Development Of White Light-emitting Diodes Research Articles

The use of CaO:Eu<sup>3+</sup> and Zn<sub>2</sub>SiO<sub>4</sub>:Mn<sup>2+</sup> phosphors to increase the color quality and illumination intensity of WLEDs

The lumen efficacy in remote phosphor structure displayed remarkable enhancements, which is notable for the development of white light-emitting diodes (WLEDs). Nevertheless, its quality of colour is deemed not as good as that of the conformal or in-cup phosphor structure. Therefore, the goal of this research is to achieve a better quality of colour and significant luminous flux value for remote phosphor configuration by using extra phosphor layers. In particular, the two-layer and three-layer structures with the implementation of green and red phosphors are proposed. Comparing these two structures can help pinpoint the best suited for the WLED production. The assessment of each structure’s effect on the WLEDs’ optical parameters was determined under various correlated temperatures of colour (5,600-8,500 K). The outcomes indicated that the three-layer structure enhanced the quality of colour with greater efficiency compared to the two-layer structure due to the increased color rendering index (CRI), color quality scale (CQS), and photoluminescence (PL), and reduced colour deviation. The scattering improvement of the three-layer structure is a key factor of these accomplishments, proven by the scattering theory of Mie. Therefore, the three-layer structure is potential for developing WLED production.

Structural, morphological, and optical characteristics of Gd2 Si2 O7 :Dy3+ nanophosphors for WLEDs.

Yellowish-white light-emitting Gd2-x Si2 O7 :xDy3+ (x = 1-5 mol%) nanophosphors were prepared using a solution combustion synthesis method. Fluorescence spectrophotometry and X-ray diffraction measurements were performed to scrutinize the optical performances and phase recognition of the designated nanophosphors. The outcomes specified that the prepared phosphors were crystallized into a triclinic phase with a P-1 space group. As the concentration of Dy3+ ions was increased, the unit-cell volume decrease proportionally due to the replacement of large-sized Gd3+ by small-sized Dy3+ ions. Under ultraviolet excitation at 349 nm, emission spectra consisted of two pronounced emission lines at ~482 nm (blue line), ~578 nm (yellow line), and a relatively weaker emission at ~670 nm (red line) due to 4 F9/2 →6 H15/2 , 4 F9/2 →6 H13/2 , and 4 F9/2 →6 H11/2 intraconfigurational transitions of Dy3+ ions, respectively. The evidence about the site symmetry around Dy3+ ions was examined by considering the ratio of yellow-to-blue emission intensity. The observed critical distance (Rc ) value was ~20.56 Å (≫5 Å), which signified that energy transfer primarily occurred due to multipolar interaction. The obtained coordinates were close to the white region of the Commission Internationale de l'Éclairage chromaticity diagram, which marked a significant milestone in the development of white light-emitting diodes.

Stereolithography 3D printing of transparent resin lens for high-power phosphor-coated WLEDs packaging

Advanced lens fabricating techniques are urgently required for the development of white light-emitting diodes (WLEDs) packaging, due to the traditional LED lenses molding possesses presents many disadvantages like high cost, long-fabrication period, less compactness and low accuracy. The current study demonstrated the fabrication of lenses with transparent resin utilizing stereolithography (SLA) 3D printing. The SLA 3D printing parameters were optimized to accurately regulate the spheric and ellipsoidal lenses with the smooth surface and the acceptable transmittance. The illuminances, lighting efficiency (LE) and lighting distribution curves of the SLA-fabricated lens packaged WLEDs highly depended on the lens structure. The WLEDs with lower lens height exhibited more intense lighting energy density, higher LE and wider light output angle. SLA 3D printing offers a flexible approach of fabricating WLED lens, which provides a novel technical route for WLEDs to meet different lighting requirements.

The local symmetry of trivalent europium ion activated Li4Ca2B8O16 red-emitting phosphors with high color purity and excellent thermal stability

Exploring for red-emitting phosphor materials with supper property plays a key role in the development of white light-emitting diodes (WLEDs). Simultaneously, the crystal structure has a crucial effect on its luminescence properties. In this work, we synthesized a type of new red-emitting Li4Ca2B8O16: Eu3+ phosphor via the solid-state reaction. The phase purity, crystal structure, surface morphology, decay behavior, thermal stability, the correspondence between local symmetry and luminescence properties were investigated in detail. Under the optimal 393 nm excitation, Li4Ca2B8O16: 0.33Eu3+ shows a strong red emission located at 612 nm ascribed to the 5D0→7F2 transition of Eu3+. The calculated Judd-Ofelt parameters (Ω2 and Ω4) have clarified that Eu3+ has lower symmetry without an inversion center, resulting in the high value of R/O (the emission intensity ratio of 5D0→7F2 to 5D0→7F1) of 7.95 at x = 0.33 mol. The Li4Ca2B8O16: 0.33Eu3+ phosphor exhibits a high color purity of 94.99% with the chromaticity coordinates of (0.6547, 0.3449), perfect internal quantum efficiency (99.75%) and excellent thermal stability at high temperature (90.91% at 150 °C). The results indicate that this new Li4Ca2B8O16: Eu3+ phosphor can be used as the potential red component for pc-WLEDs.

Better color distribution uniformity and higher luminous intensity for LED by using a three-layered remote phosphor structure

Abstract Angular color distribution uniformity has been one of the most relevant properties in the development of white light-emitting diodes (WLEDs), since color consistency and uniformity are crucial factors in quality evaluation of a WLED. Here, particularly considering the need to overcome the poor chromaticity usually associated with WLED, we introduce a new design for the remote-phosphor package, namely a three-layered or triple-layer (TL) phosphor structure. Using three phosphor layers in packaging a WLED can result in higher color quality and luminous efficacy, compared to the double-layer (DL) configuration. In the present study, the results of using three remote phosphor layers indicate that although the structure using three layers has a lower color rendering index, the color quality scale is better than that available from the package with two layers. Additionally, the color-deviation values in the TL structure are smaller than in the dual-layer one, especially at high color temperatures (7,700 K and 8,500 K). Besides, in comparison with the DL model, the TL package increases the luminous flux by 1.4%–2%. Therefore, the TL remote phosphor structure possesses the greatest potential in enhancing the WLED quality.

Sunlike White Light-Emitting Diodes Based on Rare-Earth-Free Luminescent Materials.

Solid-state lighting (SSL) sources based on light-emitting diodes represent the new generation of highly efficient illumination systems that significantly impact energy-saving. The development of white light-emitting diodes (WLEDs) with a combination of high color rendering index (CRI) and high deep-red color rendering R9 is an important challenge in the field of solid-state lighting. On the other hand, most WLEDs use rare-earth inorganic luminescent materials. The annual demand for rare-earth metals has doubled to 125,000 tons in 15 years, and the demand is projected to reach 315,000 tons in 2030. The explosion in demand for these materials, combined with a monopolistic supply source, represents a real risk for the development of WLEDs in the next few years. Luminescent organic materials are a relevant and promising alternative. Here, we report a WLED with a very high CRI of 95.7 and R9 of 78.7, obtained using a combination of a blue LED chip (excitation source) and two organic luminescent dyes (Coumarin 6 and Lumogen Red) acting as spectral converters in a multilayer remote phosphor configuration. To the best of our knowledge, this is the first rare-earth-free WLED with such high values of CRI and R9.

Robust thermal performance of red-emitting phosphor composites for white light-emitting diodes: Energy transfer and oxygen-vacancy induced electronic localization

Ce3+ ion can effectively sensitize Sm3+ ion via energy transfer, and this phenomenon can led to the development of white light-emitting diodes (WLED). However, interestingly, high correlated color temperature (CCT), poor color-rending index (CRI), poor thermal stability, and low efficacy of available red phosphor still pose immense challenges. Herein, we undertook a combined analysis: X-ray diffraction (XRD), crystal refinement, electron spin resonance (ESR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and diffuse reflection spectroscopy (DRS). We also observed the optical properties of the resulting samples. The Ce3+ and Sm3+ dopants on the Sr2+ and La3+ sites in the mixed cation borate Sr3LaAl3B4O15 (SLAB) phosphors were quantitatively evaluated. A cerium ion merged as a sensitizer, improving the red emission intensity by enhancing it 3.9 times. The energy transfer (ET) between Ce3+ and Sm3+ was examined experimentally and with theoretical models as a function of Ce3+ concentrations at ambient temperatures. Several theoretical models were employed to simulate the luminescence decays of Ce3+ and Sm3+ doped samples at different doping levels and their transfer mechanisms were studied depending on forced electric dipole at each ion. Notably, the electronic sites created by the oxygen vacancies around the Ln3+ ions can effectively justify the highly efficient bluish-red phosphor. Additionally, the SL0.95AB:0.02Ce3+,0.03Sm3+ exhibited outstanding thermal-quenching (TQ) resistance and has > 94.8% intensity at 425 K. WLEDs made with the use of SL0.95AB:0.02Ce3+,0.03Sm3+ furnished an exceptional CRI exceeding 88 and low at CCT 4503 K. These results are superior to the parameters of commercial WLED containing Y3Al5O12:Ce3+ phosphor and blue LED chip (CCT≈7746 K, CRI≈75), and they could be a cornerstone for the fabrication of warm WLEDs.

Photoluminescence enhancement of Gd2Zr2O7:Eu3+ red phosphor sensitized by co-doped Al3+ ions

The exploration of new red phosphors is important for the development of white light-emitting diodes (w-LEDs), as existing red phosphors exhibit low efficiency and low performance. This work aims to enhance the photoluminescence characteristics of a red-emitting Gd2Zr2O7:Eu3+ phosphor by co-doping with Al3+. Eu3+ single-doped and Eu3+ and Al3+ co-doped Gd2Zr2O7 nanophosphors that could be efficiently pumped by commercial near-UV LED chips were prepared by a modified liquid–solid–solution phase-transfer method. X-ray diffraction data revealed that the synthesized phosphors were well crystallized with single-phase fluorite structure. Scanning electron microscopy images showed that the particle size ranges from 15 to 25 nm. In addition, the optical performance of the samples was characterized by fluorescence spectroscopy and lifetime spectroscopy. The effect of Al3+ on the luminescence performance of the Eu3+-doped Gd2Zr2O7 phosphor was studied in detail. The emission intensity of the Gd1.93Zr1·97O7:Eu3+0.07Al3+0.03 phosphor was found to be 620% stronger than that of the single-doped Eu3+ phosphor. These results unambiguously show that the Gd1.93Zr2-xO7:Eu3+0.07Al3+x phosphors are promising candidates for application in w-LEDs.

Enhancement of radiative transitions in Sm3+ activated CaTiO3 nanophosphor by modulating co-activator concentration

In present era, rare earth doped nanophosphors are the key architecture in the development of white light-emitting diodes (WLEDs) and their performance has become a major topic of interest among the researchers. Still, the deficiency of orange phosphor has become a barrier for the commercialization of the WLED. In this work, single phase intense orange light emitting Na+ co-activated CaTiO3 (CTO):Sm3+ nanophosphor is synthesized via modified sol–gel method with an average particle size of 60 nm. The synthesized nanophosphor strongly exhibits bright orange emission under 408 nm excitation. Comparative photoluminescence (PL) analysis of CTO:Sm3+ and Na+ co-doped CTO:Sm3+ nanophosphors irrefutably reveals that incorporation of Na+ facilitates almost threefold increase in the luminescence intensity along with significant improvement in thermal stability. Obtained results conclusively suggest that strong orange emitting Na+ co-activated Sm3+ doped CTO nanophosphor could be a potential candidate for use in blue light chip based warm WLED and others lighting device applications.

White Light Emission and Enhanced Color Stability in a Single-Component Host.

Eu3+ ion can be effectively sensitized by Ce3+ ion through an energy-transfer chain of Ce3+-(Tb3+) n-Eu3+, which has contributed to the development of white light-emitting diodes (WLEDs) as it can favor more efficient red phosphors. However, simply serving for WLEDs as one of the multicomponents, the design of the Ce3+-(Tb3+) n-Eu3+ energy transfer is undoubtedly underused. Theoretically, white light can be achieved with extra blue and green emissions released from Ce3+ and Tb3+. Herein, the design of the white light based on these three multicolor luminescence centers has been realized in GdBO3. It is the first time that white light is generated via accurate controls on the Ce3+-(Tb3+) n-Eu3+ energy transfer in such a widely studied host material. Because the thermal quenching rates of blue, green, and red emissions from Ce3+, Tb3+, and Eu3+, respectively, are well-matched in the host, this novel white light exhibits superior color stability and potential application prospect.

Effect of ZnO nanostructures on the optical properties of white light-emitting diodes.

White light produced by blue LEDs with yellow phosphor is the most widely used methods, but it results in poor quality in angular CCT uniformity. In this work, a novel technique was introduced to solve this problem by integrating different ZnO nanostructures into white light-emitting diodes. The experiment of ZnO doped films and the simulation of Finite-Difference Time-Domain (FDTD) were carried out. The result indicated scattering effect of ZnO nanoparticles could improve uniformity of scattering energy effectively. Moreover, the effect of ZnO nanostructures on white light-emitting diodes (wLEDs) devices was also investigated. The CCT deviation of wLEDs devices would decrease from 3455.49 K to 96.30 K, 40.03 K and 60.09 K when the node-like (N-ZnO), sheet-like (S-ZnO) and rod-like ZnO (R-ZnO) respectively applied. The higher CCT uniformity and little luminous flux dropping were achieved when the optimal concentrations of N-ZnO, S-ZnO, and R-ZnO nanostructures were 0.25%, 0.75%, and 0.25%. This low-cost and green manufacturing method has a great impact on development of white light-emitting diodes.

Tailoring the photoluminescence properties of lanthanum strontium aluminate phosphors by controlling crystal field environment with fluorine ions

A series of novel lanthanum strontium aluminate phosphors, Ce3+-doped LaSr2AlO(5–0.5x)Fx(LSAF) phosphors were successfully synthesized using the high-temperature solid state synthesis procedure under reducing atmosphere (H2/N2=1/4). The X-ray diffraction pattern revealed that LSAF sample was a pure LaSr2AlO5 phase with a sintering temperature of 1250 °C. With the increasing amount of SrF2, the particle size of powders increased and the shape of particles changed more regularly. Being an orange/red emitting phosphors for orange and white light emitting diodes, LSAF:Ce3+ could be effectively excited by blue lights with typical 4f→5d transitions of Ce3+ ions. PL and PLE spectra showed inhomogeneous enlargement effects with the increase of F/O ratios, which suggested that electronegativity effect was promoted when F/O ratio increased. This was further confirmed by a red shift of PL spectra peak when F/O was increased. It can be concluded that the LSAF:Ce phosphors have the potential to meet the development of white light-emitting diodes.

The Morphologies and Photoluminescence of Ce<sup>3+</sup>-Doped 0.5La<sub>2</sub>O<sub>3</sub>-2SrO-0.5Al<sub>2</sub>O<sub>3</sub> Phosphors with SrF<sub>2</sub>

Ce3+-doped 0.5La2O3-2SrO-0.5Al2O3 (LSA:Ce) phosphors had been successfully synthesized using a conventional solid-state reaction method under reducing atmosphere (H2/N2 =1/5). The phase, morphologies and luminescence properties of the LSA:Ce phosphors were investigated. The emission intensity of LSA:Ce phosphors was improved by the addition of SrF2 as flux, and red shift of PL spectra peak was observed in this phosphors. Research results shown that the LSA:Ce phosphors have the potential to meet the development of white light-emitting diodes.

Solution processable MOF yellow phosphor with exceptionally high quantum efficiency.

An important aspect in the research and development of white light-emitting diodes (WLEDs) is the discovery of highly efficient phosphors free of rare-earth (RE) elements. Herein we report the design and synthesis of a new type of RE-free, blue-excitable yellow phosphor, obtained by combining a strongly emissive molecular fluorophore with a bandgap modulating co-ligand, in a three-dimensional metal organic framework. [Zn6(btc)4(tppe)2(DMA)2] (btc = benzene-1,3,5-tricarboxylate, tppe = 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene, DMA = dimethylacetamide) crystallizes in a new structure type and emits bright yellow light when excited by a blue light source. It possesses the highest internal quantum yield among all RE-free, blue-excitable yellow phosphors reported to date, with a value as high as 90.7% (λex = 400 nm). In addition to its high internal quantum yield, the new yellow phosphor also demonstrates high external quantum yield, luminescent and moisture stability, solution processability, and color tunability, making it a promising material for use in phosphor conversion WLEDs.

A self-luminous CaEuAl3O7 phosphor: Structural and optical characteristics

A self-luminous CaEuAl3O7 phosphor was synthesized by a high temperature solid-state reaction method. The photoluminescence (PL) properties were investigated to examine its application in the development of white light-emitting diodes (w-LEDs). The red emission was observed from Eu3+ ions in CaEuAl3O7 phosphor. CaEuAl3O7:Eu3+/Eu2+ prepared in a thermal-carbon reducing atmosphere shows good absorption ranging from ultraviolet to a blue region centered at 445nm. The above results indicate that CaEuAl3O7 is a good candidate as red and blue component for near UV-excited w-LEDs.

En Route to White-Light Generation Utilizing Nanocomposites Composed of Ultrasmall CdSe Nanodots and Excited-State Intramolecular Proton Transfer Dyes

One single material that emits white light is of paramount interest for the development of white light-emitting diodes (WLEDs). Here we report a novel nanocomposite, in which a new type of excited-sate intramolecular proton transfer (ESIPT) molecule, namely 5-(1,2-dithiolan-3-yl)-N-(2-{[4-(3-hydroxy-4-oxo-4H-chromen-2-yl)phenyl](methyl)amino}ethyl)pentanamide (HF-N-LA), is anchored onto the surface of ultrasmall CdSe quantum dots through dithiol functionality. Authentic white light with a CIE coordinate of (0.33, 0.33) could then be generated by confluence of 440 nm emission from CdSe and 570 nm proton-transfer tautomer emission from HF-N-LA. Moreover, linear color tunability could be achieved simply by altering relative amount of the two species, i.e., number of HF-N-LA onto CdSe, in one single nanocomposite, thus opening an innovative route toward applying nanocrystals in the field of WLEDs.