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1.
《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   

2.
Developing environment-friendly dual-emission phosphors of both blue–cyan and deep-red lights is desirable for the utilized indoor plant lighting research. Notably, the naked 6s and 6p Bi3+ ions are sensitive to the lattice sites, which emit from Ultraviolet (UV) to red lights in various crystal compounds. Meanwhile, the 2E → 4A2g transition of Mn4+ ions promises its deep-red light emissions, which satisfies the demand for specific wavelength lights for plants growth. Hence, a Bi3+/Mn4+ co-doped Sr2LaGaO5: Bi3+, Mn4+ (SLGO:Bi3+:Mn4+) phosphor was finally synthesized. The phase, micromorphology and luminescent properties were systematically evaluated. Upon excitation at 350 nm light, dual emissions of both blue–cyan (470 nm) and deep-red (718 nm) lights were observed. Besides, due to the pronounced photoluminescence (PL) spectral overlap between Bi3+ and Mn4+ ions, a potential energy transfer process from Bi3+ to Mn4+ ions was confirmed. The relative PL intensities between Bi3+ and Mn4+ ions can be tuned just by adjusting the Mn4+ ion concentration. Besides, Li+ co-doping has been evidenced to improve the deep-red emissions (718 nm) of SLGO:0.005Mn4+ due to charge compensation and rationally designed lattice distortion, together with the improved thermal stability. Finally, the emissions of SLGO:Bi3+, Mn4+, Li+ phosphor suit properly with the absorption of the four fundamental pigments for plant growth, indicating that the prepared phosphorescent materials may have a prospect in plant light-emitting diodes lighting.  相似文献   

3.
For phosphor‐converted warm white light‐emitting diodes (WLEDs), it is essential to find highly efficient red oxide phosphors, which are better chemically stable and benign to environment and can be prepared in a much milder condition. Here, we report a red phosphor LiNaGe4O9:Mn4+ with a quantum yield up to 78% after systematic optimization in synthesis temperature, dopant concentration of Mn4+, and sintering time. Best performance of the phosphor can be reached when it is synthesized in a mild reaction condition, that is, at 850°C for 3 h in air. The integrated emission intensity is more than four times stronger than commercial red phosphor 3.5MgO·0.5MgF2·GeO2:Mn4+ (MFG:Mn4+) under a blue light excitation at 470 nm. Crystal structural analysis reveals that the high efficiency Mn4+ exhibits in the compound is mainly due to the well separation of GeO6 groups from each other by GeO4 tetrahedra in the neighborhood and the ideal substitution of octahedral Ge4+ site by Mn4+ in view of both size and charge matches. The high performance of the phosphor encourages us to apply the blue absorbing red phosphor to WLED, which is based on combination of a blue LED chip and YAG:Ce3+, and the warm perception WLED is therefore achieved with a color temperature of 3353 K.  相似文献   

4.
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   

5.
《Ceramics International》2021,47(23):33172-33179
K2SiF6:Mn4+ (KSF:Mn4+), as an efficient red-emitting phosphor, has a promising application in WLEDs (white light-emitting diodes). However, poor moisture resistance performance still hinders its deeper commercialization. Here, KSF:Mn4+@ CaF2 with high water resistance and luminescent thermal stability has been prepared though H2O2-free hydrothermal method and surface coating process. Both KSF:Mn4+ and KSF:Mn4+@CaF2 all have high luminescent thermal stability, due to negative thermal quenching (NTQ) effect. Mechanism of the NTQ has been discussed and suggested as thermal-light energy conversion mechanism. Compared with KSF:Mn4+, water resistance of KSF:Mn4+@CaF2 is greatly improved by coating of CaF2, because the outer shell of CaF2 can effectively prevent the [MnF6]2- group on the surface of the phosphor from being hydrolyzed into MnO2. The results of water resistance test shows that after immersing in water for 360 min (6 h), luminescent intensity of the uncoated product drops to 41.68% of the initial one, while that of the coated product remains to have 88.24% of its initial one. Warm white light with good luminescent performances (CCT = 3956 K and Ra = 89.3) is got from prototype WLEDs assembled by using the optimal coated sample. The results suggest that the optimal coated sample has potential application in blue-based warm WLEDs.  相似文献   

6.
《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   

7.
《Ceramics International》2022,48(3):3070-3080
Red and far-red emitting phosphors have been widely used in phosphor-converted light emitting diode (pc-LED) devices to provide lighting for indoor plant growth, thus achieving desired product qualities. Among the many ways to optimize phosphors’ optical performance, cationic substitution is one of the most effective methods. In this study, red phosphors (Li2MgTi1-x-yO4: xMn4+, yGe4+) were synthesized by high temperature solid state method and the optical performance of phosphors were improved with increasing Ge4+ constituents. In particular, luminescence intensity of Li2MgTiO4: 0.002Mn4+, 0.1Ge4+ increased by 152% under 468 nm excitation, and the thermostability of emission intensity increases from 22% (y = 0) to 43% (y = 0.1), which is about twice as much. Finally, pc-LED device was fabricated via the red phosphor Li2MgTiO4: 0.002Mn4+,0.1Ge4+ coated on a 470 nm ultraviolet chip. By changing the proportion of the phosphor, the electroluminescence spectra of pc-LED device could match well with the absorption regions of plant pigments. Therefore, Li2MgTiO4: 0.002Mn4+, 0.1Ge4+ phosphor has potential application in plant lighting. Furthermore, this work can offer some helpful references for improving luminescent efficiency by simply modulating the chemical composition.  相似文献   

8.
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   

9.
Li5La3Ta2O12:Mn4+ (LLTO:Mn4+) phosphors are prepared in air via high-temperature solid-state method and investigated for their crystal structures and luminescence properties. LLTO:Mn4+ phosphor under excitation at 314 nm shows deep-red emission peaking at 714 nm due to the 2E→4A2 transition of Mn4+ ion. The excitation bands in the range 220 - 570 nm are attributed to the Mn4+ - O2- charge-transfer band and the 4A2g4T1g, 2T2g, and 4T2g transitions of Mn4+, respectively. The optimal Mn4+ ion concentration is ~0.4 mol%. The concentration quenching mechanism in LLTO:Mn4+ phosphor is electric dipole-dipole interaction. The luminous mechanism and temperature quenching phenomenon are explained by the Tanabe-Sugano energy level diagram and the configurational coordinate diagram of Mn4+ in the octahedron, respectively. The experimental results indicate that LLTO:Mn4+ phosphor has a potential application prospect as candidate of deep-red component in light-emitting diode (LED) lighting.  相似文献   

10.
《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   

11.
《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   

12.
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   

13.
《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   

14.
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   

15.
《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   

16.
Phosphors doped with Mn4+ ions have strong emission in the red and far-red light regions and are therefore used as red phosphors for indoor plant cultivation light-emitting diodes (LEDs) and white LEDs (w-LEDs). This paper introduces La2Mg(Mg1/3Ta2/3)O6: Mn4+ (Mg2La3TaO9: Mn4+) red phosphors prepared by conventional high-temperature solid-phase method. The broad excitation band of Mg2La3TaO9: Mn4+ phosphor is effectively excited by ultraviolet and blue light in the range of 250–600 nm, with the emission of 707 nm centered on far-red light. The phosphor has a high color purity of 99.07% and an internal quantum efficiency of 59.87%. To further enhance the performance of the phosphor, a cation substitution method was adopted in this paper to synthesize La2Mg(Al1/2Ta1/2)O6: Mn4+ phosphor by replacing [1/3Mg2+–2/3Ta5+] in La2Mg(Mg1/3Ta2/3)O6: Mn4+ with [1/2Al3+–1/2Ta5+]. The luminescence intensity and thermal stability of the samples were enhanced. The emission spectrum of the Mg2La3TaO9: Mn4+ samples matched well with the phytochrome PFR (phytochrome that absorbs far-red light) and is suitable for the preparation of LEDs for indoor plant cultivation. The concentration quenching effect of the samples was investigated, the main mechanism of which is the electric dipole–dipole interaction. Red LEDs and w-LEDs devices were prepared with the synthesized phosphors that produce light stably at different currents. The w-LEDs have a correlated color temperature of 5310 K and a color rendering index of 80.1. Therefore, these samples are expected to be used as red components for w-LEDs.  相似文献   

17.
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   

18.
《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   

19.
《Ceramics International》2017,43(13):9960-9967
P2-type layered Na2/3Ni1/4Mn3/4O2 has been synthesized by a solid-state method and its electrochemical behavior has been investigated as a potential cathode material in aqueous hybrid sodium/lithium ion electrolyte by adopting activated carbon as the counter electrode. The results indicate that the Na+/Li+ ratio in aqueous electrolyte has a strong influence on the capacity and cyclic stability of the Na2/3Ni1/4Mn3/4O2 electrode. Increase on the Li+ content leads to a shift of the redox potential towards a high value, which is favorable for the improvement of the working voltage of the layered material as cathode. It is found that the coexistence of Na+ and Li+ in aqueous electrolyte can improve the cyclic stability for the Na2/3Ni1/4Mn3/4O2 electrode. A reversible capacity of 54 mAh g−1 was obtained with a high cyclability as the Na+/Li+ ratio was 2:2. Furthermore, an aqueous hybrid ion cell was assembled with the as-proposed Na2/3Ni1/4Mn3/4O2 as cathode and NaTi2(PO4)3/graphite synthesized in this work as anode in 1 M Na2SO4/Li2SO4 (mole ratio as 2:2) mixed electrolyte. The cell shows an average discharge voltage at 1.2 V, delivering an energy density of 36 Wh kg−1 at a power density of 16 W kg−1 based on the total mass of the active materials.  相似文献   

20.
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   

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