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript> as a potential phosphor for ultraviolet light-emitting diodes

Eu²⁺ and Mn²⁺ co-doped SrMg₂(PO₄)₂ phosphors with blue and red two emission bands were prepared by the high temperature solid state method and their luminescent properties have been investigated as a function of activator and co-activator concentrations. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the Eu²⁺ emission spectrum and the excitation spectrum of Mn²⁺. Efficiencies of energy transfer were also calculated according to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission. According to the principle of energy transfer, we demonstrated that the phosphor SrMg₂(PO₄)₂:Eu²⁺,Mn²⁺ with double emission bands exhibited a great potential as a phosphor for ultraviolet light-emitting diodes and the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺. PACS 78.55.-m     

Nanomechanical properties inside the scratch grooves of soda–lime–silica glass

Zn_2?2x Mn_2x GeO₄ (x=0, 0.001, 0.01) phosphors were prepared by conventional solid state reaction technique. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflection spectra, photoluminescence (PL), and cathodoluminescence (CL) spectroscopy were utilized to characterize the synthesized phosphors. The Mn²⁺-activated Zn₂GeO₄ phosphors exhibit narrow emission band at 532 nm under the excitation of ultraviolet light, which due to the ⁴T₁(⁴G)–⁶A₁(⁶S) transition of Mn²⁺ ions. Also it is observed that there exists energy transfer between the Zn₂GeO₄ host lattice and the activator (Mn²⁺). Under excitation of low-voltage electron beams, Zn₂GeO₄:Mn²⁺ shows strong green emission band dominating at 535 nm, corresponding to the ⁴T₁(⁴G)–⁶A₁(⁶S) emission of Mn²⁺ ions. The emission intensity and chromaticity coordinates of Zn₂GeO₄:Mn²⁺ as a function of accelerating voltage and the filament current were also investigated.     

The magnetostriction contribution of manganese ions in spinel ferrites

The assumption that the magnetostriction contribution from manganese ions in spinel ferrites arises from Mn³⁺ ions has been tested by an ab initio calculation of the theoretical values of the coefficients λ₁₀₀ and λ₁₁₁. The Mn³⁺ contribution on octahedral sites is found to be negligible while the possible contribution from Mn³⁺ ions on tetrahedral sites cannot be fitted to the experimental results. It is possible that the contribution from a small concentration of Mn⁴⁺ ions on tetrahedral sites could give a magnetostriction contribution which fitted both λ₁₀₀ and λ₁₁₁.     

Optical spectroscopy of Mn2+ ions in CaCl2 single crystals

Abstract

In the present investigation the excitation and fluorescence spectra and lifetimes of Mn²⁺ ions in calcium chloride, for various manganese concentrations and sample temperatures have been studied for the first time. The fluorescence spectrum consists of an asymmetric broad band, which upon lowering the sample temperature, shifts its maximum from 580 nm at 300 K to 596 nm at 11 K. This luminescence band was associated with the ⁴T_lg(⁴G)→⁶A_lg(⁶S) spin-forbidden transition in the manganese ions occupying Ca-sites in the lattice of CaCl₂. The excitation spectrum of the Mn²⁺ fluorescence revealed the features of manganese ions in octahedral coordination and consisted of nine excitation peaks which were associated with Mn²⁺-crystal-field-sensitive transitions. A crystal field analysis of the wavelength positions of these transitions by means of the model developed by Curie et al. allowed us to determine the magnitude of the cubic field splitting 10Dq, the reduced Racah parameter B', the Koide-Pryce covalency parameter ε and the spin transfer coefficients f _[sgrave] and f _σ. From the measurement of the temperature dependence of the Mn²⁺ fluorescence lifetime, we have also obtained information about the different mechanisms which are involved in the relaxation of excited Mn²⁺ ions in this host crystal in the temperature range (11–300 K).     

Simulation of structured 4T1→6A1 emission bands of Mn2+ impurity in Zn2SiO4: A first-principle methodology

A sequential, fully first-principle theoretical study of the Mn²⁺ green emission bands in the Zn₂SiO₄:Mn²⁺ phosphor is presented for the first time. A combined approach is developed based on the modern periodic density-functional theory and cluster ab initio wave-function-based electronic structure methods, the linear response theory for lattice phonons, and generating function formalism of vibronic spectra within the displaced multi-mode harmonic oscillator model. We obtain fairly good agreement between the calculated low- and high-temperature emission band positions, widths, zero-phonon lines and phonon wings and the available experimental emission studies, with special emphasis on Mn²⁺ distribution over two non-equivalent Zn²⁺ sites in the Zn₂SiO₄ material. An interpretation for vibronic structure observed in the low-temperature emission spectrum of this phosphor is suggested based on the present first-principle study.     

Influence of the host lattice on the infrared-excited blue luminescence of Yb3+, Tm3+-doped compounds

The intensity of the blue emission of infrared-excited Yb³⁺, Tm³⁺-doped compounds varies in the same way with the host lattice as that of the green emission of infrared-excited Yb³⁺, Er³⁺-doped compounds. For both emissions, the highest intensity is obtained in the lattice α-NaYF₄. The emission spectrum of α-NaYF₄:Yb³⁺, Tm³⁺ shows a relatively high blue-to-red intensity ratio.     

Luminescence of Mn ions in ordered and disordered LiAl5O8

The phosphorescence and excitation spectra of Mn ions in the ordered and disordered phases of LiAl₅O₈ have been measured. In both phases Mn²⁺ ions substitute for Al³⁺ ions in two different tetrahedral sites of the LiAl₅O₈ lattice. In both sites in the ordered phase, sharp zero-phonon transitions have been observed in the low temperature phosphorescence and excitation spectra - these transitions were considerably broadened in the disordered phase due to crystal field inhomogeneity in that phase. The deviation from neutrality caused by the Mn²⁺ ions in the ordered phase is largely compensated by Mn⁴⁺ ions occupying octahedral Al³⁺ sites. On disordering, a large proportion of Mn⁴⁺ is reduced to Mn²⁺, while the remainder takes up a site with a higher proportion of Li⁺ ions as next nearest neighbours. This leads to an increase in the ionicity of the Mn⁴⁺ site in the disordered phase and hence to a larger value of the Racah parameter B.     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al₂O₃透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱，发现在Al₂O₃六配位的八面体结构中，Cr⁴⁺的荧光发射也处在1100—1600nm波段的红外区间，荧光发射峰位于1223nm附近，类似Cr⁴⁺在四面体中的发光行为.同时由于氧化铝晶格常数较小，晶体场强较强，使Cr⁴⁺:Al₂O_{3< 关键词： 4+')" href="#">Cr⁴⁺ 2}O₃透明陶瓷')" href="#">Cr:Al₂O₃透明陶瓷 光谱性质 八面体     

Photoluminescence characteristics of Se-doped ZnGa2O4:Mn2+ thin-film phosphors grown by pulsed laser deposition on Al2O3(0001) substrates

Se-doped ZnGa₂O₄:Mn²⁺ thin-film phosphors have been grown using a pulsed laser deposition technique at various growth conditions. Structural characterization was carried out on a series of Se-doped ZnGa₂O₄:Mn²⁺ films grown on Al₂O₃(0001) substrates using Zn-rich ceramic targets. The results of X-ray diffraction patterns showed that the lattice constants of the films decrease with the substitution of Se for the oxygen in the ZnGa₂O₄. Photoluminescence (PL) of Se-doped ZnGa₂O₄:Mn²⁺ thin films has indicated that Al₂O₃(0001) is a promising substrate for the growth of high-quality Se-doped ZnGa₂O₄:Mn²⁺ films. The emission spectra of Se-doped ZnGa₂O₄:Mn²⁺ films show a broad band extending from 479 to 550 nm and peaking at 508 nm. In particular, the incorporation of Se into the ZnGa₂O₄ lattice could induce an increase in the PL. The PL peak intensity of the Se-doped ZnGa₂O₄:Mn²⁺ films is a factor of 2.8 larger than that of the ZnGa₂O₄:Mn²⁺ films. This phosphor is promising for applications in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Characterization of Cu1.4Mn1.6O4/PPy composite electrodes

In this work, we have studied the multilayered polypyrrole(PPy)/oxide composite electrode on glassy carbon (GC) having the structure GC/PPy/PPy(Cu_1.4Mn_1.6O₄)/PPy using X-ray Photoelectron Spectroscopy and Mn K-edge and Cu K-edge XANES and EXAFS. The mixed oxide particles have been incorporated into the PPy matrix simultaneously to the electropolymerization of Py from a solution containing 0.1 M Py + 0.15 M KCl + Cu_1.4Mn_1.6O₄. The XPS data have shown that, prior to the incorporation of the oxide into the PPy matrix, it contains Cu⁺, Cu²⁺, Mn³⁺ and Mn⁴⁺. The XPS, XANES and EXAFS results have shown that when the oxide is incorporated into the PPy matrix, the Cu⁺ present in the original oxide suffers dismutation to give Cu²⁺ and metallic Cu. The metallic Cu is segregated out of the spinel structure. The Mn K-edge XANES and EXAFS data show that, after the incorporation into the PPy matrix, Mn is present as Mn³⁺ and Mn⁴⁺ occupying octahedral sites in a spinel-related structure while the Cu K-edge XANES and EXAFS data indicate that copper occupies tetrahedral sites predominantly in that structure but having a large degree of disorder in the second and higher coordination shells.     

Luminescent properties of Sr5(PO4)3 Cl:Eu2+, Mn2+ as?a?potential phosphor for UV-LED-based white LEDs

Eu²⁺ and Mn²⁺ co-activated Sr₅(PO₄)₃Cl phosphors with blue and orange color double emission bands, under a broad-band excitation wavelength range of 340–400 nm, were synthesized by the solid-state reaction. It was found that the processing parameters, including the fluxes, annealing time and activators concentrations, affect the emission intensity and other luminescent properties. Energy transfer between Eu²⁺ and Mn²⁺ was discovered and the transfer efficiency was also estimated based on relative intensities of Eu²⁺ and Mn²⁺ emission. Thus the relative strength of blue and orange emission intensities could be tuned by varying the relative concentration of Eu²⁺ and Mn²⁺. Since the photoluminescence excitation spectra of the newly developed Sr₅(PO₄)₃Cl:Eu²⁺, Mn²⁺ phosphors exhibit a strong absorption in the range of 340–400 nm, they are promising for producing UV-LED-based white LEDs.     

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.     

Magnetic and transport properties of double distorted perovskites CaCuMn6O12 and CaCu2Mn5O12

Magnetic and transport properties of double distorted perovskites CaCuMn₆O₁₂ and CaCu₂Mn₅O₁₂ are studied in a range 2–300 K. The leading role in magnetism of these compounds belongs to antiferromagnetic exchange interaction of Cu²⁺ in square coordination with Mn³⁺/Mn⁴⁺ in octahedral coordination. The values of saturation magnetization indicate that Mn³⁺ ions in square coordination are coupled ferromagnetically with Mn³⁺/Mn⁴⁺ in octahedral coordination. The colossal magnetoresistance in the pellet samples is due assumingly to intergranular spin-polarized tunneling of current carriers.     

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.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.