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1.
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   

2.
《Ceramics International》2017,43(7):5674-5679
Non-rare-earth, red-emitting CaAl12O19:Mn4+ nanofiber phosphors have been successfully prepared by an electrospinning technique followed by an annealing process. The as-prepared precursor fibers have smooth surfaces with an average diameter of 5 µm. After annealing at high temperature, the diameter of the fibers gradually reduces due to the decomposition of the organic polymers. The photoluminescence and crystalline properties of the fibers were investigated as a function of Mn4+ concentration and the annealing temperature. Under ultraviolet and blue light excitation, CaAl12O19:Mn4+ exhibits a characteristic red emission at 655 nm with three satellite peaks due to the 2E→4A2 transition of Mn4+. The highest PL intensity is achieved at a 0.5% Mn4+ concentration and a firing temperature of 1400 °C. In comparison to CaAl12O19:Mn4+ prepared by a usual solid-state reaction, the luminescence of the as-prepared nanofiber phosphors in the present work has been strongly enhanced by optimizing the morphology and improving the crystallinity and phase purity. The absorption band in the blue region and a bright emission in the red region make the CaAl12O19:Mn4+ nanofiber phosphor a candidate for achieving high color rendering in YAG:Ce-based WLEDs. A warm WLED with a high CRI of 88.5 at a CCT of 4553 K has been successfully achieved by coating YAG:Ce with CaAl12O19:Mn4+ nanofiber phosphors on blue InGaN chips.  相似文献   

3.
Red phosphor is indispensable to achieve warm white light in the white light diode (WLED) application. However, the current red phosphors suffer from high cost and harsh synthesis conditions. In this study, an oxide-based rare-earth-free red-emitting phosphor Li3Mg2NbO6:Mn4+ (LMN:Mn4+) has been successfully synthesized by a simple solid-state reaction method. The relationship between crystal structure and luminescence was investigated in detail. The site occupancy of the doping Mn4+ ion in the LMN host has been discussed from the point of bond valence sum. How the coordination environment of doping Mn4+ affects the energy level of doping Mn4+ ion has been illustrated via the Tanabe-Sugano energy-level diagram. Moreover, warm white light has been obtained using LMN:Mn4+ as compensator to the YAG:Ce3+.  相似文献   

4.
《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   

5.
To produce natural and vivid color, the color rendering index of white light-emitting diodes (WLEDs) with single phosphors is usually lower than 70, which is problematic for LED applications. A commonly used method to resolve this issue is to enhance the red component of WLEDs. In the present study, Hf4+ and Mn4+ co-doped Li2MgTiO4 red phosphors are synthesized using a solid-state reaction method. When this red phosphor is excited at 397 and 468?nm, it exhibits weak reabsorption in the blue region and emits a broad and deep red emission band in the range of 640–750?nm, which is attributed to the 2Eg4A2?g transition. With 5?mol% HfO2 dopant, the photoluminescence intensity is enhanced by 1.45-fold and thermal stability is increased by 7.7%. Moreover, this red phosphor was applied to a red phosphor-in-glass (RPiG) optical device with a low-melting TeO2-B2O3-ZnO-Na2O-WO3 glass system. In the RPiG melting process, Li2MgTiO4:Mn4+, Hf4+ red phosphor triggered neither a chemical reaction nor severe degradation, indicating good thermal stability. Li2MgTiO4:Mn4+, Hf4+ has potential as a red emission material for warm WLED applications.  相似文献   

6.
《Ceramics International》2017,43(17):15141-15145
Red-emitting long-persistent phosphor Mg2GeO4: Mn4+ was prepared by a high-temperature solid-state reaction. The photoluminescence and afterglow properties of Mg2GeO4: xMn4+ phosphors were studied systematically. Furthermore, to improve the afterglow performance, co-doped Re3+ (Re = Pr, Er, Nd and Yb) ions into Mg2GeO4: 0.001Mn4+ separately to adjust the trap depth or increase the trap density was performed. The duration of Mg2GeO4: 0.001Mn4+ can be observed 30 min by naked eyes, and the initial brightness and afterglow duration are significantly improved after Re3+ ions are doped respectively. Especially, the afterglow emission of Mg2GeO4: Mn4+, Yb3+ can last for 2 h. This investigation shows up a rare Mn4+-doped long-afterglow phenomenon, and provides a new and efficient red afterglow material for potential application.  相似文献   

7.
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   

8.
《Ceramics International》2022,48(12):17253-17260
Mn4+-doped fluoride phosphors can solve the problem for lack of red emitting component in commercial white light-emitting diodes (WLEDs). However, its application is seriously hindered by its easy hydrolysis. Here, we propose to use sodium sulfite as a passivator to treat K2SiF6:Mn4+. After passivation, a Mn4+-rare K2SiF6 protective layer can be formed in situ on the surface of the phosphor, and lead to improved emission intensity, luminescent thermal stability and moisture resistance. When soaking in water for 6 h, the integrated fluorescent intensity of the passivated sample maintained 90.8% of the initial value, while the intensity of the un-passivated sample sharply decreased to 10.2% of the initial value. Mechanisms to improve the emission, water resistance and thermal stability of the luminescence are proposed and discussed. WLED was assembled with the passivated sample, and good performance of warm white light (CCT = 2963 K, Ra = 90.4) was obtained.  相似文献   

9.
《Ceramics International》2022,48(24):36140-36148
Non-rare earth Mn4+ ion-doped red oxide phosphors have great potential for applications in warm white light-emitting diodes (wLEDs) due to their low cost and stable physicochemical properties. Herein, a series of Ba2LaTaO6 (BLTO): Mn4+ phosphors were successfully synthesized by the high-temperature solid-state method. The theoretical values of the band gap calculated by the density functional theory are close to the experimental values obtained by the absorption spectroscopy. In addition, the phosphors have a broad excitation band in the wavelength range of 280–550 nm and emit red light at the peak wavelength of 681 nm under excitation. The concentration quenching of the BLTO: Mn4+ phosphor was caused by dipole-dipole interactions. The activation energy and the average decay lifetimes of the samples were calculated. Meanwhile, the effects of synthesis temperature and Li+ ion doping on the luminescence performance of the samples were also investigated. Satisfactorily, the color purity and internal quantum efficiency of the phosphor reached 98.3% and 26.8%, respectively. Further, the samples were prepared as red-light components for warm wLEDs. The correlated color temperature, color rendering index, and luminous efficiency of the representative devices driven by 60 mA current were 5190 K, 83.3, and 81.59 lm/W, respectively. This work shows that the BLTO: Mn4+ red phosphor with excellent luminescence performance can be well applied to warm wLEDs.  相似文献   

10.
A novel red phosphor Li0.5Na1.5SiF6:Mn4+ (LNSF:Mn) based on the unequal dual‐alkaline hexafluorosilicate with superior optical performances has been synthesized via ion‐exchange between [MnF6]2? and [SiF6]2? at room temperature. The composition and the crystal structure of the as‐obtained phosphor LNSF:Mn were determined by energy‐dispersive x‐ray spectroscopy (EDS) and x‐ray diffraction (XRD), respectively. The formation mechanism of the red phosphor LNSF:Mn has been discussed in detail. The phosphor LNSF:Mn exhibits good chromaticity properties and a quantum yield (QY) of 96.1%, which are better than the identified fluorosilicate phosphors Na2SiF6:Mn4+ (NSF:Mn) and K2SiF6:Mn4+ (KSF:Mn). A broad and intense absorption in the blue and a bright emission in red‐shifted wavelengths make the phosphor LNSF:Mn a desired candidate for applications in warm white light‐emitting diodes.  相似文献   

11.
A series of Cs2BF6:Mn4+ (B = Ge, Si, Ti, Zr) red phosphors were synthesized by a precipitation-cation exchange route. The phase purity, morphology, and constituent were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Optical properties were investigated by photoluminescence (PL) spectra and high-resolution PL. Temperature-dependent PL examination at the range of both 273-573 K and 10-300 K was performed to investigate the emission mechanism of Mn4+ in these fluorides. The intensity for both zero-phonon lines (ZPLs) and vibration coupled emission of Mn4+ in these four systems with different crystal structures was investigated systematically. These phosphors present bright red emission under blue light (467 nm) illumination, among which Cs2GeF6:0.1Mn4+ shows the highest emission intensity with ultrahigh quantum efficiency of 94%. The white light-emitting diodes (WLEDs) fabricated with this sample, blue InGaN chips and commercial YAG:Ce3+ phosphor exhibited high luminous efficacy beyond 100 lm/w with high color rendering index (~88.6) and low color temperature (~3684 K).  相似文献   

12.
In this paper, Y4GeO8:Bi3+,Eu3+ phosphor with dual emission centers was elaborated via conventional solid-state reaction technology. Thorough research on the structure, morphology, and luminous properties of Y4GeO8:Bi3+,Eu3+ phosphor, the potential applications in optical thermometry were investigated by means of fluorescence intensity ratio and thermochromic techniques. Under 290 and 347 nm excitation, Y4GeO8:Bi3+,Eu3+ phosphor presents broadband emission from 3P1 → 1S0 transition of Bi3+ ions and characteristic emission peaks from 4f–4f transition of Eu3+ ions. Outstanding temperature-sensing capabilities are acquired from Y4GeO8:Bi3+,Eu3+ phosphor. The maximum relative sensitivity (Sr) can attain 1.51% K−1 (λex = 290 nm). With temperature raising (303–513 K), the emitted color of Y4GeO8:Bi3+,Eu3+ phosphor (λex = 290 nm) shifts from faint yellow to red with a high chromaticity shift (0.180), which can be distinguished by the unaided eye clearly. Our results indicate that Y4GeO8:Bi3+,Eu3+ phosphor has potential applications in optical temperature measurement and high-temperature safety marker.  相似文献   

13.
《Ceramics International》2022,48(20):29547-29553
Red light-emitting phosphors are important to the field of plant lighting. Therefore, it is necessary to further optimize phosphor materials. Herein, we synthesized a sequence of phosphor LaTiSbO6:Mn4+ (LTS:Mn4+). Due to the 2E to 4A2 transition, LTS:Mn4+ phosphors can emit red light in the range of 620–780 nm, with an emission peak at 687 nm. Chemical unit cosubstitution (substituting W6+ - Al3+/W6+ - Ga3+ for Ti4+ - Sb5+) was used as a method to enhance the luminescence properties of LTS:Mn4+. When the substitution ratio of W6+ - Ga3+ and W6+ - Al3+ reached 0.1% and 0.75%, respectively, the luminescence intensity increased to 204% and 182%. Using the LTS:Mn4+, W6+, Ga3+ phosphor and a 470 nm blue chip to fabricate a pc-LED device, the electroluminescence (EL) spectrum is well matched with the phytochrome absorption range. Therefore, the LTS:Mn4+ phosphor will be very promising for plant growth.  相似文献   

14.
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   

15.
《Ceramics International》2021,47(23):33152-33161
The Mn4+-doped Ca2MgTeO6 (CMTO) far-red emitting phosphors with double perovskite-type structure were successfully synthesized. Upon near-ultraviolet (n-UV, 300 nm) light excitation, the as-prepared phosphors showed far-red light at 700 nm attributed to the 2Eg4A2g transition of Mn4+ ion. The doping concentration of the CMTO:xMn4+ samples was optimized to be 0.8 mol%. The relevant mechanism of concentration quenching was demonstrated as the dipole-dipole interaction. Furthermore, solid solution and impurity doping strategies were adopted to improve the far-red emission of the luminescence-ignorable CMTO:Mn4+ phosphor. Series of Ca2MgTe(1−y)WyO6:0.8 mol%Mn4+ (y = 0–100 mol%) solid solution and Ca2−zLnzMgTe0.6W0.4O6:Mn4+ (Ln = La, Y, and Gd, z = 10 mol%) phosphors were synthesized through the above two strategies. The luminescence intensity of the optimal Ca1.9Gd0.1MgTe0.6W0.4O6:Mn4+ phosphor was 13.7 times that of the CMTO:Mn4+ phosphor and 2.51 times that of red commercial phosphor K2SiF6:Mn4+. Notably, both CMTO:Mn4+ and Ca1.9Gd0.1MgTe0.6W0.4O6:Mn4+ phosphors exhibited remarkable thermal stability compared with most Mn4+-doped phosphors. Finally, the highly efficient Ca1.9Gd0.1MgTe0.6W0.4O6:Mn4+ phosphor was successfully applied in fabricating the warm white light diode (w-LED). This working along both lines strategy exhibited great potential for luminescence optimization of Mn4+-doped oxide phosphors.  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.
《Ceramics International》2017,43(8):6353-6362
Red phosphors serve an important function as red components of warm white light-emitting diodes (WLEDs). Given their remarkable luminescent properties and low cost, Mn4+-doped phosphors are attracting significant attention. In this study, the novel red phosphor Ba2GdNbO6:Mn4+ was synthesized through high-temperature solid-state reaction. The host Ba2GdNbO6 with a double-perovskite structure was investigated. Scanning electron microscopy and thermogravimetric analysis were performed to evaluate the structure and thermal stability of the phosphor, respectively. PLE and photoluminescence spectra were further used to study the luminescence properties of the phosphor. Moreover, crystal field strength and Racah parameters were calculated to estimate the nephelauxetic effect of Mn4+ on the Ba2GdNbO6 host lattice. Thermal quenching characteristics were also analyzed. The fabricated red-emitting LED revealed its potential application in WLEDs.  相似文献   

18.
《Ceramics International》2023,49(8):12491-12498
Developing an efficient broadband yellow phosphor with more red-light components and small thermal quenching is of great significance for solid-state lighting. In this study, a broadband yellow-emitting nitridoalumosilicate Ca4SiAl3N7:Ce3+ phosphor was successfully synthesized by a solid-phase method at comparatively low temperature (1350 °C) and normal pressure. The crystal structure and electronic structure of Ca4SiAl3N7 were studied using Rietveld refinement and density functional theory. The photoluminescence properties of the Ca4SiAl3N7:Ce3+ phosphor were studied, including excitation and emission spectra, time-resolved photoluminescence spectra and temperature-dependent emission spectra. The results show that the Ca4SiAl3N7:Ce3+ phosphor can be effectively excited by the blue chip and emit a strong broadband yellow light with maximum at 568 nm and the half width of 142 nm. Moreover, the Ca4SiAl3N7:Ce3+ phosphor exhibits good thermal stability, which can still maintain 75% and 68% of the strength at room temperature when at 150 °C and 200 °C, respectively, and without spectral shift. A warm WLED can be realized by combining Ca4SiAl3N7:Ce3+ yellow phosphor and blue LED chip. This study provides insights into developing novel broadband yellow nitridoalumosilicate phosphor with more red-light components, small thermal quenching and simple synthesis conditions.  相似文献   

19.
《Ceramics International》2023,49(7):10273-10279
The photoluminescence behavior of inorganic phosphors is generally influenced by thermal stability, which determines the luminescence efficiency of the corresponding devices. Here, a series of Eu2+, Mn2+ co-doped LiAl5O8 blue-green-emitting phosphors with thermal robust are successfully fabricated. The concentration-dependent emission spectra and the decay curves of the as-obtained LiAl5O8: Eu2+, Mn2+ samples manifest the occurrence of the energy transfer from Eu2+ to Mn2+ ions via dipole-dipole interaction, and the corresponding emitted colors are gradually modulated from blue to green under the excitation of 310 nm. Moreover, the zero-thermal-quenching luminescence is observed when the operation temperature is up to 423 K, which is attributed to the energy release from the trapping centers to emitting centers (Eu2+ and Mn2+) at high temperature. Furthermore, a warm white light-emitting diodes (WLEDs) device with correlated color temperature of 5061 K, a color rendering index of 80.6 and long-term stability is fabricated by combining UV LED chip (λex = 310 nm), as-obtained LiAl5O8: Eu2+, Mn2+ phosphor, commercially available red phosphor and green phosphor. These results prove the potential application of the as-obtained LiAl5O8: Eu2+, Mn2+ phosphor for UV-pumped WLEDs devices.  相似文献   

20.
A novel Mn4+-doped strontium lanthanum gallate red phosphor SrLaGaO4:Mn4+ has been successfully prepared via the conventional solid-state reaction method. Phase purity, photoluminescence excitation/emission spectra, concentration quenching, decay curves, and temperature-dependent photoluminescence have been investigated systematically. SrLaGaO4:Mn4+ phosphor exhibits broad excitation band from 250 to 600 nm and emits intense red light centered at 716 nm arising from spin-forbidden transition, 2E → 4A2 of Mn4+. The optimal dopant concentration of Mn4+ is determined to be 0.2 mol%. Dipole-dipole interaction is supposed to be the mechanism of concentration quenching. The crystal-field strength Dq, the Racah parameters B and C, and the nephelauxetic ratio β1 of SrLaGaO4:Mn4+ have been calculated according to its luminescent spectra. Our systematic investigation on this new phosphor can provide a reference for the development of red-emitting phosphor.  相似文献   

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