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1.
In current study, only 5?mol% Mn2+ was applied to fabricate high performance microwave dielectric ZnGa2O4 ceramics, via a traditional solid state method. The crystal structure, cation distribution and microwave dielectric properties of as-fabricated Mn-substituted ZnGa2O4 ceramics were systematically investigated. Mn2+-substitution led to a continuous lattice expansion. Raman, EPR and crystal structure refinement analysis suggest that Mn2+ preferentially occupies the tetrahedral site and the compounds stay normal-spinel structure. The experimental and theoretical dielectric constant of Zn1-xMnxGa2O4 ceramics fit well. In all, this magnetic ion, Mn2+, could effectively adjust the τf value to near zero and double the quality factor from 85,824?GHz to 181,000?GHz of Zn1-xMnxGa2O4 ceramics at the meantime. Zn1-xMnxGa2O4 (x?=?0.05) ceramics sintered at 1400?°C for 2?h exhibited excellent microwave dielectric properties, with εr =?9.7(@9.85?GHz), Q?f?=?181,000?GHz, tanδ?=?5.44?×?10?5,and τf =???12?ppm/°C.  相似文献   

2.
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   

3.
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   

4.
《Ceramics International》2022,48(9):12578-12584
Rare earth ions doped luminescent materials have drawn considerable attention as they can generate both upconversion and downshifting emissions. Here, the rare earth ions Pr3+/Er3+ codoped perovskite oxide Bi4Ti3O12 is proposed as a dual-mode temperature sensor and anti-counterfeiting material based on its up/down-conversion luminescence. Under 481 nm excitation, the intensity ratio of green emission (~523 nm in Er3+) and red emission (~611 nm in Pr3+) brings about a very high absolute sensitivity (Sa) of 2% K?1 at 568 K and a maximum relative sensitivity (Sr) of 1.03% K?1 at 478 K in the temperature range of 298–568 K. In addition, the upconversion green emissions of Er3+ yield a relatively-high Sr of 1.1% K?1 at 298 K with 980 nm excitation, which can provide self-calibration coupled with down-conversion luminescence temperature sensing mode. Besides, this phosphor also shows tunable luminous colors for the potential application in the anti-counterfeiting field under various excitation wavelengths.  相似文献   

5.
The layered LiNi0.5Mn0.5O2 was synthesized by wet-chemical method and characterized by X-ray diffraction and SQUID magnetometry. The powders adopted the α-NaFeO2 structure. The ferromagnetism observed below Tc = 140 K is attributed to the linear Ni2+(3a)-O-Mn4+(3b)-O-Ni2+(3a) magnetic paths, from which we derive that 7% of the nickel occupies the (3a) Wyckoff position in place of Li, constituting a Ni2+(3a) defect. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie-Weiss law agrees well with the combination of Ni2+ (S = 1) and Mn4+ (S = 3/2) spin-only values. Results of structural and magnetic properties of chemically delithiated sample are consistent with the electronic state Mn4+/Ni4+ and the high-spin configuration for Ni4+ ions. The LiNi0.5Mn0.5O2 electrode sintered at 900 °C delivers a capacity 166 mAh/g at 0.1C rate which is capacity retention of 95%.  相似文献   

6.
A novel Mn4+ activated Ca2LaSbO6 (CLS) far-red phosphor was synthesized by high temperature solid state reaction. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photoluminescence spectra, ultraviolet-visible spectra, luminescence decay times, emission-temperature relationship and internal quantum efficiency (IQE). It is found that CLS:Mn4+ phosphor has a strong broad excitation band in the range of 200–550?nm. The samples can be excited by ultraviolet and blue light. There is a wide emission band centered at 685?nm between 600?nm and 760?nm. The optimum doping concentration of Mn4+ is approximately 0.5?mol%. In addition, all the CIE chromaticity coordinates of CLS:0.005Mn4+ located at far-red region. The concentration quenching mechanism is the dipole-dipole interaction of Mn4+ activator. Importantly, the CLS:0.005 Mn4+ sample has an IQE of up to 52.2%. Finally, a 365?nm ultraviolet light emitting diode (LED) chip combined with 0.5?mol% Mn4+ far-red phosphor was used to fabricate the LED device. All the results indicated that CLS:Mn4+ phosphors have potential applications in indoor plant cultivation.  相似文献   

7.
Tungsten trioxide (WO3) ceramics were prepared by firing Bi2O3-added WO3 compacts with atomic ratios of Bi/W?=?0.00, 0.01, 0.03, or 0.05, in which Bi2O3 was mixed as a sintering agent. Dense ceramics consisting of remarkably grown WO3 grains were obtained for Bi-containing samples with Bi/W?=?0.01, 0.03, and 0.05. The grain growth was enhanced by the liquid phase of Bi2W2O9 formed among the WO3 grains while firing. The XRD patterns did not show evidence for Bi inclusion into the WO3 lattice, but the SEM-EDX showed an intensive distribution of Bi into the grain boundaries. Electrical conductivity σ and Seebeck coefficient S were measured in a temperature range of 373–1073?K. The temperature dependences indicated that the Bi2O3-added WO3 ceramics were n-type semiconductors. It was considered that the electron carriers were generated from oxygen vacancies included into the WO3 grains. The thermoelectric power factors S2σ for the ceramics ranged from 1.5?×?10?7 W?m?1 K?2 to 2.8?×?10?5 W?m?1 K?2, and the highest value occurred at 970?K for the ceramic with Bi/W?=?0.01.  相似文献   

8.
The structural and thermoelectric (TE) properties of polycrystalline CaMn1-xNbxO3-δ (0.025?≤?x?≤?0.25) were studied with X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and electrical transport measurements, with an emphasis placed on the Nb5+ content. The CaMn1-xNbxO3-δ crystallized in an orthorhombic perovskite structure of the Pnma space group. The density and grain size of the CaMn1-xNbxO3-δ samples gradually decreased when Nb5+ ions substituted Mn4+ ions. The CaMn0.95Nb0.05O3-δ sample contained charge-ordered domains, stacking faults, and micro-twins. The substitution of Nb5+ for Mn4+ up to x?=?0.15 led to an increase in electrical conductivity, mainly due to an increased electron concentration. The CaMn1-xNbxO3-δ samples with low Nb5+ contents (0.025?≤?x?≤?0.15) showed metallic behavior, whereas those with high Nb5+ contents (0.2?≤?x?≤?0.25) showed semiconducting behavior. The Nb5+ substitution lowered the absolute value of the Seebeck coefficient for the CaMn1-xNbxO3-δ samples due to an increased electron concentration. The largest power factor (1.19?×?10?4 W?m?1 K?2) was obtained for CaMn0.95Nb0.05O3-δ at 800?°C. The partial substitution of Nb5+ for Mn4+ in CaMnO3-δ proved to be highly effective for improving high-temperature TE properties.  相似文献   

9.
Novel Mn4+-activated KLaMgWO6 red phosphors with different Mn4+ concentrations were successfully synthesized via a high-temperature solid-state reaction method. The phase formation, microstructure, photoluminescence properties, decay lifetimes and internal quantum efficiency were discussed to analyze the properties of the as-prepared phosphors. The samples belonged to monoclinic crystal system with enough WO6 octahedrons that provided suitable sites for Mn4+ ions. Upon the excitation of 348?nm, KLaMgWO6:Mn4+ phosphors gave bright far-red emission around 696?nm due to the 2Eg4A2g transition of Mn4+ ions. The critical concentration of Mn4+ was 0.6?mol% and the concentration quenching mechanism belonged to electric multipolar interaction. Besides, the CIE chromaticity coordinates of the KLaMgWO6:0.6%Mn4+ phosphor were (0.7205, 0.2794) which located in deep red range, and its color purity reached up to 96.6%. The KLaMgWO6:0.6%Mn4+ sample also exhibited high internal quantum efficiency of 43%. All of the admirable optical properties indicate that the KLaMgWO6:Mn4+ phosphors can be applied to indoor plant growth illumination.  相似文献   

10.
Layered perovskite oxides with and without Ca-doped NdBa0.5Sr0.25Ca0.25Co2O5+δ (NBSCaCO) and NdBa0.5Sr0.5Co2O5+δ (NBSCO) are studied to investigate the effects of Ca doping on the crystal structure, thermal behavior, electrical and electrochemical properties. Both NBSCO and NBSCaCO are tetragonal structure with P4/mmm space group. The average thermal expansion coefficient (TEC) value is reduced from 23.3?×?10?6 K?1 to 19.8?×?10?6 K?1 during 30–800?°C. The electrical conductivities are increased by Ca doping. Both electrical conductivities of NBSCO and NBSCaCO are higher than 600?S·cm?1 over 30–800?°C. Substitution of Sr with Ca can effectively improve the electrochemical properties of NBSCaCO. From 650?°C to 800?°C, the area specific resistance (ASR) of NBSCaCO are decreased from 0.62 to 0.062?Ω?cm2 and the corresponding output power density are increased from 258 to 812?mW?cm?2. On the basis of these results, Ca doped layered perovskite NBSCaCO can be a good cathode candidate material for SOFC application.  相似文献   

11.
The operation of the SDERF-cell in the study of the electron transfer kinetics of the Fe(CN)4?6/Fe(CN)3?6-system in 1 M KCl and 1 M KNO3-solutions at a stationary Pt-disk electrode is reported. The experimental current—overpotential curves are recorded by linear sweep voltammetry and analysed by two different methods using the theoretical relationship derived for a stationary disk electrode placed in a free rotating fluid. Both methods give the same value for the experimental rate constant k*. The effects of the temperature (0° to 40°C) and of the ratio of the rotor radius (rr) to the electrode radius (re)(rr/re = 0.50 to 0.81) have been studied. The activation energy for the redox process in 1 M KCl and 1 M KNO3 are: Ea = 3.4 ± 0.6 kcal/mol and Ea = 3.7 ± 0.7 kcal/mol respectively, while the k*-values at 25°C are: k* = (5.67 ± 0.41) × 10?3 cm.s?1 and k* = (4.53 ± 0.29) × 10?3 cm.s?1 respectively. The difference from the standard rate constant k0 ? 0.100 cm.s?1 is explained by the effect of the cell-geometry characterized by the G-factor, so that k° = Gk*, where G ? 19 for our cell.  相似文献   

12.
《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   

13.
A series of Ba2Mg1−xMnxP4O13 (x = 0-1.0) and Ba1.94Eu0.06Mg1−xMnxP4O13 (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn2+ for Mg is about 50 mol% in Ba2MgP4O13. Mn2+-singly doped Ba2MgP4O13 shows weak red-luminescence peaked at about 615 nm. The Eu2+/Mn2+ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu2+ and a broad red-emitting one peaked at 615 nm from Mn2+ ions. The luminescence of Mn2+ ions can be greatly enhanced with the co-doping of Eu2+ in Ba2MgP4O13. The efficient energy transfer from Eu2+ to Mn2+ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu2+/Mn2+ co-doped phosphor show a good thermal stability on quenching effect.  相似文献   

14.
《Ceramics International》2022,48(20):30005-30011
Self-calibrated temperature measurements combined with luminescence intensity ratio (LIR) and luminescence lifetime are more accurate. A dual-mode self-calibration optical thermometer was designed based on CaNb2O6: Tb3+/Pr3+ phosphor. The obtained sample has excellent sensitivity, with the maximum values of absolute sensitivity (Sa) and relative sensitivity (Sr) being 0.69 K-1 at 612 K and 2.50% K-1 at 532 K for LIR mode, and 0.0059 K-1 at 475 K and 2.62% K-1 at 535 K for luminescence lifetime mode, respectively. These results indicate that CaNb2O6: Tb3+/Pr3+ phosphor has valuable potential application for self-calibration optical temperature measurement.  相似文献   

15.
Eu2+ and Mn2+ singly doped and Eu2+/Mn2+-codoped Ca4Mg5(PO4)6 phosphors were synthesized via combustion synthesis. Mn2+-singly doped Ca4Mg5(PO4)6 phosphor exhibits a single red emission in the wavelength range of 500–700 nm due to the 4T1(4G)→6A1(6S) transition of Mn2+. Eu2+/Mn2+ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 442 nm originating from Eu2+ and a broad red-emitting one peaked at 609 nm from Mn2+. Energy transfers from Eu2+ to Mn2+ were discovered by directly observing significant overlap of the excitation spectrum of Mn2+ and the emission spectrum of Eu2+ as well as the systematic relative decline and growth of emission bands of Eu2+ and Mn2+, respectively. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu2+ and Mn2+.  相似文献   

16.
《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   

17.
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   

18.
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   

19.
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   

20.
In this paper, 4?mol% ZnO-doped Zr0.92Y0.08O2-α (8YSZ) and its 8YSZ+4ZnO/NaCl-KCl composite electrolyte were synthesized by a solid-state reaction. The X–ray diffraction (XRD) analysis indicates that 8YSZ+4ZnO and inorganic chlorides phases can coexist. The inorganic chlorides decrease the synthesis temperature of 8YSZ+4ZnO. The highest conductivities of 8YSZ+4ZnO and 8YSZ+4ZnO-NK are 7.0?×?10?3 S?cm?1 and 7.7?×?10?2 S?cm?1 at 700?°C, respectively. The oxygen concentration discharge cell shows that 8YSZ+4ZnO and 8YSZ+4ZnO-NK are good oxide ionic conductors under an oxygen-containing atmosphere. Finally, an H2/O2 fuel cell based on the 8YSZ+4ZnO-NK electrolyte reached the maximum power density (Pmax) of 315.5?mW?cm?2 at 700?°C.  相似文献   

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