Luminescence Tuning of Sr8MgCe(PO4)7:Eu2+,Mn2+ Phosphors: Structure Refinement,Site Occupancy,and Energy Transfer

Sr₈MgCe(PO₄)₇:Eu²⁺,Mn²⁺ phosphor with whitlockite‐type structure was prepared by a combustion‐assisted solid‐state reaction. The crystal structure and luminescence properties were investigated. Under UV radiation, Sr₈MgCe(PO₄)₇ host exhibits a violet‐blue emission band from Ce³⁺ ions. When Eu²⁺/Mn²⁺ are doped into the host, the samples excited with 270 nm UV radiation present multicolor emissions due to the energy transfer (ET) from Ce³⁺ to Eu²⁺/Mn²⁺. The emitting color of Sr₈MgCe(PO₄)₇:Eu²⁺ can be tuned from violet‐blue to yellow‐green, whereas Sr₈MgCe(PO₄)₇:Mn²⁺ can emit red light. Under excitation with long wavelength at 360 nm, Sr₈MgCe(PO₄)₇:Eu²⁺ phosphor shows a broadband emission from 390 to 700 nm, which is attributed to the 4f⁶5d¹→4f⁷ transition of Eu²⁺ without the contribution from Ce³⁺ emission. Tunable full‐color emitting light can be achieved in the Eu²⁺ and Mn²⁺‐codoped Sr₈MgCe(PO₄)₇ phosphor by ET_Eu–Mn through control of the levels of doped Eu²⁺ and Mn²⁺ ions. These results suggest that Sr₈MgCe(PO₄)₇:Eu²⁺,Mn²⁺ phosphor has potential applications in NUV chip pumped white LEDs.     

Synthesis,Persistent Luminescence,and Thermoluminescence Properties of Yellow Sr3SiO5:Eu2+,RE3+ (RE=Ce,Nd, Dy,Ho, Er,Tm, Yb) and Orange‐Red Sr3−xBaxSiO5:Eu2+, Dy3+ Phosphor

Sunlight‐excitable orange or red persistent oxide phosphors with excellent performance are still in great need. Herein, an intense orange‐red Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ persistent luminescence phosphor was successfully developed by a two‐step design strategy. The XRD patterns, photoluminescence excitation and emission spectra, and the thermoluminescence spectra were investigated in detail. By adding non‐equivalent trivalent rare earth co‐dopants to introduce foreign trapping centers, the persistent luminescence performance of Eu²⁺ in Sr₃SiO₅ was significantly modified. The yellow persistent emission intensity of Eu²⁺ was greatly enhanced by a factor of 4.5 in Sr₃SiO₅:Eu²⁺,Nd³⁺ compared with the previously reported Sr₃SiO₅:Eu²⁺, Dy³⁺. Furthermore, Sr ions were replaced with equivalent Ba to give Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ phosphor, which shows yellow‐to‐orange‐red tunable persistent emissions from λ=570 to 591 nm as x is increased from 0 to 0.6. Additionally, the persistent emission intensity of Eu²⁺ is significantly improved by a factor of 2.7 in Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ (x=0.2) compared with Sr₃SiO₅:Eu²⁺,Dy³⁺. A possible mechanism for enhanced and tunable persistent luminescence behavior of Eu²⁺ in Sr_3?xBa_xSiO₅:Eu²⁺,RE³⁺ (RE=rare earth) is also proposed and discussed.     

Synthesis,Structure, and Photoluminescence Properties of Novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+ Phosphors for White‐Light‐Emitting Diodes

A series of novel KBaSc₂(PO₄)₃:Ce³⁺/Eu²⁺/Tb³⁺phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce³⁺‐ and Eu²⁺‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc₂(PO₄)₃:Eu²⁺ and KBaSc₂(PO₄)₃:Ce³⁺ phosphors with Tb³⁺ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu²⁺ and Tb³⁺ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu²⁺→Tb³⁺ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc₂(PO₄)₃:Eu²⁺,Tb³⁺ and KBaSc₂(PO₄)₃:Ce³⁺,Tb³⁺ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.     

Energy Transfer from Ce3+ to Tb3+/Dy3+/Mn2+ in Ca9Ga(PO4)7 Phosphors: Synthesis,Structure and Tunable Multicolor Luminescent Properties

A series of Ca₉Ga(PO₄)₇:Ce³⁺/Tb³⁺/Dy³⁺/Mn²⁺ phosphors with tunable color, in which Ce³⁺ acts as the sensitizer, was synthesized. Energy transfer (ET) from Ce³⁺ to Tb³⁺/Dy³⁺/Mn²⁺ was investigated in detail. Tb³⁺/Dy³⁺/Mn²⁺ single-doped Ca₉Ga(PO₄)₇ can exhibit green, yellow, and red emission, respectively. Incorporating Ce³⁺ into a Tb³⁺/Dy³⁺/Mn²⁺ single-doped Ca₉Ga(PO₄)₇ phosphor can remarkably promote the luminous efficiency of the Tb³⁺/Dy³⁺/Mn²⁺ ions. This enhancement originates from an efficient ET from Ce³⁺ to Tb³⁺/Dy³⁺/Mn²⁺. The ET was validated by luminescence spectra, decay dynamics, and schematic energy levels. Moreover, the intensity ratio of red emission of Mn²⁺ to violet emission of Ce³⁺ was analyzed based on energy-transfer and lifetime measurements. In Ce³⁺-Tb³⁺, Ce³⁺-Dy³⁺, and Ce³⁺-Mn²⁺ doped Ca₉Ga(PO₄)₇, the emitting color changed from violet to green, yellow, and red, respectively, which indicates the potential use of this new tunable phosphor in UV light-emitting diodes.     

Ba3P5N10Br:Eu2+: A Natural‐White‐Light Single Emitter with a Zeolite Structure Type

Illumination sources based on phosphor‐converted light emitting diode (pcLED) technology are nowadays of great relevance. In particular, illumination‐grade pcLEDs are attracting increasing attention. Regarding this, the application of a single warm‐white‐emitting phosphor could be of great advantage. Herein, we report the synthesis of a novel nitridophosphate zeolite Ba₃P₅N₁₀Br:Eu²⁺. Upon excitation by near‐UV light, natural‐white‐light luminescence was detected. The synthesis of Ba₃P₅N₁₀Br:Eu²⁺ was carried out using the multianvil technique. The crystal structure of Ba₃P₅N₁₀Br:Eu²⁺ was solved and refined by single‐crystal X‐ray diffraction analysis and confirmed by Rietveld refinement and FTIR spectroscopy. Furthermore, spectroscopic luminescence measurements were performed. Through the synthesis of Ba₃P₅N₁₀Br:Eu²⁺, we have shown the great potential of nitridophosphate zeolites to serve as high‐performance luminescence materials.     

空气中合成固溶体荧光粉Ba2(Zn, Mg)Si2O7:Ce3+,Eu2+,Eu3+及其发光特性

采用高温固相法在空气中合成了Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu,yCe³⁺系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu²⁺离子的4f⁶5d¹-4f⁷跃迁,590~725 nm红光区窄带谱源于Eu³⁺的⁵D₀-⁷F_J (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu³⁺在Ba_1.97-yZn_1-xMg_xSi₂O₇基质中被还原成了Eu²⁺;当x=0.1时,荧光粉Ba_1.97Zn_0.9Mg_0.1Si₂O₇:0.03Eu的绿色发光最强,表明Eu³⁺被还原成Eu²⁺离子的程度最大。当共掺入Ce³⁺离子后,形成Ba_1.97-yZn_0.9Mg_0.1Si₂O₇:0.03Eu,yCe³⁺荧光粉体系,其发光随着Ce³⁺离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba_1.96Zn_0.9Mg_0.1Si₂O₇:0.01Ce³⁺,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba₂Zn_0.9Mg_0.1Si₂O₇基质中的能量传递与发光机理。     

Learning from a Mineral Structure toward an Ultra‐Narrow‐Band Blue‐Emitting Silicate Phosphor RbNa3(Li3SiO4)4:Eu2+

Learning from natural mineral structures is an efficient way to develop potential host lattices for applications in phosphor converted (pc)LEDs. A narrow‐band blue‐emitting silicate phosphor, RbNa₃(Li₃SiO₄)₄:Eu²⁺ (RNLSO:Eu²⁺), was derived from the UCr₄C₄‐type mineral model. The broad excitation spectrum (320–440 nm) indicates this phosphor can be well matched with the near ultraviolet (n‐UV) LED chip. Owing to the UCr₄C₄‐type highly condensed and rigid framework, RNLSO:Eu²⁺ exhibits an extremely small Stokes shift and an unprecedented ultra‐narrow (full‐width at half‐maximum, FWHM=22.4 nm) blue emission band (λ_em=471 nm) as well as excellent thermal stability (96 %@150 °C of the initial integrated intensity at 25 °C). The color gamut of the as‐fabricated (pc)LEDs is 75 % NTSC for the application in liquid crystal displays from the prototype design of an n‐UV LED chip and the narrow‐band RNLSO:Eu²⁺ (blue), β‐SiAlON:Eu²⁺ (green), and K₂SiF₆:Mn⁴⁺ (red) components as RGB emitters.     

A new disordered langbeinite‐type compound,K2Tb1.5Ta0.5P3O12, and Eu3+‐doped multicolour light‐emitting properties

For the first time, a new langbeinite‐type phosphate, namely potassium terbium tantalum tris(phosphate), K₂Tb_1.5Ta_0.5(PO₄)₃, has been prepared successfully using a high‐temperature flux method and has been structurally characterized by single‐crystal X‐ray diffraction. The results show that its structure can be described as a three‐dimensional open framework of [Tb_1.5Ta_0.5(PO₄)₃]_∞ interconnected by K⁺ ions. The Tb^III and Ta^V cations in the structure are disordered and occupy the same crystallographic sites. The IR spectrum, the UV–Vis spectrum, the morphology and the Eu³⁺‐activated photoluminescence spectroscopic properties were studied. A series of Eu³⁺‐doped phosphors, i.e. K₂Tb_1.5–xTa_0.5(PO₄)₃:xEu³⁺ (x = 0.01, 0.03, 0.05, 0.07, 0.10), were prepared via a solid‐state reaction and the photoluminescence properties were studied. The results show that under near‐UV excitation, the luminescence colour can be tuned from green through yellow to red by simply adjusting the Eu³⁺ concentration from 0 to 0.1, because of the efficient Tb³⁺→Eu³⁺ energy‐transfer mechanism.     

A New Mode of Energy Transfer between Mn2+ and Eu2+ in Nitride‐Based Phosphor SrAlSi4N7 with Tunable Light and Excellent Thermal Stability

In this work, reciprocal energy transfer between Mn²⁺ and Eu²⁺ ions in nitride SrAlSi₄N₇ has been found and investigated in detail. In contrast to Mn²⁺‐ and Eu²⁺‐activated oxide‐based phosphors, the red light centered at 608 nm is ascribed to 4f–5d transitions of Eu²⁺ ions and Mn²⁺‐activated SrAlSi₄N₇ emits a cyan light peaking at 500 nm. Additionally, the special broad excitation band of SrAlSi₄N₇:Mn²⁺ centered at 362 nm has been covered by that of Eu²⁺ ions ranging from 300 to 550 nm. The overlap of the energy level of Mn²⁺ and Eu²⁺ ions creates the conditions for reciprocal energy transfer between Eu²⁺ and Mn²⁺ ions. A series of SrAlSi₄N₇:0.002 Mn²⁺,xEu²⁺ (0≤x≤005) with tunable light emission have been synthesized and the decay curves of samples prove the reciprocal occurrence of the energy transfer between Mn²⁺ and Eu²⁺ ions. This mode of energy transfer not only prevents the loss of energy, but also improves the thermal stability, and the intensity of SrAlSi₄N₇:Mn²⁺,Eu²⁺ at 150 °C is still beyond 92 % of the initial intensity. The results provide a new mode of energy transfer, which is expected to reduce the drawbacks existing in energy transfer.     

Abnormal Anti‐Quenching and Controllable Multi‐Transitions of Bi3+ Luminescence by Temperature in a Yellow‐Emitting LuVO4:Bi3+ Phosphor for UV‐Converted White LEDs

Phosphors with an efficient yellow‐emitting color play a crucial role in phosphor‐converted white LEDs (pc‐WLEDs), but popular yellow phosphors such as YAG:Ce or Eu²⁺‐doped (oxy)nitrides cannot smoothly meet this seemingly simple requirement due to their strong absorptions in the visible range. Herein, we report a novel yellow‐emitting LuVO₄:Bi³⁺ phosphor that can solve this shortcoming. The emission from LuVO₄:Bi³⁺ shows a peak at 576 nm with a quantum efficiency (QE) of up to 68 %, good resistance to thermal quenching (T_{50 %}=573 K), and no severe thermal degradation after heating–cooling cycles upon UV excitation. The yellow emission, as verified by X‐ray photoelectron spectra (XPS), originates from the (³P₀,³P₁)→¹S₀ transitions of Bi³⁺. Increasing the temperature from 10 to 300 K produces a temperature‐dependent energy‐transfer process between VO₄^3? groups and Bi³⁺, and further heating of the samples to 573 K intensifies the emission. However, it subsequently weakens, accompanied by blueshifts of the emission peaks. This abnormal anti‐thermal quenching can be ascribed to temperature‐dependent energy transfer from VO₄^3? groups to Bi³⁺, a population redistribution between the excited states of ³P₀ and ³P₁ upon thermal stimulation, and discharge of electrons trapped in defects with a trap depth of 359 K. Device fabrication with the as‐prepared phosphor LuVO₄:Bi³⁺ has proved that it can act as a good yellow phosphor for pc‐WLEDs.     

A novel stibium phosphate,LiBa(SbO)2(PO4)3: synthesis,crystal structure and RE3+‐activated (RE = Tb3+ and Eu3+) fluorescence performance

A new stibium phosphate, lithium barium bis(antimony oxide) tris(phosphate), LiBa(SbO)₂(PO₄)₃, was prepared by the molten salt method with LiF as the flux. The crystal structure consists of an original three‐dimensional anionic framework of [(SbO)₂(PO₄)₃]_∞ built from PO₄ tetrahedra sharing their corners with SbO₆ octahedra. This framework delimits one‐dimensional tunnels where the lithium(I) and barium(II) ions are located. The UV–Vis spectrum shows that LiBa(SbO)₂(PO₄)₃ was transparent from 350 to 800 nm, and is thus suitable as a luminescent host matrix. We then used Tb³⁺ and Eu³⁺ activators to test its luminous performance and the purities of the prepared phosphors were studied by powder X‐ray diffraction analysis with Rietveld refinements. Photoluminescence (PL) studies reveal that the emission spectra of 1 mol% RE³⁺‐doped (RE = Tb and Eu) samples can be excited by 371 and 394 nm light, emitting green and orange–red light, respectively, for Tb³⁺ and Eu³⁺. The CIE coordinates were measured to be (0.295, 0.571) and (0.6027, 0.3967), and the luminescent lifetimes were calculated as 0.178 and 1.159 ms, respectively.     

Synthesis and Characterization of Europium‐exchanged Titanate Nanoporous Phosphors

Eu_x(NH₄)_2‐2xTi₃O₇ nanoporous phosphor was prepared by ion exchange method. (NH₄)₂Ti₃O₇ nanotubes were employed as the host structure by treating H₂Ti₃O₇ with NH₄OH solution and the activator, Eu²⁺, was introduced into the host via ion exchange. This is an easy and feasible way to prepare a phosphor. The synthesized samples were characterized using TEM, XRD, N₂ adsorption‐desorption isotherm, TPR, and fluorescence spectrophotometer. Experimental results showed that a portion of Eu²⁺ ions was oxidized into Eu³⁺ ions during ion exchange, resulting in the present phosphor with blue‐emitting and red‐emitting. Moreover, the tubular structure of Eu_x(NH₄)_2‐2xTi₃O₇ was distorted as Eu²⁺ was placed into the host structure. This distortion is attributed to the electrostatic interaction between Eu²⁺ and the electric field of the host structure.     

Improvement of the Water Resistance of a Narrow‐Band Red‐Emitting SrLiAl3N4:Eu2+ Phosphor Synthesized under High Isostatic Pressure through Coating with an Organosilica Layer

A SrLiAl₃N₄:Eu²⁺ (SLA) red phosphor prepared through a high‐pressure solid‐state reaction was coated with an organosilica layer with a thickness of 400–600 nm to improve its water resistance. The observed 4f⁶5d→4f⁷ transition bands are thought to result from the existence of Eu²⁺ at two different Sr²⁺ sites. Luminescence spectra at 10 K revealed two zero‐phonon lines at 15377 (for Eu(Sr1)) and 15780 cm^?1 (for Eu(Sr2)). The phosphor exhibited stable red emission under high pressure up to 312 kbar. The configurational coordinate diagram gave a theoretical explanation for the Eu^2+/3+ result. The coated samples showed excellent moisture resistance while retaining an external quantum efficiency (EQE) of 70 % of their initial EQE after aging for 5 days under harsh conditions. White‐light‐emitting diodes of the SLA red phosphor and a commercial Y₃Al₅O₁₂:Ce³⁺ yellow phosphor on a blue InGaN chip showed high color rendition (CRI=89, R9=69) and a low correlated color temperature of 2406 K.     

Ultra‐Narrow‐Band Blue‐Emitting Oxoberyllates AELi2[Be4O6]:Eu2+ (AE=Sr,Ba) Paving the Way to Efficient RGB pc‐LEDs

Highly efficient phosphor‐converted light‐emitting diodes (pc‐LEDs) are popular in lighting and high‐tech electronics applications. The main goals of present LED research are increasing light quality, preserving color point stability and reducing energy consumption. For those purposes excellent phosphors in all spectral regions are required. Here, we report on ultra‐narrow band blue emitting oxoberyllates AELi₂[Be₄O₆]:Eu²⁺ (AE=Sr,Ba) exhibiting a rigid covalent network isotypic to the nitridoalumosilicate BaLi₂[(Al₂Si₂)N₆]:Eu²⁺. The oxoberyllates’ extremely small Stokes shift and unprecedented ultra‐narrow band blue emission with fwhm ≈25 nm (≈1200 cm^?1) at λ_em=454–456 nm result from its rigid, highly condensed tetrahedra network. AELi₂[Be₄O₆]:Eu²⁺ allows for using short‐wavelength blue LEDs (λ_em<440 nm) for efficient excitation of the ultra‐narrow band blue phosphor, for application in violet pumped white RGB phosphor LEDs with improved color point stability, excellent color rendering, and high energy efficiency.     

Dual‐Shelled RbLi(Li3SiO4)2:Eu2+@Al2O3@ODTMS Phosphor as a Stable Green Emitter for High‐Power LED Backlights

The stability of luminescent materials is a key factor for the practical application in white light‐emitting diodes (LEDs). Poor chemical stability of narrow‐band green‐emitting RbLi(Li₃SiO₄)₂:Eu²⁺ (RLSO:Eu²⁺) phosphor hinders their further commercialization even if they have excellent stability against thermal quenching. Herein, we propose an efficient protection scheme by combining the surface coating of amorphous Al₂O₃ and hydrophobic modification by octadecyltrimethoxysilane (ODTMS) to construct the moisture‐resistant dual‐shelled RLSO:Eu²⁺@Al₂O₃@ODTMS composite. The growth mechanisms of both the Al₂O₃ inorganic layer and the silane organic layer on the phosphor surface are investigated. The results remarkably improve the water‐stability of this narrow‐band green emitter. The evaluation of the white LED by employing this composite as the green component demonstrates that RLSO:Eu²⁺@Al₂O₃@ODTMS is a promising candidate for the high‐performance display backlights, and this dual‐shelled strategy provides an alternative method to improve the moisture‐resistant property of humidity‐sensitive phosphors.     

Tailoring of Deep‐Red Luminescence in Ca2SiO4:Eu2+

We report a new dicalcium silicate phosphor, Ca_2?xEu_xSiO₄, which emits red light in response to blue‐light excitation. When excited at 450 nm, deep‐red emission at 650 nm was clearly observed in Ca_1.2Eu_0.8SiO₄, the external and internal quantum efficiencies of which were 44 % and 50 %, respectively. The red emission from Ca_2?xEu_xSiO₄ was strongly related to the peculiar coordination environments of Eu²⁺ in two types of Ca sites. The red‐emitting Ca₂SiO₄:Eu²⁺ phosphors are promising materials for next‐generation, white‐light‐emitting diode applications.     

Color Point Tuning in Lu3−x−yMnxAl5−xSixO12:yCe3+ for White LEDs

A series of the solid‐solution phosphors Lu_3?x?yMn_xAl_5?xSi_xO₁₂:yCe³⁺ is synthesized by solid‐state reaction. The obtained phosphors possess the garnet structure and exhibit similar excitation properties as the phosphor Lu₃Al₅O₁₂:Ce³⁺, but with an effectively improved red component in the emission spectrum. This can be attributed to the energy transfer from Ce³⁺ to Mn²⁺. Our investigation reveals that electric dipole–quadrupole interactions dominate the energy‐transfer mechanism and that the critical distance determined by the spectral overlap method is about 9.21 Å. The color‐tunable emissions of the Lu_3?x?yMn_xAl_5?xSi_xO₁₂:yCe³⁺ phosphor as a function of Mn₃Al₂Si₃O₁₂ content are realized by continuously shifting the chromaticity coordinates from (0.354, 0.570) to (0.462, 0.494). They indicate that the obtained material may have potential application as a blue radiation‐converting phosphor for white LEDs with high‐quality white light.     

Luminescence Tuning and White‐Light Emission of Co‐doped Ln–Cd–Organic Frameworks

Four new three‐dimensional isostructural lanthanide–cadmium metal–organic frameworks (Ln–Cd MOFs), [LnCd₂(imdc)₂(Ac)(H₂O)₂]?H₂O (Ln=Pr ( 1 ), Eu ( 2 ), Gd ( 3 ), and Tb ( 4 ); H₃imdc=4,5‐imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X‐ray diffraction. Single‐crystal X‐ray diffraction shows that two Ln^III ions are surrounded by four Cd^II ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln–Cd MOFs by the bridging imdc^3? ligand. Furthermore, the left‐ and right‐handed helices array alternatively in the lattice. Eu–Cd and Tb–Cd MOFs can emit characteristic red light with the Eu^III ion and green light with the Tb^III ion, respectively, while both Gd–Cd and Pr–Cd MOFs generate blue emission when they are excited. Different concentrations of Eu³⁺ and Tb³⁺ ions were co‐doped into Gd–Cd/Pr–Cd MOFs, and tunable luminescence from yellow to white was achieved. White‐light emission was obtained successfully by adjusting the excitation wavelength or the co‐doping ratio of the co‐doped Gd–Cd and Pr–Cd MOFs. These results show that the relative emission intensity of white light for Gd–Cd:Eu³⁺,Tb³⁺ MOFs is stronger than that of Pr–Cd:Eu³⁺,Tb³⁺ MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white‐light emission materials.     

空气中合成固溶体荧光粉Ba_2(Zn,Mg)Si_2O_7∶Eu~(2+),Eu~(3+),Ce~(3+)及其发光特性

采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7∶0.03Eu,y Ce3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7∶0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f 65d1-4f 7跃迁,590~725 nm红光区窄带谱源于Eu3+的5D0-7FJ(J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7∶0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7∶0.03Eu,y Ce3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7∶0.03Eu,0.01Ce3+的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。     

Three Lanthanide Metal‐Organic Frameworks Based on an Ether‐Decorated Polycarboxylic Acid Linker: Luminescence Modulation,CO2 Capture and Conversion Properties

Three new isostructural 3D lanthanide metal–organic frameworks (Ln‐MOFs), {H[LnL(H₂O)]?2 H₂O}_n ( 1‐Ln ) (Ln=Eu³⁺, Gd³⁺ and Tb³⁺), based on infinite lanthanide‐carboxylate chains were constructed by employing an ether‐separated 5,5′‐oxydiisophthalic acid (H₄L) ligand under solvothermal reaction. 1‐Eu and 1‐Tb exhibit strong red and green emission, respectively, through the antenna effect, as demonstrated through a combination of calculation and experimental results. Moreover, a series of dichromatic doped 1‐Eu_xTb_y MOFs were fabricated by introducing different concentrations of Eu³⁺ and Tb³⁺ ions, and they display an unusual variation of luminescent colors from green, yellow, orange to red. 1‐Eu with channels decorated by ether O atoms and the open metal sites displays good performance for CO₂ capture and conversion between CO₂ and epoxides into cyclic carbonates.