CN103965897A - Aluminum silicate yellow-green fluorescent powder for LED and preparation method thereof - Google Patents

Aluminum silicate yellow-green fluorescent powder for LED and preparation method thereof Download PDF

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CN103965897A
CN103965897A CN201410218773.7A CN201410218773A CN103965897A CN 103965897 A CN103965897 A CN 103965897A CN 201410218773 A CN201410218773 A CN 201410218773A CN 103965897 A CN103965897 A CN 103965897A
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presoma
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CN103965897B (en
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朱达川
赵聪
涂铭旌
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Sichuan University
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Sichuan University
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Abstract

The invention relates to aluminum silicate yellow-green fluorescent powder for LED and a preparation method thereof, belonging to the technical field of luminescent materials. The chemical formula is Ca2-xAlMg0.5Si1.5O7: xEu<2+>, wherein x is greater than 0 and less than or equal to0.05. Specifically, the preparation method comprises the steps of weighing a calcium salt, a magnesium salt, an aluminum salt, nanometer silica, europium oxide and an appropriate amount of surfactant according to the stoichiometric ratio of each element in the chemical formula; preparing a precipitant solution; dissolving europium oxide with concentrated acid, adding an appropriate amount of deionized water and carrying out bath treatment; adding the calcium salt, the magnesium salt, the aluminum salt, nanometer silica and the surfactant, continuously stirring and mixing uniformly, dropwise adding the precipitating agent, adjusting pH to be greater than or equal to 7, continuously stirring for 1-4 hours, and directly drying to obtain a precursor; placing the precursor in an atmosphere furnace with a reducing atmosphere and calcining at 1000-1300 DEG C for 2-7 hours to obtain the yellow-green fluorescent powder for LED, which is suitable for near ultraviolet radiation and has the advantages of high luminescence intensity and stability.

Description

Aluminosilicate yellow-green fluorescence powder and preparation method thereof for a kind of LED
Technical field
The invention belongs to LED luminescent material technical field, be specifically related to a kind of aluminosilicate yellow-green fluorescence powder and preparation method thereof.
Background technology
LED (light emitting diode) is a kind of novel luminescent device, under the driving of low-voltage DC (2.5～16V), and transmitting ultraviolet/near-ultraviolet light or visible ray.White light LEDs is a kind of Novel LED illuminating device emitting white light that the LED based on traditional develops out, compare with traditional lighting source there are energy-saving and environmental protection, the advantage such as life-span length, low consumption, low-heat, high brightness, waterproof, shockproof, light beam is concentrated, easy maintenance, be described as the 4th generation green illumination light source, significant to energy-conserving and environment-protective.
The method that realizes at present white light LEDs is that blue light for InGaN chip excites YAG (Y 3al 5o 12: Ce 3+) fluorescent material generation gold-tinted, become white light with chip blue light.Because YAG fluorescent material emmission spectrum lacks ruddiness composition, there is the defects such as colour rendering index is low, colour temperature is high.For addressing the above problem, generally adopt the InGaN tube core (UVLED) of near ultraviolet (350～420nm) radiation to excite three primary colors fluorescent powder to realize white light LEDs.The method can select emission wavelength more fully fluorescent material the photochromic of white light LEDs prepared, the colour rendering index of white light LEDs, colour temperature are effectively improved.Near ultraviolet phosphor for white light LED is of a great variety, aluminium wherein, silicates fluorescent material is commonplace, especially rare-earth ion activated alkaline earth metal aluminide, silicate, there is good thermostability and chemical stability, its excitation spectrum is wider, can be by ultraviolet, near ultraviolet, blue-light excited and present higher luminous efficiency, emission wavelength covers larger scope, and emission wavelength coverage more easily regulates with respect to YAG fluorescent material, therefore be subject to investigator's extensive concern, as: CN102399555B, CN102732247A, CN102250611A, CN102965102A etc.And an other class fluorescent material---aluminosilicate fluorescent powder also has the feature of aluminium, silicate substrate, as: CN1995276A, CN10142911A, CN101595201A, but alumo silicate matrix fluorescent material is also fewer, has very much DEVELOPMENT PROSPECT.
Therefore, research and development New LED is likely the key that solves present white light LEDs technical barrier with aluminosilicate fluorescent powder, have broad application prospects.
Summary of the invention
The object of the present invention is to provide aluminosilicate fluorescent powder of a kind of near ultraviolet excitation and preparation method thereof, this fluorescent material under the exciting of 270-500nm near-ultraviolet light emission peak near 525nm, by regulating luminescence center density to improve luminescent properties, be applicable near ultraviolet excited white light LED, comprise the following steps:
(1) according to chemical formula Ca 2-xalMg 0.5si 1.5o- 7: xEu 2+in (0<x≤0.05), each element chemistry metering ratio, takes respectively calcium salt, magnesium salts, aluminium salt, nano silicon, europium sesquioxide.Take respectively the tensio-active agent of above medicine total mass 0.2wt%～1wt%;
(2) preparation precipitant solution, concentration is 1～3mol/L;
(3) concentrated acid appropriate for the europium sesquioxide taking is dissolved, add appropriate deionized water post-heating to 35 ℃～80 ℃ to carry out water bath processing;
(4) calcium salt taking, magnesium salts, aluminium salt, nano silicon, tensio-active agent are added to above-mentioned solution, stir simultaneously, drip precipitation agent, until solution PH >=7 continue to stir 1～4 hour, carry out to sufficient reacting;
(5) above-mentioned solution is directly dried, obtain fluffy presoma;
(6) atmosphere furnace that presoma is placed in to reducing atmosphere protection is calcined, and calcining temperature is 1000～1300 ℃, and calcination time is 2～7 hours, obtains target product.
In the present invention, the described calcium salt of step (1) is Ca (NO 3) 24H 2o, CaCl 2, CaCO 3in a kind of; Magnesium salts is Mg (NO 3) 26H 2o or MgCl 2; Aluminium salt is Al (NO 3) 39H 2o; Tensio-active agent is polyoxyethylene glycol or Sodium dodecylbenzene sulfonate; Precipitation agent described in step (2) is (NH 4) 2c 2o 4+ NH 3h 2o, NH 4hCO 3, (NH 4) 2cO 3in a kind of; Described in step (3), concentrated acid is analytically pure nitric acid or hydrochloric acid; Described in step (6), reducing atmosphere is hydrogen (H 2) or nitrogen and hydrogen gas mixture (H 2and N 2).
Compare with existing result of study, the present invention has following beneficial effect:
1, the fluorescent powder excitation spectrum that the present invention prepares is very wide, at 270～500nm, has stronger absorption, and Emission Spectrum Peals is positioned near 525nm, and luminous intensity is large, is applicable to the yellow-green fluorescence powder that near ultraviolet LED excites.
2, the fluorescent material that the present invention prepares obtains at lower temperature lower calcination, and once calcining just completes matrix generation, doping, reduction process, and the time is short, save the energy, raw material is cheap and easy to get, technique is simple, be easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is yellow-green fluorescence powder Ca 2-xalMg 0.5si 1.5o- 7: xEu 2+preparation technology's schema;
Fig. 2 is yellow-green fluorescence powder Ca 1.985alMg 0.5si 1.5o- 7: 0.015Eu 2+x ray diffracting spectrum;
Fig. 3 is yellow-green fluorescence powder Ca 1.985alMg 0.5si 1.5o- 7: 0.015Eu 2+excite (λ em=525) with transmitting collection of illustrative plates (λ ex=372,400nm).
Concrete case study on implementation
Case study on implementation 1:
Press chemical formula Ca 1.99alMg 0.5si 1.5o- 7: 0.01Eu 2+take CaCO 3(A.R.) 1.99mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.005mol; Take again the surfactant polyethylene of above medicine total mass 0.8wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 3mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 50 ℃ to carry out water bath processing; In above-mentioned solution, add CaCO 3, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, polyoxyethylene glycol, stir simultaneously, drip precipitation agent, regulate PH=9, continue to stir 1 hour; Directly dry, obtain fluffy presoma; Presoma is placed in to the atmosphere furnace that is connected with hydrogen and calcines, calcining temperature is 1150 ℃, and calcination time is 4 hours, obtains target product.
Case study on implementation 2:
Press chemical formula Ca 1.985alMg 0.5si 1.5o- 7: 0.015Eu 2+take CaCO 3(A.R.) 1.985mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.0075mol; Take again the surfactant polyethylene of above medicine total mass 0.6wt%; Preparation precipitation agent (NH 4) 2c 2o 4+ NH 3h 2o solution, concentration is 3mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 45 ℃ to carry out water bath processing; In above-mentioned solution, add CaCO 3, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, polyoxyethylene glycol, stir simultaneously, drip precipitation agent, regulate PH=9, continue to stir 2 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1200 ℃, calcination time is 3.5 hours, obtains target product.
Case study on implementation 3:
Press chemical formula Ca 1.99alMg 0.5si 1.5o- 7: 0.01Eu 2+take CaCl 2(A.R.) 1.99mol, Al (NO 3) 39H 2o (A.R.) 1mol, MgCl 2(A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.005mol; Take again the surfactant polyethylene of above medicine total mass 0.4wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 2mol/L; By the Eu taking 2o 3with appropriate dissolving with hydrochloric acid, add appropriate deionized water post-heating to 40 ℃ to carry out water bath processing; In above-mentioned solution, add CaCl 2, Al (NO 3) 39H 2o, MgCl 2(A.R.), nanometer SiO 2, polyoxyethylene glycol, stir simultaneously, drip precipitation agent, regulate PH=8, continue to stir 3 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1250 ℃, calcination time is 3 hours, obtains target product.
Case study on implementation 4:
Press chemical formula Ca 1.99alMg 0.5si 1.5o- 7: 0.01Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.99mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.005mol; Take again the surfactant polyethylene of above medicine total mass 0.2wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 35 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, polyoxyethylene glycol, stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 4 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1300 ℃, calcination time is 2 hours, obtains target product.
Case study on implementation 5:
Press chemical formula Ca 1.985alMg 0.5si 1.5o- 7: 0.015Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.985mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.0075mol; Take again the surfactant polyethylene of above medicine total mass 1wt%; Preparation precipitation agent (NH 4) 2c 2o 4+ NH 3h 2o solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 55 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, polyoxyethylene glycol, stir simultaneously, drip precipitation agent, regulate PH=8, continue to stir 3 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1100 ℃, calcination time is 5 hours, obtains target product.
Case study on implementation 6:
Press chemical formula Ca 1.985alMg 0.5si 1.5o- 7: 0.015Eu 2+take CaCl 2(A.R.) 1.985mol, Al (NO 3) 39H 2o (A.R.) 1mol, MgCl 20.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.0075mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.2wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 2mol/L; By the Eu taking 2o 3with appropriate dissolving with hydrochloric acid, add appropriate deionized water post-heating to 60 ℃ to carry out water bath processing; In above-mentioned solution, add CaCl 2, Al (NO 3) 39H 2o, MgCl 2, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 2 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1000 ℃, calcination time is 7 hours, obtains target product.
Case study on implementation 7:
Press chemical formula Ca 1.98alMg 0.5si 1.5o- 7: 0.02Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.98mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.01mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.4wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 65 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=8, continue to stir 1.5 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1050 ℃, calcination time is 6 hours, obtains target product.
Case study on implementation 8:
Press chemical formula Ca 1.98alMg 0.5si 1.5o- 7: 0.02Eu 2+take CaCO 3(A.R.) 1.98mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.01mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.6wt%; Preparation precipitation agent (NH 4) 2c 2o 4+ NH 3h 2o solution, concentration is 3mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 70 ℃ to carry out water bath processing; In above-mentioned solution, add CaCO 3, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=9, continue to stir 3 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1200 ℃, calcination time is 3.5 hours, obtains target product.
Case study on implementation 9:
Press chemical formula Ca 1.98alMg 0.5si 1.5o- 7: 0.02Eu 2+take Ca (NO 3) 24H 2o (A.R.) is 1.98mol, Al (NO (A.R.) 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.01mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.8wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 2mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 75 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o (A.R.), Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 2 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1300 ℃, calcination time is 2 hours, obtains target product.
Case study on implementation 10:
Press chemical formula Ca 1.98alMg 0.5si 1.5o- 7: 0.02Eu 2+take CaCO 3(A.R.) 1.98mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.01mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 1wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 80 ℃ to carry out water bath processing; In above-mentioned solution, add CaCO 3, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=8, continue to stir 2.5 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1150 ℃, calcination time is 4 hours, obtains target product.
Case study on implementation 11:
Press chemical formula Ca 1.975alMg 0.5si 1.5o- 7: 0.025Eu 2+take CaCl 2(A.R.) 1.975mol, Al (NO 3) 39H 2o (A.R.) 1mol, MgCl 2(A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.0125mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 1wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate dissolving with hydrochloric acid, add appropriate deionized water post-heating to 80 ℃ to carry out water bath processing; In above-mentioned solution, add CaCl 2, Al (NO 3) 39H 2o, MgCl 2, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=8, continue to stir 2.5 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1150 ℃, calcination time is 4 hours, obtains target product.
Case study on implementation 12:
Press chemical formula Ca 1.97alMg 0.5si 1.5o- 7: 0.03Eu 2+take CaCl 2(A.R.) 1.97mol, Al (NO 3) 39H 2o (A.R.) 1mol, MgCl 2(A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.015mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.2wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 2mol/L; By the Eu taking 2o 3with appropriate dissolving with hydrochloric acid, add appropriate deionized water post-heating to 60 ℃ to carry out water bath processing; In above-mentioned solution, add CaCl 2, Al (NO 3) 39H 2o, MgCl 2, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 2 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1000 ℃, calcination time is 7 hours, obtains target product.
Case study on implementation 13:
Press chemical formula Ca 1.96alMg 0.5si 1.5o- 7: 0.04Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.96mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.02mol; Take again the tensio-active agent Sodium dodecylbenzene sulfonate of above medicine total mass 0.2wt%; Preparation precipitation agent (NH 4) 2cO 3solution, concentration is 2mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 60 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO 2, Sodium dodecylbenzene sulfonate, stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 2 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1000 ℃, calcination time is 7 hours, obtains target product.
Case study on implementation 14:
Press chemical formula Ca 1.955alMg 0.5si 1.5o- 7: 0.045Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.955mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.0225mol; Take again the surfactant polyethylene of above medicine total mass 0.2wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 35 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO2, polyoxyethylene glycol stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 4 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with nitrogen and hydrogen gas mixture (H 2and N 2) atmosphere furnace in calcine, calcining temperature is 1300 ℃, calcination time is 2 hours, obtains target product.
Case study on implementation 15:
Press chemical formula Ca 1.95alMg 0.5si 1.5o- 7: 0.05Eu 2+take Ca (NO 3) 24H 2o (A.R.) 1.95mol, Al (NO 3) 39H 2o (A.R.) 1mol, Mg (NO 3) 26H 2o (A.R.) 0.5mol, nanometer SiO 21.5mol, Eu 2o 3(99.99%) 0.025mol; Take again the surfactant polyethylene of above medicine total mass 0.2wt%; Preparation precipitation agent NH 4hCO 3solution, concentration is 1mol/L; By the Eu taking 2o 3with appropriate nitric acid dissolve, add appropriate deionized water post-heating to 35 ℃ to carry out water bath processing; In above-mentioned solution, add Ca (NO 3) 24H 2o, Al (NO 3) 39H 2o, Mg (NO 3) 26H 2o, nanometer SiO2, polyoxyethylene glycol stir simultaneously, drip precipitation agent, regulate PH=7, continue to stir 4 hours; Directly dry, obtain fluffy presoma; Presoma is placed in and is connected with hydrogen (H 2) atmosphere furnace in calcine, calcining temperature is 1300 ℃, calcination time is 2 hours, obtains target product.

Claims (1)

1. aluminosilicate yellow-green fluorescence powder and preparation method thereof for a LED, the chemical expression that it is characterized in that aluminosilicate yellow-green fluorescence powder is Ca 2-xalMg 0.5si 1.5o- 7: xEu 2+, 0<x≤0.05 wherein, concrete steps are as follows:
(1) according to chemical formula Ca 2-xalMg 0.5si 1.5o- 7: xEu 2+in (0<x≤0.05), each element chemistry metering ratio, takes respectively calcium salt, magnesium salts, aluminium salt, nano silicon, europium sesquioxide, then takes respectively the tensio-active agent of above medicine total mass 0.2wt%～1wt%;
(2) preparation precipitant solution, concentration is 1～3mol/L;
(3) concentrated acid appropriate for the europium sesquioxide taking is dissolved, add appropriate deionized water post-heating to 35 ℃～80 ℃ to carry out water bath processing;
(4) calcium salt taking, magnesium salts, aluminium salt, nano silicon, tensio-active agent are added to above-mentioned solution, stir simultaneously, drip precipitation agent, until solution PH >=7 continue to stir 1～4 hour, carry out to sufficient reacting;
(5) above-mentioned solution is directly dried, obtain fluffy presoma;
(6) atmosphere furnace that presoma is placed in to reducing atmosphere protection is calcined, and calcining temperature is 1000～1300 ℃, and calcination time is 2～7 hours, obtains target product;
The described calcium salt of step (1) is Ca (NO 3) 24H 2o, CaCl 2, CaCO 3in a kind of; Magnesium salts is Mg (NO 3) 26H 2o, MgCl 2in a kind of; Aluminium salt is Al (NO 3) 39H 2o; Tensio-active agent is polyoxyethylene glycol or Sodium dodecylbenzene sulfonate; Precipitation agent described in step (2) is (NH 4) 2c 2o 4+ NH 3h 2o, NH 4hCO 3, (NH 4) 2cO 3in a kind of; Described in step (3), concentrated acid is analytically pure nitric acid or hydrochloric acid; Described in step (6), reducing atmosphere is hydrogen (H 2) or nitrogen and hydrogen gas mixture (H 2and N 2).
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199722A (en) * 2015-07-22 2015-12-30 四川大学 Aluminosilicate blue fluorescent powder for LED and preparation method thereof
CN105199723A (en) * 2015-07-22 2015-12-30 四川大学 Preparation method of Ce<3+> doped aluminosilicate ianthinus fluorescent powder for LED
CN106544016A (en) * 2016-12-07 2017-03-29 重庆文理学院 A kind of LED aluminosilicate bluish violet fluorescent material and preparation method thereof
CN112194376A (en) * 2020-09-29 2021-01-08 华南理工大学 Red light emitting glass ceramic, preparation method thereof and LED/LD light emitting device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839219A (en) * 1971-10-07 1974-10-01 Philips Corp Europium activated alkaline earth magnesium aluminium silicate luminescent material
CN101878280A (en) * 2007-11-30 2010-11-03 日亚化学工业株式会社 Phosphor, light-emitting device using the same, and method for producing phosphor
CN103254895A (en) * 2013-05-12 2013-08-21 吉林大学 Aluminosilicate green fluorescent powder and preparation method thereof
CN103468251A (en) * 2013-04-26 2013-12-25 四川大学 Silicate green fluorescent powder used for LEDs and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839219A (en) * 1971-10-07 1974-10-01 Philips Corp Europium activated alkaline earth magnesium aluminium silicate luminescent material
CN101878280A (en) * 2007-11-30 2010-11-03 日亚化学工业株式会社 Phosphor, light-emitting device using the same, and method for producing phosphor
CN103468251A (en) * 2013-04-26 2013-12-25 四川大学 Silicate green fluorescent powder used for LEDs and preparation method thereof
CN103254895A (en) * 2013-05-12 2013-08-21 吉林大学 Aluminosilicate green fluorescent powder and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. MAIECKI等: "Spectroscopic studies of the kinetics of devitrification of Nd3+-doped glasses in the akermanite-gehlenite system", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199722A (en) * 2015-07-22 2015-12-30 四川大学 Aluminosilicate blue fluorescent powder for LED and preparation method thereof
CN105199723A (en) * 2015-07-22 2015-12-30 四川大学 Preparation method of Ce<3+> doped aluminosilicate ianthinus fluorescent powder for LED
CN105199722B (en) * 2015-07-22 2017-03-08 四川大学 A kind of LED aluminosilicate blue fluorescent powder and preparation method thereof
CN106544016A (en) * 2016-12-07 2017-03-29 重庆文理学院 A kind of LED aluminosilicate bluish violet fluorescent material and preparation method thereof
CN112194376A (en) * 2020-09-29 2021-01-08 华南理工大学 Red light emitting glass ceramic, preparation method thereof and LED/LD light emitting device
CN112194376B (en) * 2020-09-29 2021-12-21 华南理工大学 Red light emitting glass ceramic, preparation method thereof and LED/LD light emitting device

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