Pressure‐Driven Eu2+‐Doped BaLi2Al2Si2N6: A New Color Tunable Narrow‐Band Emission Phosphor for Spectroscopy and Pressure Sensor Applications

A series of BaLi₂Al₂Si₂N₆ (BLASN): xEu²⁺ phosphors are successfully synthesized and their crystal structure and luminescence properties under varying hydrostatic pressures are reported herein. Structure variation is analyzed using in situ high‐pressure X‐ray diffraction and Rietveld refinements. Based on decay curves and Gaussian fitting of emission spectra, the presence of two photoluminescence centers is demonstrated. BaLi₂Al₂Si₂N₆: 0.01Eu²⁺ exhibits an evident peak position shift from 532 to 567 nm with an increase in pressure to ≈20 GPa. The possible factors and mechanisms for the variations are studied in detail. At a pressure of 16 GPa, BLASN: Eu²⁺ realizes a narrow yellow emission with a full width at half maximum of ≈70 nm. The addition of BLASN: Eu²⁺ (16 GPa) to the commercial white light‐emitting diodes combination consisting of an InGaN chip, β‐SiAlON: Eu²⁺, and red K₂SiF₆:Mn⁴⁺, can increase the color gamut by ≈15%, demonstrating the promising potential of pressure‐driven BLASN: Eu²⁺ for wide‐color gamut spectroscopy applications. Moreover, the emission shifts arising from pressure variation and the distinct color changes enable its potential utility as an optical pressure sensor; the material exhibits high pressure sensitivity (dλ/dP ≈ 1.58 nm GPa^?1) with the advantage of visualization.     

Multi-Mode Optical Manometry Based on Li4SrCa(SiO4)2:Eu2+ Phosphors

Optical manometry is a highly promising method for measuring pressure. However, its wider application is limited by the lower sensitivity and influenced by environmental factors. Herein, multi-mode optical pressure sensors based on Eu²⁺-doped Li₄SrCa(SiO₄)₂ phosphors suitable for a variety of complex pressure-measuring environments are designed. The phosphors contain two separate luminescence centers at 443 nm (Eu_Sr) and 584 nm (Eu_Ca), respectively. In the lower pressure range, the emission peak undergoes a massive redshift of 5.19 nm GPa⁻¹ of Eu_Ca, which is 14× better than commercially available ruby sensors. In order to improve the pressure response range and the accuracy of pressure measurement, for the first time, a new approach in the pressure readout method in which single Eu²⁺ ions doping based on fluorescence intensity ratio (FIR) pressure measurement is realized in designed materials. Meanwhile, the measured full width at half maximum (FWHM) as an indicator of pressure sensor performance also reveals that the sensing performance is d FWHM/d P ≈ 1.23 nm GPa⁻¹ and d FWHM/d P ≈ 0.84 nm GPa⁻¹ for Eu_Sr and Eu_Ca positions, respectively. Additionally, the structural stability of the phosphor is confirmed by in situ Raman spectrum. The above results indicate that the Li₄SrCa(SiO₄)₂:0.04Eu²⁺ phosphor is a good candidate for multi-mode optical pressure sensors.     

Enhanced Photoluminescence and Photoresponsiveness of Eu3+ Ions-Doped CsPbCl3 Perovskite Quantum Dots under High Pressure

Metal halide perovskite quantum dots (QDs) have garnered tremendous attention in optoelectronic devices owing to their excellent optical and electrical properties. However, these perovskite QDs are plagued by pressure-induced photoluminescence (PL) quenching, which greatly restricts their potential applications. Herein, the unique optical and electrical properties of Eu³⁺-doped CsPbCl₃ QDs under high pressure are reported. Intriguingly, the PL of Eu³⁺ ions displays an enhancement with pressure up to 10.1 GPa and still preserves a relatively high intensity at 22 GPa. The optical and structural analysis indicates that the sample experiences an isostructural phase transition at approximately 1.53 GPa, followed by an amorphous state evolution, which is simulated and confirmed through density functional theory calculations. The pressure-induced PL enhancement of Eu³⁺ ions can be associated with the enhanced energy transfer rate from excitonic state to Eu³⁺ ions. The photoelectric performance is enhanced by compression and can be preserved upon the release of pressure, which is attributed to the decreased defect density and increased carrier mobility induced by the high pressure. This work enriches the understanding of the high-pressure behavior of rare-earth-doped luminescent materials and proves that high pressure technique is a promising way to design and realize superior optoelectronic materials.     

Giant Red-Shifted Emission in (Sr,Ba)Y2O4:Eu2+ Phosphor Toward Broadband Near-Infrared Luminescence

Near-infrared (NIR) light-emitting diodes (LEDs) light sources are desirable in photonic, optoelectronic, and biological applications. However, developing broadband red and NIR-emitting phosphors with good thermal stability is always a challenge. Herein, the synthesis of Eu²⁺-activated SrY₂O₄ red phosphor with high photoluminescence quantum efficiency and broad emission band ranging from 540 to 770 nm and peaking at 620 nm under 450 nm excitation is designed. Sr/Ba substitution in SrY₂O₄:Eu²⁺ has been further utilized to achieve tunable emission by modifying the local environment, which facilitates the giant red-shifted emission from 620 to 773 nm while maintaining the outstanding thermal stability of SrY₂O₄:Eu²⁺. The NIR emission is attributed to the enhanced Stokes shift and crystal field strength originated from the local structural distortions of [Y1/Eu1O₆] and [Y2/Eu2O₆]. The investigation in charge distribution around Y/Eu provides additional insight into increasing covalency to tune the emission toward the NIR region. As-fabricated NIR phosphor-converted LEDs demonstration shows its potential in night-vision technologies. This study reveals the NIR luminescence mechanism of Eu²⁺ in oxide-based hosts and provides a design principle for exploiting Eu²⁺-doped NIR phosphors with good thermal stability.     

Multimode Emission from Lanthanide-Based Metal–Organic Frameworks for Advanced Information Encryption

Although remarkable progress on luminescent materials is made in advanced optical information storage and anti-counterfeiting applications, many challenges still remain in these fields. Currently, most luminescent materials are based on a single photoluminescent model that can be easily imitated by substitutes. In this work, a series of multimodal emission lanthanide-based metal–organic frameworks (MOFs) are developed, where they emit red and green light originating from Eu³⁺ and Tb³⁺ under ultraviolet light irradiation. Meanwhile, under 980 nm near-infrared laser irradiation, these MOFs show cyan upconversion cooperative luminescence derived from Yb³⁺ and characteristic upconversion luminescence from lanthanide activators (Eu³⁺, Tb³⁺, or Ho³⁺), respectively. Based on the integrated optical functionality, the functional information storage applications are successfully designed, which indicates that multimodal emission features can be easily detected under ultraviolet lamps (254 or 393 nm) or 980 nm near-infrared laser. And, the unique optical features show a high level of security in the advanced information storage application, which would be sufficiently complex to be forged.     

Effect of europium doping levels on photoluminescence and thermoluminescence of strontium yttrium oxide phosphor

The present paper deals with the effect of europium (Eu³⁺) doping concentration (0.1–2.5 mol%) on photoluminescence (PL) and thermoluminescence (TL) of strontium yttrium oxide (SrY₂O₄) phosphor. The sample was prepared by the modified solid state reaction method, which is the most suitable method for large-scale production. The prepared phosphor sample was characterized by using X-ray Diffraction (XRD), field emission gun scanning electron microscopy, fourier transform infrared spectroscopy, high resolution transmission electron microscopy, photoluminescence, thermoluminescence and commission internationale de I׳Eclairage techniques. The PL emission was observed in the range of 410–630 nm for the SrY₂O₄ phosphor doped with Eu³⁺. Excitation spectrum was found at 254 and 325 nm, sharp peaks were found around 593, 615 and 625 nm with high intensity. From the XRD data, using Scherrer׳s formula, calculated average crystallite size of Eu³⁺ doped SrY₂O₄ phosphor is around 32 nm. Thermoluminescence study was carried out for the phosphor with UV and gamma irradiation. The TL response of SrY₂O₄:Eu³⁺ phosphor for two different radiations was compared and studied in detail. The present phosphor can act as a single host for white light emission in display devices. The detailed process and possible mechanisms for PL and TL are studied and discussed. For the variable concentration of Eu³⁺ on PL studies the PL intensity increases with increasing the concentration of dopant and the concentration quenching found after 2 mol% of Eu³⁺ the optimized concentration was 2 mol%, which is suitable for the display device application. In TL glow curve the optimized concentration was 1 mol% for the UV irradiated sample and 0.2 mol% of Eu³⁺ for the gamma irradiated sample and beta irradiated sample for 10 Gy dose. The kinetic parameters were calculated by the computerized glow curve deconvolution (CGCD) technique.     

Application research of CdS: Eu3+ quantum dots-sensitized TiO2 nanotube solar cells

Trivalent Eu³⁺-doped CdS quantum dot (CdS: Eu³⁺ QD)-sensitized TiO₂ nanotube arrays (TNTAs) solar cells are prepared by using the direct adsorption method. The influences of sensitization time, sensitization temperature, and Eu³⁺ ion concentrations are investigated systematically. The photo-current of the CdS: Eu³⁺ QDs/TiO₂ nanotubes appear at the main absorption region of 320–480 nm, and the maximum incident photon to the current conversion efficiency (IPCE) value is 21% at 430 nm when the sensitization condition is 4% doping Eu³⁺ concentration, 60 °C sensitization temperature, 8 h sensitization time. Compared with the un-doped CdS QD-sensitized TNTAs, the conversion efficiency and IPCE of CdS: Eu³⁺ QDs/TNTAs are two times and three times than that of un-doped CdS QDs sensitized TNTAs. This scenario exhibits the potential applications of rare earth elements in QD-sensitized solar cells.     

Direct white-light from core-shell-like sphere with Sr3Mg-Si2O8: Eu2+, Mn2+ coated on Sr2SiO4:Eu2+

A method of color mixture for white light is presented with Sr3MgSi2O8:Eu2+, Mn2+ shell coated on Sr2SiO4:Eu2+ core by spray pyrolysis procedure. Upon near ultraviolet (NUV) excitation, a 550 nm band emission of Eu2+ from core host combines with the simultaneous emissions of Eu2+ at 457 nm and Mn2+ at 683 nm based on energy transfer in the shell lattice to generate warm white light with color rendering index (CRI) of 91. With such a core-shell-like structure, the re-absorption of blue light from shell layer can be effectively suppressed, and the chemical stability of the phosphor is verified experimentally to be superior to that of the Sr2SiO4:Eu2+. This new proposed phosphor provides great potential in the color mixture of blending-free phosphor converted white NUV light emitting diode (LED) devices.     

BaSi2O5荧光粉中Eu2+的制备，电子结构和荧光性质

绿色发射磷光剂BaSi2O5：Eu2+是由常见的固体反应合成。在CASTEP代码中,BaSi2O5可视为存在3.2eV直能隙的媒介带隙半导体。正如预期所料的,BaSi2O5光学带隙的计算值比对应的实验值低。200-400nm宽光谱范围可以有效地激活活化的Eu2 的BaSi2O5磷光剂,当最大半宽为95nm时,500nm处有一个发射峰。浓度和发射强度的研究表明Eu2 的最优浓度是0.05mol,当Eu2 容量超过临界值时,会出现浓度淬灭。最优条件的BaSi2O5的外量子效率：在315nm、350nm和365nm的激发下,Eu2 分别是96.1%、70.2%和62.1%。样品优越的光学性能表明绿色发射磷光剂可替代白光LED。     

Enhanced efficiency of organic photovoltaic cells with Sr2SiO4:Eu2+ and SrGa2S4:Eu2+ phosphors

We report the effect of yellow Sr₂SiO₄:Eu²⁺ and green SrGa₂S₄:Eu²⁺ phosphors on the efficiency of organic photovoltaic (OPV) cells. Each phosphor was coated on the back side of indium tin oxide (ITO)/glass substrates by spin coating with poly(methyl methacrylate) (PMMA). The maximum absorption wavelength of the active layer in the OPV cells was ～512 nm. The emission peaks of Sr₂SiO₄:Eu²⁺ and SrGa₂S₄:Eu²⁺ were maximized at 552 nm and 534 nm, respectively. The short circuit current density (J_sc) and power conversion efficiency (PCE) of the OPV cells with Sr₂SiO₄:Eu²⁺ (8.55 mA/cm² and 3.25%) and with SrGa₂S₄:Eu²⁺ (9.29 mA/cm² and 3.3%) were higher than those of the control device without phosphor (7.605 mA/cm² and 3.04%). We concluded that phosphor tuned the wavelength of the incident light to the absorption wavelength of the active layer, thus increasing the J_sc and PCE of the OPV cells.     

Fluorescence enhancement of single-phase red-blue emitting Ba3MgSi2O8:Eu2+,Mn2+ phosphors via Dy3+ addition for plant cultivation

Fluorescence enhancement of red and blue concurrently emitting Ba₃MgSi₂O₈:Eu²⁺,Mn²⁺ phosphors for plant cultivation has been investigated by Dy³⁺ addition. The Ba₃MgSi₂O₈:Eu²⁺,Mn²⁺,Dy³⁺(BMS-EMD) phosphors have two-color emissions at the wavelength peak values of 437 nm and 620 nm at the excitation of 350 nm. The two emission bands are coincident with the absorption spectrum for photosynthesis of plants. An obvious enhancement effect has been observed upon addition of Dy³⁺ with amount of 0.03 mol%, in which the intensities of both blue and red bands reach a maximum. The origin of red and blue emission bands is analysed. The photochromic parameters of the samples at the nearly UV excitation are tested. This fluoresence enhancement is of great significance for special solid state lighting equipment used in plant cultivation. This work has been supported by National Natural Science Foundation of China (Grant No 50872091) and the Natural Science Foundation of Tianjin, China (06YFJMJC02300, 06TXTJJC14602).     

Polyhedron Transformation toward Stable Narrow‐Band Green Phosphors for Wide‐Color‐Gamut Liquid Crystal Display

A robust and stable narrow‐band green emitter is recognized as a key enabler for wide‐color‐gamut liquid crystal display (LCD) backlights. Herein, an emerging rare earth silicate phosphor, RbNa(Li₃SiO₄)₂:Eu²⁺ (RN:Eu²⁺) with exceptional optical properties and excellent thermal stability, is reported. The resulting RN:Eu²⁺ phosphor presents a narrow green emission band centered at 523 nm with a full width at half maximum of 41 nm and excellent thermal stability (102%@425 K of the integrated emission intensity at 300 K). RN:Eu²⁺ also shows a high quantum efficiency, an improved chemical stability, and a reduced Stokes shift owing to the modified local environment, in which [NaO₈] cubes replace [LiO₄] squares in RbLi(Li₃SiO₄)₂:Eu²⁺ via polyhedron transformation. White light‐emitting diode (wLED) devices with a wide color gamut (113% National Television System Committee (NTSC)) and high luminous efficacy (111.08 lm W^?1) are obtained by combining RN:Eu²⁺ as the green emitter, K₂SiF₆:Mn⁴⁺ as the red emitter, and blue‐emitting InGaN chips. Using these wLEDs as backlights, a prototype 20.5 in. LCD screen is fabricated, demonstrating the bright future of stable RN:Eu²⁺ for wide‐color‐gamut LCD backlight application.     

An Advanced Tunable Multimodal Luminescent La4GeO8: Eu2+, Er3+ Phosphor for Multicolor Anticounterfeiting

The development of advanced luminescent materials is of great importance to the anticounterfeiting application and still confronts with lots of challenges. At present, most anticounterfeiting luminescent materials are based on a monotonous photoluminescence model, which is easily faked by substitutes. Therefore, in this work, a multimodal La₄GeO₈: Eu²⁺, Er³⁺ material is reported, which can emit red, purple, baby blue, and green light under the increased excitation wavelength from 250 to 380 nm. Meanwhile, the phosphor also shows green upconversion luminescence under the NIR (980 and 808 nm) laser irradiation. Moreover, the phosphor features excellent stability and humidity resistance against harsh conditions. Based on the integrated feature, a functional anticounterfeiting application is designed. Results demonstrate that the multimodal luminescent feature can be easily detected by using a portable ultraviolet lamp or NIR (808 or 980 nm) laser. The unique characteristic will be complicated to counterfeit and show high-level security in the field of advanced anticounterfeiting.     

White OLED based on a temperature sensitive Eu3+/Tb3+ β-diketonate complex

A mixed lanthanide β-diketonate complex of molecular formula [Eu_0.45Tb_0.55(btfa)₃(4,4′-bpy)(EtOH)] (btfa^– = 4,4,4–trifluoro–1–phenyl–1,3–butanedionate; 4,4′-bpy = 4,4′-dipyridyl; EtOH = ethanol) was synthesized and its structure was elucidated by single crystal X-ray diffraction. The temperature dependence of the complex emission intensity between 11 and 298 K is illustrated by the Commission Internacionale l’Éclairage (CIE) (x, y) color coordinates change within the orange-red region, from (0.521, 0.443) to (0.658, 0.335). The existence of Tb³⁺-to-Eu³⁺ energy transfer was observed at room temperature and as the complex presents a relatively high emission quantum yield (0.34 ± 0.03) it was doped in a 4,4′-bis(carbazol-9-yl)biphenyl (CBP) organic matrix to be used as emitting layer to fabricate a white organic light-emitting diode (WOLED). Continuous electroluminescence emission was obtained varying the applied bias voltage showing a wide emission band from 400 to 700 nm. The white emission results from a combined action between the Eu³⁺ and Tb³⁺ peaks from the mixed Eu³⁺/Tb³⁺ complex and the other organic layers forming the device. The intensity ratio of the peaks is determined by the layer thickness and by the bias voltage applied to the OLED, allowing us to obtain a color tunable light source.     

The Effects of Heat Treatment on the Crystallinity and Luminescence Properties of YInGe<Subscript>2</Subscript>O<Subscript>7</Subscript> Doped with Eu<Superscript>3+</Superscript> Ions

Yttrium indium germanate, YInGe₂O₇, doped with Eu³⁺ ions was synthesized by a solid-state reaction using a vibrating mill with metal oxides. The compound was characterized and its optical properties were investigated. The yielded powders were heated at various temperatures from 1100°C to 1400°C in air for 10 h. The X-ray diffraction profiles showed that all peaks could be attributed to the monoclinic YInGe₂O₇ phase at the various calcination temperatures for YInGe₂O₇ doped with 5 mol.% Eu³⁺ ions. A second phase of In₂O₃ was observed in the X-ray powder diffractometry pattern when the calcination temperature was over 1200°C. Scanning electron microscopy showed that the particle sizes increased significantly with increasing calcination temperature. The calcined powders emitted a reddish luminescence centered at 611 nm under excitation of 393 nm due to the electric dipole transition ⁵D₀ → ⁷F₂. Powders fired at 1200°C were found to have the maximum photoluminescent intensity for YInGe₂O₇ doped with 5 mol.% Eu³⁺ ions. Furthermore, the existence of the second phase caused the decay time to decrease with increasing calcination temperature.     

Preparation and luminescence of europium-doped lanthanum fluoride–benzoic acid hybrid nanostructures

Europium-doped lanthanum fluoride (LaF₃:Eu³⁺) nanoparticles were synthesized using a solvothermal method, and they were then capped with benzoic acid (BA) ligands to form LaF₃:Eu³⁺–BA hybrid nanostructures. The LaF₃:Eu³⁺–BA hybrid nanostructures showed strong luminescence as a result of energy transfer from BA to the Eu³⁺ ions of the LaF₃:Eu³⁺ nanoparticles. The dominant excitation band for the LaF₃:Eu³⁺–BA hybrid nanostructures ranged from 200 nm to 300 nm. It has been shown that the luminescence of LaF₃:Eu³⁺–BA hybrid nanostructures strongly depends on the pH value and content of benzoic acid used in the preparation of the hybrid nanostructures. An X-ray diffraction technique, transmission electron microscopy, luminescence spectroscopy, Fourier transform infrared spectroscopy and a UV–vis spectrophotometer were used to characterize the products.     

Fluorosilicate and fluorophosphate superfluorescent multicore optical fibers co-doped with Nd3+/Yb3+

In the paper spectroscopic properties of two fluorosilicate and fluorophosphate glass systems co-doped with Nd³⁺/Yb³⁺ ions are investigated. As a result of optical excitation at the wavelength of 808 nm strong and wide emission in the 1 μm region corresponding to the superposition of optical transitions ⁴F_3/2 → ⁴I_11/2 (Nd³⁺) and ²F_5/2 → ²F_7/2 (Yb³⁺) can be observed. The optimization of Nd³⁺ → Yb³⁺ energy transfer in both glasses allows to manufacture multicore optical fibers with narrowing and red-shifting of amplified spontaneous emission (ASE) at 1.1 μm.     

Fabrication and study of properties of the PLA/Sr2MgSi2O7:Eu2+, Dy3+ long-persistent luminescence composite thin films

In this paper, Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ (SMS) particles were first synthesized by sol–gel method and then modified with 3-aminopropyltriethoxysilane (APS) to improve their dispersibility and compatibility in the polylactic acid (PLA) matrix. The structure of pure SMS particles was analyzed by XRD and XPS. The properties of SMS particles before and after modification were characterized by FT-IR and SEM. PLA/SMS composite films containing 15 wt% of SMS particles were prepared by spin coating on silicon wafer. Their morphology and luminescence properties were examined. It was found that the composite films can be excited by a broad band from 330 nm to 425 nm with the highest excitation intensity at 360 nm. The fluorescent and phosphorescent emission bands of the composite films and SMS particles all have a major emission peak at 468 nm. Decay curves of the composite films have a similar tendency with that of the pure SMS particles, except for the lower intensity.     

Composition-induced valence variation of europium and the photoluminescence properties for Eu2+ doped borophosphate luminous glass in air

A simultaneous blue-light and red-light emitting glass of SrO-B2O3-P2O5 doped with Eu2O3 is prepared in air, and then heat-treated without any reductive reagent. A transition combination is found to consist of a band emission peaked around 430 nm and a series of line emission from 593 nm to 611 nm, corresponding to the typical 4f65d→ 4f7 transition of Eu2+ and 5D0 → 7FJ (J = 0, 1, 2, 3, 4) transitions of Eu3+, respectively. Some unidentified crystals such as Sr (PO3)2 and SrB2O4 as hosts for Eu2...     

Preparation and luminescent properties of novel red phosphors for white-light emitting diodes (W-LEDs) application

A series of Eu³⁺–Gd³⁺ co-doped solid solution of Ca_0.54Sr_{0.46–1.5x–1.5z}Eu_zGd_x (MoO₄)_y (WO₄)_1−y (x=0.01–0.20, y=0–1.0, z=0.01–0.30) have been prepared by solid-state reactions. It is found that appropriate amount of Mo⁶⁺ or W⁶⁺, Eu³⁺ and Gd³⁺concentrations can enhance the luminescent intensity and improve crystal structure. These phosphors can be effectively excited by ultraviolet light at 394 nm and blue light at 465 nm (f–f transition) and emits red light (616 nm) with line spectrum. The wavelengths at 394 and 465 nm are nicely fitted in with the widely applied output wavelengths of ultraviolet or blue LED chips.