CN112608742A - beta-Al activated by europium2O3Defect structure blue fluorescent powder and preparation method thereof - Google Patents

beta-Al activated by europium2O3Defect structure blue fluorescent powder and preparation method thereof Download PDF

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CN112608742A
CN112608742A CN202011583566.3A CN202011583566A CN112608742A CN 112608742 A CN112608742 A CN 112608742A CN 202011583566 A CN202011583566 A CN 202011583566A CN 112608742 A CN112608742 A CN 112608742A
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fluorescent powder
blue fluorescent
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CN112608742B (en
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王逸超
朴司琪
陈宝玖
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Dalian Maritime University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
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Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to europium-activated beta-Al2O3A defect structure blue fluorescent powder and a preparation method thereof. The chemical structural formula of the blue fluorescent powder is K0.8‑2x‑2yBa0.1+xEuyAl11O17Wherein x is more than or equal to 0 and less than or equal to 0.3; y is more than or equal to 0.025 and less than or equal to 0.175. Grinding the raw materials, mixing uniformly, sintering in stages under the condition of introducing reducing atmosphere, cooling to room temperature, and grinding into powder to obtain the blue fluorescent powder. The blue fluorescent powder has a wide excitation band, can be effectively excited by ultraviolet light and near ultraviolet light, has high quantum efficiency (the internal quantum efficiency is more than 90 percent), has better thermal stability than the prior blue commercial fluorescent powder, and has basically unchanged emission intensity along with the temperature rise from room temperature to 200 ℃.

Description

beta-Al activated by europium2O3Defect structure blue fluorescent powder and preparation method thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to europium-activated beta-Al2O3A defect structure blue fluorescent powder and a preparation method thereof.
Background
White light emitting diodes (abbreviated as WLEDs) have been generally accepted as a new generation of illumination light source, and fluorescence conversion type white light LEDs (abbreviated as pc-WLEDs) dominate the field of general illumination. The fluorescent powder is an important component of pc-WLEDs and determines the characteristics of light-emitting efficiency, color rendering index, service life and the like of the LED equipment.
In the case of pc-WLEDs, the production process has been commercialized as follows: a typical yellow phosphor (YAG: Ce)3+) Coating on an InGaN blue chip. A part of blue light emitted by the chip is used for exciting the fluorescent powder to generate yellow light, and the other part of blue light is combined with the generated yellow light to obtain white light. The method has simple manufacturing process and high luminous efficiency, but the obtained white light has low color rendering index (less than 80) due to lack of green and red spectrum components, and cannot meet the requirement of a general illumination light source on color rendering property. At present, due to the advantages of high color rendering index (more than 85), good spectral stability and the like, a method for obtaining white light by covering red, green and blue fluorescent powder with a near ultraviolet (n-UV, 360-410nm) chip attracts people's extensive attention. Wherein, the currently commonly used commercial blue fluorescent powder is mainly BaMgAl10O17:Eu2+，(Ca,Sr,Ba)10(PO4)6Cl2:Eu2+，Ba3MgSi2O8:Eu2+. The BaMgAl with the best comprehensive effect at present10O17:Eu2+In addition, the quantum yield can reach more than 90%, the luminous intensity can be kept about 91% at room temperature at 200 ℃, and how to obtain the blue fluorescent powder with better comprehensive performance is still significant.
Based on this, research on blue fluorescent powder with near ultraviolet excitation, high quantum yield and good thermal stability is one of the key points for obtaining high color rendering WLEDs.
Disclosure of Invention
Aiming at the requirement of further improving the performance of commercial blue fluorescent powder, the invention provides the near ultraviolet excited europium-activated beta-Al with high quantum yield and good thermal stability2O3Structural blue fluorescent powder and a preparation method thereof.
To achieve the above object, one aspect of the present inventionProviding a europium activated beta-Al2O3The blue fluorescent powder with a defect structure has a chemical structural formula of K0.8-2x-2yBa0.1+xEuyAl11O17Wherein x is more than or equal to 0 and less than or equal to 0.3; y is more than or equal to 0.025 and less than or equal to 0.175.
In another aspect of the present invention, there is provided the above europium-activated beta-Al2O3A method for preparing structural blue fluorescent powder. The method comprises the following steps:
step 1: according to the chemical formula K0.8-2x-2yBa0.1+xEuyAl11O17Weighing K, Ba-containing carbonate or nitrate and Al-Eu-containing oxide according to the stoichiometric ratio of the chemical compositions; weighing a fluxing agent;
step 2: grinding the raw materials in the step 1, and uniformly mixing to obtain a mixture;
and step 3: carrying out sectional sintering on the mixture obtained in the step 2 under the condition of introducing a reducing atmosphere, and then cooling to room temperature to obtain a sintered material;
and 4, step 4: and (4) crushing the sinter obtained in the step (3) into powder, and sieving the powder by using a 300-600-mesh sieve to obtain the blue fluorescent powder.
Further, in the step 3, the reducing atmosphere is composed of 5-10% of H by volume percentage2And 95 to 90% of N2And (4) forming.
Further, the step 3 of segmented sintering comprises: firstly, raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min, and preserving the temperature for 1-2h to promote the decomposition of carbonate or nitrate; then the temperature is raised to 1400 ℃ and 1600 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is preserved for 4-8 hours to ensure the synthesis of the product.
Further, the fluxing agent in the step 1 is AlF3、BaF2、H3BO3、CaF2One or more of the above; the adding amount of the fluxing agent is 3-5% of the total mass of the raw materials.
The principle of the preparation method of the invention is as follows: the reactants are intimately contacted with each other in intimate contact, and at high temperatures the ions near the contact surface possess sufficient energy to break free of their solid phaseLattice point constraint and diffusion, and a layer of hexagonal K is locally generated on the contact surface through further structural rearrangement0.8-2x-2yBa0.1+xEuyAl11O17(nuclei), then the nuclei grow gradually with the increase of the reaction time, and finally K is substantially formed0.8-2x-2yBa0.1+xEuyAl11O17A product phase.
K0.8-2x-2yBa0.1+xEuyAl11O17(wherein 0. ltoreq. x.ltoreq.0.3; 0.025. ltoreq. y.ltoreq.0.175) is a hexagonal system which exhibits a typical beta-Al2O3A structure consisting of a spinel layer and Ba/KO9Layers are alternately arranged, activator Eu2+Is expected to enter Ba/KO9Ba/K sites of the layer, substituted for Ba2+Or K+Thereby the prepared fluorescent powder has luminescence property. K0.8-2x- 2yBa0.1+xEuyAl11O17(wherein x is 0. ltoreq. x.ltoreq.0.3; y is 0.025. ltoreq. y.ltoreq.0.175) has a metal cation defect structure VK ’The existence of such a defective structure has a certain relationship with thermal stability, specifically: when using Ba2+Substituted K+To satisfy the charge conservation of the compound, K is formed+Vacancy defect, Ba2+The greater the content, K+The greater the number of vacancy defects. K+The vacancy defects can form defect energy levels in the band gap of the material, and the energy level positions of the vacancy defects are close to the conduction band bottom, so that when the blue fluorescent powder is applied to white light LED illumination, the defect energy levels can store photons in a photoluminescence process; with the rise of the external environment temperature, under the action of thermal disturbance, the defect energy level releases photons at a higher temperature, and the speed of storing and releasing the photons is dependent on the temperature. Thus, K+The presence of defects can affect the rate of photon release at different temperatures, thereby controlling the luminous intensity of the material at different temperatures. Controlling K in a material by varying the value of x+The number of defects can improve the thermal quenching performance of the material, so that the luminous intensity of the material at high temperature is kept close to that at room temperature.
The invention has the beneficial effects that:
1) the blue fluorescent powder has high quantum efficiency (the internal quantum efficiency is more than 90 percent), the thermal stability is superior to that of the prior blue commercial fluorescent powder, and the emission intensity of the fluorescent powder is basically unchanged along with the temperature rising from room temperature to 200 ℃.
2) The blue fluorescent powder has a wide excitation band (250nm-430nm), can be effectively excited by ultraviolet light and near ultraviolet light, has strong absorption in a near ultraviolet band of 300-400nm, emits blue light with a main peak of about 450nm, has high color purity, and has high matching degree with an emission spectrum of a near ultraviolet chip.
3) The blue fluorescent powder is prepared by adopting a high-temperature solid-phase method, has simple and easy preparation process, low cost, no toxicity and no pollution, and can be industrially produced.
Drawings
FIG. 1 is an XRD spectrum of a blue phosphor prepared in example 1;
FIG. 2 shows the excitation and emission spectra of the blue phosphor prepared in example 1;
FIG. 3 is a graph showing the change of emission intensity with temperature of the blue phosphor prepared in example 1, with an excitation wavelength of 365 nm.
Detailed Description
The present invention will now be further described with reference to the following detailed description and the accompanying drawings, which are illustrative, but not limiting, of the invention.
Example 1
(1) According to K0.6Ba0.1Eu0.1Al11O17In the stoichiometric ratio of the chemical compositions, 0.2225gK is weighed2CO3、0.15884gBaCO3、4.51387gAl2O3、0.0708gEu2O3And 0.2gAlF3As a raw material;
(2) fully grinding the raw materials, and uniformly mixing to obtain a mixture;
(3) placing the mixture in a corundum crucible, then placing the corundum crucible into a tube furnace, and introducing 5% of H by volume percentage2And 95% of N2Under the condition of reducing atmosphere, the temperature rise rate is 5 ℃/minHeating to 900 ℃, preserving heat for 2h to promote the decomposition of carbonate, then heating to 1400 ℃ at the same heating rate, preserving heat for 6h, and naturally cooling to room temperature to obtain a sinter;
(4) and grinding the sintered substance into powder, and sieving the powder by using a 300-mesh sieve to obtain the blue fluorescent powder.
FIG. 1 is an XRD spectrum of the blue phosphor prepared in example 1, and it can be seen from FIG. 1 that the blue phosphor has beta-Al2O3KAl of structure11O17Compared with a standard card, the blue fluorescent powder is well matched and has higher diffraction peak intensity, which indicates that the blue fluorescent powder has the advantages of KAl11O17Uniform beta-Al2O3Crystal structure and no other impurity phase.
FIG. 2 is a spectrum of excitation and emission light of the blue phosphor prepared in example 1, and it can be seen from FIG. 2 that the blue phosphor absorbs light from the ultraviolet region to the visible region (250-430nm), indicating that the blue phosphor has a wide excitation band; meanwhile, the blue fluorescent powder emits blue light with a main peak at 450nm under the excitation of 365nm near ultraviolet light, which indicates that the fluorescent powder prepared by the preparation method is the blue fluorescent powder.
Fig. 3 is a graph showing the change of the fluorescence emission intensity of the blue phosphor prepared in example 1 with the temperature under the excitation of 365nm near ultraviolet light, and it can be seen from fig. 3 that when the temperature is increased from 25 ℃ to 225 ℃, the emission intensity of the blue phosphor has little fluctuation and does not significantly decrease, the overall intensity tends to be stable, and the thermal stability is better.
Example 2
(1) According to K0.4Ba0.2Eu0.1Al11O17In the stoichiometric ratio of the chemical compositions, 0.14833gK is weighed2CO3、0.31768gBaCO3、4.51387gAl2O3、0.0708gEu2O3And 0.2gAlF3As a raw material;
(2) fully grinding the raw materials, and uniformly mixing to obtain a mixture;
(3) placing the mixture in a corundum crucible, and then placing the corundum crucible into a tube furnaceAfter introducing 5% by volume of H2And 95% of N2Heating to 900 ℃ at the heating rate of 5 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 2h to promote the decomposition of carbonate, then heating to 1400 ℃ at the same heating rate, preserving heat for 6h, and naturally cooling to room temperature to obtain a sinter;
(4) and grinding the sintered substance into powder, and sieving the powder by using a 300-mesh sieve to obtain the blue fluorescent powder.
Example 3
(1) According to K0.2Ba0.3Eu0.1Al11O170.22250g K is weighed according to the stoichiometric ratio of the chemical components2CO3、0.47652gBaCO3、4.51387gAl2O3、0.0708gEu2O3And 0.2gAlF3As a raw material;
(2) fully grinding the raw materials, and uniformly mixing to obtain a mixture;
(3) placing the mixture in a corundum crucible, then placing the corundum crucible into a tube furnace, and introducing 5% of H by volume percentage2And 95% of N2Heating to 900 ℃ at the heating rate of 5 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 2h to promote the decomposition of carbonate, then heating to 1400 ℃ at the same heating rate, preserving heat for 6h, and naturally cooling to room temperature to obtain a sinter;
(4) and grinding the sinter into powder, and sieving the powder with a 300-mesh sieve to obtain the blue fluorescent powder.
Example 4
(1) According to K0.45Ba0.1Eu0.175Al11O17In the stoichiometric ratio of the chemical compositions, 0.16688gK is weighed2CO3、0.15884gBaCO3、4.51387gAl2O3、0.1239gEu2O3And 0.2gAlF3As a raw material;
(2) fully grinding the raw materials, and uniformly mixing to obtain a mixture;
(3) placing the mixture in a corundum crucible, then placing the corundum crucible into a tube furnace, and introducing 5% of H by volume percentage2And 95% of N2Heating to 900 ℃ at the heating rate of 5 ℃/min under the condition of the formed reducing atmosphere, preserving heat for 2h to promote the decomposition of carbonate, then heating to 1400 ℃ at the same heating rate, preserving heat for 6h, and naturally cooling to room temperature to obtain a sinter;
(4) and grinding the sinter into powder, and sieving the powder by using a 300-mesh sieve to obtain the fluorescent powder.

Claims (5)

1. beta-Al activated by europium2O3The blue fluorescent powder with a defect structure is characterized in that the chemical structural formula of the blue fluorescent powder is K0.8-2x-2yBa0.1+xEuyAl11O17Wherein x is more than or equal to 0 and less than or equal to 0.3; y is more than or equal to 0.025 and less than or equal to 0.175.
2. The europium-activated β -Al of claim 12O3The preparation method of the defect structure blue fluorescent powder is characterized by comprising the following steps:
step 1: according to the chemical formula K0.8-2x-2yBa0.1+xEuyAl11O17Weighing K, Ba-containing carbonate or nitrate and Al-Eu-containing oxide according to the stoichiometric ratio of the chemical compositions; weighing a fluxing agent;
step 2: grinding the raw materials in the step 1, and uniformly mixing to obtain a mixture;
and step 3: carrying out sectional sintering on the mixture obtained in the step 2 under the condition of introducing a reducing atmosphere, and then cooling to room temperature to obtain a sintered material;
and 4, step 4: and (4) crushing the sinter obtained in the step (3) into powder, and sieving the powder by using a 300-600-mesh sieve to obtain the blue fluorescent powder.
3. The preparation method according to claim 2, wherein the reducing atmosphere in the step 3 is composed of 5-10% by volume of H2And 95 to 90% of N2And (4) forming.
4. The preparation method according to claim 2, wherein the segmented sintering in the step 3 is as follows: firstly, raising the temperature to 900 ℃ at the temperature rise rate of 5 ℃/min, and preserving the temperature for 1-2 h; then the temperature is raised to 1400 ℃ and 1600 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is preserved for 4 to 8 hours.
5. The method according to claim 2, wherein the flux in step 1 is AlF3、BaF2、H3BO3、CaF2One or more of the above; the adding amount of the fluxing agent is 3-5% of the total mass of the raw materials.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956880A (en) * 2021-11-10 2022-01-21 大连海事大学 Mn (manganese)2+Activated beta-Al2O3Narrow-band green fluorescent powder and preparation method thereof
CN115558493A (en) * 2022-09-07 2023-01-03 湖南师范大学 High-efficiency thermostable divalent europium ion cyan fluorescent powder and preparation method and application thereof

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CN107418575A (en) * 2017-05-22 2017-12-01 兰州大学 A kind of europkium-activated silicate blue-green fluorescent powder and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1198182A (en) * 1996-05-31 1998-11-04 菲利浦电子有限公司 Luminescent aluminate
CN107418575A (en) * 2017-05-22 2017-12-01 兰州大学 A kind of europkium-activated silicate blue-green fluorescent powder and preparation method thereof

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956880A (en) * 2021-11-10 2022-01-21 大连海事大学 Mn (manganese)2+Activated beta-Al2O3Narrow-band green fluorescent powder and preparation method thereof
CN115558493A (en) * 2022-09-07 2023-01-03 湖南师范大学 High-efficiency thermostable divalent europium ion cyan fluorescent powder and preparation method and application thereof

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