Cr3+‐activated Li5Zn8Al5Ge9O36: A near‐infrared long‐afterglow phosphor

Near‐infrared long‐afterglow (LAG) materials have attracted considerable attention owing to their high potential for in vivo imaging applications. Here, we present a series of near‐infrared LAG phosphors Li₅Zn₈Al_5?xGe₉O₃₆:xCr³⁺ (LZAG:Cr³⁺), which were synthesized using a solid‐state reaction method. The pure LZAG host exhibits blue photoluminescence and LAG emission. We investigated the effect of the zinc vacancy contents on the photoluminescence and LAG performance by adjusting the zinc content and introducing Ga³⁺ ions to substitute the Zn²⁺ sites in LZAG host. When Cr³⁺ ions were introduced into the LZAG host, LZAG:Cr³⁺ produced a strong, broad blue emission band centered at 456 nm and a near‐infrared emission band at 700 nm caused by the ²E → ⁴A₂ transition of Cr³⁺. The energy transfer processes from the LZAG host to Cr³⁺ were identified in the photoluminescence and LAG process. After irradiation at 258 nm for 10 minutes, the LAG emission of LZAG:0.008Cr³⁺ can last nearly 2.5 hours. Moreover, the LAG intensity and duration of LZAG: 0.008Cr³⁺ were significantly improved by introducing a small dose of Ga³⁺ ions. Finally, the traps and mechanism of LAG in LZAG, LZAG:Ga³⁺, and LZAG:Cr³⁺ were discussed in detail.     

Significantly improved photoluminescence of the green-emitting β-sialon:Eu2+ phosphor via surface coating of TiO2

The β-sialon:Eu²⁺ phosphor particles were successfully coated by TiO₂ nanoparticles via the sol-gel method. The TiO₂-coated β-sialon:Eu²⁺ phosphor had a significantly improved photoluminescence (PL) performance under the 365 nm excitation, due to the localized surface plasmon resonance (LSPR) at the interface between the TiO₂ coating layer and phosphor surface. The emission intensity of the TiO₂-coated β-sialon:Eu²⁺ prepared with the titanium (IV) tetrabutoxide (Ti(OC₄H₉)₄, TTBO):H₂O = 1:0.5 volume ratio was dramatically increased by ~24%. When the preparation temperature was 500°C, it was responsible for superior PL intensity by considering the important domination factors of higher anatase content and spherical particle shape of the TiO₂ coating layer to the LSPR effect. The coating around the phosphor surface by the TiO₂ nanoparticles would be an effective technique to improve the PL efficiency of phosphor for the application in the white light-emitting diodes (LEDs), by utilizing the LSPR effect of the semiconductor coating layer, instead of conventional metal plasmonic materials.     

Cooperative cation substitution facilitated construction of garnet oxynitride MgY2Al3Si2O11N:Ce3+ for white LEDs

Structural modification is an important means to induce redshift of Ce³⁺ emission in garnet phosphor. We intend to design and synthesize garnet oxynitride compounds which combine attributes of rigidity inherited from garnet structure and of high covalence characteristic of oxynitride compounds. However, impurity phase usually occurs in the nitridation of garnet phosphor, due to the low solubility of nitrogen in oxides. We herein exploit the cooperative cation substitution strategy to facilitate the incorporation of nitrogen in Y₃Al₅O₁₂. It is found that partial substitution of Y³⁺‐Al_tet³⁺ pairs by Mg²⁺‐Si⁴⁺ pairs can diminish the phase instability caused by the replacement of Al_tet³⁺‐O^2? by Si⁴⁺‐N^3?. A novel pure garnet phase oxynitride phosphor MgY₂Al₃Si₂O₁₁N:Ce³⁺ with a higher substitution content of N has been obtained and the successful incorporation of N in the garnet phosphor is confirmed by the Rietveld refinements of XRD, XPS, and TEM. The emission and excitation spectra indicate that the blue‐light‐excitable MgY₂Al₃Si₂O₁₁N:Ce³⁺ phosphor exhibited a bright yellow‐orange emission peaking at 570 nm, which is redshifted by 28 nm when compared to YAG:Ce³⁺. The garnet oxynitride phosphor exhibit excellent thermal stability with high quantum efficiency and is a promising candidate for warm white LED.     

White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+=Eu3+, Dy3+) phosphors

A series of Eu³⁺- or Dy³⁺-doped and Eu³⁺/Dy³⁺ co-doped Y₂WO₆ in pure phase was synthesized via high-temperature solid-state reaction. X-ray diffraction, diffuse reflection spectra, photoluminescence excitation and emission spectra, the CIE chromaticity coordinates and temperature-dependent emission spectra were exploited to investigate the phosphors. Upon UV excitation at 310 nm, efficient energy transfer from the host Y₂WO₆ to dopant ions in Eu³⁺ or Dy³⁺ single-doped samples was demonstrated and those phosphors were suitable for the UV LED excitation. The intense red emission was observed in Y₂WO₆: Eu³⁺, and blue and yellow ones were observed in Y₂WO₆: Dy³⁺. Concentration quenching in Y₂WO₆: Dy³⁺ phosphors could be attributed to the electric dipole-dipole interaction. In Eu³⁺/Dy³⁺ co-doped Y₂WO₆ phosphors energy transfer process only took place from the host to Eu³⁺/Dy³⁺ ions and warm white-light emission can be obtained by adjusting the dopant concentrations. The temperature-dependent luminescence indicated Eu³⁺/Dy³⁺ co-doped Y₂WO₆ was thermally stable. Our overall results suggested that Y₂WO₆: Ln³⁺ (Ln³⁺=Eu³⁺, Dy³⁺) as warm white-light emitting host-sensitized phosphor might be potentially applied in WLEDs.     

白光LED用荧光粉的研究进展

白光LED被誉为第四代照明光源,有着显著的节能前景和庞大的应用市场,荧光粉光转换型是未来白光LED发展的主流方向。本文重点介绍了蓝光芯片激发的黄色,绿色和红色荧光粉以及紫光芯片激发的红色,绿色荧光粉的研究进展,和该领域存在的问题及其发展趋势。     

The hydrothermally synthesis of K3AlF6:Cr3+ NIR phosphor and its performance optimization based on phase control

Phosphor-convert (pc) near-infrared (NIR) LED is the next-generation smart NIR light sources. Thus, NIR phosphors are quickly developed. The K₃Al_1−xF₆:xCr³⁺ (KAF:Cr³⁺) NIR phosphor shows broadband emission from 650 to 900 nm under 430 nm and can be used to fabricate NIR LEDs. In this work, KAF:Cr³⁺ phosphors were prepared by a hydrothermal method for the first time. Morphologies and NIR properties are tuned by controlling the hydrothermal processes. Different from the cubic KAF:Cr³⁺ synthesized by a coprecipitation method, KAF:Cr³⁺ synthesized by the hydrothermal method shows the tetragonal phase. The optimized KAF:3%Cr³⁺ shows an internal quantum efficiency of about 31.4%. A NIR pc-LED device was fabricated by integrating the KAF:3%Cr³⁺ phosphor with a blue LED chip (~450 nm). The output power of NIR light is about 5.5 mW driven at 150 mA.     

Synthesis,crystal structure,and anti-thermal quenching performance of Lu2Sr(1−x)Al4SiO12:xEu2+ phosphors

With high-temperature solid-state reaction method, a series of Lu₂Sr_(1−x)Al₄SiO₁₂:xEu²⁺ phosphors have been synthesized. With Rietveld refinement method, the crystal structure of Lu₂SrAl₄SiO₁₂ has been refined. Under the excitation of the ultraviolet and violet band light, Lu₂Sr_(1−x)Al₄SiO₁₂:xEu²⁺ emits the Eu²⁺ characteristic blue broadband light. The photoluminescence properties of concentration quenching, emission peak shift, reflectance spectra, and luminescence decay have been investigated. With the structure analyses, the corresponding physical mechanisms have been discussed. With the increased temperature, this phosphor shows well thermal stabilities. For the x_Eu = 0.06, 0.08, and 0.1 phosphors, the strong anti-thermal quenching performance has been observed. The reason for the anti-thermal quenching of this phosphor has been discussed. The trap capture mechanism may be the suitable physical mechanism to explain the anti-thermal quenching of this phosphor. This phosphor shows the potential applications in the white LED lighting fields.     

A novel Mn4+‐activated red phosphor for use in light emitting diodes,K3SiF7:Mn4+

Phosphors that exhibit a narrow red emission are particularly interesting due to the advantage of providing a more extensive color gamut and better rendering in LED applications such as displays and solid‐state lighting. Although some Eu²⁺‐activated nitridosilicates have been discovered in this regard, K₂SiF₆:Mn⁴⁺ phosphors are the only option in actual LED applications thus far. We discovered a novel phosphor, K₃SiF₇:Mn⁴⁺, with P4/mbm symmetry. The luminescent properties of K₃SiF₇:Mn⁴⁺ are almost identical to those of the K₂SiF₆:Mn⁴⁺ phosphor, but its materials identity is distinct due to a completely different crystallographic structure, which leads to reduced decay time. The fast decay is one of the most serious disadvantages of existing K₂SiF₆:Mn⁴⁺ phosphors. The K₃SiF₇:Mn⁴⁺ phosphor was examined in comparison to the K₂SiF₆:Mn⁴⁺ via density functional theory calculation, Rietveld refinement, X‐ray photoelectron spectroscopy, X‐ray absorption near‐edge structure spectroscopy, and time‐resolved photoluminescence.     

LED发光材料的制备及应用前景

发光二极管（Light Emitting Diodes LED）在日常生活生产中得到了广泛的应用。本文对发光材料进行了分类,详细介绍了发光材料研究进展及具体制备方法,并对LED的研究进展、应用情况以及目前存在的一些问题进行阐述。     

Influence of Oxygen Vacancies on the Electronic Structure of Yttrium Oxide

The influence of oxygen vacancies on the electronic structure of yttrium oxide was investigated both experimentally and theoretically. By means of X-ray absorption spectroscopy, at the yttrium K and L ₁₁ edges and at the oxygen K edge, information on the local densities of states of various orbital symmetries, around each type of atom, was obained. The total density of states in the valence band was studied using X-ray photoelectron spectroscopy. Experimental results were compared with those obtained on stoichiometric yttria. The evolution of the densities of states is well reproduced by self-consistent, semiempirical tight-binding calculations applied to clusters of increasing size, in which oxygen vacancies are introduced. The charge transfer between oxygen and yttrium is modified, as experimentally observed from the study of the O KLL Auger line shape. The decrease of the local atomic charge on oxygen is theoretically confirmed by the tight-binding calculations, showing a tendency toward a more covalent bond in nonstoichiometric yttria.     

白光LED用新型荧光粉的探索

白光LED具有效率高、寿命长、响应快、安全、环保等优点,被誉为继白炽灯、荧光灯和高强度气体放电灯后的“第四代照明光源”.白光LED用荧光材料的制备及其发光性能的研究已成为半导体照明领域的一个热点.本文主要从蓝光芯片激发和近紫外光芯片激发的角度分别介绍了钼酸盐红色荧光粉和单一基质白光荧光粉的研究概况.     

Enhancing photoluminescence properties of Mn4+-activated Sr4−xBaxAl14O25 red phosphors for plant cultivation LEDs

Non–rare earth Mn⁴⁺-activated strontium aluminate phosphor is considered to be a promising material for plant cultivation field owing to their advantage of inexpensively, environment friendly, nontoxic, and appropriate spectral range. In this paper, a Sr_4−xBa_xAl_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ strontium aluminate phosphor is synthesized by a convenient high-temperature solid-state reaction. The photoluminescence spectra located at red region with a peak at 655 nm in the range of 600 to 750 nm that can be excited under the excitation of ultraviolet (~346 nm) or blue light (~450 nm). The shape emission band at 655 nm is attributed to the transition of ²E_g-⁴A_2g. Furthermore, the emission intensity of Sr_4−xBa_xAl_13.99O₂₅: 0.01Mn⁴⁺,1.4H₃BO₃ phosphor is conducted in detail with the variety of Ba²⁺ doping concentration and the intensity can be enhanced to 140.9% than the Sr₄Al_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ when the value of Ba²⁺ concentration equal to 0.1 mol. In addition, the X-ray diffraction spectra, element mapping, composition modifying, optical properties, FT-IR spectra, diffuse reflectance spectra, thermal stability, and fluorescence lifetime are systematically investigated. According to the electro-luminescent spectra of as-packaged LED, indicating that the Sr_3.9Ba_0.1Al_13.99O₂₅:0.01Mn⁴⁺,1.4H₃BO₃ phosphor will become a great candidate for plant cultivation LEDs due to the emission spectra match well the plant pigment spectrum.     

Tunable magnetic coupling and dipole polarization of core-shell Magnéli Ti4O7 ceramic/magnetic metal possessing broadband microwave absorption properties

There are few reports on the application of Magnéli Ti₄O₇ in the field of electromagnetic wave absorption. Herein, we designed and prepared a Ti₄O₇/magnetic metal composite via an electrostatic assembly with in-situ reduction reaction. This system utilized distinct magnetic coupling deriving from the subtle designed structures and magnetic-dielectric synergy. The core-shell magnetic metallic nanoparticles/oxygen deficient Ti₄O₇ are useful microwave absorbers in terms of wide broadband, strong absorption and ultra-low filler amount. The optimal reflection loss of Ti₄O₇@CoNi composite was −43.6 dB at 2.5 mm, meanwhile the effective absorbing band could reach over 5.12 GHz at only a 2.7 mm thickness. The results confirm that the dependence of the electromagnetic characteristics of the absorber on the filler ratio, frequency, and absorber thickness. Therefore, this work may be beneficial in constructing core-shell structured magnetic metal/Magnéli Ti₄O₇ composites to tune electromagnetic parameters and strengthen electromagnetic absorption.     

Crystal structure and luminescence mechanism of novel Fe3+-doped Mg0.752Al2.165O4 deep red-emitting phosphors

Nonstoichiometric alumina-rich spinel provides diverse and changeable local environments for transition-metal dopants. In this contribution, novel Mg_0.752Al_2.165−xO₄:xFe³⁺ deep red-emitting phosphors were designed and prepared by the solid-state reaction method. The red emission presents an unexpected shift from 735 to 770 nm by comparing with Fe³⁺-doped MgAl₂O₄. The excitation spectrum of Mg_0.752Al_2.165−xO₄:xFe³⁺ is broadened in the UV region with a new strong peak at 320 nm. The crystal structure refinement and NMR spectra fitting reveal that the cation vacancies and disorder increase with excess Al³⁺ entering the spinel crystal lattice. According to the results of EPR, NMR, and PL/PLE measurements, it was proposed that the Fe³⁺ ions locate at the distorted octahedral coordination. The changes of the local structure of Fe³⁺ ions promote the doublet state's involvement in the d−d transition. It was proposed that the new excitation peak at 320 nm in Mg_0.752Al_2.165−xO₄:xFe³⁺ is associated with the transitions from the ground state ⁶A_1g(⁶S) to the ⁴A_2g(⁴F)/T_1g(⁴P) and doublet states. The transition between the lower energy excited state of ²T_2g(²I) and ⁶A_1g(⁶S) mainly contributes to the deep red emission and the red-shifting effect.