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It has been one of the hot issues to prepare the red‐emitting Mn4+‐doped fluoride phosphors with highly efficient and waterproofness for warm white‐light‐emitting diodes (WLEDs) by the green and environmentally friendly method. Herein, we design a novel green molten salt route to synthesize K2SiF6:Mn4+ red powder using molten NH4HF2 salt instead of HF liquor as the reaction medium. The results show that KMnO4 and MnF2 could produce Mn4+ in NH4HF2 molten salt through a reduction reaction, and the resulting Mn4+‐doped K2SiF6 exhibited a bright red emission peaked at 632 nm under blue light excitation. The luminescence intensity of the as‐obtained product after immersing into water for 24 hours maintain nearly 100% of that before soaking and emission peak shape remains unchanged. The thermal stability of the sample was evaluated by temperature‐dependent luminescence spectral intensity during heating and cooling. Furthermore, a warm white‐light‐emitting diodes (WLEDs) with an excellent color rendering index (Ra = 87.1), lower correlated color temperature (CCT = 3536K), and high luminous efficacy (116.99 lm·W−1) was fabricated based on blue chip and K2SiF6:Mn4+ and commercial yellow phosphor (Y3Al5O12:Ce3+). [ABSTRACT FROM AUTHOR]

Fluoride phosphors as red components for warm white LEDs have attracted a tremendous amount of research attention. But these phosphors are extremely sensitive to moisture, which seriously limits their practical industrial applications. To tackle this problem, unlike all the straightforward preventive strategies, a reverse strategy "Good comes from bad" was successfully developed to treat the degraded K2SiF6 : Mn4+ (D‐KSFM) phosphor in the present study, which not only completely restores the luminescence properties, but also significantly enhances the moisture resistance at the same time. After treatment with an oxalic acid solution as restoration modifier, the emission intensity of the D‐KSFM phosphor can be restored to 103.7% of the original K2SiF6 : Mn4+ red phosphor (O‐KSFM), and the moisture resistance is remarkably improved. The restored K2SiF6 : Mn4+ (R‐KSFM) maintains approximately 62.3% of its initial relative emission intensity after immersing in deionized water for 300 min, while the reference commercial K2SiF6 : Mn4+ with a protective coating (C‐KSFM) is only 33.2%. As a proof of general applicability, this strategy was also conducted to K2TiF6 : Mn4+ phosphor, which is less moisture‐stable than K2SiF6 : Mn4+. The luminescence intensity of the degraded K2TiF6 : Mn4+ (D‐KTFM) phosphor can be restored to 162.6% of original level of the K2TiF6 : Mn4+ synthesized through a cation exchange approach without any treatment (O‐KTFM). The emission intensity of the restored K2TiF6 : Mn4+ (R‐KTFM) phosphor retains 62.8% of its initial emission intensity after soaking in deionized water for 300 min. Finally, the R‐KSFM phosphors were packaged into white light‐emitting diodes with blue InGaN chips and Y3Al5O12 : Ce3+ yellow phosphors. The WLEDs display excellent color rendition with higher color rendering index, lower color temperature (WLED‐II: Ra=83.6, R9=57.3, 3743 K, ηl=199.68 lm/W; WLED‐III: Ra=90.4, R9=94.2, 2892 K, ηl=183.3 1 m/W). The above results show that the reverse strategy can be applied in those phosphor materials with poor moisture resistance to restore luminescence properties and improve moisture resistance without excessively care about the deterioration during the production, storage and transportation. [ABSTRACT FROM AUTHOR]

Bi 3+ , P O 4 3 − and B O 3 3 − doped Sc 0.73 Y 0.2 VO 4 : Eu 0 . 07 3 + phosphors were synthesized by solid state reaction at 1200 °C. The structure, morphology and luminescence properties were investigated. The synthesized phosphors show narrow particle distribution with average size around 2 μm. Under 365 nm excitation, integrate emission intensity increases after doping with Bi 3+ , P O 4 3 − and BO 3 3 − . The optimal doping concentrations are 1%, 20%, 10% for Bi 3+ , P O 4 3 − and BO 3 3 − , respectively. The thermal stability is greatly improved, especially for BO 3 3 − doped sample, whose intensity is about 92% of its original intensity even at 200 °C. [ABSTRACT FROM AUTHOR]

• A novel red phosphor Ca 9 Nd(PO 4) 7 :Eu3+ was synthesized for the first time. • The occupation and crystalline structure of Ca 9 Nd(PO 4) 7 :xEu3+phosphors were thoroughly determined by DFF simulation and Rietveld refinement. • This phosphor can be efficiently excited by near-ultraviolet light to present intense red light emission. • The phosphor exhibits good property of thermal stability. • The WLED fabricated with Ca 9 Nd(PO 4) 7 :xEu3+ has shown superb color temperature and color purity. A series of Ca 9 Nd(PO 4) 7 :xEu3+ (abbreviates as CNP:xEu3+, where x varies from 0.1 to 0.5) phosphors were prepared via conventional solid-state reaction. The X-ray diffraction (XRD) data and Rietveld refinement suggested a successful preparation of CNP:xEu3+ with no sign of impurities. The structure of CNP:Eu3+ belongs to a trigonal crystal system the same as that of β-Ca 3 (PO 4) 2. Thus, Eu3+ ions should theoretically occupy the Ca sites in CNP. All CNP:xEu3+ phosphors showed red emission under excitation in the near-ultraviolet (n-UV) range. The optimal dosage with the best luminescent performance was found at x = 0.3 with critical interaction radius (Rc) of 15.57 Å. The electric dipole-dipole interaction was suggested to be the reason that leads to concentration quenching. The relative luminous intensity of CNP:0.3Eu3+ phosphor at 373 K can remain 70.4% of the initial value at room temperature (RT). The color purity of CNP:0.3Eu3+ phosphor is 92.8%, which is much higher than many other red phosphors. A white light emitting diode (WLED) fabricated with CNP:Eu3+ exhibited correlated color temperature (CCT) of 4602 K and a high Ra of 74.7. The above results illustrate that Ca 9 Nd(PO 4) 7 :Eu3+ could serve as a promising red phosphor for n-UV WLEDs. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract Lack of red-light of current w-LEDs restricts their applications in the field of high color rendering index warm solid-state lighting. Fluoride phosphors doped with Mn4+ provide an efficient way to resolve the problem. Unfortunately, these excellent Mn4+ activated fluoride red phosphors are generally synthesized in highly toxic HF solution. In this paper, we report a novel green synthetic route to prepare a non-rare-earth and nonequivalent doping type of K 2 NbF 7 :Mn4+ red phosphor with micro-rod-like morphology. The results of XRD and its Rietveld refinement reveal that all the samples possessed only a single phase with monoclinic P21/c structure and the Mn4+ ions were successfully incorporated into the crystal lattice. The Mn4+ ions in K 2 NbF 7 matrix have a highly distorted octahedral environment, which strengthen the intensity of zero phonon line (ZPL). The strongest absorption and excitation bands appear in blue region of diffuse refection spectra (DRS) and the photoluminescence excitation (PLE) of K 2 NbF 7 :Mn4+ sample, which demonstrates the product perfectly match with the most popular GaN-based blue chip. Under blue light illumination, the as-prepared K 2 NbF 7 :Mn4+ sample exhibits intense sharp-line red fluorescence (∼628 nm) with internal quantum yield (QY) of 71.3%, an extreme narrow full width at half-maximum (FWHM) of ∼2.8 nm, and an ultra-high-color purity of 99.2%. Impressively, by incorporating K 2 NbF 7 :Mn4+ as a red component, a warm w-LED with high CRI of 83.8, low color temperature of 3010 K and high luminous efficiency of 115.91 lm/W is obtained, demonstrating great validity of K 2 NbF 7 :Mn4+ red phosphor for white LED devices. Highlights • The K 2 NbF 7 :Mn4+ red phosphor with high luminous efficiency was obtained successfully via a novel HF-free approach. • Reaction mechanism of K 2 NbF 7 :Mn4+ red phosphor, including incorporation mode of Mn4+ into K 2 NbF 7 host, were investigated carefully. • Optical properties of K 2 NbF 7 :Mn4+ red phosphor, especially the intense ZPL emission, were investigated carefully. • Addition of K 2 NbF 7 :Mn4+ red phosphor, a warm w-LED with high CRIand low color temperature is obtained. [ABSTRACT FROM AUTHOR]

Mn4+-activated (oxy)fluoride-based red phosphors have received extensive attention. In this work, a phase transformation from K 2 NbF 7 to K 3 HF 2 NbOF 5 was successfully achieved by stoichiometric control during coprecipitation process, resulting in a novel red phosphor K 3 HF 2 NbOF 5 :Mn4+ with narrow-band emission. A systematic study was carried out on its crystal structure and luminescent properties. By introducing O ions into the local coordinated structure, the emission intensity of K 3 HF 2 NbOF 5 :Mn4+ phosphors is 2.15 times as high as that of K 2 NbF 7 :Mn4+ with a photoluminescence internal quantum yield (IQE) of 73.28% and absorption efficiency (AE) of 49.68%, which could be attributed to the layered structure of the oxyfluoride host. High quenching concentration of 8.39 mol% and short decay lifetime of 4.19 ms are realized. Based on K 3 HF 2 NbOF 5 :Mn4+ and commercial YAG:Ce3+, a white light-emitting diode (WLED) for solid state lighting was fabricated, which has low CCT of 3802 K, high Ra of 86.3 and high luminous efficiency (LE) of 126.23 lm/W. Moreover, by employing commercial β-sialon:Eu2+ and K 3 HF 2 NbOF 5 :8.39%Mn4+, another WLED with high LE of 95.78 lm/W and wide color gamut of 108.6% National Television Standard Committee (NTSC) standard for backlight lighting was packaged, indicating a great potential of K 3 HF 2 NbOF 5 :Mn4+ as a red component in the application of backlight lighting. • Phase transformation from K 2 NbF 7 to K 3 HF 2 NbOF 5 was achieved by stoichiometric control. • Accompanying with fluoride to oxyfluoride phase transformation, the fluorescence intensity was greatly enhanced. • High photoluminescence quantum yield, wide color gamut and short fluorescence lifetime suit backlight applications. [ABSTRACT FROM AUTHOR]

• A novel CsMoO 2 F 3 :Mn4+ oxyfluoride phosphor with high color purity was synthesized. • The CsMoO 2 F 3 :Mn4+ phosphor exhibits a remarkable negative thermal quenching. • The CsMoO 2 F 3 :Mn4+ phosphor demonstrates admirable color stability. Red-emitting phosphors composed of Mn4+-activated fluorides have attracted considerable interest for their applications in warm white light-emitting diodes (WLEDs). However, in addition to moisture instability, the unsatisfactory thermal stability of these phosphors limits their industrial applications. In this study, a novel red phosphor of CsMoO 2 F 3 :Mn4+ was synthesized via simple coprecipitation. This red phosphor exhibits an orthorhombic structure with a bandgap of ~3.43 eV. The Mn4+ ions occupy Mo6+ sites at the centers of [MoO 2 F 4 ]2− octahedrons. This phosphor shows narrow emission around ~633 nm excited by 450 nm blue-chip with high color purity of 99.58%. Satisfactorily, this phosphor exhibits excellent thermal stability and a strong negative-thermal-quenching. The total PL intensity of CsMoO 2 F 3 :3.88%Mn4+ phosphor at 275 K strengthens to ~540% relative to that at 25 K, and its relative emission intensity preserves about 129.3% when the temperature rises from room temperature to 423 K (150 ℃). It also shows admirable color stability with a slight chromaticity shift (ΔE) of only ~ 33.9 × 10 - 3 in the temperature region from 298 to 473 K. Furthermore, a warm WLED was fabricated by the mixture of red-emitting CsMoO 2 F 3 :3.88%Mn4+ and the yellow-emitting YAG:Ce3+ phosphors with a blue-emitting InGaN LED chip. The device exhibits low correlated color temperature (3983 K) and high color-rendering index (Ra = 81.3). With the increasing drive current from 20 mA to 120 mA, the chromaticity coordinate variation (CCV) is only (−0.0163, 0.0202). All these results indicate that the CsMoO 2 F 3 :Mn4+ phosphor holds tremendous potential for practical applications in high-power lighting and display with high-performance WLEDs. [ABSTRACT FROM AUTHOR]