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1.
Phosphors that exhibit a narrow red emission are particularly interesting due to the advantage of providing a more extensive color gamut and better rendering in LED applications such as displays and solid‐state lighting. Although some Eu2+‐activated nitridosilicates have been discovered in this regard, K2SiF6:Mn4+ phosphors are the only option in actual LED applications thus far. We discovered a novel phosphor, K3SiF7:Mn4+, with P4/mbm symmetry. The luminescent properties of K3SiF7:Mn4+ are almost identical to those of the K2SiF6:Mn4+ phosphor, but its materials identity is distinct due to a completely different crystallographic structure, which leads to reduced decay time. The fast decay is one of the most serious disadvantages of existing K2SiF6:Mn4+ phosphors. The K3SiF7:Mn4+ phosphor was examined in comparison to the K2SiF6:Mn4+ via density functional theory calculation, Rietveld refinement, X‐ray photoelectron spectroscopy, X‐ray absorption near‐edge structure spectroscopy, and time‐resolved photoluminescence.  相似文献   

2.
In this article, we propose a facile method for synthesis of K2SiF6:Mn4+ phosphor and discuss its promising application in warm‐white light emitting diodes (LED). The K2SiF6:Mn4+ was synthesized from SiO2 powders through redox reaction in HF/KMnO4 solution. The optical properties of LEDs containing different ratios of K2SiF6:Mn4+ phosphor and commercial Ce3+‐doped garnets (YAG‐40) yellow–green phosphor were studied. A warm‐white LED, with color temperature of 3510 K and color rendering index of 90.9 and efficacy of 81.56 lm/W was demonstrated.  相似文献   

3.
Herein, a series of Eu2+&Mn2+substituted fluorophosphates Ca6Gd2Na2(PO4)6F2 phosphor with apatite structure have been synthesized and investigated by the powder X‐ray diffraction, photoluminescence spectra, fluorescence decay curves, thermal quenching, and chromaticity properties. Particularly, both Eu2+ and Mn2+ emissions at the two different lattice sites 4f and 6h in Ca6Gd2Na2(PO4)6F2 matrix have been identified and discussed. The dual energy transfer of Eu2+→Mn2+ and Gd3+→Mn2+ in Ca6Gd2Na2(PO4)6F2:Eu2+,Mn2+ samples have been validated and confirmed by the photoluminescence spectra. The dependence of color‐tunable on the activator concentration of Mn2+ was investigated to realize white light emission. By varying the doping concentration of the Mn2+ ion, a series of tunable colors including pure white light and candle light are obtained under the excitation of 350 nm. Moreover, the fluorescence decay curves have been fitted and analyzed using the Inokuti–Hirayama theoretical model to estimate the Eu–Mn interaction mechanism. We also investigated temperature‐dependent photoluminescence quenching characteristics according to the Arrhenius equation. Preliminary studies on the properties of the phosphor indicated that the obtained phosphors might have potential application as a single‐component white‐emitting phosphor for UV‐based white LEDs.  相似文献   

4.
《Ceramics International》2020,46(7):8811-8818
K2SiF6:Mn4+ phosphor is well known for its excellent red emission performance which is vital for improving the color rendering of white light-emitting diodes. However, the poor moisture resistance limits its application in optical devices. In this paper, K2SiF6:Mn4+ phosphor is coated with an inorganic hydrophobic protective layer to obtain good moisture resistance. Chemical vapor deposition method was used to decompose acetylene at high temperature, and the generated nanoscale carbon layer worked as a hydrophobic protective coating on the surface of the phosphor. Microstructure, compositions and properties of the synthesized K2SiF6:Mn4+@C phosphor were investigated in detail. It is found that most of the deposited carbon is coated on the surface of phosphor crystals in amorphous state. The carbon atoms are bonded with the fluorine element in K2SiF6:Mn4+ phosphor, forming carbon-fluorine (C–F) covalent bonds. The moisture resistance of K2SiF6:Mn4+@C phosphor is improved owing to the protection of the hydrophobic carbon. The relative emission intensity of K2SiF6:Mn4+@C phosphor could maintain 73% of the initial luminous intensity after immersing in the aqueous solution at room temperature for 8 h, whereas K2SiF6:Mn4+ phosphor without carbon coating was only 0.7% remaining of the initial value under the same conditions.  相似文献   

5.
《Ceramics International》2023,49(8):12088-12096
Mn4+ activated fluoride red phosphors, as candidate red materials in white light-emitting diodes (WLEDs), have received widespread attention. However, the poor water stability limits their application. Herein, a novel dodec-fluoride red phosphor Na3Li3In2F12:Mn4+ with good waterproof stability was successfully synthesized by solvothermal method. The crystal structure, optical property, micro-morphology, element composition, waterproof property and thermal behavior of Na3Li3In2F12:Mn4+ phosphor were analyzed. Under the 468 nm blue light excitation, the Na3Li3In2F12:Mn4+ phosphor has narrow emission bands in the area of 590–680 nm. Compared with commercial red phosphor K2SiF6:Mn4+, the Na3Li3In2F12:Mn4+ phosphor possesses better waterproof stability. When soaked in water for 360 min, the PL intensity of the Na3Li3In2F12:Mn4+ phosphor remains at initial 80%. Finally, warm WLEDs with CRI of 87 and CCT of 3386 K have been fabricated using blue InGaN chip, YAG:Ce3+ yellow phosphor and Na3Li3In2F12:Mn4+ red phosphor.  相似文献   

6.
The Mn4+ activated fluostannate Na2SnF6 red phosphor was synthesized from starting materials metallic tin shots, NaF, and K2MnF6 in HF solution at room temperature by a two‐step method. The formation mechanism responsible for preparing Na2SnF6:Mn4+ (NSF:Mn) has been investigated. The influences of synthetic parameters: such as concentrations of HF and K2MnF6 in reaction system, reaction time, and temperature on crystallinity, microstructure, and luminescence intensity of NSF:Mn have been investigated based on detailed experimental results. The actual doping concentration of Mn4+ in the NSF:Mn host lattice is less than 0.12 mol%. The most of K2MnF6 is decomposed in HF solution especially in hydrothermal system at elevated temperatures. The color of the as‐prepared NSF:Mn samples changes from orange to white when the temperature is higher than 120°C, which indicates the lower concentration of luminescence centers in the crystals. A series of “warm” white light‐emitting diodes with color rendering index (CRI) higher than 88 and correlated color temperatures between 3146 and 5172 K were obtained by encapsulating the as‐prepared red phosphors NSF:Mn with yellow one Y3Al5O12:Ce3+ (YAG:Ce) on 450 nm blue InGaN chips. The advantage of the synthetic strategy to obtain NSF:Mn can be extended to developing Mn4+‐doped red phosphors from low‐costing metals at room temperature for large‐scale industrial applications.  相似文献   

7.
Red phosphor BaSiF6:Mn4+ has been synthesized by a hydrothermal method at 120°C for 24 h, in which either Si or SiO2 is used as silicon source. HF as weak acid performs a complex agent for the formation of anion groups [SiF6]2? and [MnF6]2?. The luminescence properties of undoped BaSiF6 have been firstly observed. The dependence of luminescence intensities of BaSiF6:Mn4+ on the concentrations of HF and KMnO4 in precursory solution has been investigated. The as‐prepared BaSiF6:Mn4+ exhibits high chemical stability even in deionized water.  相似文献   

8.
A single‐phase full‐color emitting phosphor Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ has been synthesized by high‐temperature solid‐state method. The crystal structure is measured by X‐ray diffraction. The emission can be tuned from blue to green/red/white through reasonable adjustment of doping ratio among Eu2+/Tb3+/Mn2+ ions. The photoluminescence, energy‐transfer efficiency and concentration quenching mechanisms in Eu2+‐Tb3+/Eu2+‐Mn2+ co‐doped samples were studied in detail. All as‐obtained samples show high quantum yield and robust resistance to thermal quenching at evaluated temperature from 30 to 200°C. Notably, the wide‐gamut emission covering the full visible range of Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ gives an outstanding thermal quenching behavior near‐zero thermal quenching at 150°C/less than 20% emission intensity loss at 200°C, and high quantum yield‐66.0% at 150°C/56.9% at 200°C. Moreover, the chromaticity coordinates of Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ keep stable through the whole evaluated temperature range. Finally, near‐UV w‐LED devices were fabricated, the white LED device (CCT = 4740.4 K, Ra = 80.9) indicates that Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ may be a promising candidate for phosphor‐converted near‐UV w‐LEDs.  相似文献   

9.
Ca14Al10Zn6O35:Mn4+ (CAZ:Mn) phosphor material, which shows deep-red luminescence, was synthesized by the coprecipitation (COP) method using a Na2CO3/NaOH solution as the precipitant. COP–CAZ:Mn phosphor exhibited a 2.1 times higher luminescence intensity than the corresponding phosphor prepared using the conventional solid-state reaction (SSR) method. This substantial increase in luminescence was mainly ascribed to the existence of a greater proportion of tetravalent manganese in COP–CAZ:Mn phosphor. Furthermore, COP–CAZ:Mn phosphor was modified with SiO2 via hydrolysis of tetraethoxysilane (TEOS) to waterproof the compound because it is easily decomposed through hydrolysis under humid conditions. The SiO2-modified CAZ:Mn phosphor maintained its crystal structure and high photoluminescence intensity after the water-resistance test. Therefore, waterproof CAZ:Mn phosphor with a high luminescence intensity was successfully discovered by utilizing the coprecipitation method and SiO2 modification.  相似文献   

10.
Searching for an efficient non rare earth‐based oxide red phosphor, particularly excitable by light in the wavelength from 380 to 480 nm and unexcitable by green light, is essential for the development of warm white light emitting diodes (WLEDs). Here, we report a promising and orderly‐layered candidate: Sr4Al14O25:Mn4+ with CIE color coordinates (0.722, 0.278). It has higher luminescence efficiency particularly upon blue excitation and is much cheaper than the commercial red phosphor 3.5MgO·0.5MgF2·GeO2:Mn4+ (MMG:Mn4+). In sharp contrast to Eu2+‐doped (oxy)nitrides, the phosphor can be synthesized by a standard solid‐state reaction at 1200°C in air. The effects of flux boron content, environment, and preparation temperature, sintering dwelling time as well as Mn concentration have been systematically investigated for establishing the optimal synthesis conditions. The low temperature emission spectra reveal that there are at least three types of Mn4+ ions in Sr4Al14O25:Mn4+ due to the substitution for the distorted octahedral Al3+ sites. The AlO6 layers where Mn4+ prefers to reside are well separated from one another by AlO4 tetrahedra in one dimension parallel to axis a. This scenario can efficiently isolate Mn4+ ions from local perturbations, thereby enabling the high efficiency of luminescence. The energy transfer rates and mechanism are discussed.  相似文献   

11.
The cation exchange method has been demonstrated to be efficient in doping Mn4+ ions into various fluorides to synthesize the red-emitting LED phosphors. This paper, however, reports the challenge in using this method to dope Mn4+ into the Na2SiF6 single crystals, to prepare the fluoride phosphor in single-crystal form, a state-of-the-art study in the white LED lighting field. The millimeter-sized Na2SiF6 single crystals with a uniform columnar morphology (2–3 mm in length) were successfully grown in solution by a slow cooling process after optimizing the precursors. Then, the crystals were soaked in the HF solution dissolved with K2MnF6 to implement Mn4+-doping via the cation exchange process. Evaluation of the Mn4+-doping behavior reveals that the Mn4+ ↔ Si4+ cation exchange is less efficient in the case of single crystal host compared with the polycrystalline powdery ones and by-reactions also occur which generates new phases. The Na2SiF6 single crystals doped with Mn4+ exhibit a series of discrete sharp peaks with intense zero phonon line emission at 617 nm under 450 nm blue irradiation. This study may trigger the exploration of new single crystal fluoride phosphor.  相似文献   

12.
《Ceramics International》2023,49(16):27024-27029
Mn4+-activated fluoride is one of the most important red phosphors for white light-emitting diodes (WLEDs) with high color rendering index (CRI). Due to a lack of water resistance, their potential applications are limited. Although surface coating strategies improve the waterproof stability of fluoride red phosphors, they have downsides. It was found that Nb5+ plays an important role in improving the water resistance of Mn4+-activated oxyfluorides by preventing the hydrolysis of [MnF6]2-. In this work, the influence of Nb5+ on the waterproof stability of Mn4+-activated fluorides was explored. A set of synthesized K2Ta1-xNbxF7:Mn4+ phosphors exhibit tunable and superior water resistance. The photoluminescence (PL) intensity of the representative sample K2Ta0.6Nb0.4F7:5%Mn4+ remains nearly 100% of its initial value even after being immersed in water for 60 min, which is significantly higher than the commercial K2SiF6:Mn4+ red phosphor (8.7%). Our findings open up new possibilities for the development of waterproof fluoride red phosphors.  相似文献   

13.
Eu2+ and Eu2+/Mn2+‐activated Na5Ca2Al(PO4)4 phosphors have been synthesized by the combustion method. X‐ray powder diffraction profiles, luminescence spectra, chromaticity variation, and energy transfer of Na5Ca2Al(PO4)4:Eu2+, Mn2+ were investigated as a function of the Eu2+ and Mn2+ concentrations in Na5Ca2Al(PO4)4. The Na5Ca2Al(PO4)4:Eu2+,Mn2+ phosphors can be effectively excited at wavelength ranging from 300 to 430 nm, which matches well with that for near‐ultraviolet (UV) light‐emitting diode (LED) chips. Under excitation at 354 nm, Na5Ca2Al(PO4)4:Eu2+,Mn2+ not only exhibits blue‐green emission band attributed to 4f65d1→4f7 of Eu2+ but also gives an orange emission band attributed to 4T16A1 of Mn2+. The emission color of the phosphor can be systematically tuned from blue‐green through white and eventually to orange by adjusting the relative content of Eu2+ and Mn2+ through the principle of energy transfer. The results indicated that Na5Ca2Al(PO4)4:Eu2+, Mn2+ may serve as a potential color‐tunable phosphor for near UV white‐light LED.  相似文献   

14.
The mechanism of the enhancement in the ionic conductivity resulting from cubic phase stabilization in MgO partially stabilized zirconia (MgPSZ) by Mn doping was studied by examining the local Zr‐O structure. Cubic phase (14 vol%) in MgPSZ was increased with the addition of MnO2, and 10 mol% Mn‐doped MgPSZ exhibited the highest cubic phase fraction (98.72%), which was analyzed by Rietveld refinement. In addition, only the cubic phase, not the monoclinic and tetragonal phases, was observed in the TEM‐SAED pattern of 10 mol% Mn‐doped MgPSZ. Doped Mn exhibited a high Mn2+/Mn4+ ratio, which was identified by X‐ray photoelectron spectroscopy (XPS). In addition, it indicates that oxygen vacancy formation by substitution of Mn2+ in the Zr4+ site in MgPSZ increased cubic phase fraction. Ionic conductivity of MgPSZ was improved by the cubic phase increase attributed to Mn doping, and 10 mol% Mn‐doped MgPSZ exhibited higher ionic conductivity than MgPSZ. To investigate the mechanism of the ionic conductivity improvement, Zr‐O local structure in Mn‐doped MgPSZ was analyzed by Zr K‐edge EXAFS of MgPSZ, and the number of bonding of the Zr‐O first shell decreased with increased Mn substitution. Therefore, it was considered that the oxygen vacancy generation led to an increase in the cubic phase and the number of ionic conduction sites.  相似文献   

15.
A novel non‐rare‐earth doped phosphor La2MgGeO6:Mn4+ (LMG:Mn4+) with near‐infrared (NIR) long persistent luminescence (LPL) was successfully synthesized by solid‐state reaction. The phosphors can be effectively excited using ultraviolet light, followed by a sharp deep‐red emission peaking at 708 nm, which is originated from 2Eg → 4A2g transition of Mn4+ ions. The luminescent performance was analyzed by photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The crystal field parameters were calculated to describe the environment of Mn4+ in LMG host. The LPL behaviors as well as the mechanisms were systematically discussed. This study suggests that the phosphors will broaden new horizons in designing and fabricating novel NIR long phosphorescent materials.  相似文献   

16.
A novel blue‐emitting phosphor Na2ZnGeO4 and a novel green‐emitting phosphor Na2ZnGeO4:Mn2+ have been newly developed via high‐temperature solid‐state reaction. The crystal structure of Na2ZnGeO4 has been identified. Energy transfer from Na2ZnGeO4 host to Mn2+ ions was affirmed. Undoped and Mn2+‐doped Na2ZnGeO4 phosphors exhibit blue and green long persistent luminescence (LPL) with persistent duration more than 40 min and 4 h, respectively. The traps created in host lattice were clarified. The LPL mechanism in Na2ZnGeO4 and Na2ZnGeO4: Mn2+ was discussed briefly. This investigation provides two new and efficient long persistent phosphors (LPPs).  相似文献   

17.
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+).  相似文献   

18.
The electronic, structural, and optical properties of 2 red phosphors, Rb2HfF6:Mn4+ and Cs2HfF6:Mn4+, are evaluated using the first‐principles and crystal field theory methods. The calculated trigonal splitting of the Mn4+ orbital triplets perfectly matches the experimental excitation spectra. The structural and electronic properties of the mixed compound RbCsHfF6 are also studied theoretically. In the mixed compound, the inversion center symmetry around the Hf site is removed. This symmetry lowering may result in an increase in the Mn4+ 2E→4A2 zero phonon line (ZPL) intensity, which is very weak in the 2 end members. This finding may be of interest for increasing the phosphor luminosity. It is believed that such a mechanism of local site symmetry lowering by preparing solid solutions may be used for other systems as well, to gain ZPL intensity and perhaps to minimize thermal losses, eventually leading to improved phosphor materials.  相似文献   

19.
Self‐activated compound serving as host sensitizer for trivalent rare‐earth ions has been intensively studied, but only in more recent years did it extend to non‐rare‐earth ions. In the present work, it is demonstrated for the first time that the parity‐forbidden Mn4+ red emission can be effectively enhanced by utilizing the strong parity‐allowed absorption of O2?–W6+ charge transfer band and the energy transfer from “WO2” groups to Mn4+ ions. Hopefully, the presently studied self‐activated Na2WO2F4 can be developed as stable color converter for field‐emission displays.  相似文献   

20.
A single-phase and optimized pure white light emitting Dy3+-doped and Dy3+/Mn2+ codoped Na3Y(PO4)2 phosphors (NYPO) were synthesized by traditional solid state reaction process. The as-synthesized phosphors were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectra and photoluminescence studies. The results suggested that the NYPO: Dy, Mn phosphors were crystallized in orthorhombic structures. The presence of dopants Dy and Mn was quantified by XPS analysis. All of the phosphors were effectively excited using a light of wavelength 351?nm and emissions in two regions, blue (~482?nm, 4F9/26H15/2) and yellow (~573?nm, 4F9/26H13/2), were obtained due to the f-f transitions of Dy3+ ions. The maximum intensities of Dy and Mn obtained were 0.07 and 0.05 for NYPO:Dy and NYPO:0.07Dy, Mn, respectively. The chromaticity coordinates, color temperatures, and color rendering indices of NYPO: 0.07Dy ((0.32, 0.33), 6194?K, and 48) and NYPO:0.07Dy, 0.05Mn phosphors ((0.33, 0.33), 5688?K, and 62) were determined. The energy transfer mechanism and oxygen vacancies that arise due to the introduction of Mn2+ ions in the NYPO:Dy phosphors, are responsible for the tuning of cool white light to pure day white light. The introduction of Mn in the Dy doped NYPO phosphor enhances the emission intensity in the phosphor.  相似文献   

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