CN111139073B - Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof - Google Patents

Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof Download PDF

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CN111139073B
CN111139073B CN201911381917.XA CN201911381917A CN111139073B CN 111139073 B CN111139073 B CN 111139073B CN 201911381917 A CN201911381917 A CN 201911381917A CN 111139073 B CN111139073 B CN 111139073B
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fluorescent powder
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CN111139073A (en
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乔学斌
许臣臣
王胜家
邢进
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Jiangsu Normal University
Binzhou University
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Binzhou University
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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
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7732—Halogenides
    • C09K11/7733—Halogenides with alkali or alkaline earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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

Abstract

The invention relates to a Eu3+Ion activated tantalate fluorescent powder and synthesis method and application thereof, wherein the chemical general formula of the ion activated tantalate fluorescent powder is Na2‑ 2xEu2xTa2‑2xGa2xNbO6F5Wherein x is Eu3+Ions and Ga3+Ion substitution of Na+And Ta5+X is more than or equal to 0.001 and less than or equal to 0.15. The synthetic method of the invention is a solid phase synthetic method. The fluorescent ceramic can be used for preparing LED lighting or display devices which take near ultraviolet and blue semiconductor chips as excitation light sources, and can also be used for manufacturing light-emitting diodes, display materials, three-primary-color fluorescent lamps and field emission displays. Eu of the invention3+The activated tantalate phosphor has clear advantages: the fluorescent powder can stably emit red light, has excellent thermal stability, higher color temperature and color rendering index, high luminous efficiency and high cleanliness; has strong excitation efficiency in near ultraviolet and blue light wavelength regions.

Description

Eu (Eu)3+Ion activated tantalate fluorescent powder and synthetic method and application thereof
Technical Field
The invention relates to the technical field of inorganic fluorescent materials, in particular to Eu3+An ion activated tantalate fluorescent powder and a synthetic method and application thereof.
Background
In recent years, with the development of semiconductor materials, semiconductor LED illumination is greatly emphasized, and blue light and near ultraviolet light semiconductor chips become mainstream commercial white light LED illumination devices at present; compared with the traditional fluorescent lamp, energy-saving lighting and other light sources, the new generation lighting based on the LED chip has great advantages, long service life, capability of working for more than 50000 hours without faults, power consumption of the LED chip is only 1/10 of an incandescent lamp, wide service voltage range and high brightness.
There are two main ways for white light LEDs to generate white light: the first is to combine the red, green and blue LEDs to generate white light; the second is to mix the LED deexcitation light conversion fluorescent powder to form white light, and the approach has two realization schemes, wherein the mature method is to match the blue LED chip with the YAG: Ce yellow fluorescent powder to realize white light emission, but because of lack of red light, the white light obtained by compounding is cold white light, therefore, the scheme still needs to add proper red fluorescent powder to improve the color rendering index, and the other scheme is to combine the near-purple LED chip (390 plus 410nm) with red/green/blue three primary color fluorescent powder; therefore, the red phosphor plays a very important role. The effective excitation range of the existing red fluorescent powder is mostly in a short-wave UV region, the luminous efficiency of the existing red fluorescent powder under the excitation of ultraviolet light is low, the chromaticity is not pure, and the thermal stability is poor; meanwhile, the synthesis process of the red fluorescent powder is complex and inconvenient to operate, and the synthesis equipment is expensive.
Disclosure of Invention
The invention aims to provide Eu3+The ion-activated tantalate phosphor can realize stable red emission, has excellent color temperature and color rendering index, and has excellent thermal stability and very high luminous efficiency. Another object of the present invention is to provide Eu3+The synthesis method of the ion activated tantalate fluorescent powder has the advantages of simple synthesis process, convenient operation and low equipment requirement.
In order to achieve the purpose, the invention adopts the technical scheme that: eu (Eu)3+The ion-activated tantalate fluorescent powder is characterized in that the chemical general formula of the ion-activated tantalate fluorescent powder is Na2-2xEu2xTa2-2xGa2xNbO6F5Wherein x is Eu3+Ions and Ga3+Ion substitution of Na+And Ta5+X is more than or equal to 0.001 and less than or equal to 0.15.
The invention also provides Eu3+The synthesis method of the ion activated tantalate fluorescent powder is a solid-phase reaction synthesis method and comprises the following steps:
(1) according to the formula Na2-2xEu2xTa2-2xGa2xNbO6F5The stoichiometric ratio of each element in the raw materials is more than or equal to 0.001 and less than or equal to 0.15, and the raw materials are weighed: the preparation method comprises the following steps of weighing the compounds containing sodium ions twice, wherein the weighed sodium ions account for half of the stoichiometric ratio of Na in a chemical formula;
(2) putting one part of the compound containing sodium ions, the compound containing europium ions, the compound containing tantalum ions, the compound containing gallium ions and the compound containing niobium ions, which are weighed in the step (1), into an agate mortar for grinding to obtain a mixed raw material, and performing primary calcination on the mixed raw material in an air atmosphere, wherein the calcination temperature is 800-1250 ℃, and the calcination time is 1-10 hours;
(3) grinding the primary calcined product obtained in the step (2) in an agate mortar, pressing into blocks, and calcining for the second time in an air atmosphere at the calcining temperature of 1200-1400 ℃ for 1-10 hours;
(4) naturally cooling the secondary calcined product obtained in the step (3), putting the secondary calcined product into an agate mortar for grinding until the secondary calcined product becomes powder, and thoroughly grinding and mixing the powder and the other part of the compound containing sodium ions and the compound containing fluoride ions, which are weighed in the step (1); pressing the obtained mixture into blocks, and calcining for the third time in an air atmosphere, wherein the calcining temperature is 850-1000 ℃, and the calcining time is 1-10 hours; after the product calcined for the third time is naturally cooled, grinding the obtained block-shaped sample into powder to obtain Eu3+Activated tantalate phosphor.
Preferably, said composition containsThe compound of sodium ion is sodium carbonate Na2CO3Or sodium fluoride NaF; the compound containing europium ions is europium oxide Eu2O3(ii) a The compound containing tantalum ions is tantalum oxide Ta2O5(ii) a The compound containing gallium ions is gallium oxide Ga2O3(ii) a The compound containing niobium ions is niobium oxide Nb2O5(ii) a The compound containing fluorinion is ammonium fluoride NH4F。
The invention also provides Eu3+The ion activated tantalate fluorescent powder can be used for preparing LED lighting or display devices which take near ultraviolet and blue semiconductor chips as excitation light sources, and can also be used for manufacturing light-emitting diodes, display materials, three-primary-color fluorescent lamps and field emission displays.
Compared with the prior products of the same type, the Eu of the invention3+The activated tantalate fluorescent powder has obvious advantages:
(1) eu according to the invention3+The activated tantalate fluorescent powder has matrix lattice comprising several ion polyhedrons (Nb, Ta, Ga) and F ion in the lattice, so that the lattice has very high strength, excellent heat stability, high color temperature and color rendering index and is suitable for making high-power lighting equipment.
(2)Na+Ion-filled in a skeleton having high rigidity and strength and Eu3+The doping of ions can lead the luminescence center to be fully disturbed, and Eu3+The forbidden transition of the ions is thoroughly broken, and red light is stably and efficiently emitted.
(3)Ga3+Co-doping of ions to make Eu3+The charge caused by doping tends to balance, and the cleanliness and the intensity of red light emitted by the fluorescent powder are enhanced.
(4) The preparation process of the matrix material has no pollution, and the invention has the advantages of simple synthesis process, convenient operation, low requirement on equipment, energy saving and environmental protection.
(5) The fluorescent powder has strong excitation efficiency in near ultraviolet and blue light wavelength regions, and is suitable for being matched with a near ultraviolet LED chip to prepare white light LED lighting equipment.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of phosphor prepared according to the embodiment 1 of the present invention;
FIG. 2 is an SEM image of phosphor prepared according to the technical scheme of example 1 of the invention;
FIG. 3 is a graph of the excitation spectrum of a phosphor prepared according to the embodiment 1 of the present invention;
FIG. 4 is a spectrum of an emission spectrum obtained by 393 nm excitation of near ultraviolet light in a phosphor prepared according to the embodiment 1 of the present invention;
FIG. 5 is a graph showing the luminescence decay curve of the phosphor prepared according to the embodiment 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples.
Example 1
According to the chemical formula Na1.7Eu0.3Ta1.7Ga0.3NbO6F5Weighing the following elements in stoichiometric ratio: na (Na)2CO3: 3.71 g; eu (Eu)2O3: 5.279 g; ta2O5: 34.84 g; ga2O3: 2.812 g; nb2O5: 13.29 g; putting the weighed raw materials into an agate mortar, grinding to obtain a mixed raw material, and calcining for the first time in an air atmosphere at the calcining temperature of 1250 ℃ for 5 hours;
and grinding the obtained primary calcined product in an agate mortar, pressing into blocks, and calcining for the second time in an air atmosphere at 1400 ℃ for 1 hour.
The obtained second calcined product was naturally cooled, put into an agate mortar for grinding until it became a powder, and the powder was mixed with 4.2 g of NaF and NH which were previously weighed414.8 g of F, grinding and mixing, pressing the obtained mixture into blocks, and carrying out third calcination in air atmosphere at 850 ℃ for 5 hoursAnd grinding the naturally cooled block sample to obtain the Eu3+ activated tantalate fluorescent powder.
Referring to the attached figure 1, the X-ray powder diffraction pattern of the fluorescent powder prepared by the technical scheme of the embodiment 1 shows that the prepared material is a single phase;
referring to the attached figure 2, the SEM image of the phosphor prepared according to the technical scheme of the embodiment 1 is good in crystallization property;
referring to fig. 3, the excitation spectrum obtained by monitoring emitted light 622 nm of the phosphor prepared according to the technical scheme of embodiment 1, the excitation source of red light is mainly in the ultraviolet to blue light region between 300-500 nm, and can be well matched with the emission of an ultraviolet to blue light LED chip;
referring to fig. 4, it is the spectrum obtained by the excitation of the phosphor prepared according to the technical scheme of example 1 by the near ultraviolet 393 nm, and the luminescence is shown to be red luminescence with pure chromaticity and a central luminescence wavelength of 622 nm.
Example 2
According to the chemical formula Na1.998Eu0.002Ta1.998Ga0.002NbO6F5Weighing the following elements in stoichiometric ratio: na (Na)2CO3: 5.2894 g; eu (Eu)2O3: 0.035 g; ta2O5: 40.95 g; ga2O3: 0.019 g; nb2O5: 13.29 g; putting the weighed raw materials into an agate mortar, grinding to obtain a mixed raw material, and calcining for the first time in an air atmosphere at the calcining temperature of 800 ℃ for 1 hour;
and grinding the obtained primary calcined product in an agate mortar, pressing into blocks, and calcining for the second time in an air atmosphere at the calcining temperature of 1200 ℃ for 10 hours.
The obtained second calcined product was naturally cooled, put into an agate mortar for grinding until it became a powder, and the powder was mixed with 4.2 g of NaF and NH which were previously weighed414.8 g of F, grinding and mixing, pressing the obtained mixture into blocks, carrying out third calcination in air atmosphere at the calcination temperature of 1000 ℃,calcining for 1 hour, and grinding the naturally cooled block sample to obtain the Eu3+Activated tantalate phosphor.
The main structural properties, excitation spectrum, emission spectrum and luminescence lifetime are similar to those of example 1.
Example 3
According to the chemical formula Na1.9Eu0.1Ta1.9Ga0.1NbO6F5Weighing the following elements in stoichiometric ratio: na (Na)2CO3: 4.77 g; eu (Eu)2O3: 1.759 g; ta2O5: 38.94 g; ga2O3: 0.94 g; nb2O5: 13.29 g; putting the weighed raw materials into an agate mortar, grinding to obtain a mixed raw material, and calcining for the first time in an air atmosphere at the calcining temperature of 1000 ℃ for 10 hours;
the obtained primary calcined product is put into an agate mortar for grinding, pressed into blocks and subjected to secondary calcination in air atmosphere, wherein the calcination temperature is 1350 ℃ and the calcination time is 3.5 hours.
The obtained second calcined product was naturally cooled, put into an agate mortar for grinding until it became powder, and the powder was mixed with 4.2 g of NaF and NH which were previously weighed414.8 g of F, grinding and mixing, pressing the obtained mixture into blocks, carrying out third calcination in air atmosphere at 900 ℃ for 10 hours, and grinding the naturally cooled block sample to obtain the Eu3+Activated tantalate phosphor.
The main structural properties, excitation spectrum, emission spectrum and luminescence lifetime are similar to those of example 1.

Claims (4)

1. Eu (Eu)3+The ion-activated tantalate fluorescent powder is characterized in that the chemical general formula of the ion-activated tantalate fluorescent powder is Na2-2xEu2xTa2- 2xGa2xNbO6F5Wherein x is Eu3+Ions and Ga3+Ion substitution of Na+And Ta5+X is more than or equal to 0.001 and less than or equal to 0.15.
2. Eu (Eu)3+The synthesis method of the ion activated tantalate fluorescent powder is a solid-phase reaction synthesis method and is characterized by comprising the following steps of:
(1) according to the formula Na2-2xEu2xTa2-2xGa2xNbO6F5The stoichiometric ratio of each element in the formula (I), wherein x is more than or equal to 0.001 and less than or equal to 0.15, and the following raw materials are weighed: the preparation method comprises the following steps of weighing the compounds containing sodium ions twice, wherein the weighed sodium ions account for half of the stoichiometric ratio of Na in a chemical formula;
(2) putting one part of the compound containing sodium ions, the compound containing europium ions, the compound containing tantalum ions, the compound containing gallium ions and the compound containing niobium ions weighed in the step (1) into an agate mortar for grinding to obtain a mixed raw material, and calcining the mixed raw material for the first time in an air atmosphere at the temperature of 800-1250 ℃ for 1-10 hours;
(3) grinding the primary calcined product obtained in the step (2) in an agate mortar, pressing into blocks, and calcining for the second time in an air atmosphere at the calcining temperature of 1200-1400 ℃ for 1-10 hours;
(4) naturally cooling the secondary calcined product obtained in the step (3), putting the secondary calcined product into an agate mortar for grinding until the secondary calcined product becomes powder, and thoroughly grinding and mixing the powder and the other part of the compound containing sodium ions and the compound containing fluoride ions, which are weighed in the step (1); pressing the obtained mixture into blocks, and calcining for the third time in an air atmosphere, wherein the calcining temperature is 850-1000 ℃, and the calcining time is 1-10 hours; after the product calcined for the third time is naturally cooled, grinding the obtained block-shaped sample into powder to obtain Eu3+Activated tantalate phosphor.
3. A Eu according to claim 23+The method for synthesizing the ion activated tantalate fluorescent powder is characterized in that the compound containing sodium ions is sodium carbonate Na2CO3Or sodium fluoride, NaF; the compound containing europium ions is europium oxide Eu2O3(ii) a The compound containing tantalum ions is tantalum oxide Ta2O5(ii) a The compound containing gallium ions is gallium oxide Ga2O3(ii) a The compound containing niobium ions is niobium oxide Nb2O5(ii) a The compound containing fluorinion is ammonium fluoride NH4F。
4. Eu according to claim 13+The application of the ion activated tantalate fluorescent powder is characterized in that the fluorescent powder is used for preparing LED lighting or display devices which take near ultraviolet and blue semiconductor chips as excitation light sources, and is also used for manufacturing light-emitting diodes, display materials, three-primary-color fluorescent lamps and field emission displays.
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