A combinatorial approach to the discovery and optimization of YCa4O(BO3)3-based luminescent materials

Thin films of YCa₄O(BO₃)₃ (YCOB)-based new luminescent materials were explored by the combinatorial pulsed laser deposition (PLD) method which enabled us to fabricate continuous composition spread film libraries. Strong red and green luminescence were found in the Y_1−xEu_xCOB (0 ≤ x ≤ 1), (YEuCOB) and Y_1−yTb_yCOB (0 ≤ y ≤ 1) (YTbCOB) films, respectively. The film libraries were characterized by photoluminescence (PL), PL decay, an electron-probe microanalyzer and an electron diffraction analysis. The luminescent intensities in the amorphous film libraries strongly depended on the chemical composition of each rare-earth (RE) ion. The optimum concentration of rare-earth ions in YEuCOB and YTbCOB were experimentally determined to be Eu = 7.5% and Tb = 20-30%, respectively.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

Effect of sintering atmosphere on the electrical and optical properties of (ZnO)1−x(MnO2)x NTCR ceramics

Nominal composition of (ZnO)_1−x(MnO₂)_x (0.005≤x≤0.2) ceramics have been prepared by the standard solid-state reaction method in three different sintering atmospheres: Ar, air, and reductive atmosphere. The effect of sintering atmosphere on the electron spin resonance (ESR), negative temperature coefficient of resistivity (NTCR), and photoluminescence (PL) properties of (ZnO)_1−x(MnO₂)_x ceramics has been investigated in detail. The results demonstrate that the sintering atmosphere has significant effects on the ESR signals of (ZnO)_1−x(MnO₂)_x; the NTCR of the samples sintered in air is larger than those sintering in Ar and reductive atmosphere; the deep-level PL related to oxygen vacancy increases when sintered in the reductive atmosphere.     

A novel UV-emitting phosphor: Li6CaB3O8.5:Pb

Pure Li₆CaB₃O_8.5 and Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) materials were prepared by a solution combustion synthesis method. The phase of synthesized materials was determined using the powder XRD and FTIR. The synthesized materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of the synthesized phosphors were observed at 307 and 268 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for the Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) was studied and observed that the optimum concentration of Pb²⁺ in phosphor is 0.01 mol. The Stokes shift of the synthesized phosphor was calculated to be 4740 cm^-1.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Structure and magnetostriction of Tb0.2Pr0.8(Fe0.4Co0.6)1.93−xCx intermetallic compounds

The structure and magnetostriction of Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.93−xC_x intermetallic compounds were studied by X-ray diffraction and magnetic measurements. Almost a single cubic Laves phase forms in the alloys for x ≤0.20, and a small amount of C can inhibit the formation of the 1:3 phase. The lattice parameter increases when 0≤x≤0.15, while the T_c and the spontaneous magnetization decreases with increasing x. The lattice parameter decreases slowly when 0.15≤x≤0.30, while the T_c decreases evidently with increasing x. The magnetostriction λ_a (=λ_∥-λ_⊥) is improved at low magnetic fields at room temperature for the compounds with 0.05≤x≤0.10, indicating that these C-containing compounds are promising magnetostrictive materials.     

Low voltage electron induced cathodoluminescence degradation and surface characterization of Sr3(PO4)2:Tb phosphor

Tb³⁺-doped Sr₃(PO₄)₂ phosphor was prepared by a sol-gel combustion method. A trigonal structure having Sr and O atoms occupying two different lattice sites were obtained. Scanning Auger nanoprobe was used to analyze the morphology of the particles. Photoluminescence (PL) and cathodoluminescence (CL) properties of Sr₃(PO₄)₂:Tb powder phosphors were evaluated and compared. In addition, the CL intensity degradation of Sr₃(PO₄)₂:Tb was evaluated when the powders were irradiated with a beam of electrons in a vacuum chamber maintained at an O₂ pressure of 1 × 10⁻⁶ Torr or a background pressure of 1 × 10⁻⁸ Torr O₂. The surface chemical composition of the degraded powders, analyzed by X-ray photoelectron spectroscopy (XPS), suggests that new compounds (metal oxides) of strontium and phosphorous were formed on the surface. It is most likely that these compounds contributed to the CL intensity degradation of the Sr₃(PO₄)₂:Tb phosphors. The CL properties and possible mechanism by which the new metal oxides were formed on the surface due to a prolonged electron beam irradiation are discussed.     

High magnetostriction at low fields of (Tb1−xDyx)0.2Pr0.8(Fe0.4Co0.6)1.88C0.05 intermetallic compounds

The structure and magnetostriction of the (Tb_1−xDy_x)_0.2Pr_0.8(Fe_0.4Co_0.6)_1.88C_0.05 intermetallic compounds (0≤x≤1) were studied by X-ray diffraction and magnetic measurements. The formation of an approximate single Laves phase with a MgCu2-type cubic structure was observed in this series of compounds. It was found that the Curie temperature and the saturation magnetization of the compounds would decrease with increase in the Dy content up to x=1. The magnetostriction λ_a (λ_a=λ_‖-λ_⊥) gently rises when x≤0.6, and follows with a precipitous fall when x exceeds 0.6, with the highest value of λ_a being reached in the compounds with x=0.6. The magnetostriction of all the samples was observed to approach their own saturation in the magnetic fields higher than 4 kOe. This indicates that the addition of a small amount of Dy could effectively improve the low-field magnetostriction of the Tb_0.2Pr_0.8(Fe_0.4Co_0.6)_1.88C_0.05 compounds, which could become a kind of promising magnetostrictive material.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

Effects of Tb doping on the photoluminescence of Y2O3:Tb nanophosphors

The effects of Tb doping on the photoluminescence (PL) of Y₂O₃:Tb nanophosphors have been investigated. Nanophosphors were prepared by the glycine-nitrate solution combustion technique using yttria and terbia powders as precursors. PL excitation spectra at room temperature consist of two overlapping bands centered at 277 and 304 nm, whereas emission spectra comprise several groups of lines corresponding to the ⁵D₄→⁷F_J (J=1-6) 4f electronic transitions of the Tb⁺³ ions. A direct comparison of nanophosphor and bulk concentration-quenching curves was obtained by annealing the nanophosphor powder and converting it to bulk material without altering the Tb concentration. The peak in the nanophosphor concentration-quenching curve occurs at a concentration ∼3 times higher than that of the bulk.     

Synthesis and luminescence properties of europium doped YBa3B9O18

Europium (Eu³⁺) doped YBa₃B₉O₁₈ were synthesized by conventional solid state solidification methods. (Y_1−xEu_x)Ba₃B₉O₁₈ formed solid solutions in the range of x=0–1.0. The luminescence property measurements upon excitation in ultraviolet–visible range show well-known Eu³⁺ excitation and emission. The charge transfer excitation band of Eu³⁺ dominates the excitation spectra. The emission spectrum of Eu³⁺ ions consists mainly of several groups of lines in the 550–720 nm region, due to the transitions from the ⁵D₀ level to the levels ⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions. The dependence of luminescence intensity on Eu³⁺ concentration shows no concentration quenching for fully concentrated EuBa₃B₉O₁₈. Eu³⁺ doped YBa₃B₉O₁₈ are promising phosphors for applications in displays and optical devices.     

Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.     

Dielectric characteristics of cation deficient TbMnO3

Cation deficient polycrystalline Tb_1−xMnO₃ (x= 0.05, 0.10) and TbMn_1−yO₃ (y =0.05, 0.10) samples were fabricated by conventional solid-state reaction. The complex dielectric properties of the cation deficient TbMnO₃ were investigated as the function of temperature (77 K≤T≤350 K) and frequency (100 Hz≤ f≤ 200 kHz) separately. Compared to the parent TbMnO₃, the cation deficient TbMnO₃ samples exhibit not only high dielectric constant but also low dissipation factor. Nyquist plots of complex impedance show that the dielectric properties originate from two main relaxation sources, i.e. bulk contributions and grain boundary effects.     

Piezoelectric properties of [Li0.03(K0.48Na0.52)0.97](Nb0.97Sb0.03)O3-(Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 lead-free piezoelectric ceramics

[Li_0.03(K_0.48Na_0.52)_0.97](Nb_0.97Sb_0.03)O₃-(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ [(1−x)LKNNS-xBCTZ] lead-free piezoelectric ceramics were prepared by the conventional solid state method, and effects of BCTZ content on the piezoelectric properties of LKNNS ceramics were mainly investigated. A stable solid solution has been formed between LKNNS and BCTZ, and a morphotropic phase boundary of (1−x)LKNNS-xBCTZ ceramics is identified in the range of 0 < x ≤ 0.02. The Curie temperature of (1−x)LKNNS-xBCTZ ceramics decreases with increasing BCTZ content. A higher ?_r value and a lower tan δ value are demonstrated for the (1−x)LKNNS-xBCTZ ceramic with x = 0.02. The (1−x)LKNNS-xBCTZ ceramic with x = 0.02 has an enhanced electrical behavior of d₃₃ ∼ 237 pC/N, k_p ∼ 48.6%, ?_r ∼ 1451, tan δ ∼ 0.037, and T_c ∼ 335 °C. As a result, (1−x)LKNNS-xBCTZ ceramics are promising candidate materials for the field of lead-free piezoelectric materials.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Effect of Y2O3 additive on the microstructure and high-frequency properties of Z-type hexaferrites

In order to improve the high-frequency electromagnetic properties of Z-type hexaferrites such as high cut-off frequency and low dielectric constant, Y₂O₃ was introduced. The influence of Y₂O₃ additive on the phase composition, densification, microstructural and electromagnetic properties of the ceramics with composition of Ba₃(Co_0.4Zn_0.6)₂Y_xFe_24−xO₄₁ (x=0−1) was investigated. The results show that as the amount of Y₂O₃ additive increased, the major phase changed to Z-phase; simultaneously, a small amount of garnet phase appeared. With increasing Y₂O₃ content, the garnet phase separated out on grain boundaries as a secondary phase restraining grain growth. When x was varied from 0 to 1, the dielectric constant decreased and the ferroelectric resonance peak shifted toward a higher frequency. Meanwhile, the initial permeability increased at first, and then decreased with further increasing x, which could be mainly attributed to the change of phase composition and sintering density. With increasing Y₂O₃ content, the minimum reflection point of the samples shifted toward a higher frequency.     

Influence of valence states and co-ordination of cobalt ions on dielectric properties of PbO-Bi2O3-As2O3:CoO glass system

The glasses of the composition (40−x) PbO-15Bi₂O₃-45As₂O₃-xCoO, with 0≤x≤0.6 mol% in the steps of 0.1 were synthesized. The dielectric properties viz., dielectric constant, loss and ac conductivity over moderately larger ranges of frequency and temperature were investigated. The results were analyzed with the aid of the data on optical absorption and IR spectra. The analysis indicated that there is an increase in the insulating strength of the glasses with increase in the concentration of CoO up to 0.4 mol%.