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1.
《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   

2.
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   

3.
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   

4.
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   

5.
K2TiF6:Mn4+ is an attractive narrow-band red-emitting phosphor for warm white light-emitting diodes (LEDs). Nevertheless, the hexafluoride phosphor is liable to deliquesce in moist environments, which leads to a sharp deterioration performance of luminescence. Surface modification of K2TiF6:Mn4+ phosphor with SrF2 coating has been introduced, with the aid of KHF2 transition layer to moderate the lattice mismatch. The reaction mechanism is discussed in detail, as so as the influence of SrF2 coating on the luminescence intensity. The SrF2 coating is able to prevent the hydrolysis of internal [MnF6]2− group; thereby, the luminescence intensity retains over 90% of initial value after being immersed in distilled water for 2 h. The LED devices fabricated with commercial Y3Al5O12:Ce3+ and as-modified K2TiF6:Mn4+ phosphors exhibit bright white light with tunable chromaticity coordinate, correlated color temperature, and color rendering index. It enlightens a convenient method to enhance the moisture resistance of Mn4+ doped fluoride phosphors for commercial application in the field of white LEDs.  相似文献   

6.
《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   

7.
《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   

8.
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   

9.
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   

10.
Chemical stability of phosphors is critical to the efficiency and lifetime of the white light-emitting diodes. Therefore, many strategies have been adopted to improve the stability of phosphors. However, it is still lack of report on the improvement of thermal stability and hydrolysis resistance of phosphors by a single layer coating. Due to the high transmittance and high chemical inertness of graphene, it was coated on the surface of Sr2Si5N8:Eu2+ phosphor by chemical vapor deposition, aiming to improve its thermal stability and hydrolysis resistance. The chemical composition and microstructure of the coating were characterized and analyzed. A nanoscale carbon layer was attached on the surface of Sr2Si5N8:Eu2+ phosphor particles in an amorphous state. In coated Sr2Si5N8:Eu2+ phosphor, the oxidation degree of Eu2+ to Eu3+ was significantly suppressed. At the same time, the surface of Sr2Si5N8:Eu2+ particle turned from hydrophilic to hydrophobic after carbon coating, and consequently the hydrolysis resistance of Sr2Si5N8:Eu2+ phosphor was greatly improved. After tests at 85 °C and 85% humidity for 200 h, the carbon coated Sr2Si5N8:Eu2+ phosphor still maintained about 95% of its initial luminous intensity as compared with 35% of the uncoated. By observing the in-situ microstructure evolution of coated phosphor in air-water vapor environment, remained presence of the carbon layer even at 500 °C explained the excellent chemical stability of carbon coated Sr2Si5N8:Eu2+ phosphor in complex environment. These results indicate that a nanoscale carbon layer can be used to provide superior thermal stability and hydrolysis resistance of (oxy) nitrides phosphors.  相似文献   

11.
《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   

12.
《Ceramics International》2022,48(4):5009-5016
Poor water stability is the main problem of commercialized Mn4+-doped fluorides for white light emitting diode (WLED) application. This work proposes a surface engineering strategy to rebuild a Mn4+-free fluoride shell on fluorides to effectively resist the destruction from water molecules. By simple processing using glyoxylic acid (GA) solution, the moisture resistance of the red-emitting fluorides can be significantly improved. The photoluminescence (PL) quantum efficiency (QE) of the surface-engineered K2SiF6:Mn4+ (KSFM-GA) still maintain 98.43% after water immersion for 360 h, in sharp contrary to the untreated one (its PLQE decreases to 59.79%). Additionally, PL intensity of the hydrolyzed KSFM can be recovered to 99.1% through the treatment of the reducing GA solution. By using the high-stability KSFM-GA red phosphor, the as-fabricated high-performance warm-WLED device can still maintain 84.6% in luminous efficacy, higher than that (79.6%) with the untreated KSFM, after 500 h of aging in a high temperature (85 °C) and high humidity (85%) environment.  相似文献   

13.
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   

14.
《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   

15.
Performing carbon coating on the surface of phosphors has been proven to be an effective strategy to enhance the oxidation resistance, which is an important factor to achieve stable luminescent devices. Therefore, a good understanding of the protection mechanism favors a continuous improvement of oxidation resistance of phosphors. In present paper, the evolution of the carbon layer, Eu valence (Eu2+/Eu3+), and luminescent properties for the C coated BaMgAl10O17: Eu2+ phosphor when annealed at high temperature is investigated carefully. Decrease of carbon layer promotes the appearance color transition from black to white as the annealing temperature rises to 1000?°C in air. As expected, the decrease of carbon layer will enhance the luminescence intensity, but risk the possible oxidation of Eu2+ to Eu3+, which inhibits the blue emission ascribed to Eu2+. The results indicate that luminescence intensity of phosphor is dependent on the synergistic effect of carbon thickness and Eu2+/Eu3+ ratio. Additionally, a reduction reaction of Eu3+ to Eu2+ is observed in C coated BaMgAl10O17: Eu2+ phosphor when annealed at high temperature, which also contributes to the higher luminescence intensity.  相似文献   

16.
Artificial light source for indoor cultivation has been vastly impeded by the lack of high far red emitting phosphors. Recently, Mn4+ activated phosphors were reported to be promising luminescent materials to solve above matter. In this study, controllable design of Ca14Al10Zn6O35:0.15Mn4+ (CAZO:0.15Mn4+) far red emitting phosphors was realized via pH assisted hydrothermal approach. The pure CAZO:0.15Mn4+ phosphors were obtained merely when the reaction pH was 1 or 2. Meanwhile, by adjusting the pH value of the reaction solution, far red emission CAZO:0.15Mn4+ phosphors with grains, sphere-like as well as aggregated bulk particles can be achieved at pH =?4, pH =?6 and pH =?10, respectively. Furthermore, the structures and morphologies depended photoluminescence (PL) performances of CAZO:0.15Mn4+ were checked. The best PL performance was found for the phosphor produced at pH =?6, while over acidic or alkaline conditions would lower the emission intensity. In addition, this phosphor also exhibit good thermal resistance which can maintain 78% initial intensity at 150?°C. The practical indoor tobacco cultivation demonstrated that CAZO:0.15Mn4+ obtained through this pH adjusted hydrothermal route is a promising phosphor for indoor plant growth lighting.  相似文献   

17.
《Ceramics International》2016,42(15):16817-16821
Novel double-perovskite Sr2ZnWO6:Mn4+(SZW:Mn4+) phosphor is synthesized by high-temperature solid-state reaction method in air. SZW:Mn4+ phosphor with excitation at 325 and 526 nm emits deep-red light, the chromaticity coordinate is (0.7315,0.2685), and the emission band peaking at ~702 nm within the range 640–760 nm is assigned to the 2E→4A2 transition of Mn4+ ion. The influences of “Mn4+- ligand” bonding and crystal field strength to emission properties of Mn4+ ion are analyzed. The optimal Mn4+ ion concentration in SZW:Mn4+ phosphor is ~0.8 mol%. Lifetime of SZW:Mn4+ phosphor decreases from 554.77 to 401.35 μs with increasing Mn4+ ion concentration in the range of 0.2–1.0 mol%. The lifetime data and decay curves indicate that there is only a single type of Mn4+ ion luminescent center in SZW:Mn4+ phosphor. The luminous mechanism of SZW:Mn4+ phosphor is analyzed by Tanabe-Sugano energy level diagram of Mn4+ in the octahedron together with the simple energy level diagram. The experimental results are helpful to research the influences of the neighboring coordination environment around Mn4+ and host crystal structure to the luminescence properties of Mn4+ ion and to deeply understand other Mn4+-dopedmaterials.  相似文献   

18.
《Ceramics International》2017,43(9):6949-6954
Mn4+ doped and Mn4+/Cr3+ co-doped alkali metal titanate phosphors have been prepared by solid state reaction method. A part of Li+ ions in the Li2MgTiO4: Mn4+ are substituted with Na+ and K+ ions and consequently the intensity of Mn4+ emission at 678 nm is enhanced by 1.7 and 2.5 times, respectively. In the Mn4+/Cr3+ co-doped (Li0.95K0.05)2MgTi0.999O4, both emission of Cr3+at 726 nm and emission of Mn4+ at 678 nm of Mn4+ are observed. It is interesting to find that the intensity ratio of 726–678 nm emissions in the Mn4+/Cr3+ phosphor continually increases with excitation wavelength increasing from 290 nm to 455 nm, which means that the intensity ratio in turn can be used to identify the excitation light wavelength. This refers a possible approach to design novel compact light-wavelength detector or spectrometer based on the phosphor. The mechanism of Na+ or K+ substitution induced luminescence enhancement in the Mn4+ phosphor and the competition between the Cr3+ and Mn4+ emissions in the Mn4+/Cr3+ co-doped has been discussed.  相似文献   

19.
《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   

20.
《Ceramics International》2022,48(22):33167-33176
This study evaluates the luminescence performance of fired clay bricks coated with SrAl2O4:Eu/Dy phosphor. To do so, SrAl2O4:Eu/Dy phosphor was first produced using the traditional solid-state reaction synthesis technique. The prepared phosphor was then used for coating fired clay bricks to analyze the luminescence performance via spectral analysis, decay characteristics, and microstructure of the bricks. The results reveal that excitation and emission spectra of the phosphor coated bricks range from 200 to 480 nm and 455 to 650 nm, respectively, suggesting that the phosphor coated bricks have the capacity of absorbing light with a wide range of wavelengths. The peak wavelength projected at 511 nm in the emission spectrum is achieved, which indicates 4f65 d1-4f7 transition of Europium (Eu2+). The repeated excitation and deexcitation of Eu2+ by using hole traps and trap levels offered by Dysprosium (Dy3+), exist between the ground and the excited state of Eu2+ leads to luminescent phenomenon. Moreover, the decay characteristics has revealed that phosphor coated bricks can emit light for a considerable amount of time (>8.5 min) upon the removal of the excitation source. The results reveal that phosphor coated bricks has the potential of increasing energy efficiency of residential and commercial buildings.  相似文献   

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