CN116144359A - Fluorescent powder, preparation method and white light LED - Google Patents

Fluorescent powder, preparation method and white light LED Download PDF

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CN116144359A
CN116144359A CN202310176431.2A CN202310176431A CN116144359A CN 116144359 A CN116144359 A CN 116144359A CN 202310176431 A CN202310176431 A CN 202310176431A CN 116144359 A CN116144359 A CN 116144359A
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oxide
gallium
yttrium
atom
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温红丽
沓崇锷
阿卜杜勒·哈基姆·德仕穆仁
余林
罗莉
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09K11/7783—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
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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    • H01—ELECTRIC ELEMENTS
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier 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
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The application belongs to the technical field of inorganic luminescent materials, and particularly relates to fluorescent powder, a preparation method and a white light LED; the chemical composition formula of the fluorescent powder provided by the application is as follows: y is Y 2‑x/y/z Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ Wherein by reacting garnet-type fluorescent material Y 2 Ca 2 Ga 3 VO 12 Eu is carried out 3+ /Sm 3+ /Dy 3+ The doped fluorescent powder can be excited by ultraviolet light to respectively obtain orange red light/yellow light emission, and white light emission is obtained after the doped fluorescent powder is proportioned with blue and green fluorescent powder excited by the ultraviolet light, so that the technical problem that the fluorescent powder for a white light LED excited by the ultraviolet light is lacking in the prior art is solved.

Description

Fluorescent powder, preparation method and white light LED
Technical Field
The application belongs to the technical field of inorganic luminescent materials, and particularly relates to fluorescent powder, a preparation method and a white light LED.
Background
White LEDs (White Light-Emitting Diodes) have the characteristics of high efficiency, energy conservation, difficult damage, long service life, no pollution and the like, and are widely applied to the fields of indoor, outdoor, display screens, mobile phones, computers and the like.
Commercial white LEDs are mainly manufactured by blue InGaN chips and Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) The yellow fluorescent powder is compounded to obtain, the blue InGaN chip emits blue light under current drive, after the blue light excites the fluorescent powder, the fluorescent powder emits yellow light, white light is synthesized under the action of a lens, however, the mode of synthesizing the white light LED lacks red components, and high color temperature (CCT) exists>4500K) And low color rendering index (CRI; ra (Ra)<80 A) problems with; in the mode that the ultraviolet LED chip excites the red, green and blue three-primary-color fluorescent powder to synthesize the white light LED, a light source emitted by the ultraviolet LED chip is not used as a primary color for synthesizing the white light LED, and only plays a role in exciting the fluorescent powder, so that the obtained white light LED has the advantages of uniform color, higher color rendering index, stable light emission and higher ultraviolet energy than blue light, and can excite more kinds of fluorescent powder by taking the ultraviolet LED chip as an excitation light source.
However, most of the phosphors for white light LED which can be excited by ultraviolet light are blue phosphor and green phosphor, and many of the red and yellow phosphors are not enough, and the phosphors for white light LED which can be excited by ultraviolet light are lacking.
Disclosure of Invention
In view of the above, the present application provides a phosphor, a preparation method thereof and a white LED for solving the technical problem that the phosphor for a white LED which can be excited by ultraviolet light is lacking in the prior art.
The first aspect of the present application provides a fluorescent powder, which has a chemical composition formula:
Y 2-x/y/z Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ a formula I;
in the formula I, the numerical range of x is 0.03-0.30; the value range of y is 0.015-0.20; the value range of z is 0.01-0.20.
Preferably, in the formula I, the value of x is 0.18, and the chemical composition formula of the fluorescent powder is as follows:
Y 1.82 Ca 2 Ga 3 VO 12 :0.18Eu 3+ 。
preferably, in the formula I, the value of y is 0.06, and the chemical composition formula of the fluorescent powder is as follows:
Y 1.94 Ca 2 Ga 3 VO 12 :0.06Sm 3+ 。
preferably, in the formula I, the value of z is 0.03, and the chemical composition formula of the fluorescent powder is as follows:
Y 1.97 Ca 2 Ga 3 VO 12 :0.03Dy 3+ 。
the second aspect of the present application provides a method for preparing the above phosphor, comprising the steps of:
step S1, mixing and grinding yttrium source, calcium source, gallium source, vanadium source and doped rare earth source according to the stoichiometric ratio of the formula I for 60-120 min to obtain a premixed solid reactant;
s2, pre-calcining the solid reactant to obtain a pre-calcined reaction product;
step S3, grinding the pre-calcined reaction product for 5-15 min, and calcining to obtain fluorescent powder;
in the step S1, the doped rare earth source is selected from europium source, samarium source or dysprosium source;
in the step S3, the calcining temperature is 1300-1400 ℃, the calcining time is 10-12 h, and the atmosphere is oxygen.
Preferably, in step S3, the calcination temperature is 1350 ℃ and the calcination time is 12 hours.
Preferably, in step S2, the temperature of the pre-calcination is 600-800 ℃ and the time is 4-6 hours.
Preferably, in step S1, the calcium source is selected from calcium carbonate or/and calcium oxide;
the gallium source is selected from gallium oxide or/and gallium acetate;
the vanadium source is selected from ammonium metavanadate or/and vanadium pentoxide;
the europium source is selected from europium oxide or/and europium acetate;
the samarium source is selected from samarium oxide or/and samarium acetate;
the dysprosium source is selected from dysprosium oxide or/and dysprosium acetate.
Preferably, in step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the europium source is europium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the europium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide are respectively 1.82 mol parts, 2 mol parts, 3 mol parts, 1 mol part and 0.18 mol part.
In the step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the samarium source is samarium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the samarium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide are respectively 1.94 mole parts, 2 mole parts, 3 mole parts, 1 mole part and 0.06 mole part.
In the step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the dysprosium source is dysprosium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the dysprosium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the dysprosium oxide are respectively 1.97 mol parts, 2 mol parts, 3 mol parts, 1 mol part and 0.03 mol part in terms of mol parts.
A third aspect of the present application provides a white LED comprising the above Y 2-x/y Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy3 + Green and blue phosphors that are excitable by ultraviolet light, and an ultraviolet light source.
Preferably, the green phosphor that can be excited by ultraviolet light is selected from: (Sr, ba) 2 SiO 4 :Eu 2+ ；
The blue fluorescent powder capable of being excited by ultraviolet light is selected from the following components: baMgAl 10 O 17 :Eu 2+ 。
Preferably, the white light LED is an LED lighting lamp or an LED display.
In summary, the application provides a fluorescent powder, a preparation method and a white light LED, wherein the chemical composition formula of the fluorescent powder is as follows: y is Y 2-x/y/z Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ In the chemical composition formula of the fluorescent powder, the numerical value range of x is 0.03-0.30; the value range of y is 0.015-0.20; the value of z ranges from 0.01 to 0.20, eu 3+ Doped Y 2 Ca 2 Ga 3 VO 12 The fluorescent powder can be excited by a 394nm light source to emit orange-red fluorescence, sm 3+ Doped Y 2 Ca 2 Ga 3 VO 12 The fluorescent powder can be excited by a 405nm light source to emit red fluorescence, dy 3+ Doped Y 2 Ca 2 Ga 3 VO 12 The fluorescent powder can be excited by a 365nm light source to emit yellow fluorescence, eu 3+ /Sm 3+ /Dy 3 Doped Y 2 Ca 2 Ga 3 VO 12 After the fluorescent powder is mixed with the green fluorescent powder which can be excited by ultraviolet light and the blue fluorescent powder which can be excited by ultraviolet light, white light emission can be realized through ultraviolet light excitation, so Eu provided by the application 3+ /Sm 3+ /Dy 3 Doped Y 2 Ca 2 Ga 3 VO 12 The fluorescent powder can be matched with the emission wavelength of ultraviolet light sources such as ultraviolet LED chips and the like, and Eu is as follows 3+ /Sm 3+ /Dy 3 Doped Y 2 Ca 2 Ga 3 VO 12 The fluorescent powder has high phase purity, high luminous intensity after being excited, low color temperature and stable luminescence, thereby solving the technical problem that the fluorescent powder for the white light LED which can be excited by ultraviolet light is lacking in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a phosphor Y according to example 2 of the present application 2-x Ca 2 Ga 3 VO 12 :xEu 3+ An XRD pattern of (x= 0,0.03,0.09,0.15,0.18,0.21);
FIG. 2 is a diagram of a phosphor Y according to example 3 of the present application 2-y Ca 2 Ga 3 VO 12 :ySm 3+ An XRD pattern of (y= 0.015,0.06,0.09,0.12,0.15);
FIG. 3 is a fluorescent powder Y according to example 4 of the present application 2-z Ca 2 Ga 3 VO 12 :zDy 3+ (z= 0.01,0.03,0.06,0.09,0.12);
FIG. 4 shows a phosphor Y according to examples 2 to 4 of the present application 1.82 Ca 2 Ga 3 VO 12 :0.18Eu 3+ 、Y 1.94 Ca 2 Ga 3 VO 12 :0.06Sm 3+ 、Y 1.97 Ca 2 Ga 3 VO 12 :0.03Dy 3+ Is a FT-IR spectrum of (2);
FIG. 5 shows a phosphor Y according to example 2 of the present application 2-x Ca 2 Ga 3 VO 12 :xEu 3+ (x= 0,0.09,0.15,0.21) UV-Vis spectrum of phosphor;
FIG. 6 is a phosphor Y according to example 2 of the present application 2-x Ca 2 Ga 3 VO 12 :xEu 3+ (x= 0.03,0.09,0.15,0.18,0.21) fluorescence spectrum of the phosphor;
FIG. 7 is a phosphor Y according to example 3 of the present application 2-y Ca 2 Ga 3 VO 12 :ySm 3+ (y= 0.015,0.06,0.09,0.12,0.15) fluorescence spectrum of the phosphor;
FIG. 8 is a phosphor Y according to example 4 of the present application 2-z Ca 2 Ga 3 VO 12 :zDy 3+ (z= 0.01,0.03,0.06,0.09,0.12) fluorescence spectrum of the phosphor;
FIG. 9 is a diagram of a phosphor Y according to example 2 of the present application 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ And phosphor Y provided in example 5 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ An XRD pattern of (a);
FIG. 10 shows a phosphor Y according to example 2 of the present application 2 Ca 2 Ga 3 VO 12 And phosphor Y provided in example 6 2 Ca 2 Ga 3 VO 12 An XRD pattern of (a);
fig. 11 is a physical diagram of the phosphor provided in example 6 of the present application.
Detailed Description
The application provides fluorescent powder, a preparation method and a white light LED (light-emitting diode), which are used for solving the technical problem that the fluorescent powder which can be excited by ultraviolet light and is used for the white light LED is lacking in the prior art.
The following description of the embodiments of the present application will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Example 1
In view of the prior art of ultraviolet light excitable phosphors for white LEDs, mainly blue and green phosphors, e.g. BaMgAl 10 O 17 :Eu 2+ And (Sr, ba) 2 SiO 4 :Eu 2+ The method comprises the steps of carrying out a first treatment on the surface of the The fluorescent powder for the white light LED, which can be excited by ultraviolet light, is not much in red and yellow fluorescent powder, and the fluorescent powder provided in the embodiment 1 of the application can be excited by ultraviolet light to generate orange light, red light and yellow light, and can be mixed into the white light LED after being compounded with the blue fluorescent powder and the green fluorescent powder, so that the technical problem of the lack of the fluorescent powder for the white light LED, which can be excited by ultraviolet light, is solved; the chemical composition formula of the fluorescent powder provided in the embodiment 1 of the application is as follows: y is Y 2-x/y/z Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ A formula I; in the formula I, the numerical range of x is 0.03-0.30; the value range of y is 0.015-0.20; the value range of z is 0.01-0.20.
Preferably, in example 1 of the present application, the luminescence intensity of the phosphor is further improved by optimizing the phosphor formulation, and the first optimized phosphor formulation provided includes yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and europium oxide, wherein the yttrium atom, calcium atom, gallium atom, vanadium atom and europium atom in the yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and europium oxide are 1.82 mol parts, 2 mol parts, 3 mol parts, 1 mol part and 0.18 mol part respectively, and the first optimized phosphor formulation improves the fluorescence intensity of orange red emitted; the second optimized fluorescent powder formula comprises, by mole parts, 1.94 mole parts, 2 mole parts, 3 mole parts, 1 mole part and 0.06 mole part of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and samarium oxide, wherein the second optimized fluorescent powder formula improves the emitted red fluorescent intensity; the third optimized fluorescent powder formula comprises, in terms of mole parts, yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide, wherein yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the dysprosium oxide are respectively 1.97 mole parts, 2 mole parts, 3 mole parts, 1 mole part and 0.03 mole part, and the third optimized fluorescent powder formula improves the emitted yellow fluorescent intensity.
Example 2
Example 2 of the present application provides a method for preparing a phosphor for a white LED, which is excited by ultraviolet light and is described in example 1, and the method comprises the steps of weighing yttrium source, calcium source, gallium source, vanadium source and europium source, grinding, pre-calcining and calcining.
The method comprises the steps of weighing an yttrium source, a calcium source, a gallium source, a vanadium source and a europium source, wherein the steps comprise: weighing five europium-doped fluorescent powder formulas, and analyzing the influence of different europium doping on the fluorescent intensity of the fluorescent powder to optimize the europium-doped fluorescent powder formulas; the formula of the five europium-doped fluorescent powders comprises the following specific steps: the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and europium oxide is 2:2:3:1:0; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.97:2:3:1:0.03; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.91:2:3:1:0.09; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.85:2:3:1:0.15; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.82:2:3:1:0.18; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.79:2:3:1:0.21.
the grinding step comprises the following steps: transferring the weighed five europium-doped fluorescent powder formulas into agate mortar respectively, adding a proper amount of ethanol, grinding for 1h to obtain five premixed solid reactants with smaller sizes respectively, adding all the grinded premixed solid reactants into an alumina crucible and capping, wherein the grinding is carried out for 1 hour or more, and the europium-doped fluorescent powder formulas with uniform mixing degree can be obtained, so that the doping of trivalent europium ions is facilitated;
the precalcination step comprises: placing an alumina crucible filled with a premixed solid reactant into a muffle furnace for pre-calcining, heating to 600 ℃, and preserving heat for 5 hours to obtain a pre-calcining reaction product;
the calcining step comprises the following steps: transferring the pre-calcined reaction product into an agate mortar for grinding for 10min, adding the reactants into an alumina crucible again, capping, placing into a muffle furnace for re-calcining, heating to 1350 ℃, and preserving the temperature for 12h in an oxygen atmosphere to obtain five trivalent europium doped ultraviolet light excitable applicationsFluorescent powder Y of white light LED 2-x Ca 2 Ga 3 VO 12 :xEu 3+ (x＝0,0.03,0.09,0.15,0.18,0.21)。
Example 3
Example 3 of the present application provides a method for preparing the phosphor for white LED capable of being excited by ultraviolet light according to example 1, which comprises weighing yttrium source, calcium source, gallium source, vanadium source and samarium source, grinding step, precalcination step and calcination step.
The method comprises the steps of weighing an yttrium source, a calcium source, a gallium source, a vanadium source and a samarium source, wherein the steps comprise: weighing five samarium-doped fluorescent powder formulas for analyzing the influence of different samarium doping on fluorescent powder fluorescence intensity so as to optimize the samarium-doped fluorescent powder formulas, wherein the five samarium-doped fluorescent powder formulas specifically comprise: the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide is 1.985:2:3:1:0.015; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide is 1.94:2:3:1:0.06; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide is 1.91:2:3:1:0.09; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide is 1.88:2:3:4:0.12; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and samarium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide is 1.85:2:3:1:0.15.
the grinding step comprises the following steps: transferring the weighed five samarium-doped fluorescent powder formulas into an agate mortar respectively, adding a proper amount of ethanol, grinding for 1h to obtain five premixed solid reactants with smaller sizes respectively, adding all the grinded premixed solid reactants into an alumina crucible and capping, wherein the grinding is carried out for 1 hour or more, thereby obtaining the samarium-doped fluorescent powder formulas with uniform mixing degree, and being beneficial to doping trivalent samarium ions;
the precalcination step comprises: placing an alumina crucible filled with a premixed solid reactant into a muffle furnace for pre-calcining, heating to 600 ℃, and preserving heat for 5 hours to obtain a pre-calcining reaction product;
the calcining step comprises the following steps: transferring the pre-calcined reaction product into an agate mortar for grinding for 10min, adding all reactants into an alumina crucible again, capping, placing into a muffle furnace for re-calcining, heating to 1350 ℃, and preserving heat for 12h in an oxygen atmosphere to obtain five trivalent samarium doped fluorescent powder Y which can be excited by ultraviolet light and is applied to white light LEDs 2-y Ca 2 Ga 3 VO 12 :ySm 3+ (y＝0.015,0.06,0.09,0.12,0.15)。
Example 4
Example 4 of the present application provides a method for preparing a phosphor for a white LED, which is excited by ultraviolet light and is described in example 1, and the method comprises the steps of weighing yttrium source, calcium source, gallium source, vanadium source and dysprosium source, grinding, pre-calcining and calcining.
The method comprises the steps of weighing yttrium source, calcium source, gallium source, vanadium source and dysprosium source, wherein the steps comprise: five dysprosium doped phosphor formulas are weighed and used for analyzing the influence of different dysprosium doping on the phosphor fluorescence intensity so as to optimize the dysprosium doped phosphor formulas, wherein the five dysprosium doped phosphor formulas specifically comprise: the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide is 1.99:2:3:1:0.01; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide is 1.97:2:3:1:0.03; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide is 1.94:2:3:1:0.06; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide is 1.91:2:3:4:0.09; the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and dysprosium atoms in yttrium oxide, calcium carbonate, gallium oxide, ammonium metavanadate and dysprosium oxide is 1.88:2:3:1:0.12.
the grinding step comprises the following steps: transferring the weighed five europium-doped fluorescent powder formulas into agate mortar respectively, adding a proper amount of ethanol, grinding for 1h to obtain five premixed solid reactants with smaller sizes respectively, adding all the grinded premixed solid reactants into an alumina crucible and capping, wherein the grinding is carried out for 1 hour or more, and the dysprosium-doped fluorescent powder formulas with uniform mixing degree can be obtained, so that the doping of trivalent dysprosium ions is facilitated;
the precalcination step comprises: placing an alumina crucible filled with a premixed solid reactant into a muffle furnace for pre-calcining, heating to 600 ℃, and preserving heat for 5 hours to obtain a pre-calcining reaction product;
the calcining step comprises the following steps: transferring the pre-calcined reaction product into an agate mortar for grinding for 10min, adding all reactants into an alumina crucible again, capping, placing into a muffle furnace for re-calcining, heating to 1350 ℃, and preserving heat for 12h in an oxygen atmosphere to obtain five kinds of trivalent dysprosium doped fluorescent powder Y which can be excited by ultraviolet light and is applied to white light LEDs 2-z Ca 2 Ga 3 VO 12 :zDy 3+ (z＝0.01,0.03,0.06,0.09,0.12)。
Example 5
Embodiment 5 of the present application provides a method for preparing a europium-doped fluorescent powder, wherein the chemical composition formula of the europium-doped fluorescent powder is specifically Y 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ The preparation method differs from example 2 in that the calcination temperature in the calcination step is 1250 ℃ for analyzing the effect of different calcination temperatures on the crystallization phase of the phosphor, and the preparation method includes the steps of weighing yttrium source, calcium source, gallium source, vanadium source and europium source, grinding step, pre-calcination step and calcination step.
The method comprises the steps of weighing an yttrium source, a calcium source, a gallium source, a vanadium source and a europium source, wherein the steps comprise: weighing a europium-doped fluorescent powder formula, wherein the europium-doped fluorescent powder formula specifically comprises the following components: the molar ratio of yttrium atoms, calcium atoms, gallium atoms, vanadium atoms and europium atoms in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide is 1.85:2:3:1:0.15.
the grinding step comprises the following steps: transferring the weighed europium-doped fluorescent powder formula into an agate mortar respectively, adding a proper amount of ethanol, grinding for 1h to obtain premixed solid reactants with smaller sizes respectively, adding all the grinded premixed solid reactants into an alumina crucible, and capping;
the precalcination step comprises: placing an alumina crucible filled with a premixed solid reactant into a muffle furnace for pre-calcining, heating to 600 ℃, and preserving heat for 5 hours to obtain a pre-calcining reaction product;
the calcining step comprises the following steps: transferring the precalcination reaction product into an agate mortar for grinding for 10min, adding the reactants into an alumina crucible again, capping, placing into a muffle furnace for recalcination, heating to 1250 ℃, and preserving the temperature for 12h in an oxygen atmosphere to obtain europium-doped fluorescent powder Y 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ 。
Example 6
Embodiment 6 of the present application provides a method for preparing undoped phosphor, wherein the chemical composition formula of the undoped phosphor is specifically Y 2 Ca 2 Ga 3 VO 12 The preparation method differs from example 2 in that the calcination temperature in the calcination step is 1200 ℃, the calcination atmosphere is 95% nitrogen/5% hydrogen atmosphere, and the method is used for analyzing the influence of different calcination atmospheres on the crystal phase of the fluorescent powder, and comprises the steps of weighing yttrium source, calcium source, gallium source, vanadium source, grinding step, precalcination step and calcination step.
The method comprises the following steps of weighing an yttrium source, a calcium source, a gallium source and a vanadium source: weighing an undoped fluorescent powder formula, wherein the undoped fluorescent powder formula specifically comprises the following steps: the molar ratio of yttrium atoms, calcium atoms, gallium atoms and vanadium atoms in yttrium oxide, calcium carbonate, gallium oxide and ammonium metavanadate is 2:2:3:1.
the grinding step comprises the following steps: transferring the weighed undoped fluorescent powder formula into an agate mortar respectively, adding a proper amount of ethanol, grinding for 1h to obtain premixed solid reactants with smaller sizes respectively, adding all the grinded premixed solid reactants into an alumina crucible, and capping;
the precalcination step comprises: placing an alumina crucible filled with a premixed solid reactant into a muffle furnace for pre-calcining, heating to 600 ℃, and preserving heat for 5 hours to obtain a pre-calcining reaction product;
the calcining step comprises the following steps: transferring the precalcination reaction product into an agate mortar for grinding for 10min, adding the reactant into an alumina crucible again, capping, placing into a muffle furnace for calcining again, heating to 1200 ℃, and preserving heat for 12h in a 95% nitrogen/5% hydrogen atmosphere to obtain undoped fluorescent powder Y 2 Ca 2 Ga 3 VO 12 。
Experimental example 1
Experimental example 1 of the present application was used to perform performance tests on the phosphors provided in examples 2-4 and 5-6, including X-ray diffraction analysis, infrared spectroscopy analysis, UV-Vis spectroscopy analysis, and fluorescence spectroscopy analysis on the phosphors provided in examples 2-4.
As can be seen from XRD patterns shown in figures 1-3, five trivalent europium-doped ultraviolet-excited phosphors Y for white light LEDs provided in example 2 2-x Ca 2 Ga 3 VO 12 :xEu 3+ Each characteristic peak position of (x= 0,0.03,0.09,0.15,0.18,0.21) corresponds to a standard card, indicating that the phases of the five trivalent europium doped fluorescent powders for the white light LED are all single phases with cubic crystal system, eu 3+ Doping of ions does not introduce new impurity phases into the matrix; example 3 provides five trivalent samarium doped ultraviolet excitable phosphors Y for white light LEDs 2-y Ca 2 Ga 3 VO 12 :ySm 3+ Each characteristic peak position of (y= 0.015,0.06,0.09,0.12,0.15) corresponds to a standard card, indicating that the phases of the five trivalent samarium doped fluorescent powders for the white light LED are all single phases with a cubic crystal system, sm 3+ Doping of ions does not introduce new impurity phases into the matrix; example 4 provides five trivalent dysprosium doped ultraviolet excitable phosphors Y for white light LEDs 2-z Ca 2 Ga 3 VO 12 :zDy 3 + Each characteristic peak position of (z= 0.01,0.03,0.06,0.09,0.12) corresponds to a standard card, which shows that the phases of the five trivalent dysprosium doped fluorescent powders for the white light LED are single phases with a cubic crystal system and Dy 3+ Doping of ions does not introduce new impurity phases into the matrix, and the FT-IR spectrum provided in FIG. 4 also shows Eu 3+ Ions, sm 3+ Ions and Dy 3+ Doping of the ions results in a slight shift in the infrared absorption peak of the phosphor.
As can be seen from FIGS. 5, 6-8, which are graphs of UV-Vis spectrum analysis results of the phosphor provided in example 2 and fluorescence spectrum analysis results of the phosphors provided in examples 2-4, emission peaks of the phosphor provided in example 2 are located at 592, 614, 650 and 706nm, respectively, corresponding to Eu, respectively, under excitation of a 394nm xenon lamp (xenon lamp power 500W), respectively 3+ A kind of electronic device 5 D 0 → 7 F 1 , 5 D 0 → 7 F 2 , 5 D 0 → 7 F 3 And 5 D 0 → 7 F 4 the transition, example 3 provides phosphor emission peaks at 568, 612, 656 and 711nm, respectively, corresponding to Sm 3+ A kind of electronic device 4 G 5/2 → 6 H 5/2 , 4 G 5/2 → 6 H 7/2 , 4 G 5/2 → 6 H 9/2 , 4 G 5/2 → 6 H 11/2 Transition, the fluorescent powder emission peaks provided in example 4 are respectively located at 480 and 577nm, respectively corresponding to Dy 3+ A kind of electronic device 4 F 9/2 → 6 H 15/2 And 4 F 9/2 → 6 H 13/2 and (5) transition. The UV-Vis spectrum analysis shown in FIG. 5 also illustrates that the phosphor provided in example 2 has a strong and broad absorption peak at 280nm, which corresponds to VO 4 3- The charge transfer from O to V in the radical corresponds to Eu in the absorption peak at 394nm 3+ Of ions 7 F 0 → 5 L 6 Is a transition of (2); and, as can be confirmed from the fluorescence spectrograms shown in the accompanying figures 6-8, different europium, samarium or dysprosium doping has an effect on the fluorescence intensity of the fluorescent powder,when the chemical composition formula of the fluorescent powder is as follows: y is Y 1.82 Ca 2 Ga 3 VO 12 :0.18Eu 3+ In this case, the fluorescent powder provided in example 2 has the highest orange fluorescence intensity under ultraviolet excitation, and the chemical composition formula of the fluorescent powder is: y is Y 1.94 Ca 2 Ga 3 VO 12 :0.06Sm 3+ In this case, the fluorescent powder provided in example 3 has the highest red fluorescence intensity under ultraviolet excitation, and the chemical composition formula of the fluorescent powder is: y is Y 1.97 Ca 2 Ga 3 VO 12 :0.03Dy 3+ When the fluorescent powder provided in the example 4 emits yellow fluorescent light with highest intensity under ultraviolet excitation, the fluorescent powder provided in the examples 2-4 is subjected to fluorescence spectrum analysis, so that the formula of the fluorescent powder is optimized.
As can be seen from FIG. 9, the X-ray diffraction analysis result of the phosphor provided in example 5 is shown in FIG. 9, and the calcination temperature of the phosphor Y in the calcination step is 1350 DEG C 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ In contrast, phosphor Y having a calcination temperature of 1250 DEG C 1.85 Ca 2 Ga 3 VO 12 :0.15Eu 3+ An impurity peak exists at the angle of 37.18 degrees, and is compared with the standard card JCPDS No.71-0790, and the impurity peak corresponds to Ca 3 (VO 4 ) 2 This means that the impurity phase is introduced at 1250℃in the calcination step, which is detrimental to the luminescence properties of the phosphor.
As can be seen from FIG. 10, the X-ray diffraction analysis result of the phosphor powder provided in example 6 is shown in FIG. 10, and the phosphor powder Y calcined in the oxygen atmosphere in the calcination step 2 Ca 2 Ga 3 VO 12 In contrast, the phosphor Y obtained by calcination in an atmosphere of 95% nitrogen/5% hydrogen 2 Ca 2 Ga 3 VO 12 Many impurity peaks appear, which indicates that when the atmosphere of 95% nitrogen/5% hydrogen is selected in the calcination step, an impurity phase is introduced, which is unfavorable for the luminescence property of the fluorescent powder; the physical diagram of the phosphor provided in example 6 is shown in FIG. 11, and it can be seen from FIG. 11 that the phosphor provided in example 6 is calcined in a 95% nitrogen/5% hydrogen atmosphere to give a distinct region of the appearanceUnlike conventional phosphors.
Through the embodiment and experimental example, it can be determined that in the fluorescent powder and the preparation method provided by the application, the fluorescent powder is prepared by performing the following steps on Y 2 Ca 2 Ga 3 VO 12 Eu with phosphor 3+ /Sm 3+ /Dy 3+ The fluorescent powder obtained by doping can be respectively excited by 394/405/365nm xenon lamp to obtain orange red light, red light and yellow light emission, the excitation wavelength of the fluorescent powder is matched with the emission wavelength of an ultraviolet LED chip, and the fluorescent powder can be matched with BaMgAl 10 O 17 :Eu 2+ Or (Sr, ba) 2 SiO 4 :Eu 2+ The white light emission is obtained by ultraviolet excitation after the blue fluorescent powder and the green fluorescent powder are proportioned, so that the technical problem that the existing fluorescent powder for a white light LED lacks ultraviolet light as an excitation light source is solved;
meanwhile, in the fluorescent powder and the preparation method, as the formula and the preparation process of the fluorescent powder are optimized, the fluorescent powder has higher luminous intensity, low color temperature and stable luminescence, and Eu is further improved 3+ /Sm 3+ /Dy 3+ The performance of the phosphor obtained by doping.
The above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims (10)

1. The fluorescent powder is characterized by comprising the following chemical compositions:
Y 2-x/y/z Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ a formula I;
in the formula I, the numerical range of x is 0.03-0.30; the value range of y is 0.015-0.20; the value range of z is 0.01-0.20.
2. The phosphor of claim 1, wherein in formula i, x has a value of 0.18, and the phosphor has a chemical composition of formula:
Y 1.82 Ca 2 Ga 3 VO 12 :0.18Eu 3+ 。
3. the phosphor of claim 1, wherein in formula i, y has a value of 0.06, and the phosphor has a chemical composition of formula:
Y 1.94 Ca 2 Ga 3 VO 12 :0.06Sm 3+ 。
4. the phosphor of claim 1, wherein in formula i, z has a value of 0.03, and the phosphor has a chemical composition of formula:
Y 1.97 Ca 2 Ga 3 VO 12 :0.03Dy 3+ 。
5. a method of producing a phosphor according to any one of claims 1 to 4, comprising the steps of:
step S1, mixing and grinding yttrium source, calcium source, gallium source, vanadium source and doped rare earth source according to the stoichiometric ratio of the formula I for 60-120 min to obtain a premixed solid reactant;
s2, pre-calcining the solid reactant to obtain a pre-calcined reaction product;
step S3, grinding the pre-calcined reaction product for 5-15 min, and calcining to obtain fluorescent powder;
in the step S1, the doped rare earth source is selected from europium source, samarium source or dysprosium source;
in the step S3, the calcining temperature is 1300-1400 ℃, the calcining time is 10-12 h, and the atmosphere is oxygen.
6. The method of claim 5, wherein,
in the step S3, the calcining temperature is 1350 ℃ and the calcining time is 12h.
7. The method of claim 5, wherein,
in the step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the europium source is europium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the europium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the europium oxide are respectively 1.82 mol parts, 2 mol parts, 3 mol parts, 1 mol part and 0.18 mol part.
8. The method of claim 5, wherein in step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the samarium source is samarium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the samarium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the samarium oxide are respectively 1.94 mole parts, 2 mole parts, 3 mole parts, 1 mole part and 0.06 mole part.
9. The method of claim 5, wherein in step S1, the yttrium source is yttrium oxide, the calcium source is calcium carbonate, the gallium source is gallium oxide, the vanadium source is ammonium metavanadate, and the dysprosium source is dysprosium oxide;
the yttrium atom, the calcium atom, the gallium atom, the vanadium atom and the dysprosium atom in the yttrium oxide, the calcium carbonate, the gallium oxide, the ammonium metavanadate and the dysprosium oxide are respectively 1.97 mol parts, 2 mol parts, 3 mol parts, 1 mol part and 0.03 mol part in terms of mol parts.
10. A white LED comprising Y as set forth in claim 1 2-x/y Ca 2 Ga 3 VO 12 :xEu 3+ /ySm 3+ /zDy 3+ Green and blue phosphors that are excitable by ultraviolet light, and an ultraviolet light source.
CN202310176431.2A 2023-02-28 2023-02-28 Fluorescent powder, preparation method and white light LED Pending CN116144359A (en)

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