CN113717718A - Preparation method and application of terbium ion-doped three-dimensional porous-structure alumina aerogel fluorescent powder - Google Patents
Preparation method and application of terbium ion-doped three-dimensional porous-structure alumina aerogel fluorescent powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052771 Terbium Inorganic materials 0.000 title claims abstract description 22
- 239000004964 aerogel Substances 0.000 title claims abstract description 19
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003755 preservative agent Substances 0.000 claims description 27
- 230000002335 preservative effect Effects 0.000 claims description 27
- 238000007789 sealing Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 9
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 108010043121 Green Fluorescent Proteins Proteins 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- -1 terbium ion Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 230000005284 excitation Effects 0.000 description 9
- 238000001879 gelation Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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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
- C09K11/7706—Aluminates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The invention relates to the field of rare earth luminescence, in particular to a preparation method and application of terbium ion-doped aluminum oxide aerogel fluorescent powder with a three-dimensional porous structure. Converting TbCl3Mixed with Al3Cl3·6H2In the water solution of O, the green fluorescent powder for the ultraviolet LED can be prepared by sol-gel, drying, calcining and grinding, and the components and the molar ratio can be represented by the following chemical general formula:xTb3+：Al2O3wherein x is more than 0 and less than or equal to 1. The alumina aerogel is used as the luminescent substrate of terbium, so that the problems of reduction of luminescent sites and reduction of luminescent performance caused by the problems of agglomeration, aggregation or shedding of luminescent centers and the like of the rare earth luminescent material after high-temperature calcination can be effectively solved.
Description
Technical Field
The invention relates to the field of rare earth luminescence, in particular to a preparation method and application of terbium ion-doped aluminum oxide aerogel fluorescent powder with a three-dimensional porous structure.
Background
The rare earth luminescent material has the advantages of high color purity, strong absorption capacity, bright color, high conversion efficiency, stable property, various types of emitted spectrums and the like, and has wide application prospect in the field of illumination. With the development of society, the application of white light LEDs is becoming more and more extensive, the technology thereof is being continuously introduced and innovated, the rare earth luminescent material industry is being developed, the source must be emphasized, and the problems of quality improvement, variety development, application expansion and the like of rare earth fluorescent powder are solved. On the basis of photoelectric technical indexes and product consistency, the method reduces the dosage, optimizes the utilization and further improves the utilization efficiency and the luminous efficiency, and is also one of important methods for protecting rare earth from sources, which is also one of the key research directions in the scientific field all the time.
The light source of the white light LED has the advantages of high luminous efficiency, good luminous monochromaticity, energy conservation, long service life, high safety, uniform and comfortable light, environmental friendliness and the like. At present, the following 2 methods are mainly used for realizing white light LEDs: the first is to package chips which can respectively emit red, green and blue colors, and regulate and control the chips by a certain means to mix the chips to emit white light; the second is that the fluorescent powder which can be excited by blue light to emit yellow is packaged with the blue LED chip, so that white light can be emitted; the method has the advantages of simple process and low cost, but the white light synthesized by the second method is lack of green light components, and although the color temperature is high, the color rendering coefficient is low. Therefore, in the method of realizing the white light LED by the fluorescent powder, green light plays a crucial role, and therefore, in the process of converting the fluorescent powder into the white light LED, the green fluorescent powder is a key for restricting the development of the white light LED. For the efficient green phosphor, terbium ion (Tb)3+) Often used as green high-efficiency active ion, and the transition emission of terbium ion is respectivelyFrom5D4→7FJAnd5D3→7FJaccording to the existing experimental data, the metal ion is terbium ion around 550nm5D4→7FJThe green light emitted by the transition is generated, so the terbium ion is widely applied to the preparation and research of green fluorescent powder.
Non-rare earth oxides as a matrix are a type of system in luminescent materials, and common non-rare earth oxide matrices of terbium ions mainly include: TiO 22、ZnO、ZrO2、Al2O3And the ZnO matrix has good stability, but because the lattice valence and the ion size of the ZnO matrix are not matched with trivalent rare earth metal ions, the rare earth metal ions are mainly distributed on the surface of the matrix and are difficult to enter the crystal lattice, so that the actual doping concentration is far lower than the theoretical calculated value. ZrO (ZrO)2It is necessary to form a solid solution with another oxide and to form ZrO2The light is converted into a stable cubic phase, and the luminous efficiency is better. However, the structure of the solid solution is greatly influenced by the sintering temperature, and the lower sintering temperature is not beneficial to the formation of the structure, thereby increasing the cost invisibly. TiO 22The substrate can not be doped with high-concentration rare earth ions, so that the improvement of the luminous efficiency is limited, and when the doping amount exceeds 15%, the concentration quenching phenomenon can occur; when the excitation temperature exceeds 467K, the luminous efficiency begins to decrease.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a novel method for preparing green fluorescent powder with high-efficiency luminescence.
Rare earth ions are doped in aluminum salt, and the rare earth luminescent material prepared by sol-gel can effectively solve the problems of reduced luminescent sites and reduced luminescent performance caused by the problems of agglomeration, aggregation or falling off of luminescent centers and the like of the rare earth luminescent material after high-temperature calcination. The preparation method has the advantages of good stability, high load rate, strong binding force between the matrix and the rare earth ions, economic cost and the like, and has important practical significance for promoting and developing white light LED technology.
The preparation method of the terbium ion-doped three-dimensional porous structure alumina aerogel fluorescent powder comprises the following steps:
(1) TbCl is added3With Al3Cl3·6H2Mixing O according to molar ratio, dissolving in a conical flask with deionized water and ethanol, stirring and dissolving completely with a constant-temperature magnetic stirrer, and dripping HCl to promote Al3Cl3·6H2Hydrolysis of O;
wherein, TbCl3With AlCl3·6H2The molar ratio of O is 1: 10-20, and the volume ratio of deionized water to absolute ethyl alcohol is 1: 1-1: 5; the adding amount of the HCl solution is 0.5-3% of the volume of the solution after mixing and dissolving.
(2) After the aluminum salt in the step (1) is completely hydrolyzed, sealing the conical flask, placing the conical flask into a water bath kettle at a set temperature for reaction, transferring the solution into a beaker after the reaction is completely finished, placing the beaker on a magnetic stirrer, and stirring and cooling the beaker to room temperature;
wherein the water bath reaction temperature is 60-100 ℃, and the reaction time is 1-1.5 h;
(3) after the solution in the step (2) is cooled to room temperature, placing the beaker in an ice-water bath environment, and slowly dropwise adding propylene oxide; after the propylene oxide is dripped, sealing the opening of the beaker by using a disposable preservative film, and placing the beaker into a constant temperature incubator to stand for 20-30 minutes at the temperature of 45-50 ℃ to obtain gel;
the adding amount of the propylene oxide is 40 to 70 percent of the volume of the mixed and dissolved solution;
(4) after the material in the step (3) is gelled, uncovering the preservative film, slowly pouring absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing the gel by using the preservative film, and aging the gel in a thermostat at 45-50 ℃ for 2-3 days; after the aging is finished, pouring the absolute ethyl alcohol out and placing the absolute ethyl alcohol in a vacuum drying oven for drying;
(5) after the gel in the step (4) is dried, placing the dried gel into a muffle furnace, and calcining in an air atmosphere; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Wherein the calcining temperature is 550-750 ℃, the heating rate is 3-5 ℃/min, and the constant temperature time is 2.5-4 h.
Has the advantages that:
according to the invention, the alumina aerogel is used as a luminescent substrate of terbium, and the rare earth ions are doped in the alumina aerogel, so that the problems of reduction of luminescent sites and reduction of luminescent performance caused by the problems of aggregation, aggregation or falling off of luminescent centers and the like of the rare earth luminescent material after high-temperature calcination can be effectively solved. The prepared three-dimensional nano porous alumina aerogel has the advantages of stable luminous performance, high luminous efficiency and the like.
Description of the drawings:
FIG. 1 is a graph of the present invention prepared using example 10.1Tb3+：Al2O3Green fluorescent luminescent material.
FIG. 2 shows the present inventionxTb3+：Al2O3And (3) a relational graph of terbium ion doping concentration and luminous intensity in the green fluorescent luminescent material prepared in the air atmosphere.
FIGS. 3(a-d) are prepared in accordance with the present invention using example 10.1Tb3+：Al2O3Electron micrographs of the dispersibility of the green fluorescent light-emitting material.
Detailed Description
The embodiments are supplemented and described in detail below.
Example 1
Converting TbCl3With Al3Cl3·6H2O is as follows: mixing at 10 mol ratio, weighing 0.6g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 14mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelation, the preservative film is uncovered, 10mL of absolute ethyl alcohol is slowly poured along the inner wall of the beaker, and the mixture is driedImmersing the whole gel, sealing with preservative film, and aging in a constant temperature oven at 45 deg.C for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere, wherein the calcining temperature is 650 ℃, the heating rate is 5 ℃/min, and the constant temperature time is 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 2
Converting TbCl3With Al3Cl3·6H2Mixing O according to the molar ratio of 1:10, weighing 0.6g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 14mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere at 550 ℃, heating at 5 ℃/min and keeping the temperature for 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 3
Converting TbCl3With Al3Cl3·6H2Mixing O in the molar ratio of 1 to 15, weighing 0.44g TbCl3And 6gAl3Cl3·6H2O, mixed materials used 6mL deionized water 14mLDissolving the water ethanol in a 250mL conical flask, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 14mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere, wherein the calcining temperature is 750 ℃, the heating rate is 5 ℃/min, and the constant temperature time is 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 4
Converting TbCl3With Al3Cl3·6H2Mixing O in the molar ratio of 1 to 15, weighing 0.44g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 14mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; old ageAfter the reaction is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere, wherein the calcining temperature is 650 ℃, the heating rate is 5 ℃/min, and the constant temperature time is 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 5
Converting TbCl3With Al3Cl3·6H2Mixing O in the molar ratio of 1 to 15, weighing 0.44g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 19mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere at 550 ℃, heating at 5 ℃/min and keeping the temperature for 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 6
Converting TbCl3With Al3Cl3·6H2Mixing O in the molar ratio of 1 to 20, weighing 0.33g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; charging deviceAfter the components are mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 80 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 25mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere, wherein the calcining temperature is 750 ℃, the heating rate is 5 ℃/min, and the constant temperature time is 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
Example 7
Converting TbCl3With Al3Cl3·6H2Mixing O in the molar ratio of 1 to 20, weighing 0.33g TbCl3And 6gAl3Cl3·6H2O, dissolving the mixed material in a 250mL conical flask by using 6mL deionized water and 14mL absolute ethyl alcohol, and fully stirring and dissolving by using a constant-temperature magnetic stirrer; after being fully mixed and dissolved, 1mL of 1mol/L HCl is added dropwise to promote Al3Cl3·6H2Hydrolysis of O; then sealing the conical flask, and continuously reacting for 1h at the constant temperature of 90 ℃; after the reaction is finished, transferring the solution into a beaker, placing the beaker on a magnetic stirrer, stirring and cooling the beaker to room temperature; placing the beaker in an ice-water bath environment, and slowly dropwise adding 25mL of propylene oxide; after the dripping is finished, sealing the mouth of the beaker by using a disposable preservative film and placing the beaker into a constant temperature incubator to stand for 30min at 45 ℃ until gelation; after gelling, uncovering the preservative film, slowly pouring 10mL of absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing by using the preservative film, and aging in a constant temperature oven at 45 ℃ for 3 days; after the aging is finished, pouring the absolute ethyl alcohol into a vacuum drying oven, wherein the drying temperature is 80 DEG CThe drying time is 24 hours; after drying, placing the dried gel into a muffle furnace, calcining in an air atmosphere, wherein the calcining temperature is 750 ℃, the heating rate is 5 ℃/min, and the constant temperature time is 2.5 h; after calcining and sintering, grinding the mixture into powder in an agate mortar.
FIG. 1 shows Tb prepared from example 1-example 33+Doped Al2O3The aerogel rare earth luminescent material respectively emits light under the excitation of 254nm and 365nm ultraviolet light. It can be seen that the material emits bright green light after 550 ℃ calcination, whether under 254nm or 365nm excitation. Furthermore, after the calcination temperature is increased to 650 ℃ and 750 ℃, the luminescent color of the material is not obviously changed, and the luminescent intensity is not reduced.
FIG. 2 shows that the samples prepared in examples 2,5 and 7 emit stronger emission wavelengths than the excitation light with the excitation wavelengths of 284nm and 350nm under the same conditions and under the irradiation of the excitation light with the excitation wavelength of 260nm, so that 260nm is the optimal excitation wavelength of the sample, and Tb is shown according to the test results3+There are 4 emission peak positions with peak values of 489nm, 543nm, 584nm and 622nm, respectively, corresponding to5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3Is detected. At the same time, different Tb3+The doped concentration also has different emission wavelengths at excitation wavelengths of 260nm, 284nm and 350nm, and Tb can be seen from the graph3+：Al2O3The luminescence properties of the samples were best at 1:15, probably due to Tb3+The concentration is lower than the doping and does not reach a certain saturation; above this doping ratio, concentration quenching may occur, which may result in agglomeration and accumulation on the micro-morphology, which is not favorable for the improvement of the luminescence performance.
Figure 3 shows a TEM picture of a sample prepared from example 4 after treatment at an annealing temperature of 550 ℃. As can be seen from the transmission electron microscope image, the microstructure of the material after being stripped and unfolded is still in an irregular gauze shape without obvious agglomeration, which indicates thatTb3+So that Al is doped2O3A uniform powder structure with good dispersibility is formed. Doped rare earth ions Tb3+Is also dispersedly anchored in the matrix skeleton, and no active ion Tb occurs3+Stacking and agglomeration phenomena.
Claims (9)
1. A preparation method of terbium ion-doped three-dimensional porous structure alumina aerogel fluorescent powder is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) TbCl is added3With Al3Cl3·6H2Mixing O according to molar ratio, dissolving in a conical flask with deionized water and ethanol, stirring and dissolving completely with a constant temperature magnetic stirrer, and dripping HCl to promote Al3Cl3·6H2Hydrolysis of O;
(2) after the aluminum salt in the step (1) is completely hydrolyzed, sealing the conical flask, placing the conical flask into a water bath kettle at a set temperature for reaction, transferring the solution into a beaker after the reaction is completely finished, placing the beaker on a magnetic stirrer, and stirring and cooling the beaker to room temperature;
(3) after cooling to room temperature in the step (2), placing the beaker in an ice-water bath environment, and slowly dropwise adding propylene oxide; after the dripping of the epoxypropane is finished, sealing the opening of the beaker by using a disposable preservative film and putting the beaker into a constant-temperature incubator for standing and gelling;
(4) after the material in the step (3) is gelled, uncovering the preservative film, slowly pouring absolute ethyl alcohol along the inner wall of the beaker, immersing the whole piece of gel, sealing the gel by using the preservative film, and placing the gel in a constant temperature box for aging; after the aging is finished, pouring the absolute ethyl alcohol out and placing the absolute ethyl alcohol in a vacuum drying oven for drying;
(5) after the gel in the step (4) is dried, placing the dried gel into a muffle furnace, and calcining in an air atmosphere; after calcining and sintering, grinding the mixture into powder in an agate mortar.
2. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: TbCl in step (1)3And Al3Cl3·6H2The molar ratio of O is 1: 10-20, and the volume ratio of deionized water to absolute ethyl alcohol is 1: 1-1: 5; the adding amount of the HCl solution is 0.5-3% of the volume of the solution after mixing and dissolving.
3. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: the water bath reaction temperature in the step (2) is 60-100 ℃, and the reaction time is 1-1.5 h.
4. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: the dropping amount of the propylene oxide in the step (3) is 40 to 70 percent of the volume of the mixed and dissolved solution.
5. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: and (3) standing at the temperature of 40-50 ℃ for 20-30 min.
6. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: and (4) aging the gel for 2-3 days.
7. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: in the step (4), the vacuum drying temperature is 80-100 ℃, and the drying time is 12-24 hours.
8. The method for preparing terbium ion-doped three-dimensional porous structure alumina aerogel phosphor according to claim 1, wherein: in the step (5), the calcining temperature is 550-750 ℃, the heating rate is 3-5 ℃/min, and the constant temperature time is 2.5-4 h.
9. The terbium ion-doped three-dimensional porous structure alumina aerogel phosphor prepared according to the method of claim 1, for use as a green phosphor for ultraviolet LEDs.
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| Title |
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| HENG CHEN ET AL.: "Preparation and Characterization of Monolithic Al2O3 Aerogels", 《MATERIALS SCIENCE FORUM》 * |
| JOSÉ M. A. CAIUT ET AL.: "Luminescent Terbium Doped Aluminate Particles: Properties and Surface Modification with Asparagine", 《 J. BRAZ. CHEM. SOC.》 * |
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