CN112480910A - Blue-green silicate fluorescent powder and preparation method and application thereof - Google Patents
Blue-green silicate fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 58
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 8
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 21
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 7
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 238000000904 thermoluminescence Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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Abstract
The invention discloses blue-green silicate fluorescent powder, and the molecular formula of the blue-green silicate fluorescent powder is BaaCabSiO4:xEu2+,yR3+Wherein a is more than or equal to 0.3 and less than or equal to 1.7, b is more than or equal to 0.3 and less than or equal to 1.7, and x is more than or equal to 0.001 and less than or equal to 0.02; y is more than or equal to 0.001 and less than or equal to 0.065, and R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy; the invention takes silicate as a substrate and is doped with Eu2+、R3+Ion obtaining a Eu2+、R3+Activated blue-green silicate fluorescent powder. The fluorescent powder has good thermal stability, long afterglow, can be excited by ultraviolet light, and has a wider emission band.
Description
Technical Field
The invention relates to the technical field of photoluminescence materials, and particularly relates to blue-green silicate fluorescent powder and a preparation method and application thereof.
Background
The white light LED has the advantages of small volume, short response time, environmental protection, no pollution, high luminous efficiency, long service life and the like, has huge market and wide application prospect, and is always used as a green illumination light source in the 21 st century. The fluorescent powder is an important solid luminescent material, is a main raw material for preparing a white light LED, and is the key for determining the performances of the LED lighting device, such as luminous efficiency, energy consumption and the like.
In recent years, the technology of the present invention has been developedIn the past, the combination of ultraviolet LED chips (350-. Many research reports about the combination of three-primary-color fluorescent powder and ultraviolet LED chip to realize white LED, wherein the blue-green fluorescent powder accounts for a large proportion, such as Ca3Sc2Si3O12:Ce3+(“Ca3Sc2Si3O12:Ce3+,Nd3+Preparation and luminescence properties of near-infrared phosphor ", Wanwenjiao et al, silicate school newspapers, volume 38, phase 10, page 1862-1866, published 10 months 2010), Ba2SiO4:Eu2+("near ultraviolet excited Ba2SiO4:Eu2+The development of green powder, Dinghong et al, light source and illumination, 3 rd-5 th page, published in 2008, 9 months) can enable the LED to obtain higher luminous efficiency and longer service life, but the development of the fluorescent powder is hindered due to poor electronic storage effect, fast afterglow attenuation and poor thermal stability. Therefore, it is necessary to find a new blue-green phosphor to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the blue-green silicate fluorescent powder which has good thermal stability, long afterglow, capability of being excited by ultraviolet light and wider emission band.
The invention further aims to provide a preparation method of the blue-green silicate fluorescent powder.
The invention also aims to provide the application of the blue-green silicate fluorescent powder.
The above object of the present invention is achieved by the following technical solutions:
the blue-green silicate fluorescent powder has a molecular formula of BaaCabSiO4：xEu2 +，yR3+Wherein a is more than or equal to 0.3 and less than or equal to 1.7, b is more than or equal to 0.3 and less than or equal to 1.7, and x is more than or equal to 0.001 and less than or equal to 0.02; y is more than or equal to 0.001 and less than or equal to 0.065, and R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
Preferably, the molecular formula of the blue-green silicate fluorescent powder is BaaCabSiO4：xEu2+，yR3+Wherein a is more than or equal to 1.0 and less than or equal to 1.6, b is more than or equal to 0.4 and less than or equal to 1.0, and x is more than or equal to 0.01 and less than or equal to 0.02; y is more than or equal to 0.05 and less than or equal to 0.065, and R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
The invention is realized by adding BaaCabSiO4As a matrix, doped with Eu2+Ion and R3+Ion preparation to obtain the blue-green silicate fluorescent powder. Eu (Eu)2+The doping of the ions enables the traps of the material to be distributed at about 150 ℃, so that the thermal stability of the material is improved; further doping with R3+After ionization, the electron storage capacity is improved, and the long afterglow is realized.
In the invention, the excitation wavelength of the blue-green silicate fluorescent powder is 375 nm-425 nm, and the emission peak is 475 nm-525 nm, preferably 500 nm-525 nm.
A preparation method of blue-green silicate fluorescent powder comprises the following steps:
s1, mixing BaCO3And/or BaO, CaCO3And/or CaO, Eu2O3，SiO2，R2O3Mixing, grinding, sintering in reducing atmosphere, and cooling to obtain the blue-green silicate fluorescent powder, wherein R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
Preferably, the reducing atmosphere is H2And N2The mixed atmosphere of (3).
Preferably, said N is2And H2Is 1: (10-20).
Preferably, the sintering is to raise the temperature to 1000-1320 ℃ at a temperature rise rate of 2-6 ℃/min and keep the temperature for 3-5 h.
More preferably, the sintering is carried out by raising the temperature to 1200-1300 ℃ at a temperature raising rate of 2-4 ℃/min and keeping the temperature for 4-5 h.
In the invention, the sintering adopts a high-temperature tube furnace, and the high-temperature tube furnace is preferably a muffle furnace.
Preferably, the raw material BaCO3And/or BaO, CaCO3And/or CaO, Eu2O3，SiO2，R2O3In a molar ratio of 1600: 400: 1000: (1-20): (1-65).
The blue-green silicate fluorescent powder disclosed by the invention is good in thermal stability, can be excited by ultraviolet light, has a wider emission band, meets the performance requirements of a white light LED on the fluorescent powder, has long afterglow and a good electronic storage effect, and can be used in the field of optical storage. Therefore, the application of the blue-green silicate fluorescent powder in the white light LED illumination field and the light storage field should also be within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses BaaCabSiO4As a matrix, doped with Eu2+、R3+Ion obtaining a Eu2+、R3+Activated blue-green silicate fluorescent powder. The fluorescent powder prepared by the invention has the trap distribution at about 150 ℃, has further enhanced thermal stability compared with the common fluorescent powder, has long afterglow, can be excited by ultraviolet light, has strong luminous intensity and has a wide luminous band.
Drawings
FIG. 1 is an X-ray diffraction pattern of the phosphor prepared in example 1.
FIG. 2 is a diffuse reflectance spectrum of the phosphor prepared in example 1.
FIG. 3 is an excitation spectrum of the phosphor prepared in example 1.
FIG. 4 is an emission spectrum of the phosphor prepared in example 1.
FIG. 5 is a thermoluminescence of the phosphor prepared in example 1.
FIG. 6 is a long persistence luminescence decay curve of the phosphor prepared in example 1.
FIG. 7 shows thermoluminescence of the phosphor prepared in comparative example 1.
FIG. 8 is a long-lasting luminescence decay curve of the phosphor prepared in comparative example 1.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention. In the present invention, the source of the raw material for preparation is not particularly limited, and the raw material may be commercially available.
In the following examples, X-ray diffraction detection of a sample to be detected adopts a Beijing Pujingyu XD-2X-ray diffractometer; the excitation spectrum detection adopts an Edinburgh FLS-980 fluorescence spectrometer; the diffuse reflection spectrum detection adopts an Evolution-220 ultraviolet-visible spectrophotometer; the excitation spectrum detection adopts an Edinburgh FLS-980 fluorescence spectrometer.
Example 1
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+,0.065Dy3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Dy2O3The molar ratio is 1.6:0.4:1:0.02:0.065, the mixture is fully mixed and is put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:10 is introduced2And N2Heating to 1200 ℃ at the heating rate of 2 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 4h, and naturally cooling to obtain the fluorescent powder.
Example 2
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+，0.02Dy3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Dy2O3The molar ratio is 1.6:0.4:1:0.02:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:14 is introduced2And N2Heating to 1300 ℃ at the heating rate of 4 ℃/min under the condition of the formed reducing atmosphere, preserving the heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 3
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+,0.09Dy3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Dy2O3The molar ratio is 1.6:0.4:1:0.02:0.09, the materials are fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:16 is introduced2And N2Heating to 1300 ℃ at the heating rate of 4 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 4h, and naturally cooling to obtain the fluorescent powder.
Example 4
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+,0.02Ho3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Ho2O3The molar ratio is 1.6:0.4:1:0.02:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:20 is introduced2And N2Heating to 1250 ℃ at the heating rate of 3 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 5
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+,0.02Er3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Er2O3The molar ratio is 1.6:0.4:1:0.02:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:18 is introduced2And N2Heating to 1200 ℃ at the heating rate of 6 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 6
According to the chemical composition of the fluorescent powder: BaCaSiO4:0.02Eu2+,0.02Dy3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Dy2O3The molar ratio is 1:1:0.02:0.02, fully mixing, grinding uniformly in a mortar, putting into a muffle furnace, and introducing H with the volume ratio of 1:122And N2Heating to 1000 ℃ at the heating rate of 6 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 7
According to the chemical composition of the fluorescent powder: BaCaSiO4:0.02Eu2+,0.02Ho3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Ho2O3The molar ratio is 1:1:1:0.02:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:12 is introduced2And N2Heating to 1200 ℃ at a heating rate of 6 ℃/min under the condition of a reducing atmosphere, preserving heat for 3h, and naturally cooling to obtain the fluorescent powder.
Example 8
According to the chemical composition of the fluorescent powder: BaCaSiO4:0.02Eu2+,0.02Er3+Respectively weighing BaCO3、CaCO3、SiO2、Eu2O3And Er2O3The molar ratio is 1:1:1:0.02:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:12 is introduced2And N2Heating to 1200 ℃ at the heating rate of 6 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 9
According to the chemical composition of the fluorescent powder: ba0.3Ca0.3SiO4:0.001Eu2+，0.001Nd3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Nd2O3The molar ratio is 0.3:0.3:1:0.001:0.001, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:14 is introduced2And N2Heating to 1320 deg.C at 4 deg.C/min under reducing atmosphere, keeping the temperature for 5h, and naturally coolingAnd then obtaining the fluorescent powder.
Example 10
According to the chemical composition of the fluorescent powder: ba1.7Ca1.7SiO4:0.02Eu2+，0.065Lu3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Lu2O3The molar ratio is 1.7:1.7:1:0.02:0.065, the mixture is fully mixed and is put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:14 is introduced2And N2Heating to 1320 ℃ at the heating rate of 4 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Example 11
According to the chemical composition of the fluorescent powder: ba1.0Ca0.4SiO4:0.01Eu2+，0.05Yb3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Yb2O3The molar ratio is 1:0.4:1:0.01:0.05, the mixture is fully mixed and is put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:10 is introduced2And N2Heating to 1250 ℃ at the heating rate of 4 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 3h, and naturally cooling to obtain the fluorescent powder.
Example 12
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+，0.02Gd3+Separately weighing BaCO3、CaCO3、SiO2、Eu2O3And Gd2O3The molar ratio is 1.6:1:1:0.02:0.065, the mixture is fully mixed and is put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:10 is introduced2And N2Heating to 1320 ℃ at the heating rate of 4 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 5h, and naturally cooling to obtain the fluorescent powder.
Comparative example 1
According to the chemical composition of the fluorescent powder: ba1.6Ca0.4SiO4:0.02Eu2+Separately weighing BaCO3、CaCO3、SiO2And Eu2O3The molar ratio is 1.6:0.4:1:0.02, the mixture is fully mixed and put into a muffle furnace after being evenly ground in a mortar, and H with the volume ratio of 1:10 is introduced2And N2Heating to 1200 ℃ at the heating rate of 2 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 4h, and naturally cooling to obtain the fluorescent powder.
Characterization of
FIG. 1 is an X-ray diffraction diagram of the phosphor of example 1, in which diffraction peaks appearing at respective positions correspond to Ba1.6Ca0.4SiO4Typical diffraction peak of (B) indicating that Ba was obtained1.6Ca0.4SiO4Pure phase; FIG. 2 is a diffuse reflection spectrum of the phosphor of example 1, in which an obvious absorption peak appears at 400-600 nm, indicating that the phosphor can be effectively excited by the wavelength in this range; FIG. 3 is an excitation spectrum obtained by detecting the phosphor of example 1 at a wavelength of 340nm, wherein an obvious excitation peak appears in 400-600 nm, and the excitation peak belongs to Eu2+Indicating that the phosphor described in example 1 can be excited by visible light; FIG. 4 is an emission spectrum obtained by excitation of the phosphor of example 1 at a wavelength of 500nm, showing a distinct emission peak at a wavelength of 510nm, belonging to Eu2+The characteristic emission peak of the fluorescent powder shows that the fluorescent powder can emit blue-green light.
FIG. 5 is a thermoluminescence spectrum of the phosphor of example 1, and it can be seen from the graph that the peak position of thermoluminescence is around 150 ℃, which indicates that the phosphor prepared in this example has better thermal stability; FIG. 6 is a long afterglow luminescence decay curve of the phosphor described in example 1, from which it can be seen that the afterglow time exceeds 60min, which is significantly higher than the afterglow time disclosed in the prior art, and the relative intensity only decays to below 0.1 at 60min, indicating that the afterglow decay is greatly improved.
FIG. 7 is a thermoluminescence spectrum of the phosphor of comparative example 1, and it can be seen from the graph that the peak position of thermoluminescence is around 150 ℃, which indicates that the phosphor prepared in comparative example 1 has better thermal stability; FIG. 8 is a graph showing a graph of comparative example 1The long afterglow luminescence decay curve of the phosphor can be seen from the figure, Eu is singly doped2+In the case of (2), the relative intensity decayed to 0.01 or less in 60 minutes.
The peak positions of thermoluminescence of the phosphors described in examples 2 to 12 are similar to those of example 1 and are all around 150 ℃; the afterglow time of the phosphors of examples 2 to 12 was similar to that of example 1, i.e., the afterglow time at 60 minutes decreased to 0.1 or less.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The blue-green silicate fluorescent powder is characterized in that the molecular formula of the blue-green silicate fluorescent powder is BaaCabSiO4：xEu2+，yR3+Wherein a is more than or equal to 0.3 and less than or equal to 1.7, b is more than or equal to 0.3 and less than or equal to 1.7, and x is more than or equal to 0.001 and less than or equal to 0.02; y is more than or equal to 0.001 and less than or equal to 0.065, and R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
2. The blue-green silicate phosphor of claim 1, wherein the blue-green silicate phosphor has a molecular formula of aBa1bCa1SiO4：xEu2+，yR3+Wherein a is more than or equal to 1.0 and less than or equal to 1.6, b is more than or equal to 0.4 and less than or equal to 1.0, and x is more than or equal to 0.01 and less than or equal to 0.02; y is more than or equal to 0.05 and less than or equal to 0.065, and R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
3. The blue-green silicate phosphor of claim 1, wherein the excitation wavelength of the blue-green silicate phosphor is 375nm to 425nm, and the emission peak is 475nm to 525 nm.
4. The method for preparing blue-green silicate phosphor according to any one of claims 1 to 3, comprising the steps of:
s1, proportionally mixing BaCO3And/or BaO, CaCO3And/or CaO, Eu2O3，SiO2，R2O3Mixing, grinding, sintering in reducing atmosphere, and cooling to obtain the blue-green silicate fluorescent powder, wherein R is one of Er, Nd, Lu, Yb, Gd, Ho and Dy.
5. The method of claim 4, wherein the reducing atmosphere is H2And N2The mixed atmosphere of (3).
6. The method of claim 5, wherein N is the blue-green silicate phosphor2And H2Is 1: (10-20).
7. The method for preparing blue-green silicate phosphor according to claim 4, wherein the sintering is carried out by raising the temperature to 1000-1320 ℃ at a rate of 2-6 ℃/min and maintaining the temperature for 3-5 h.
8. The method for preparing blue-green silicate phosphor according to claim 7, wherein the sintering is carried out by raising the temperature to 1200-1300 ℃ at a rate of 2-4 ℃/min and keeping the temperature for 4-5 h.
9. The method of claim 4, wherein the raw material BaCO is selected from the group consisting of BaCO3And/or BaO, CaCO3And/or CaO, Eu2O3，SiO2，R2O3In a molar ratio of 1600: 400: 1000: (1-20): (1-65).
10. Use of the blue-green silicate phosphor of any one of claims 1 to 3 in the field of white light LED illumination and light storage.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080185956A1 (en) * | 2007-02-01 | 2008-08-07 | Kabushiki Kaisha Toshiba | Luminescent material |
| CN106497555A (en) * | 2016-11-01 | 2017-03-15 | 兰州大学 | Long persistence luminescent silicate material and preparation method thereof |
| CN107974250A (en) * | 2017-11-28 | 2018-05-01 | 兰州大学 | A kind of blue-green silicate ultra-long afterglow luminescent material and preparation method thereof |
-
2020
- 2020-12-04 CN CN202011402689.2A patent/CN112480910A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080185956A1 (en) * | 2007-02-01 | 2008-08-07 | Kabushiki Kaisha Toshiba | Luminescent material |
| CN106497555A (en) * | 2016-11-01 | 2017-03-15 | 兰州大学 | Long persistence luminescent silicate material and preparation method thereof |
| CN107974250A (en) * | 2017-11-28 | 2018-05-01 | 兰州大学 | A kind of blue-green silicate ultra-long afterglow luminescent material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHUANLONG WANG ET AL.: "Trap distribution tailoring guided design of super-long-persistent phosphor Ba2SiO4:Eu2+,Ho3+ and photostimulable luminescence for optical information storage", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| KAZUKI ASAMI ET AL.: "Development of persistent phosphor of Eu2+ doped Ba2SiO4 by Er3+ codoping based on vacuum referred binding energy diagram", 《OPTICAL MATERIALS》 * |
| ZHI HUANG ET AL.: "Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu2+,Mn2+ phosphors via Dy3+ addition and their color-tunable properties", 《CERAMICS INTERNATIONAL》 * |
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