CN113150783A - Color-adjustable afterglow luminescent material, preparation method thereof and lighting product - Google Patents
Color-adjustable afterglow luminescent material, preparation method thereof and lighting product Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7768—Chalcogenides with alkaline earth metals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/60—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction
- F21K9/64—Optical arrangements integrated in the light source, e.g. for improving the colour rendering index or the light extraction using wavelength conversion means distinct or spaced from the light-generating element, e.g. a remote phosphor layer
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Abstract
The invention relates to the technical field of luminescent materials, in particular to a color-adjustable afterglow luminescent material, a preparation method thereof and an illumination product. The luminescent material has the following general formula: MR2‑x‑yAl4‑ aGaaSiO12:xCe3+,yBi3+(ii) a In the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4. The afterglow luminescent material can be effectively excited by blue light, particularly 460nm blue light, and has the advantages of bright afterglow, long afterglow time which can last for 3 hours at most; meanwhile, the long afterglow material has the advantages of simple preparation process, low raw material cost, stable chemical property of the product, fluffiness, easy grinding, no radioactivity and no harm to the environment.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a color-adjustable afterglow luminescent material, a preparation method thereof and an illumination product.
Background
Long persistence luminescent materials, also known as light-storing materials or luminescent materials, can absorb ultraviolet or visible light efficiently, store energy, and release this energy in the form of light after excitation ceases, with the duration of luminescence varying from seconds to weeks in different host materials. So far, long-afterglow luminescent materials are widely used in the fields of illumination, emergency indication, photocatalysis, alternating current LED, anti-counterfeiting, biological fluorescence imaging and the like.
At present, white light LEDs are regarded as the fourth generation light source after incandescent lamps and fluorescent lamps as the new generation green lighting products, have the advantages of high lighting efficiency, low energy consumption, long service life, no pollution and the like, and are the strategic emerging high-technology industries of the key development in the world. The LED lighting source used at present consists of a semiconductor chip and luminous powder, the chip uses direct current as drive, and commercial power is alternating current, so that the LED lighting source needs to be subjected to alternating current and direct current conversion when in use. Therefore, the problems of complex power supply, overstaffed device, short service life of the electrolytic capacitor for filtering, high heat production, high cost and the like are caused. Direct driving of LEDs with alternating current is one of the important research and development directions. The frequency of the alternating current used in all countries in the world is 50 or 60 Hz. Because alternating current is subjected to the process that the current value is from large to small and the alternating current is in the positive and negative directions in the period, when the alternating current is used for driving the LED chip, the light emission of the chip has the same fluctuation change process, the light emission of the existing LED light-emitting material also fluctuates along with the fluctuation of the light emission, so that light emission stroboflash is caused, which is a worldwide problem facing the development of the alternating current LED. Therefore, the research and development of the long afterglow fluorescent material which can be effectively excited by the blue light chip have important research significance.
Disclosure of Invention
In view of the above, the invention provides a color-adjustable afterglow luminescent material, a preparation method thereof and an illumination product. The luminescent material is a novel color-adjustable afterglow luminescent material, can emit blue light to green light to be adjustable under the excitation of the blue light, and can generate a long afterglow luminescent effect with adjustable blue light to green light after a light source is removed.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a color-adjustable afterglow luminescent material, which has a general formula shown in a formula I:
MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+formula I;
in the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4.
x denotes the molar ratio coefficient occupied by the corresponding doping ion with respect to the R atom, y denotes the molar ratio coefficient occupied by the corresponding doping ion with respect to the R atom, and a denotes the molar fraction occupied by Ga ions with respect to Al.
Preferably, x satisfies the following condition: x is more than or equal to 0.001 and less than or equal to 0.1, and y meets the following conditions: y is more than or equal to 0.001 and less than or equal to 0.06, and a meets the following conditions: a is more than or equal to 1 and less than or equal to 3.
More preferably, x satisfies the following condition: x is more than or equal to 0.01 and less than or equal to 0.08, and y meets the following conditions: y is more than or equal to 0.005 and less than or equal to 0.03, and a meets the following conditions: a is more than or equal to 1.5 and less than or equal to 2.5.
In the invention, the long afterglow luminescent material has the general formula of MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+. Wherein, MR2Al4-aGaaSiO12As basic components, alumina and gallium oxide are regulating matrix components, trivalent Ce is luminescent ion, and Bi is co-doped ion.
Preferably, M is one of Sr or Ba, preferably Ba.
R is one of rare earth elements Lu, Sc and Y. Preferably Lu, Y, more preferably Lu.
In the invention, the long afterglow luminescent material is:
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaY1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaSc1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
SrLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.9399Al2Ga2SiO12:0.06Ce3+,0.0001Bi3+，
BaLu1.9Al2Ga2SiO12:0.06Ce3+,0.04Bi3+，
BaLu1.84Al2Ga2SiO12:0.06Ce3+,0.1Bi3+，
BaLu1.9399Al2Ga2SiO12:0.06Ce3+,
BaLu1.9Al2Ga2SiO12:0.06Ce3+,0.04Bi3+，
BaLu1.84Al2Ga2SiO12:0.06Ce3+,0.1Bi3+，
BaLu1.9799Al2Ga2SiO12:0.0001Ce3+,0.02Bi3+，
BaLu1.88Al2Ga2SiO12:0.1Ce3+,0.02Bi3+，
BaLu1.78Al2Ga2SiO12:0.2Ce3+,0.02Bi3+，
BaLu1.92Al4SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al3GaSiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Ga4SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+，
BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+。
the invention also provides a preparation method of the color-adjustable afterglow luminescent material, which comprises the following steps:
mixing an M source, an R source, an aluminum source, a gallium source, a silicon source, a cerium source and a bismuth source, and roasting in a certain sintering atmosphere to obtain the color-adjustable afterglow luminescent material;
the obtained long-afterglow luminescent material has a general formula shown in a formula I:
MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+formula I;
in the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4.
Preferably, the M source is one or more of oxides, carbonates, hydroxides, nitrates, oxalates or acetates thereof;
preferably, the M source comprises one or more of oxides, hydroxides, carbonates and nitrates thereof.
Preferably, the R source is one or more of oxides, hydroxides, nitrates, carbonates, oxalates or acetates thereof.
Preferably, the R source is one or two of oxides, carbonates and nitrates thereof.
Preferably, the aluminum source is one or more of oxides, hydroxides, nitrates, carbonates, oxalates or acetates of aluminum;
preferably, the aluminum source is one or more of oxides, carbonates and nitrates thereof.
Preferably, the gallium source is one or more of oxides, carbonates, nitrates, oxalates or acetates of gallium;
preferably, the gallium source is one or more of oxides, carbonates and nitrates thereof.
Preferably, the silicon source is an oxide of silicon.
Preferably, the cerium source is one or more of oxides, carbonates and nitrates thereof;
preferably, the bismuth source is one or more of oxides, carbonates and nitrates thereof.
Preferably, the molar ratio of the M source, the R source, the aluminum source, the gallium source, the silicon source, the cerium source and the bismuth source is as follows: 1: (1.7-1.9998): (0-4): (0-4): 1: (0.0001-0.2): (0.0001-0.1).
Preferably, the molar ratio of the M source, the R source, the aluminum source, the gallium source, the silicon source, the cerium source and the bismuth source is as follows: 1: (1.84-1.998): (1-3): (1-3): 1: (0.001-0.1): (0.001-0.06).
Preferably, the sintering atmosphere is one or more of air, nitrogen-hydrogen mixed gas, hydrogen or carbon monoxide.
Preferably, the sintering atmosphere in the preparation method is air, nitrogen or a nitrogen-hydrogen mixed gas.
Preferably, the roasting temperature is 1200-1500 ℃, and the roasting time is 1-24 hours.
Preferably, the roasting temperature is 1200-1500 ℃, and the roasting time is 3-5 hours.
Preferably, the roasting temperature is 1200-1500 ℃, and the roasting time is 4 hours.
The invention also provides an illumination product comprising the color-adjustable afterglow luminescent material.
The invention provides a color-adjustable afterglow luminescent material, a preparation method thereof and an illumination product. The luminescent material has the following general formula: MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+(ii) a In the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4. The invention provides a method for using MR2Al4-aGaaSiO12As matrix, trivalent Ce ion as luminous center, trivalent bismuth ion and trivalent rare earth ion doped long afterglow material. Compared with the prior art, the invention has the technical effects that: the long afterglow material of the system can be effectively excited by blue light, particularly 460nm blue light, and has bright afterglow, long afterglow time which can last for 3 hours at most; meanwhile, the long afterglow material has the advantages of simple preparation process, low raw material cost, stable chemical property of the product, fluffiness, easy grinding, no radioactivity and no harm to the environment.
Drawings
For a clearer explanation of the embodiments or technical solutions in the prior art, the drawings used in the description of the embodiments and the prior art will be briefly described below, and it is obvious that the following drawings are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD powder diffractogram of the long-lasting phosphor provided in example 1 of the present invention;
FIG. 2 is an excitation emission spectrum of a long-afterglow luminescent material provided in embodiment 1 of the present invention;
FIG. 3 is an afterglow luminescence spectrum of a long afterglow luminescent material provided in example 1 of the present invention;
FIG. 4 is an afterglow decay curve of a long afterglow luminescent material provided in embodiment 1 of the present invention;
FIG. 5 is an excitation emission spectrum of a long-afterglow luminescent material provided in embodiment 8 of the present invention;
FIG. 6 is an afterglow luminescence spectrum of a long afterglow luminescent material provided in embodiment 8 of the present invention;
FIG. 7 is an excitation emission spectrum of a long-afterglow luminescent material provided in embodiment 10 of the present invention;
FIG. 8 is an afterglow luminescence spectrum of a long afterglow luminescent material provided in example 10 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a long-afterglow luminescent material, which has a general formula shown in a formula I:
MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+formula I
Wherein M is one or two of Sr or Ba, R is one or more of rare earth elements Lu, Sc and Y, x refers to the molar ratio coefficient occupied by the corresponding doped ions relative to R atoms, Y refers to the molar ratio coefficient occupied by the corresponding doped ions relative to R atoms, and a refers to the molar fraction occupied by Ga ions relative to Al, wherein x is more than or equal to 0.0001 and less than or equal to 0.2, Y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4.
In the invention, the long afterglow luminescent material has the general formula of MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+. Wherein, MR2Al4-aGaaSiO12As basic components, aluminum oxide and gallium oxide are regulating matrix components, trivalent Ce is a luminescent ion, Bi is a co-doping ion, M is one or two of Sr or Ba, preferably Ba; r is one or more of rare earth elements Lu, Sc and Y, preferably Lu and Y, and more preferably Lu. In the present invention,
0.0001. ltoreq. x.ltoreq.0.2, preferably: 0.001. ltoreq. x.ltoreq.0.1, more preferably: x is more than or equal to 0.01 and less than or equal to 0.08;
0.0001. ltoreq. y.ltoreq.0.1, preferably: 0.001. ltoreq. y.ltoreq.0.06, more preferably: y is more than or equal to 0.005 and less than or equal to 0.03;
0. ltoreq. a.ltoreq.4, preferably 1. ltoreq. a.ltoreq.3, more preferably 1.5. ltoreq. a.ltoreq.2.5.
In a preferred embodiment of the present invention, M is Ba, R is Lu, x is 0.06, y is 0.02, and b is 2, and the composition of the long afterglow material is BaLu1.92Al2Ga2SiO12:0.06Ce，0.02Bi。
The invention also provides a preparation method of the garnet-based long-afterglow luminescent material, which comprises the following steps:
mixing an M source, an R source, an aluminum source, a gallium source, a silicon source, a cerium source and a bismuth source, and roasting in a certain atmosphere to obtain the garnet-based long-afterglow luminescent material capable of emitting blue and cyan light;
the mixing process is not particularly limited in the present invention, and the M source, the R source, the aluminum source, the gallium source, the silicon source, the cerium source, and the bismuth source are mixed by a mixing method known to those skilled in the art.
After the mixing is finished, the mixture obtained after the mixing is sintered under a certain atmosphere to obtain the long-afterglow luminescent material. The sintering apparatus of the present invention is not particularly limited, and a high temperature furnace well known to those skilled in the art is used, and in the present invention, the sintering temperature is preferably 1200 to 1500 ℃, more preferably 1300 to 1450 ℃, and most preferably 1400 ℃; the sintering time is 1-24 hours, more preferably 3-8 hours, and most preferably 4 hours.
In the present invention, the sintering process is performed in a certain atmosphere. In the present invention, the atmosphere is preferably air, nitrogen gas or a nitrogen-hydrogen mixture gas, and most preferably air.
After the sintering process is finished, the obtained product is naturally cooled to room temperature, and the long-afterglow luminescent material is obtained after grinding.
The invention is further illustrated by the following examples:
example 1
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, as shown in FIG. 2; under the excitation of 430nm blue light, the maximum emission peak of the emission spectrum is about 490nm, the emission covers blue-green light, the afterglow emission spectrum and the afterglow attenuation curve of the material are shown in figures 3 and 4, and the afterglow can last for more than 3 hours.
Example 2
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportionAnd uniformly mixing, placing into a corundum crucible, placing into a tubular furnace, roasting at 1400 ℃ for 4 hours in nitrogen atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow can last for more than 2.5 hours.
Example 3
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a tubular furnace, roasting at 1400 ℃ for 4 hours in a nitrogen-hydrogen reducing atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow can last for more than 2.5 hours.
Example 4
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, and then placing into a tubular furnaceRoasting at 1400 deg.c for 4 hr in argon atmosphere, and cooling naturally to room temperature to obtain the garnet-base long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow can last for more than 2.5 hours.
Example 5
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1200 ℃ for 4 hours in the air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 6
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1300 ℃ for 4 hours in air atmosphere, and naturally cooling to a roomAnd (4) heating to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 7
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1500 ℃ for 4 hours in the air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 8
The raw material is BaCO3(analytical grade), Y2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnetThe base phosphor is cyan powder with BaY molecular formula1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 440nm, the maximum emission peak of the emission spectrum is about 540nm under the excitation of blue light at 440nm, as shown in figure 5, the light emission covers green light, the afterglow can last for more than 2 hours, and the afterglow spectrum is shown in figure 6.
Example 9
The raw material is BaCO3(analytically pure) Sc2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaSc1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 440nm, the maximum emission peak of the emission spectrum is about 540nm under the excitation of 440nm blue light, the light is emitted to cover green light, and the afterglow can last for more than 1 hour.
Example 10
The raw material is SrCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powderMolecular formula is SrLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 440nm, the maximum emission peak of the emission spectrum is about 520nm under the excitation of blue light with the wavelength of 440nm, as shown in figure 7, the light emission covers green light, the afterglow can last for more than 2 hours, and the afterglow spectrum is shown in figure 8.
Example 11
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96995: 1: 1: 1: 0.03: 0.00005, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.9399Al2Ga2SiO12:0.06Ce3+,0.0001Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 1 hour.
Example 12
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.95: 1: 1: 1: 0.03: 0.02, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula ofBaLu1.9Al2Ga2SiO12:0.06Ce3+,0.04Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 13
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.92: 1: 1: 1: 0.03: 0.05, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.84Al2Ga2SiO12:0.06Ce3+,0.1Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 1 hour.
Example 14
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.98995: 1: 1: 1: 0.00005: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.9799Al2Ga2SiO12:0.0001Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 1 hour.
Example 15
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.94: 1: 1: 1: 0.05: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.88Al2Ga2SiO12:0.1Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 16
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.89: 1: 1: 1: 0.1: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.78Al2Ga2SiO12:0.2Ce3+,0.02Bi3+Maximum of excitation spectrumThe excitation peak is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue-green light is covered by the luminescence, and the afterglow can last for more than 1 hour.
Example 17
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 2: 1: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al4SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 1.5 hours.
Example 18
The raw material is BaCO3(analytically pure) Lu2O3(analytical grade), Al2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1.5: 0.5: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al3GaSiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, and the emission covers blue and green light, the restThe glow can last for more than 1.5 hours.
Example 19
The raw material is BaCO3(analytically pure) Lu2O3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) Ce2(CO3)3(spectral purity) Bi2O3(spectral purity), the molar ratio between them is 1: 0.96: 1: 2: 0.03: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Ga4SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 1.5 hours.
Example 20
The raw material is Ba (OH)2(analytically pure), Lu (OH)3(analytically pure), Al (OH)3(analytically pure), Ga (OH)3(spectral purity), SiO2(analytically pure), Ce (OH)3(Spectrum pure), Bi (OH)3(spectral purity), the molar ratio between them is 1: 1.92: 2: 2: 1: 0.06: 0.02, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 21
The raw material is Ba (NO)3)2(analytically pure), Lu (NO)3)3(analytically pure), Al (NO)3)3(analytically pure), Ga (NO)3)3(spectral purity), SiO2(analytically pure), Ce (NO)3)3(Spectrum pure) Bi (NO)3)3(spectral purity), the molar ratio between them is 1: 1.92: 2: 2: 1: 0.06: 0.02, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
Example 22
The raw materials are BaO (analytically pure) and Lu2(CO3)3(analytical grade), Al2(CO3)3(analytically pure) Ga2O3(spectral purity), SiO2(analytically pure) CeO2(spectral purity) Bi2(CO3)3(spectral purity), the molar ratio between them is 1: 0.96: 1: 1: 1: 0.06: 0.01, weighing the raw materials according to the proportion, uniformly mixing, placing into a corundum crucible, placing into a high-temperature furnace, roasting at 1400 ℃ for 4 hours in air atmosphere, and naturally cooling to room temperature to obtain the garnet-based long-afterglow luminescent powder. The obtained garnet-based phosphor is cyan powder with a molecular formula of BaLu1.92Al2Ga2SiO12:0.06Ce3+,0.02Bi3+The maximum excitation peak of the excitation spectrum is about 430nm, the maximum emission peak of the emission spectrum is about 490nm under the excitation of 430nm blue light, the blue and green light is covered by the light emission, and the afterglow lasts for more than 2 hours.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A color tunable afterglow luminescent material, which is characterized in that the material has a general formula shown in formula I:
MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+formula I;
in the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4.
2. The color tunable afterglow luminescent material of claim 1, wherein M is one of Sr or Ba, and R is one of rare earth elements Lu, Sc, Y.
3. A method for preparing the color tunable afterglow luminescent material of claim 1 or 2, which comprises the following steps:
mixing an M source, an R source, an aluminum source, a gallium source, a silicon source, a cerium source and a bismuth source, and roasting in a certain sintering atmosphere to obtain the color-adjustable afterglow luminescent material;
the obtained long-afterglow luminescent material has a general formula shown in a formula I:
MR2-x-yAl4-aGaaSiO12:xCe3+,yBi3+formula I;
in the formula I, M is one or two of Sr or Ba, and R is one or more of rare earth elements Lu, Sc and Y; x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, and a is more than or equal to 0 and less than or equal to 4.
4. The preparation method of claim 3, wherein the M source is one or more of an oxide, a carbonate, a hydroxide, a nitrate, an oxalate or an acetate thereof;
the R source is one or more of oxide, hydroxide, nitrate, carbonate, oxalate or acetate of the R source.
5. The preparation method of claim 3, wherein the aluminum source is one or more of an oxide, a hydroxide, a nitrate, a carbonate, an oxalate or an acetate of aluminum;
the gallium source is one or more of gallium oxide, carbonate, nitrate, oxalate or acetate;
the silicon source is an oxide of silicon.
6. The preparation method according to claim 3, wherein the cerium source is one or more of an oxide, a carbonate and a nitrate thereof;
the bismuth source is one or more of oxides, carbonates and nitrates thereof.
7. The preparation method according to claim 3, wherein the molar ratio of the M source, the R source, the aluminum source, the gallium source, the silicon source, the cerium source and the bismuth source is: 1: (1.7-1.9998): (0-4): (0-4): 1: (0.0001-0.2): (0.0001-0.1).
8. The preparation method according to claim 3, wherein the sintering atmosphere is one or more of air, nitrogen, a nitrogen-hydrogen mixture, hydrogen or carbon monoxide.
9. The method according to any one of claims 3 to 8, wherein the temperature of the calcination is 1200 to 1500 ℃ and the time of the calcination is 1 to 24 hours.
10. An illumination product comprising the color tunable afterglow luminescent material of claim 1 or 2.
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