Luminescence of NaGdFPO4:Ln after VUV excitation: A comparison with GdPO4:Ln (Ln=Ce, Tb)

The phosphors NaGdFPO₄:Ln³⁺ and GdPO₄:Ln³⁺ (for Ln³⁺=Ce³⁺ and Tb³⁺) were prepared by solid-state reaction technique, the VUV-vis spectroscopic properties of the phosphors were investigated, and we vividly compare the luminescence of Ce³⁺ and Tb³⁺ in the hosts. For phosphors GdPO₄:Ln³⁺, the band near 155 nm in VUV excitation spectrum is assumed to be the host-related absorption, and for NaGdFPO₄:Ln³⁺ the absorption is moved to longer wavelength, near 170 nm, showing the P-O bond covalency increased after fluoridation. The f-d transitions of Ce³⁺ and Tb³⁺ in the host lattices are assigned and corroborated, and it was found that the 5d states are with lower energy in NaGdFPO₄:Ln³⁺ than those in GdPO₄:Ln³⁺. For fluoridation of GdPO₄:Ln³⁺ to NaGdFPO₄:Ln³⁺, the energy change of Ln³⁺ (Ln=Ce, Tb) 5d states is consistent with that of host-related absorption.     

Luminescence of Sb3+ in rare earth orthoborates LnBO3 (Ln = Sc,Y, La,Gd, Lu)

The luminescence of several Sb³⁺-activated rare earth orthoborates (LnBO₃Sb³⁺; Ln = Sc, Y, La, Gd, Lu) are reported. In all compositions the Stokes shift of the Sb³⁺ luminescence is rather large, resulting in rather low quenching temperatures (200 K or lower). The Stokes shift appears to be dependent on the coordination number and on the radius of the host lattice cation. This is explained from the assumed tendency of the Sb³⁺ ion to occupy an off-center position which becomes more apparent when the space available for the Sb³⁺ ion increases. The present results are compared with those on LnBO₃Bi³⁺. It appears that the Stokes shift of the Bi³⁺ luminescence is more sensitive to the host lattice and is smaller than the Stokes shift of the Sb³⁺ luminescence. This is explained by the large radius of the Bi³⁺ ion compared to the Sb³⁺ ion. In GdBO₃Sb³⁺ thermally activated energy transfer is observed from Gd³⁺ to Sb³⁺.     

First-principles relativistic calculation for 4f-5d transition energy of Ce in various fluoride hosts

In this paper, we investigated the 4f-5d transition energy of Ce³⁺ in various fluoride hosts based on the first-principles discrete-variational Dirac-Slater (DV-DS) calculations using Slater's transition-state theory. Especially, we focused on the lowest energy peak (1st peak) of 4f-5d transition for Ce³⁺ impurities. As the host crystals, we adopted the 15 fluorides, for which the experimental data of the lowest energy peak (1st peak) in 4f-5d transitions were available from literature except for NaMgF₃ and BaMgF₄. A high correlation between the experimental 1st peak energies and the theoretical ones was obtained which suggests a possibility to predict the 4f-5d transition energy of Ce³⁺ in various fluoride hosts using the first-principles calculation.     

稀土掺杂Lu3Al5O12荧光粉的发光特性及能量传递

采用高温固相法制备了Ce、Sm共掺Lu_3Al_5O_(12)荧光粉。通过X射线衍射分析、荧光光谱分析研究了样品的结构、发光特性,并通过理论计算研究了能量传递效率、能量传递的临界距离以及能量传递方式。X射线衍射分析表明所制备的荧光粉具有单一的石榴石结构;荧光光谱分析表明,在464 nm蓝光激发下,Sm~(3+)的引入可增加Lu_3Al_5O_(12)∶Ce,Sm发射光谱中红光成分,并且随着Sm~(3+)浓度的增加,Ce~(3+)发光强度逐渐减弱。计算出Ce~(3+)、Sm~(3+)之间的能量传递效率高达77.42%,确定了Ce~(3+)、Sm~(3+)之间的能量传递机制为偶极-偶极相互作用。     

BaLaB9O16中Ce3+敏化Dy3+发光的机理

在紫外光激发下,研究了BaLaB₉O₁₆中Dy³⁺、Ce³⁺的发光光谱、激发光谱、发光强度及荧光寿命随着组成变化的规律性.结果表明;De³⁺对Dy³⁺的发光有相当强的敏化作用,Ce³⁺→Dy³⁺的能量传递效率可高达93%,能量传递的机理为电偶极-偶极相互作用的共振传递.根据349nm激发下Dy³⁺发光强度与浓度的关系,证明了Dy³⁺发光的自身浓度猝灭机理也为电偶极-偶极相互作用.     

Luminescence Properties of Terbium-, Cerium-, or Europium-Doped α-Sialon Materials

New interesting luminescent α-sialon (M_(m/val+)^val+ Si_12-(m+n) Al_(m+n)OnN_(16−n)) (M=Ca, Y) materials doped with Ce, Tb, or Eu have been prepared and their luminescence properties studied. These show that Tb and Ce are in the 3+ and Eu in the 2+ state. Low-energy 4f↔5d transitions are observed as compared to the luminescence of these ions doped in oxidic host-lattices. This is partially explained by the nitrogen-rich coordination of the rare-earth ion and partially by the narrow size of the lattice site. The latter gives rise to a strong crystal-field splitting of the 5d band and a rather large Stokes shift for Ce³⁺ and Eu²⁺ (6500-7500 and 7000-8000 cm⁻¹, respectively). For (Y,Tb)-α-sialon the Tb³⁺ 4f→5d excitation band (∼260 nm) is in the low-energy host-lattice absorption band (?290 nm), giving rise to a strong absorption for 254-nm excitation, but a low quantum efficiency. The latter is due to photoionization processes or selective excitation of Tb³⁺ at the defect-rich surface, resulting in radiationless transitions. Ce- and Eu-doped Ca-α-sialon show bright long-wavelength luminescence (maxima at 515-540 and 560-580 nm for Ce and Eu, respectively) with a high quantum efficiency and high absorption for 365- and 254-nm excitation. The Eu²⁺ emission intensity and absorption increases for increasing m, which is explained by the Eu²⁺ richer α-sialon composition. The position of the Eu^2α emission does not shift with changing composition of the host-lattice (m, n values), indicating that the local coordination of the Eu²⁺ ion is hardly dependent on the matrix composition.     

Crystal, electronic structures and photoluminescence properties of rare-earth doped LiSi2N3

The crystal and electronic structures, and luminescence properties of Eu²⁺, Ce³⁺ and Tb³⁺ activated LiSi₂N₃ are reported. LiSi₂N₃ is an insulator with an indirect band gap of about 5.0 eV (experimental value ∼6.4 eV) and the Li 2s, 2p states are positioned on the top of the valence band close to the Fermi level and the bottom of the conduction band. The solubility of Eu²⁺ is significantly higher than Ce³⁺ and Tb³⁺ in LiSi₂N₃ which may be strongly related to the valence difference between Li⁺ and rare-earth ions. LiSi₂N₃:Eu²⁺ shows yellow emission at about 580 nm due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. Double substitution is found to be the effective ways to improve the luminescence efficiency of LiSi₂N₃:Eu²⁺, especially for the partial replacement of (LiSi)⁵⁺ with (CaAl)⁵⁺, which gives red emission at 620 nm, showing highly promising applications in white LEDs. LiSi₂N₃:Ce³⁺ emits blue light at about 450 nm arising from the 5d¹→4f¹5d⁰ transition of Ce³⁺ upon excitation at 320 nm. LiSi₂N₃:Tb³⁺ gives strong green line emission with a maximum peak at about 542 nm attributed to the ⁵D₄→⁷F_J (J=3-6) transition of Tb³⁺, which is caused by highly efficient energy transfer from the LiSi₂N₃ host to the Tb³⁺ ions.     

Luminescence Quenching between Ce and Eu in LAB3O6

The Ce³⁺ and Eu³⁺ ions in LaB₃O₆ quench each other's luminescence. However, Ce³⁺ quenches Eu³⁺ more effectively than Eu³⁺ quenches Ce³⁺. The critical distances for this quenching are about 15 and 6 Å respectively.     

Ca9Y(PO4)7:Ce3+,Tb3+纳米荧光粉的制备及发光性能

采用水热法制备出Ca₉Y（PO₄）₇：Ce³⁺,Tb³⁺纳米荧光粉,通过XRD、SEM和荧光光谱等对样品进行了分析,研究在Ca₉Y（PO₄）₇基质中引入Ce³⁺,Tb³⁺离子对发光性能的影响规律。研究发现因Tb³⁺离子自身能量交叉驰豫的存在,使得单掺Tb³⁺时,通过调节Tb³⁺离子的浓度可以实现对发光颜色的控制。同时研究了Ce³⁺-Tb³⁺之间的能量传递为电多极相互作用的偶极-四极机制,Ce³⁺-Tb³⁺之间最大的能量传递效率为55.6%。Ca₉Y（PO₄）₇：Ce³⁺,Tb³⁺的发光颜色可以通过激活离子之间的能量传递和共发射得到可控调节。SEM分析表明荧光粉颗粒尺寸在100 nm左右,分散性好。     

Sensitization of Tb3+ luminescence with Ce3+ in LaOBr: Tb3+, Ce3+

Luminescence emission and uv-excitation properties of LaOBr: Tb³⁺, LaOBr: Ce³⁺, and LaOBr: Tb³⁺, Ce³⁺ phosphors were studied. The visible emission spectra of La_0.995Tb_0.005OBr consists of⁵D_3,4 →⁷F_3–6 transitions in the wavelength range of 410–630 nm. The excitation of the Tb³⁺ ion gives a broad 4f → 5d transition band at 254 nm and weaker4f → 4f transition lines above 300 nm. The uv-excitation and emission of La_0.995Ce_0.005OBr at 290, 315, 355 (excitation), and 440 nm (emission) originate from transitions between the 4f-ground state and the four crystal field components of the5d²D excited state. The sensitization of Tb³⁺ luminescence in LaOBr with Ce³⁺ at varying concentrations is described and discussed. With increasing Ce³⁺ concentration the ⁵D₃ →⁷F transitions of Tb³⁺ quench totally and the⁵D₄ →⁷F transitions begin to quench gradually. The excitation spectrum of the⁵D₄ →⁷F₅ transition of Tb³⁺ consists of four bands due to Tb³⁺ and Ce³⁺, of which the three Ce³⁺ bands increase in intensity and the Tb³⁺ band decreases as the Ce³⁺ concentration is increased.     

Sensitized red luminescence from Ce, Mn-doped glaserite-type alkaline-earth silicates

Bright red luminescence is observed from Ce, Mn-doped glaserite-type alkaline-earth silicates with M₂BaMgSi₂O₈ (M: Ba, Sr, Ca) chemical composition. Under UV excitation, Ce-doped M₂BaMgSi₂O₈ exhibits strong near-UV emission with asymmetric peak shape. UV-excited Mn-doped M₂BaMgSi₂O₈ compounds show visible red emission only when Ce³⁺ ions are doped together. These results indicate that Mn²⁺-derived red emission is caused by an efficient energy transfer from Ce³⁺ to Mn²⁺. The red emission becomes intense with an increase in Ba-amount. This trend originates from the relaxation of the selection rule for 3d-3d transition in Mn²⁺ ions, which is caused by the structural deformation due to Ba²⁺ occupation for layer-pockets.     

Synthesis and spectral characteristics of Sr2Y8(SiO4)6O2: Eu polycrystals

Spectral-luminescent characteristics of Sr₂Y₈(SiO₄)₆O₂: Eu powder crystal phosphor with the apatite structure and high-intensity luminescence of Eu³⁺ ions have been studied. The charge state of europium in the samples has been characterized by means of X-ray L₃-adsorption spectroscopy. It was established that Eu³⁺ forms two types of optical centers. Besides, luminescence of Eu²⁺ions was found. Reduction Eu³⁺→Eu²⁺ was considered, which may be due to vacancy formation in the 4f crystal lattice position and to negative charge transfer by this vacancy to two ions. Thus, in the silicate lattice there exist inhomogeneously distributed oxygen-deficient centers, which are responsible for nonradiative transfer of excitation energy to Eu³⁺ and Eu²⁺ ions. To study electron-vibrational interactions in the crystal phosphor samples, their IR and Raman spectra were examined. In the luminescence spectrum of Eu²⁺, a series of low-intensity bands caused by interaction of the 4f⁶5d state of Eu²⁺ with silicate lattice vibrations was observed.     

Synthesis and photoluminescence properties of tunable emission phosphors Ca4Si2O7F2:Ce3+

The Ce³⁺ activated phosphors Ca₄Si₂O₇F₂:Ce³⁺ are prepared by a solid state reaction technique. The UV–vis luminescence properties as well as fluorescence decay time spectra are investigated and discussed. The results revealed that there were two kinds of Ce³⁺ luminescence behavior with 408 and 470 nm emissions, respectively. Under 355 nm excitation, the Ce(1) emission (408 nm) is dominant at low doping concentration, and then the Ce(2) emission (470 nm) get more important with increasing of Ce³⁺ concentrations in the host. The phosphors Ca₄Si₂O₇F₂:xCe³⁺ show tunable emissions from blue area to green-blue area under near-ultraviolet light excitation, indicating a potential application in near-UV based w-LEDs.     

Sol-gel deposition and luminescent properties of LaMgAl11O19:Ce/Tb phosphor films

Rare earth ions (Ce³⁺, Tb³⁺)-doped LaMgAl₁₁O₁₉ phosphor films were deposited on quartz glass substrates by Pechini sol-gel and dip coating method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), field emission scanning electronic microscopy (FESEM), photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the magnetoplumbite structure LaMgAl₁₁O₁₉ phase can be obtained at 1200 °C on quartz glass substrates. This was further verified by the results of FT-IR and TG-DTA. AFM study showed that uniform films have an average grain size of 150 nm and a root mean square (RMS) roughness of 4 nm. The thickness of the films characterized by FESEM is about 340 nm. LaMgAl₁₁O₁₉:Ce³⁺ film showed the parity and spin allowed 5d-4f band emission of Ce³⁺ with a maximum at 350 nm. Ce³⁺, Tb³⁺-codoped LaMgAl₁₁O₁₉ films showed the band emission of Ce³⁺ and characteristic emission of Tb³⁺, namely, ⁵D_3,4-⁷F_J (J=6, 5, 4, 3) due to an efficient energy transfer from Ce³⁺ to Tb³⁺ in the host.     

Optical properties of green-blue-emitting Ca-α-Sialon:Ce,Li phosphors for white light-emitting diodes (LEDs)

Ce³⁺,Li⁺-codoped Ca-α-Sialon phosphors with the formula [Ca_(1−2x)Ce_xLi_x]_m/2Si_12−(m+n)Al_m+nO_nN_16−n (0≤x≤0.25, 0.5≤m≤3.5, and 0.16≤n≤2.0) have been synthesized by gas pressure sintering (GPS). The effects of the activator concentration and the overall composition of host lattice on the phase evolution, morphology, and optical properties were investigated. The single-phase Ca-α-Sialon:Ce³⁺,Li⁺ can be synthesized at x<0.1, 1.0≤m≤2.5, and n≤1.2. The synthesized powders exhibit a relatively dispersive and uniform morphology. Under the near UV excitation, the bright green-blue emission centered at 500-518 nm is observed. The photoluminescence can be tailored by controlling Ce³⁺ concentration and the overall composition of the α-Sialon host lattice. With increasing the Ce concentration and m value both excitation and emission bands show a red shift, which perfectly matches with the near-UV LEDs in the range of 360-410 nm. The strongest luminescence is achieved at x=0.08-0.1, m=2.0-2.5, and n=1.0. Simultaneously, the highest quantum efficiency and better thermal stability are also present.     

Photoluminescence of Ce, Pr and Tb activated Sr3Ln(PO4)3 under VUV-UV excitation

The spectroscopic properties in VUV-Vis range for the eulytite structural phosphors Sr₃Gd(PO₄)₃:Ln³⁺ (Ln³⁺=Ce³⁺, Pr³⁺, Tb³⁺), Sr₃Ce(PO₄)₃, Sr₃Gd(PO₄)₃ and Sr₃Tb(PO₄)₃ were investigated. The bands near 170 nm in VUV excitation spectra are assumed to connect with the host lattices related absorption. The f-d transitions of Ce³⁺, Pr³⁺ and Tb³⁺ in the host lattices are assigned and corroborated. A convenient experiment formulation on the relationship between the lowest f-d transition energies and n value for trivalent 4fⁿ-series rare earth ions in these host lattices is applied.     

Electronic state of Fe used as Mössbauer probe in the perovskites LaMO3 (M=Ni and Cu)

For the first time a comparative study of rhombohedral LaNiO₃ and LaCuO₃ oxides, using ⁵⁷Fe Mössbauer probe spectroscopy (1% atomic rate), has been carried out. In spite of the fact that both oxides are characterized by similar crystal structure and metallic properties, the behavior of ⁵⁷Fe probe atoms in such lattices appears essentially different. In the case of LaNi_0.99Fe_0.01O₃, the observed isomer shift (δ) value corresponds to Fe³⁺ (3d⁵) cations in high-spin state located in an oxygen octahedral surrounding. In contrast, for the LaCu_0.99Fe_0.01O₃, the obtained δ value is comparable to that characterizing the formally tetravalent high-spin Fe⁴⁺(3d⁴) cations in octahedral coordination within Fe(IV) perovskite-like ferrates. To explain such a difference, an approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that in the case of LaNi_0.99Fe_0.01O₃, electronic state of nickel is dominated by the d⁷ configuration corresponding to the formal ionic “Ni³⁺-O²⁻” state. On the other hand, in the case of LaCu_0.99Fe_0.01O₃ a large amount of charge is transferred via Cu-O bonds from the O:2p bands to the Cu:3d orbitals and the ground state is dominated by the d⁹L configuration (“Cu²⁺−O” state). The dominant d⁹L ground state for the (CuO₆) sublattice induces in the environment of the ⁵⁷Fe probe cations a charge transfer Fe³⁺+O⁻(L)→Fe⁴⁺+O²⁻, which transforms “Fe³⁺” into “Fe⁴⁺” state. The analysis of the isomer shift value for the formally “Fe⁴⁺” ions in perovskite-like oxides clearly proved a drastic influence of the 4s iron orbitals population on the Fe−O bonds character.     

Structure and photoluminescence properties of Ce-doped novel silicon-oxynitride Ba4−zMzSi8O20−3xN2x (M=Mg, Ca, Sr)

Structural and photoluminescence properties of undoped and Ce³⁺-doped novel silicon-oxynitride phosphors of Ba_4−zM_zSi₈O_20−3xN_2x (M=Mg, Sr, Ca) are reported. Single-phase solid solutions of Ba_4−zM_zSi₈O_20−3xN_2x oxynitride were synthesized by partial substitutions of 3O²⁻→2N³⁻ and Ba→M (M=Mg, Ca, Sr) in orthorhombic Ba₂Si₄O₁₀. The influences of the type of alkaline earth ions of M, the Ce³⁺ concentration on the photoluminescence properties and thermal quenching behaviors of Ba₃MSi₈O_20−3xN_2x (M=Mg, Ca, Sr, x=0.5) were investigated. Under excitation at about 330 nm, Ba₃MSi₈O_20−3xN_2x:Ce³⁺ (x=0.5) exhibits efficient blue emission centered at 400-450 nm in the range of 350-650 nm owing to the 5d→4f transition of Ce³⁺. The emission band of Ce³⁺ shifts to long wavelength by increasing the ionic size of M due to the modification of the crystal field, as well as the Ce³⁺ concentrations due to the Stokes shift and energy transfer or reabsorption of Ce³⁺ ions. Among the silicon-oxynitride phosphors of Ba₃MSi₈O_18.5N:Ce³⁺, M=Sr_0.6Ca_0.4 possesses the best thermal stability probably related to its high onset of the absorption edge of Ce³⁺.     

Preparation and luminescence properties of Ce and/or Tb doped LaPO4 nanofibers and microbelts by electrospinning

Ce³⁺ and/or Tb³⁺ doped LaPO₄ nanofibers and microbelts have been prepared by a combination method of sol-gel process and electrospinning. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), low voltage cathodoluminescence (CL) and time-resolved emission spectra as well as kinetic decays were used to characterize the resulting samples. SEM and TEM results indicate the as-formed precursor fibers and belts are smooth, and the as-prepared nanofibers and microbelts consist of nanoparticles. The doped rare-earth ions show their characteristic emission under ultraviolet excitation, i.e. Ce³⁺ 5d-4f and Tb³⁺⁵D₄-⁷F_J (J=6-3) transitions, respectively. The energy transfer process from Ce³⁺ to Tb³⁺ in LaPO₄:Ce³⁺, Tb³⁺ nanofibers was further studied by the time-resolved emission spectra. Under low-voltage electron beam excitation, LaPO₄:Ce³⁺, Tb³⁺ microbelt phosphors have a higher intensity than that of nanofiber phosphors.     

Research on Molecular Structure and Electronic Properties of Ln3+ (Ce3+, Tb3+, Pr3+)/Li+ and Eu2+ Co-Doped Sr2Si5N8 via DFT Calculation

We use density functional theory (DFT) to study the molecular structure and electronic band structure of Sr₂Si₅N₈:Eu²⁺ doped with trivalent lanthanides (Ln³⁺ = Ce³⁺, Tb³⁺, Pr³⁺). Li⁺ was used as a charge compensator for the charge imbalance caused by the partial replacement of Sr²⁺ by Ln³⁺. The doping of Ln lanthanide atom causes the structure of Sr₂Si₅N₈ lattice to shrink due to the smaller atomic radius of Ln³⁺ and Li⁺ compared to Sr²⁺. The doped structure’s formation energy indicates that the formation energy of Li⁺, which is used to compensate for the charge imbalance, is the lowest when the Sr2 site is doped. Thus, a suitable Li⁺ doping site for double-doped lanthanide ions can be provided. In Sr₂Si₅N₈:Eu²⁺, the doped Ce³⁺ can occupy partly the site of Sr₁²⁺ ([SrN₈]), while Eu²⁺ accounts for Sr₁²⁺ and Sr₂²⁺ ([SrN₁₀]). When the Pr³⁺ ion is selected as the dopant in Sr₂Si₅N₈:Eu²⁺, Pr³⁺ and Eu²⁺ would replace Sr₂²⁺ simultaneously. In this theoretical model, the replacement of Sr²⁺ by Tb³⁺ cannot exist reasonably. For the electronic structure, the energy level of Sr₂Si₅N₈:Eu²⁺/Li⁺ doped with Ce³⁺ and Pr³⁺ appears at the bottom of the conduction band or in the forbidden band, which reduces the energy bandgap of Sr₂Si₅N₈. We use DFT+U to adjust the lanthanide ion 4f energy level. The adjusted 4f-CBM of Ce_Sr1Li_Sr1-Sr₂Si₅N₈ is from 2.42 to 2.85 eV. The energy range of 4f-CBM in Pr_Sr1Li_Sr1-Sr₂Si₅N₈ is 2.75–2.99 eV and its peak is 2.90 eV; the addition of Ce³⁺ in Eu_Sr1Ce_Sr1Li_Sr1 made the 4f energy level of Eu²⁺ blue shift. The addition of Pr³⁺ in Eu_Sr2Pr_Sr2Li_Sr1 makes part of the Eu²⁺ 4f energy level blue shift. Eu²⁺ 4f energy level in Eu_Sr2Ce_Sr1Li_Sr1 is not in the forbidden band, so Eu²⁺ is not used as the emission center.