CN105647525A - Method for preparing MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder for LED - Google Patents
Method for preparing MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder for LED Download PDFInfo
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Abstract
The invention belongs to the technical field of preparing fluorescent powder through the wet chemical method, and particularly relates to a method for preparing MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder for an LED. The MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder (0<x</=0.5) for the LED is prepared through the solvothermal method. The MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder can be obtained through low-temperature forging in the later stage. The MAlSiO4:Tb3+, Eu2+ yellow light fluorescent powder obtained through the solvothermal method is uniform in particle size distribution, high in excitation efficiency and good in color zone uniformity, and the fluorescent powder can be matched with blue light excitation to achieve white light emission.
Description
Technical field
The invention belongs to wet chemistry method and prepare phosphor technologies field, be specifically related to a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder.
Background technology
At present, rare earth luminescent material have become as information show, the core material in the field such as lighting source, photoelectric device. Wherein, what be most widely used is can be excited by ultraviolet light-blue light (200��500nm) and produce the phosphor material powder of different glow color. The high luminous intensity of fluorescent material, high color purity and uniform particle size can significantly improve the serviceability of photoelectric device. At present, fluorescent material matrix material mainly includes aluminate, silicate, tungstates and titanate etc., but the fluorescent material of different system there are differences on color developing and luminous intensity.
2011, Huang Yanlin et al. was with alkaline earth carbonate, SiO2��Eu2O3Deng for raw material, under reducing atmosphere condition, at 1000��1500 DEG C, calcine 1��15h, obtain Ca7-7x-7yM7yEu7x(SiO4)4, Mn4+Huang-blue light fluorescent powder. Find that this fluorescent material can be launched under ultraviolet near ultraviolet excitation, Mn4+Huang-blue light, luminous efficiency is high, the feature of excitation wave length and width. 2012, Chen Lei et al. was with nano-micrometre SiO2��Eu2O3And alkaline earth metal carbonate, alkaline earth oxide etc. are raw material, under hydrogen, nitrogen mixture atmosphere, at 1400��1700 DEG C, calcine 4��20h, obtain (Ae1-xEux)3SiO5Red light fluorescent powder, under 460nm is blue-light excited, phosphor emission goes out the HONGGUANG that wavelength is 600nm, and the luminous intensity of fluorescent material is high, chemical stability is good.
At present, the preparation method of the silicate fluorescent powder reported mostly is high temperature solid-state method, and after high-temperature calcination, in powder body, activator mixing is uneven, causes that the launching efficiency of fluorescent material is low, and in later stage application, the zone concordance of device is poor. Meanwhile, high temperature solid-state method gained fluorescent powder grain size is uneven, also strong influence fluorescent material actually used performance in the devices.
Summary of the invention
For this, the technical problem to be solved is in that to overcome traditional method activator to mix the technical bottleneck that launching efficiency uneven, fluorescent material is low, zone concordance poor and distribution of particles is uneven, thus the granule proposing a kind of fluorescent material is uniform, launching efficiency is high, the LED MAlSiO that zone concordance is good4:Tb3+, Eu2+The preparation method of yellow fluorescent powder.
For solving above-mentioned technical problem, a kind of LED MAlSiO of disclosure of the invention4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, wherein, described method comprises the steps:
1) Al (NO is weighed3)3��9H2O, adds dehydrated alcohol and distilled water, treats Al (NO3)3��9H2O dissolves and forms Al (NO3)3Solution;
2) M is weighed2O, MOH or MNO3In one, SiO2With Si (OC2H5)4In one; And Tb4O7, Eu2O3; Then mix four, obtain mixture; M element can be at least one in Li, Na, K, Ag;
3) by step 2) mixture be stirred, make each reactant be sufficiently mixed;
4) by step 3) material of gained carries out solvent thermal reaction, obtains solvent thermal product;
5) by step 4) the described solvent thermal product of gained is dried process, obtains reactant to be restored;
6) by step 5) reactant to be restored of gained carries out reduction treatment, and then grind, obtain MAlSiO4:Tb3+, Eu2+Yellow fluorescent powder.
Preferably, described preparation method, wherein, step 1) described in the volume ratio of dehydrated alcohol and distilled water be 0.1��0.6: 1.
Preferably, described preparation method, wherein, step 1) described in Al (NO3)3The concentration of solution is 0.20��1.0mol/L.
Preferably, described preparation method, wherein, step 1) Al (NO of gained3)3A1 element in solution and step 2) described mixture in the mol ratio of each metallic element be Al: M: Si: Tb: Eu=1: 1: 1: 0.01��0.1: 0.002��0.1.
Preferably, described preparation method, wherein, step 1) and 2) in each material of weighing all need to be placed in high-pressure bottle, wherein said Al (NO3)3��9H2It is 10%��80% that O granule accounts for the ratio of described high-pressure bottle volume.
Preferably, the preparation method described in any one, wherein, step 3) described in stirring agitator used be magnetic stirring apparatus, magnetic rotor rotating speed is 240rpm, and temperature is 50 DEG C, and heat time heating time is 30min.
Preferably, the preparation method described in any one, wherein, step 4) in solvent thermal reaction particularly as follows: the programming rate first carrying out hyperthermic treatment is 5 DEG C/min, be warming up to 100��200 DEG C, the time is 1��6h; Carrying out slow cooling process again, cooling rate is 0.1��0.3 DEG C/min, is cooled to 60 DEG C.
Preferably, the preparation method described in any one, wherein, step 5) described in the temperature of dried be 60 DEG C.
It is more highly preferred to, the preparation method described in any one, wherein, described step 6) in, reduction treatment is particularly as follows: by step 5) the described solvent thermal presoma that obtains is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas, H2Concentration is 5%, and gaseous mixture rate of flow of fluid is 25��300mL/min, is warming up to 750��1000 DEG C of calcining 10��24h with the programming rate of 5 DEG C/min, takes out after furnace cooling.
The technique scheme of the present invention has the advantage that compared to existing technology
(1) present invention adopts solvent-thermal method to prepare MAlSiO4:Tb3+, Eu2+Yellow fluorescent powder, under later stage low temperature calcination, (700��1000 DEG C) can obtain MAlSiO4:Tb3+, Eu2+Yellow fluorescent powder. Compared with traditional high temperature solid-state method, needed for solvent-thermal method, calcining heat is low the later stage, and technique is simple, and energy consumption is relatively low, is suitable for industrialized production.
(2) present invention adopts solvent-thermal method to prepare MAlSiO4:Tb3+, Eu2+Yellow fluorescent powder, the Tb compared with conventional solid-state method, in solvent-thermal method gained fluorescent material3+It is uniformly dispersed, easily enters MAlSiO4In realize energy transmission, gained, the emission peak half-wave width of Huang-blue light fluorescent powder is narrower, and excitation is higher.
(3) present invention adopts solvent-thermal method to prepare MAlSiO4:Tb3+, Eu2+Yellow fluorescent powder, compared with conventional solid-state method, the grain diameter size distribution of gained fluorescent material is uniform, is conducive to the Homogeneous phase mixing with glue in the application of fluorescent material later stage.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to specific embodiments of the invention and in conjunction with accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the Na of embodiment 1 preparation0.9Ag0.1AlSiO4:0.1Tb3+, 0.1Eu2+The emission spectrum of yellow fluorescent powder;
Fig. 2 is the KAlSiO of embodiment 2 preparation4:0.02Tb3+, 0.005Eu2+The XRD figure spectrum of yellow fluorescent powder.
Detailed description of the invention
Embodiment 1 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 12.004g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 40% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.6: 1, adds the C of 12mL in high-pressure bottle2H5The H of O and 20mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 1.0mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
(2) according to the mol ratio of Na: Ag: Al: Si=0.9: 0.1: 1: 1, the AgNO of NaOH, 0.544g of 1.152g is weighed3SiO with 1.923g2. According to Tb3+Molar concentration be that 10mol% (refers to Tb3+Account for matrix material Na0.9Ag0.1AlSiO4Molar concentration), Eu2+��Tb3+=1: 1, weigh the Tb of 0.598g4O7Eu with 0.562g2O3Powder body. By NaOH, AgNO3��SiO2��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 240rpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 100 DEG C, be incubated 4h. Again with the slow cooling speed of 0.2 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 200mL/min, is warming up to 900 DEG C of calcining 24h with the programming rate of 5 DEG C/min, takes out, be ground, obtain Na after furnace cooling0.9Ag0.1AlSiO4:0.1Tb3+, 0.1Eu2+Yellow fluorescent powder. Gained fluorescent material is carried out dependence test, as shown in Figure 1, it has been found that Na0.9Ag0.1AlSiO4:0.1Tb3+, 0.1Eu2+Phosphor emission wavelength be 453nm blue-light excited under, the peak wavelength at peak is 556nm, and chromaticity coordinates is (x=0.3473, y=0.6207).
Embodiment 2 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 4.502g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 30% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.25: 1, adds the C of 4.8mL in high-pressure bottle2H5The H of O and 19.2mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 0.5mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
According to the mol ratio of K: Al: Si=1: 1: 1, weigh the KHCO of 1.201g3SiO with 0.721g2. According to Tb3+Molar concentration be that 2mol% (refers to Tb3+Account for matrix material KAlSiO4Molar concentration), Eu2+��Tb3+=1: 4, weigh the Tb of 0.045g4O7Eu with 0.011g2O3Powder body. By KHCO3��SiO2��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 240rpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 190 DEG C, be incubated 3h. Again with the slow cooling speed of 0.25 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 240mL/min, is warming up to 800 DEG C of calcining 18h with the programming rate of 5 DEG C/min, takes out, be ground, obtain KAlSiO after furnace cooling4:0.02Tb3+, 0.005Eu2+Yellow fluorescent powder. Gained fluorescent material is carried out dependence test, as shown in Figure 2, it has been found that KAlSiO4:0.02Tb3+, 0.005Eu2+The peak wavelength at phosphor emission peak is 561nm, and chromaticity coordinates is (x=0.3454, y=0.6317).
Embodiment 3 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 6.302g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 60% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.2: 1, adds the C of 8mL in high-pressure bottle2H5The H of O and 40mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 0.35mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
(2) according to the mol ratio of Li: Na: Al: Si=0.5: 0.5: 1: 1, the LiOH H of 0.352g is weighed2Si (the OC of NaOH and the 3.450g of O, 0.336g2H5)4. According to Tb3+Molar concentration be that 5mol% (refers to Tb3+Account for matrix material Li0.5Na0.5AlSiO4Molar concentration), Eu2+��Tb3+=1: 2.5, weigh the Tb of 0.157g4O7Eu with 0.059g2O3Powder body. By LiOH H2O��NaOH��Si(OC2H5)4)��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 240rpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 180 DEG C, be incubated 1h. Again with the slow cooling speed of 0.15 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 160mL/min, is warming up to 950 DEG C of calcining 10h with the programming rate of 5 DEG C/min, takes out, be ground, obtain Li after furnace cooling0.5Na0.5AlSiO4:0.05Tb3+, 0.02Eu2+Yellow fluorescent powder.Gained fluorescent material is carried out dependence test, it has been found that Li0.5Na0.5AlSiO4:0.05Tb3+, 0.02Eu2+The peak wavelength at phosphor emission peak is 552nm, and chromaticity coordinates is (x=0.3420, y=0.6208).
Embodiment 4 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 2.251g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 10% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.45: 1, adds the C of 2.5mL in high-pressure bottle2H5The H of O and 5.5mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 0.75mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
(2) according to the mol ratio of Ag: Al: Si=1: 1: 1, the AgNO of 1.019g is weighed3SiO with 0.361g2. According to Tb3+Molar concentration be that 7mol% (refers to Tb3+Account for matrix material AgAlSiO4Molar concentration), Eu2+��Tb3+=1: 5, weigh the Tb of 0.079g4O7Eu with 0.015g2O3Powder body. AgNO3��SiO2��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 24Orpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 160 DEG C, be incubated 6h. Again with the slow cooling speed of 0.10 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 300mL/min, is warming up to 750 DEG C of calcining 20h with the programming rate of 5 DEG C/min, takes out, be ground, obtain AgAlSiO after furnace cooling4:0.07Tb3+, 0.014Eu2+Yellow fluorescent powder. Gained fluorescent material is carried out dependence test, it has been found that AgAlSiO4:0.07Tb3+, 0.014Eu2+The peak wavelength at phosphor emission peak is 555nm, and chromaticity coordinates is (x=0.3490, y=0.6102).
Embodiment 5 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 6.002g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 80% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.1: 1, adds the C of 5.8mL in high-pressure bottle2H5The H of O and 58.2mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 0.25mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
(2) according to the mol ratio of Na: K: Al: Si=0.25: 0.75: 1: 1, the KHCO of NaOH, 1.022g of 0.162g is weighed3SiO with 0.961g2. According to Tb3+Molar concentration be that 1mol% (refers to Tb3+Account for matrix material Na0.25K0.75AlSiO4Molar concentration), Eu2+��Tb3+=1: 2, weigh the Tb of 0.030g4O7Eu with 0.014g2O3Powder body.By NaOH, KHCO3��SiO2��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 240rpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 130 DEG C, be incubated 5h. Again with the slow cooling speed of 0.12 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 25mL/min, is warming up to 1000 DEG C of calcining 16h with the programming rate of 5 DEG C/min, takes out, be ground, obtain Na after furnace cooling0.25K0.75AlSiO4:0.01Tb3+, 0.005Eu2+Yellow fluorescent powder. Gained fluorescent material is carried out dependence test, it has been found that Na0.25K0.75AlSiO4:0.01Tb3+, 0.005Eu2+The peak wavelength at phosphor emission peak is 553nm, and chromaticity coordinates is (x=0.3455, y=0.6242).
Embodiment 6 present embodiment discloses a kind of LED MAlSiO4:Tb3+, Eu2+The preparation method of yellow fluorescent powder, specifically comprises the following steps that
(1) Al (NO of 3.001g is weighed3)3��9H2O granule is placed in high-pressure bottle (high-pressure bottle volume is 80mL, and material is polytetrafluoroethyllining lining, stainless steel casing, and pressure limit is 0��10Mpa), is 50% (referring to that solvent volume accounts for the ratio of high-pressure bottle volume) in packing ratio, C2H5O (dehydrated alcohol): H2The volume ratio of O (distilled water)=0.29: 1, adds the C of 9mL in high-pressure bottle2H5The H of O and 31mL2O, treats Al (NO3)3��9H2After O granule fully dissolves, high-pressure bottle forms the Al (NO that concentration is 0.2mol/L3)3Solution (refers to Al3+Account for C2H5O and H2The concentration of O mixed liquor cumulative volume);
(2) according to the mol ratio of Li: Al: Si=1: 1: 1, the LiOH H of 0.336g is weighed2Si (the OC of O and 1.667g2H5)4. According to Tb3+Molar concentration be that 4mol% (refers to Tb3+Account for matrix material LiAlSiO4Molar concentration), Eu2+��Tb3+=1: 3, weigh the Tb of 0.060g4O7Eu with 0.019g2O3Powder body. By LiOH H2O��Si(OC2H5)4)��Tb4O7And Eu2O3Powder body adds step 1 jointly) high-pressure bottle in.
(3) by step 2) high-pressure bottle be placed on magnetic stirring apparatus, control magnetic rotor rotating speed be 240rpm, temperature is at 50 DEG C, stirs and heats 30min, makes each reactant be sufficiently mixed.
(4) by step 3) in high-pressure bottle be placed in baking oven, with the programming rate of 5 DEG C/min, be warming up to 200 DEG C, be incubated 2h. Again with the slow cooling speed of 0.3 DEG C/min, it is cooled to 60 DEG C, takes out after then cooling to room temperature with the furnace.
(5) by step 4) gained solvent thermal product at 60 DEG C, air atmosphere is dried, is subsequently placed in mortar and grinds uniformly, namely obtain solvent thermal presoma.
(6) by step 5) gained solvent thermal presoma is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas (controls H2Concentration is 5%), gaseous mixture rate of flow of fluid is 120mL/min, is warming up to 850 DEG C of calcining 12h with the programming rate of 5 DEG C/min, takes out, be ground, obtain LiAlSiO after furnace cooling4:0.04Tb3+, 0.013Eu2+Yellow fluorescent powder. Gained fluorescent material is carried out dependence test, it has been found that LiAlSiO4:0.04Tb3+, the peak wavelength at 0.013Eu2+ phosphor emission peak is 556nm, and chromaticity coordinates is (x=0.3430, y=0.6259).
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the restriction to embodiment. For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description. Here without also cannot all of embodiment be given exhaustive. And the apparent change thus extended out or variation are still among the protection domain of the invention.
Claims (9)
1. a LED MAlSiO4: Tb3+, Eu2+The preparation method of yellow fluorescent powder, it is characterised in that described method comprises the steps:
1) Al (NO is weighed3)3��9H2O, adds dehydrated alcohol and distilled water, treats Al (NO3)3��9H2O dissolves and forms Al (NO3)3Solution;
2) M is weighed2O, MOH or MNO3In one, SiO2With Si (OC2H5)4In one; And Tb4O7, Eu2O3; Then mix four, obtain mixture; M element can be at least one in Li, Na, K, Ag;
3) by step 2) mixture be stirred, make each reactant be sufficiently mixed;
4) by step 3) material of gained carries out solvent thermal reaction, obtains solvent thermal product;
5) by step 4) the described solvent thermal product of gained is dried process, obtains reactant to be restored;
6) by step 5) reactant to be restored of gained carries out reduction treatment, and then grind, obtain MAlSiO4: Tb3+, Eu2+Yellow fluorescent powder.
2. preparation method as claimed in claim 1, it is characterised in that step 1) described in the volume ratio of dehydrated alcohol and distilled water be 0.1��0.6: 1.
3. preparation method as claimed in claim 2, it is characterised in that step 1) described in Al (NO3)3The concentration of solution is 0.20��1.0mol/L.
4. preparation method as claimed in claim 3, it is characterised in that step 1) Al (NO of gained3)3Al element in solution and step 2) described mixture in the mol ratio of each metallic element be Al: M: Si: Tb: Eu=1: 1: 1: 0.01��0.1: 0.002��0.1.
5. preparation method as claimed in claim 4, it is characterised in that step 1) and 2) in each material of weighing all need to be placed in high-pressure bottle, wherein said Al (NO3)3��9H2It is 10%��80% that O granule accounts for the ratio of described high-pressure bottle volume.
6. the preparation method as described in any one of claim 1-5, it is characterised in that step 3) described in the used agitator of stirring be magnetic stirring apparatus, magnetic rotor rotating speed is 240rpm, and temperature is 50 DEG C, and heat time heating time is 30min.
7. the preparation method as described in any one of claim 1-5, it is characterised in that step 4) in solvent thermal reaction particularly as follows: the programming rate first carrying out hyperthermic treatment is 5 DEG C/min, be warming up to 100��200 DEG C, the time is 1��6h; Carrying out slow cooling process again, cooling rate is 0.1��0.3 DEG C/min, is cooled to 60 DEG C.
8. the preparation method as described in any one of claim 1-5, it is characterised in that step 5) described in the temperature of dried be 60 DEG C.
9. the preparation method as described in any one of claim 1-5, it is characterised in that described step 6) in, reduction treatment is particularly as follows: by step 5) the described solvent thermal presoma that obtains is placed in high-temperature tubular atmosphere furnace, passes into H2��N2Mixing gas, H2Concentration is 5%, and gaseous mixture rate of flow of fluid is 25��300mL/min, is warming up to 750��1000 DEG C of calcining 10��24h with the programming rate of 5 DEG C/min, takes out after furnace cooling.
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