Collection of LED Luminous Materials
The stable and reliable red phosphor with high-photon energy emission (620-650 nm) is critical for the fabrication of the phosphor-converted white light-emitting diode (WLED) with low correlated color temperature and high color rendering index. Mn 4+-activated phosphor is an emerging kind of red-emitting phosphor for WLED. Herein, the energy levels transition and photoluminescence characteristics of the Mn 4+ ion were introduced; then, the preparation, crystal structure and luminescent properties of as-far reported seven kinds of Mn 4+-doped oxyfluoride red phosphors (such as Na2WO2F4:Mn 4+) containing d 0, d 10 or s 0 cations were reviewed. Currently, only in quite rare case of oxyfluoride, Mn 4+ was found to exhibit strong R-line emission, with local coordination remaining as either [MnF6] or [MnO6]. The studies on the chemical stability and quantum efficiency of Mn 4+-doped oxyfluoride phosphors are still insufficient. Finally, we prospected the future development of Mn 4+-doped oxyfluoride phosphor.
Cu-In-Zn-S (CIZS) quantum dots (QDs) are considered as promising fluorescent materials owing to their low toxicity, wide emission range and large Stokes shifts, which have a wide prospect in lighting field. CIZS QDs were prepared via ionic liquid assisted microwave method in aqueous solution. The effects of reaction time, addition amount of ligand and pH of precursor solution on phase composition, microscopic morphology and photoluminescence (PL) property were investigated. Results showed that the reaction rate could be accelerated with the assistance of ionic liquid, i.e. the reaction time reducing from 180 min to 30 min. The size of QDs gradually increased with the increase of reaction time, resulting in red shift of emission peak from 609.2 to 634.6 nm. Moreover, the particle size of CIZS QDs increased with the increase of nGSH/n(CuInZn) ratios, resulting in the red shift of emission peak from 622.6 nm to 631.6 nm. Meanwhile, the PL intensity of QDs increased and reached the maximum at nGSH/n(CuInZn)=15. Furthermore, the surface defect state was effectively passivated with the increase of pH of precursor solution due to enhanced bonding force between deprotonized groups (-SH, -NH2) and QDs, resulting in enhancement of PL intensity. And the optimal pH was 8.5. The average hydrodynamic size of CIZS QDs increased from 99 nm to 241 nm with the increase of pH, and the relative Zeta potential ranged from -27.7 mV to -41.1 mV, indicating the excellent stability of CIZS QDs solution. Emission intensity of QDs could be enhanced significantly after coating with ZnS shells. White LED device was fabricated by combining CIZS QDs and a blue chip, the color rendering index and luminous efficiency of device were 85.6 and 34.8 lm/W, respectively, which provided a reference for the application of water soluble multiple QDs in white LEDs.
LED has the advantages of high efficiency, energy saving and environmental protection. It is widely used in the field of lighting. Improving the luminous efficiency of LED has always been a research difficulty and hot spot in this field. To reduce the total reflection phenomenon between GaN material and air and to improve the light extraction efficiency, fabrication and properties of the anodized aluminum oxide (AAO) nanostructured LED device were studied. Through inductively coupled plasma (ICP) etching process, large-area ordered pore nanostructure arrays were successfully fabricated on the surface of p-GaN layer, and the quasi-photonic crystal structure with apertures of 250-500 nm and pore depths of 50-150 nm were obtained. The crystal structure greatly increases the luminous intensity of the LED, and the nano-array LED with pore diameter of 400 nm and depth of 150 nm is improved by 3.5 times in contrast to the LED without the nano-array.
Mn4+ activated red phosphor is one of the current research hot-spots in the field of white light emitting diodes (wLEDs). The shortest emission of Mn4+ 2E→4A2 transition in aluminate is 651 nm realized in MgAl2O4, but the doped manganese ions exists in multiple valence states (+2/+4/+3, etc.) due to the fact that there exist two cationic sites (Mg2+/Al3+) forming tetrahedron or octahedron coordination in the spinel structure. In this study, variation of the Al2O3 polymorphs (γ/α ratio) in the starting materials and post-annealing were used to control the doping sites and valence state of manganese ions in the MgAl2O4 structure. The results show that a high α/(α+γ) ratio of starting Al2O3 favors the formation of Mn2+ while a low α/(α+γ) ratio of starting Al2O3 favors the formation of Mn4+ dopant. By using highly active nano-γ-Al2O3 as the Al3+-bearing source, the occupancy of manganese ions in the Mg2+ site and the formation of Mn2+ valence state were effectively suppressed. Bright and pure MgAl2O4:Mn4+ phosphors in which only the red luminescence from Mn4+ was observed in the visible spectral region were successfully prepared via once heat treatment at 1550 ℃ for 5 h in air. The intrinsic reason for the dependence of manganese doping valence state on the Al2O3 polymorph lies in that the reactivity of Al2O3 determined the sequences of doping reactions and then the doping site/valence of manganese ions in MgAl2O4:Mn. All the above data demonstrated that the control of reaction sequences was a new method to regulate the valence state of manganese in aluminate phosphors.
Due to high power, high brightness, small size, energy saving, and environment friendliness, solid-state lighting has been becoming the most promising lighting technology in this century. As the key material of solid-state lighting, the luminescent properties of phosphors directly determine the crucial parameters such as the color rendering index, luminous efficacy and reliability of solid-state lighting devices. Compared with single crystals, phosphor glasses, phosphor films and quantum-well LEDs, phosphor ceramics have become the most excellent phosphor materials for high-power solid-state lighting due to its excellent thermal and optical properties and easy control of microstructure. In the future, phosphor ceramics is expected to be more widely used and developed in automotive headlights, outdoor lighting, laser TVs, laser cinema projectors, and other fields, and have a broad market prospect. In this review, design principles of high-power solid-state lighting phosphor ceramics are put forward firstly, and then their research progress of oxide phosphor ceramics (mainly refers to Y3Al5O12) and nitrogen/oxynitride phosphor ceramics are reviewed mainly. Finally, the development of phosphor ceramics for high-power solid-state lighting is prospected.
The sensitivity of optical temperature sensing based on the conventional rare-earth ion doped upconversion (UC) materials is limited by the energy gap between thermally coupled levels (TCLs) of rare-earth ions. Therefore, it is of great theoretical and technical interest to explore UC luminescent materials for optical temperature sensing with ultra-sensitive temperature characteristic. In this work, the UC luminescence properties and temperature sensing characteristics were studied for Er 3+ single-doped BiOCl excited by 1550 nm laser. Under near-infrared (NIR) excitation, BiOCl:Er 3+ exhibits strong red emission at 670 nm, weak green emissions at 525 and 542 nm, extremely weak violet emission at 406 nm, and near-infrared emission at 983 nm. Red and green emissions of the UC system exhibit strong temperature dependence, and in the temperature range of 300-563 K, the maximum absolute sensitivity (SA) obtained by employing the non-thermally coupled levels (NTCLs, 4F9/2/ 4S3/2) is 95.3×10 -3K -1, which is 21 times more than that obtained by employing the thermally coupled levels (TCLs, 2H11/2/ 4S3/2), and the maximum relative sensitivity (SR) is as high as 1.19% K -1. The results show that the intense red UC luminescence and temperature sensing with ultra-high sensitivity in BiOCl:Er 3+ under 1550 nm excitation may have potential application prospect in display and optical temperature sensing.
NaBiF4:Yb3+/Er3+ upconversion materials modified by different organic ligands were synthesized by solvent thermal method, and then their morphology and luminescence properties were studied. The results show that the soft template and orientation of the organic ligands can tune the particle size and morphology of the UCNPs, and the defect passivation of the surface organic ligands enhances the luminescence intensity. Especially, the cetyl trimethylammonium bromide (CTAB) and the cetyl trimethylammonium chloride (CTAC) modified materials have the most significant enhancement effect (9 times). Furthermore, the effects of temperature and pH on luminescent properties of the materials were investigated. Results show that, within the range of experimental conditions, the luminescence intensity of the materials decreases with the increase of temperature from 30 to 90 ℃ and significantly reduces under strong acid and alkaline conditions, with maximum at pH 5-6.