With superior photoluminescent properties, the recently discovered A 2 MF 6 :Mn 4+ material holds the potential in replacing the commercial rare-earth-doped (oxy)nitride phosphors for solid state lighting and display. We report here a green synthetic route to synthesize narrow red emitting K 2 SiF 6 :Mn 4+ without the usage of toxic and volatile HF solution. We show that K 2 SiF 6 :Mn 4+ is produced in common low-toxic H 3 PO 4 /KHF 2 liquid instead of high-toxic HF liquid and systematically investigate its morphology and photoluminescence properties. Moreover, the reaction mechanism is comprehensively discussed in detail. We find that not only does H 3 PO 4 /KHF 2 play the same key roles as HF in the process of stabilizing Mn 4+ and promoting Mn 4+ into the host K 2 SiF 6 , but also it exhibits more excellent ability than HF in controlling the concentration of Mn 4+ ion in the host K 2 SiF 6 . By demonstrating its application in white light-emitting diode (LED) with tunable chromaticity coordinate and correlated color temperature, we show that our hydrothermal strategy based on low-toxic H 3 PO 4 /KHF 2 solution system will open the opportunity for the narrow red emitting A 2 MF 6 :Mn 4+ to be synthesized in large scale toward white LED industry adoptions.

Thermal management is still a great challenge for high-power phosphor-converted white-light-emitting diodes (pc-WLEDs) intended for future general lighting. In this paper, a series of single-component white-emitting silicate SiO2-Li2O-SrO-Al2O3-K2O-P2O5: Ce(3+), Tb(3+), Mn(2+) (SLSAKP: Ce(3+), Tb(3+), Mn(2+)) glasses that simultaneously play key roles as a luminescent convertor and an encapsulating material for WLEDs were prepared via the conventional melt-quenching method, and systematically studied using their absorption spectra, transmittance spectra, photoluminescence excitation and emission spectra in the temperature range 296-498 K, decay curves, and quantum efficiency. The glasses show strong and broad absorption in 250-380 nm region and exhibit intense white emission, produced by in situ mixing of blue-violet, green, and orange-red light from Ce(3+), Tb(3+), and Mn(2+) ions, respectively, in a single glass component. The quantum efficiency of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass is determined to be 19%. More importantly, this glass shows good thermal stability, exhibiting at 373 and 423 K about 84.56 and 71.02%, respectively, of the observed room temperature (298 K) emission intensity. The chromaticity shift of SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) is 2.94 × 10(-2) at 498 K, only 57% of the commercial triple-color white-emitting phosphor mixture. Additionally, this glass shows no transmittance loss at the 370 nm emission of a UV-Chip-On-Board (UV-COB) after thermal aging for 240 h, compared with the 82% transmittance loss of epoxy resin. The thermal conductivity of the glass is about 1.07 W/mK, much larger than the 0.17 W/mK of epoxy resin. An organic-resin-free WLEDs device based on SLSAKP: 0.3%Ce(3+), 2.0%Tb(3+), 2.0%Mn(2+) glass and UV-COB is successfully demonstrated. All of our results demonstrate that the presented Ce(3+)/Tb(3+)/Mn(2+) tridoped lithium-strontium-silicate glass may serve as a promising candidate for high-power WLEDs.

Poor water resistance and nongreen synthesis remain great challenges for commercial narrow red-emitting phosphor AMF:Mn (A = alkali metal ion; M = Si, Ge, Ti) for solid-state lighting and display. We develop here a simple and green growth route to synthesize homogeneous red-emitting composite phosphor KSiF:Mn@KSiF (KSFM@KSF) with excellent water resistance and high efficiency without the usage of toxic and volatile hydrogen fluoride solution. After immersing into water for 6 h, the as-obtained water-resistant products maintain 76% of the original emission intensity, whereas the emission intensity of non-water-resistant ones steeply drops down to 11%. A remarkable result is that after having kept at 85% humidity and at 85 °C for 504 h (21 days), the emission intensity of the as-obtained water-resistant products is at 80-90%, from its initial value, which is 2-3 times higher than 30-40% for the non-water-resistant products. The surface deactivation-enabled growth mechanism for these phosphors was proposed and investigated in detail. We found that nontoxic HPO/HO aqueous solution promotes the releasing and decomposition of the surface [MnF] ions and the transformation of the KSFM surface to KSF, which finally contributes to the homogeneous KSFM@KSF composite structure. This composite structure strategy was also successfully used to treat KSFM phosphor prepared by other methods. We believe that the results obtained in the present paper will open the pathway for the large-scale environmentally friendly synthesis of the excellent antimoisture narrow red-emitting AMF:Mn phosphor to be used for white light-emitting diode applications.

The design of luminescent materials with widely and continuously tunable excitation and emission is still a challenge in the field of advanced optical applications. In this paper, we reported a Eu(2+)-doped SiO2-Li2O-SrO-Al2O3-K2O-P2O5 (abbreviated as SLSAKP:Eu(2+)) silicate luminescent glass. Interestingly, it can give an intense tunable emission from cyan (474 nm) to yellowish-green (538 nm) simply by changing excitation wavelength and adjusting the concentration of Eu(2+) ions. The absorption spectra, photoluminescence excitation (PLE) and emission (PL) spectra, and decay curves reveal that there are rich and distinguishable local cation sites in SLSAKP glasses and that Eu(2+) ions show preferable site distribution at different concentrations, which offer the possibility to engineer the local site environment available for Eu(2+) ions. Luminescent glasses based color and white LED devices were successfully fabricated by combining the as-synthesized glass and a 385 nm n-UV LED or 450 nm blue LED chip, which demonstrates the potential application of the site engineering of luminescent glasses in advanced solid-state lighting in the future.