2D photonic crystal layer assisted thiosilicate ceramic plate with red‐emitting film for high quality w‐LEDs

In this work, we have succeeded in obtaining high quality warm w‐light‐emitting‐diodes (LEDs) by adopting hybrid two‐dimensional (2D) structure of SiN_x photonic crystal layer (PCL) assisted cyan‐emitting ceramic‐plate thiosilicate SrLa₂Si₂S₈:Ce³⁺ with red‐emitting film SrLiAl₃N₄:Eu²⁺ phosphor on a 430 nm blue LED chip at 350 mA. 2D SiN_x PCL was capped with thiosilicate is because it can enhance the luminous efficacy and maintain the low correlated color temperature (CCT) and high color‐rendering index (CRI). High luminous efficacy (82.3 lm/W), high special CRI (R₉=75) as well as the low CCT (5431 K) of the optimal w‐LED was obtained due to the assistances of 2D SiN_x PCL and narrow‐band red‐emitting phosphor with the doping percentage at 10 wt%. The synthesis processes, structural analysis, optical properties and LED device performances were detailed investigated to find out the relationship between the optimum composition and good optical properties. Based on intriguing luminescence properties by the 2D SiN_x PCL and red‐emitting film phosphor introducing, we proclaim this method could also have high potential application in other phosphor‐converted w‐LEDs.     

Enhanced Optical Properties of Bredigite‐Structure Ca13.7Eu0.3Mg2[SiO4]8 Phosphor: Effective Eu Reduction by La Co‐Doping

A green phosphor, La_0.4Ca_13.3Eu_0.3Mg₂Si₈O_31.6+δN_0.4?δ (LaCMSN:Eu²⁺), was prepared by a solid‐state reaction and an efficient green emission was observed at 506 nm under near‐ultraviolet (NUV) excitation. The structural and optical properties of LaCMSN:Eu²⁺ phosphors as well as their thermal quenching were investigated. The partial substitution of La³⁺ and N^3? in Ca_13.7Eu_0.3Mg₂Si₈O₃₂ led to a considerable enhancement in the peak emission intensity by as much as 194%. This demonstrates not only that the total number of Eu²⁺ activators increased, but also that the probability of a nonradiative transition between Eu²⁺ and Eu³⁺ could be reduced as the increase in concentration of the former is at the expense of the later. The white light‐emitting diode (LED) was fabricated using phosphor with a NUV LED chip. The LED showed warm white light with an excellent color rendering index of 91. The LaCMSN:Eu²⁺ is thus a potential green‐emitting phosphor for white LEDs.     

Efficiency Enhancement of Bredigite‐Structure Ca14Mg2[SiO4]8:Eu2+ Phosphor via Partial Nitridation for Solid‐State Lighting Applications

We have synthesized a partially nitridated Ca_13.7Eu_0.3Mg₂Si₈O₃₂ (CMSN:Eu²⁺) using Si₃N₄ with a conventional solid‐state reaction and successfully determined the structural parameters by a combined Rietveld refinement method. The partial nitridation of Ca_13.7Eu_0.3Mg₂Si₈O₃₂ (CMS:Eu²⁺) led to a large enhancement in the luminescence intensity, as much as 148%. From the Rietveld refinement results, the anisotropic changes of the lattice parameters were observed for the partially nitridated samples. By incorporating this phosphor + red phosphor with an encapsulant on an InGaN light‐emitting diode (LED) (λ_max = 395 nm), white light with a color rendering index of 92 and a color temperature of 5320 K under 20 mA was obtained.     

Sr-induced color-tunable and thermal stability enhancing in the phosphor (Ba1-xSrx)9Lu2Si6O24:Eu2+ for solid-state lighting

Rare earth ions’ site occupation is significant for studying luminescence properties by changing the host composition. The (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ (x = 0-0.4) tunable-color phosphors were synthesized via a high temperature solid-state reaction. With the Sr²⁺ ions concentration increase, the luminescent color could be tuned from blue to green. This phenomenon is discussed in detail through the ions occupation in the host lattice. More importantly, the temperature-dependent luminescence of (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphors was investigated and exhibited excellent thermal stability. Furthermore, white LED device has been fabricated using (Ba_1-xSr_x)₉Lu₂Si₆O₂₄:Eu²⁺ phosphor mixed with commercial red phosphor Sr₂Si₅N₈:Eu³⁺ combined with a 370 nm UV-chip. This device showed correlated color temperature (CCT) of 5125 K and high color render index (CRI) of 91. This phosphor will be a promising candidate as a tunable-color phosphor for UV-based white LEDs.     

Improving white light emission and quantum yield of Ce@Eu co-doped silicate glass by reducing Eu3+ to Eu2+ with Si3N4

Rare-earth-doped transparent glass shows great potential in white light-emitting diodes (wLEDs) application due to its excellent optical and luminous properties. Currently reported commercial wLEDs have a drawback in red emission missing, which leads to a relatively low color rendering index (CRI) and a relatively high correlated color temperature (CCT). In this work, Ce@Eu Sr–Si–O glass is fabricated using a high-temperature quenching method. The white light is available when the ratio of Ce³⁺/Eu³⁺ equals 1, and the emitting color can be adjusted from blue to red by controlling the ratio of Ce³⁺/Eu³⁺. To further optimize the white light, Eu³⁺ ions can be reduced to Eu²⁺ according to the reaction of 6Eu³⁺ + 2N³⁻ → 6Eu²⁺ + N₂↑ by introducing Si₃N₄. As a result, the standard white light emission can be achieved in the Ce@Eu silicate glass contributed by the blue light from Ce³⁺, red light from Eu³⁺, and yellow–green light from Eu²⁺ (two elements, three emission). This glass shows excellent luminous properties, such as a color coordinate is (0.3651, 0.3269) in CIE 1931 color coordinate diagram, a CRI is over 70, a high quantum yield of 36.02%, and a CCT of 4117 K.     

Color conversion properties of various thick-film phosphor-in-glasses depending on structural design for white LEDs

Thick-film phosphor-in-glasses (PiGs) were fabricated via a screen-printing method with various phosphor layer structures, to compose a white light emitting diode (LED). Green (Lu₃Al₅O₁₂:Ce³⁺) and red (CaAlSiN₃:Eu²⁺) phosphors were mixed, layered, and patterned on a glass substrate. The chromaticity of each structured PiG was tuned to achieve a white LED by varying phosphor content and thickness. The emission spectra and the related various color conversion properties, including color coordinates, correlated color temperature (CCT), color rendering index (CRI), luminous efficacy (LE) and the color gamut of the mounted PiGs with different phosphor layer structures were examined and compared. Time-resolved photoluminescence (TRPL) measurements of the white LEDs with various phosphor layer structural designs were also obtained and compared. It was observed that spectral variation depended on the PiG layer structure. A proper PiG layer structural design was discussed for practical applications.     

LiCaAlN2:Eu3+/Tb3+: Red and green phosphors for LEDs and FEDs with charge transfer transition in n‐UV region

LiCaAlN₂:Eu³⁺/Tb³⁺ red/green phosphors were successfully prepared by conventional solid‐state reaction. The photoluminescence (PL) properties and cathodoluminescence (CL) properties of LiCaAlN₂:Eu³⁺/Tb³⁺ were investigated in detail. The Eu³⁺ (Tb³⁺) doped LiCaAlN₂ shows red (green) emission peaking at 615 nm (550 nm). Monitored at 615 nm (550 nm), it is interesting to found that LiCaAlN₂:Eu³⁺ (LiCaAlN₂:Tb³⁺) has a broad charge transfer transition in the range of 350‐450 nm (275‐375 nm) peaking at 380 nm (343 nm), which can be efficiently excited by n‐UV light‐emitting diodes (LEDs). Under electron beam excitation, LiCaAlN₂:Tb³⁺ exhibited a good resistance to the current saturation. The white LED has also been fabricated with blue, green, and LiCaAlN₂:Eu³⁺ red phosphor. The results indicate that LiCaAlN₂:Eu³⁺/Tb³⁺ could be conducive to the development of phosphor‐converted LEDs and field emission displays (FEDs).     

Tunable chromaticity and enhanced luminous efficacy of white LEDs with phosphor-in-glass coating via multilayer screen-printing

The phosphor-in-glass (PiG) coating was fabricated via multilayer screen-printing and low-temperature sintering. The PiG coating consisted of Eu₂O₃-doped P₂O₅-ZnO-B₂O₃ (PZB) glass, Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) yellow phosphor, and CaAlSiN₃:Eu²⁺ (CASN:Eu) red phosphor. Eu₂O₃ and CASN:Eu were used to provide red emission for tunable chromaticity of white light-emitting diodes (LEDs), and surprisingly, the luminous efficacy was also enhanced. The impact of the variation in the B₂O₃ content on the PZB glass and the effect of Eu₂O₃, YAG: Ce, and CASN:Eu on the luminescent properties of the PiG coating were investigated. The glass matrix with 8 mol% B₂O₃ showed the lowest transition temperature and a suitable coefficient of thermal expansion. The spectra showed that the coating can be excited by blue light and produce yellow light and red light. The spatial distribution of the PiG coating was inspected by scanning electron microscopy, and it was observed that only a low erosion of phosphor by the glass matrix occurred. Furthermore, the white LEDs devices were constructed with the PiG coating on the blue LED chips. This method showed a decreased correlated colour temperature of 5137, a increased colour rendering index of 82.8 and an improvement in the luminous efficacy. The PiG coating for tunable chromaticity and enhanced luminous efficacy of white LEDs shows potential for application.     

Warm with high color rendering index white light from hybridization of Ca2BO3Cl:Eu2+ yellow phosphor and CdSe/ZnS nanocrystals

Yellow emitting Ca₂BO₃Cl:Eu²⁺ phosphor was prepared by solid state reaction at 900 °C. The particle was monoclinic crystal structure, and showed broad band emission at around 540–590 nm due to the 5d–4f transition. Single Ca₂BO₃Cl:Eu²⁺ phosphor converted white LED exhibited the CIE coordinates of (0.3441, 0.2675) with low CRI of 67.4. Hybridization of Ca₂BO₃Cl:Eu²⁺ with 535 and 610 nm emitting CdSe/ZnS nanocrystals contributed to increasing white spectrum and generated the warm color temperature (4055 K) with high CRI (83.9) of white light. The acceptable color stability was also observed from (0.3687, 0.3051) at 20 mA to (0.3645, 0.3101) at 80 mA.     

Insight into a concentration-sensitive red-emitting phosphor Li2Ca4Si4O13:Eu3+ for multifunctional applications: Crystal structure,electronic structure and luminescent properties

Lithium-containing silicate compounds have attracted so much attention in recent years for applications in energy storage and illumination source due to their rigid structure and good electrical conductivity. In this study, a Eu³⁺ doped lithium-containing silicate red phosphor, Li₂Ca₄Si₄O₁₃:Eu³⁺, was explored by using structural computational simulations and systematic experiments for multifunctional applications. As a result, due to the quite non-central symmetry of the Ca²⁺ sites (C₁ symmetry), the strong 4f-4f excitations in near ultraviolet region were observed. Under near ultraviolet and cathode ray light excitation, Li₂Ca₄Si₄O₁₃:Eu³⁺ phosphor has an efficient red emission with good thermal stability and ageing resistance. Furthermore, Li₂Ca₄Si₄O₁₃:Eu³⁺ phosphor exhibits a concentration-sensitive behavior induced by the change of site symmetry. The results show that it is feasible to develop near-ultraviolet and cathode ray light excited red phosphors in lithium-containing silicate compounds.     

Achieving thermally stable and anti-hydrolytic Sr2Si5N8:Eu2+ phosphor via a nanoscale carbon deposition strategy

Chemical stability of phosphors is critical to the efficiency and lifetime of the white light-emitting diodes. Therefore, many strategies have been adopted to improve the stability of phosphors. However, it is still lack of report on the improvement of thermal stability and hydrolysis resistance of phosphors by a single layer coating. Due to the high transmittance and high chemical inertness of graphene, it was coated on the surface of Sr₂Si₅N₈:Eu²⁺ phosphor by chemical vapor deposition, aiming to improve its thermal stability and hydrolysis resistance. The chemical composition and microstructure of the coating were characterized and analyzed. A nanoscale carbon layer was attached on the surface of Sr₂Si₅N₈:Eu²⁺ phosphor particles in an amorphous state. In coated Sr₂Si₅N₈:Eu²⁺ phosphor, the oxidation degree of Eu²⁺ to Eu³⁺ was significantly suppressed. At the same time, the surface of Sr₂Si₅N₈:Eu²⁺ particle turned from hydrophilic to hydrophobic after carbon coating, and consequently the hydrolysis resistance of Sr₂Si₅N₈:Eu²⁺ phosphor was greatly improved. After tests at 85 °C and 85% humidity for 200 h, the carbon coated Sr₂Si₅N₈:Eu²⁺ phosphor still maintained about 95% of its initial luminous intensity as compared with 35% of the uncoated. By observing the in-situ microstructure evolution of coated phosphor in air-water vapor environment, remained presence of the carbon layer even at 500 °C explained the excellent chemical stability of carbon coated Sr₂Si₅N₈:Eu²⁺ phosphor in complex environment. These results indicate that a nanoscale carbon layer can be used to provide superior thermal stability and hydrolysis resistance of (oxy) nitrides phosphors.     

Eu3+‐doped glass as a color rendering index enhancer in phosphor‐in‐glass

A new method for improving color rendering index (CRI) and low correlated color temperature (CCT) in high‐power white‐light‐emitting diodes (WLEDs) is proposed. We used a configuration of phosphor‐in‐glass (PIG) and studied light output changes with the increment in concentration of yellow‐emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) phosphor. The PIG was coupled on the top of blue‐light‐emitting diodes (LED) chip (465 nm). To compensate the lack of red emission in the phosphor, Eu³⁺‐doped tellurium glass with different europium content was employed as a red emitter. The suitable contents of YAG:Ce³⁺ and Eu³⁺ were 7.5 weight percent (wt%) and 3 mol percent (mol%), respectively. The CRI value went from 72 to 82, whereas the CCT was reduced from 24 933 to 6434 K. The proposed structure can improve CCT as well as CRI of WLEDs just by placing a glass on top.     

Facile synthesis and spectroscopic characterization of siliconitride phosphors for white light‐emitting diodes

A modified chemical vapor deposition (CVD) technique is used to synthesize the color‐tunable siliconitride Sr_2‐1.5x‐yCe_xEu_ySi₅N₈ (x = 0.000‐0.016 and y = 0.000‐0.020) phosphors. In comparison with the conventional solid‐state method, the CVD approach successfully improved the crystallinity, particle size distribution, and photoluminescence through the enhanced gas‐solid reaction. Under blue excitation, Sr_1.98Eu_0.02Si₅N₈ exhibited a red emission band at 618 nm. The incorporation of Ce³⁺ ions increased the emission intensity of Eu²⁺ ions by approximately 10% owing to the enhanced absorption and dipole‐dipole energy transfer process from Ce³⁺ to Eu²⁺ ions. It resulted in a shift of the emission colors from yellow to red region. The external and internal quantum efficiencies of Sr_1.906Ce_0.06Eu_0.004Si₅N₈ were calculated as 54% and 70%, respectively. The activation energy of thermal stability for Sr_1.906Ce_0.06Eu_0.004Si₅N₈ was evaluated as 0.31 eV. A white LED with a color rendering index of 80 and a CCT of 4964 K was successfully fabricated with the present phosphors. The current research demonstrated a new series of Sr₂Si₅N₈:Ce³⁺, Eu²⁺ phosphors with color‐tunability for fabricating white LEDs with high color‐rendering index.     

A novel Eu2+/Tb3+ co-doped phosphor with pyroxene structure applied for cryogenic thermometric sensing

Pyroxene-type phosphors were widely developed due to the advantages of high chemical stability, luminous efficiency, and low production cost. In this contribution, a series of Eu²⁺/Tb³⁺ co-doped Ca_0.75Sr_0.2Mg_1.05Si₂O₆ (CSMS) phosphors with pyroxene structure were successfully synthesized by the solid-state method. Under the 340 nm excitation, the emission peaks of the phosphor show a redshift with the increase of Eu²⁺ concentration. The emitting color of Eu²⁺/Tb³⁺ co-doped samples shows a redshift attributed to the energy transfer from Eu²⁺ to Tb³⁺. Simultaneously, acquired thermometer exposes superbly temperature-sensitive properties (S_a and S_r having maximum values 4.7% K⁻¹ and 0.6% K⁻¹, respectively) over the cryogenic temperature range (77–280 K). Furthermore, it has good stability and precision at cryogenic temperatures, indicating that CSMS:0.03Eu²⁺/0.03Tb³⁺ phosphor is a very promising fluorescent material suitable for cryogenic temperature sensing.     

Efficient and tunable Mn2+ sensitized luminescence via energy transfer of a novel red phosphor Ca19Mn2(PO4)14: Eu2+ for white LED

The exploration of efficient and high-purity red phosphors is an urgent need in LED development. Due to the compact and compositional-tunable structure of whitlockite compound, manganese-based Ca₁₉Mn₂(PO₄)₁₄ is chosen as phosphor host for Eu²⁺ sensitization. Rietveld refinement, steady-state spectra, decay lifetime analysis and temperature-dependent emission spectra were investigated and clearly discussed. Under 360 nm excitation, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ shows a strong Mn²⁺ sensitized emission at 655 nm with FWHM of 82 nm, benefiting from the short-distance-induced high-efficient Eu² -Mn²⁺ energy transfer. Emission engineering of Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ is achieved by Sr²⁺ co-doping, leading to both tunable peak wavelength (ranging from 650 to 610 nm) and improved intensity (130% of original value). Moreover, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ exhibits a promising thermal stability where only 40% of emission intensity is lost at 200 °C. Finally, we explored the working performance of the fabricated RGB phosphor-converted white LED. The present work indicates that Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ phosphor is of great potential as a promising and efficient red phosphor in phosphor-converted white LED.     

Novel cyan-emitting KBaScSi2O7:Eu2+ phosphors with ultrahigh quantum efficiency and excellent thermal stability for WLEDs

Owing to the conventional phosphor-converted white LEDs (pc-WLEDs) generally suffer from blue-green cavity, thus, developing an appropriate phosphors covering both the blue and green regions in their emission spectra are very urgent. Herein, a novel Sc silicate phosphor, KBaScSi₂O₇:Eu²⁺ (KBSS:Eu²⁺), has been successfully designed and prepared via a solid-state reaction. The crystal structure, luminescent properties, thermal quenching, quantum efficiency as well as its application in UV-pumped WLEDs have been investigated systematically. The KBSS:Eu²⁺ phosphor exhibits a strong and broad excitation band ranging from 290 to 450 nm, and gives a sufficient cyan emission of 488 nm with a full-width half-maximum (FWHM) of 70 nm, which filled the blue-green cavity. Importantly, the optimized KBSS:Eu²⁺ phosphor possesses an ultrahigh quantum efficiency (QE) up to 91.3% and an excellent thermal stability retaining 90% at 423 K with respect to that measured at room temperature. Finally, the as-fabricated UV-based WLEDs device, with only coupled the mixture of KBSS:Eu²⁺ cyan phosphor and CaAlSiN₃:Eu²⁺ red ones to a commercial 365nm UV chip, exhibits a satisfactory color-rendering index (Ra = 88.6), correlated color temperature (CCT = 3770K), and luminous efficiency (LE = 21 lm/W).     

Highly reflective interface design for phosphor-in-glass converter enabling ultrahigh efficiency laser-driven white lighting

To address the problems of low luminous efficacy and poor thermal stability of reflective phosphor-in-glass (PiG) converter, a thermally robust and highly reflective PiG-boron nitride (BN)-aluminum nitride (AlN) converter was designed for enabling ultrahigh efficiency laser-driven white lighting. Benefiting from the ingenious sandwich design with the thermally conductive AlN substrate and highly reflective BN-glass interface, a La₃Si₆N₁₁:Ce³⁺ (LSN) PiG-BN-AlN converter achieves white light emission with a high luminous efficacy of 214.2 lm/W under the 3.15 W blue laser excitation, which is the best recorded value for the reflective PiG-based converters thus far, and the surface temperature of LSN PiG is low to 126 °C. Furthermore, the LSN PiG-BN-AlN converter incorporates CaAlSiN3:Eu²⁺ (CASN) red phosphor to enable high-quality white light emission with high luminous flux and good color quality. The results reveal that the designed PiG-BN-AlN converter provides a promising strategy for achieving ultrahigh efficiency laser-driven white lighting.     

Soluble silica assisted synthesis and luminescent characteristics of yellow emitting CaSrSiO4:Eu2+ phosphors for warm white light production

To meet the challenges and additional requirements towards the development of white LED׳s with utmost efficacy, a sol–gel approach is adopted wherein a water soluble silicon compound is used as a silica source. The phosphor material obtained is subjected to detailed structural, morphological and luminescent studies. The results obtained show that the XRD patterns of Eu²⁺ doped CaSrSiO₄ phosphors are in good agreement with the CaSrSiO₄ (ICSD no. 49660) whose structure is orthorhombic. The output of the luminescence studies clearly portrays a broad yellow emission between 450 and 750 nm with a peak at ~600 nm under the broad excitation range. This confirms its efficient emission towards the development of a warm white light using blue LEDs. A red shift in the peak emission wavelength was observed for the prepared samples. This longer shift in wavelength can be credited to the sol–gel method adopted and is not offered by the conventional solid state reaction method. A warm white emitting LED was fabricated by combining near ultraviolet LED (400 nm) chip with our sol–gel synthesized CaSrSiO₄:Eu²⁺ phosphor. The CIE chromaticity coordinates (0.44 and 0.41), color correlated temperature (CCT) <4000 K, color rendering index (CRI) >80 provide their emission potentiality in the warm white light region.     

A low sintering temperature glass based on SiO2–P2O5–ZnO–B2O3–R2O system for white LEDs with high color rendering index

A low sintering temperature glass based on the SiO₂–P₂O₅–ZnO–B₂O₃–R₂O (R=K and Na) system was studied as a matrix for embedding phosphors to fabricate color tunable white LEDs. The proposed system, which uses no heavy‐metal elements and can be sintered at 500°C, incorporates thermally weak commercial phosphors such as CaAlSiN₃:Eu²⁺ to produce phosphor‐in‐glasses (PiGs). Changing the mixing ratio of glass to phosphors affected the photo‐luminescence spectra and color coordinates of the PiGs when mounted on a blue LED. The color rendering index (CRI) and color correlated temperature (CCT) of the LEDs were also varied with the mixing ratio, providing color tunable white LEDs. A high CRI, up to 93, as well as highly improved thermal stability were obtained, along with a low sintering temperature compared to other glass systems, suggesting the practical feasibility of the proposed system.     

Enhancing emission intensity and thermal stability by charge compensation in Sr2Mg3P4O15:Eu3+

Charge compensation was the effective methods to enhance the luminescence properties of phosphors. In this paper, novel single‐phased orange light emitting Sr₂Mg₃P₄O₁₅:Eu³⁺ phosphors were prepared by solid state method. The phase purity and luminous characteristics were examined in detail. Meanwhile, three kinds of charge compensation methods (co‐doping the alkali metal R⁺ (R⁺ = Li, Na, and K), substituting Si⁴⁺ for P⁵⁺ and self‐compensation) were employed to solve the charge imbalance problem between Sr²⁺ and Eu³⁺. The results showed that emission intensity of Eu³⁺ was improved by 1.43 (Li⁺), 1.58 (Na⁺), 1.53 (K⁺), 1.61 (Si⁴⁺), and 1.30 (self) times than that of Sr_1.6Mg₃P₄O₁₅:0.40Eu³⁺, respectively, and there was no change in the emitting color simultaneously. Furthermore, as the temperature reached at 423 K, the emission intensity increased from 41.67% of Sr_1.6Mg₃P₄O₁₅:0.40Eu³⁺ to 55.69% (Li⁺), 61.62% (Na⁺), 58.98% (K⁺), 71.15% (Si⁴⁺), and 80.59% (self) of that at room temperature. The reasons of those phenomena were the reduction in ion vacancies caused by charge imbalance through the charge compensation process. The specific mechanisms were elaborated in detail. Overall, this research validated that the charge compensation strategies could be severed as the key method to improve the luminescence properties, especially the thermal stability of phosphor.