CN104610968B - LED fluorescent powder and preparation method thereof - Google Patents
LED fluorescent powder and preparation method thereof Download PDFInfo
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- CN104610968B CN104610968B CN201510083382.3A CN201510083382A CN104610968B CN 104610968 B CN104610968 B CN 104610968B CN 201510083382 A CN201510083382 A CN 201510083382A CN 104610968 B CN104610968 B CN 104610968B
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Abstract
The invention belongs to the field of luminescent materials, and particularly relates to LED fluorescent powder and a preparation method thereof. Molybdate fluorescent powder is prepared through Al＜3+＞ doping modification; a general formula of the molybdate fluorescent powder is Ca0.95-xAlxTb0.02Eu0.03MoO4; x is 0.02-0.1; and the method comprises the following technological processes: preparing a solution; carrying out precipitation reaction; cleaning and drying precipitation products; sintering the dried products; and grinding into samples. Raw materials simultaneously precipitate by adjusting the pH value during precipitation reaction, so that the prepared fluorescent powder is uniform in component distribution and high in light emitting efficiency.
Description
Technical field
The invention belongs to field of light emitting materials, be specifically related to a kind of LED fluorescent powder and preparation method thereof.
Background technology
White light LEDs is as a kind of novel solid state light emitter, compared with the light sources such as traditional electric filament lamp and fluorescent lamp, there is the advantages such as environmental protection, energy-conservation, efficient, response is fast, be described as the forth generation green light source after electric filament lamp, fluorescent lamp and the big light source of high-voltage gas discharging light three.Since Japanese Ya chemical company in 1996 releases InGaN/YAG:Ce white light LEDs, research and the exploration of new system material to fluorescent material for white light LED, rapidly become the focus of luminescent material research field.Fluorescent material is as an important component part of white light LEDs, and to realizing high efficiency, low energy consumption white light LEDs plays an important role.Molybdate material has that crystal structure is stable, phonon energy is low and the advantage such as preparation temperature is low, and can effectively absorb purple light and blue light, transfer energy to the rare earth activation ion being entrained in molybdate substrate, be a kind of white light LED fluorescent powder host material with bigger application prospect.It is the highest that the application of molybdate system fluorescent material at present is largely determined by its luminous efficiency, and therefore, research improves the method tool of molybdate system light-emitting phosphor efficiency and is of great significance.High-temperature solid phase reaction method, hydro-thermal method and chemical coprecipitation is mainly used to prepare silicate system fluorescent material both at home and abroad at present.But, these preparation methoies have limitation in one aspect.High-temperature solid phase reaction method sintering temperature is higher, and energy consumption is high, and local organization is uneven, easily contain impurity, and the particle size distribution that solid reaction process obtains uniformity wider, product is difficult to control to；The luminous intensity of hydro-thermal method products therefrom is more weak, is unsuitable for application.Chemical precipitation method has the advantages such as sintering temperature is low, with low cost, purity is high, chemical uniformity is good compared with high temperature solid-state method, but this method is difficult to control to suitable pH value makes each component in multicomponent system precipitate within the identical time completely, and granule is easily reunited.Therefore, explore improve luminous efficiency, energy-conservation, easy, low cost, free of contamination molybdate system phosphor technologies of preparing become research emphasis.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of LED fluorescent powder and preparation method thereof.The present invention is by introducing Al in molybdate fluorescent material system3+, it is possible not only to modulate the localised crystal field around rare earth activation ion, improves the luminous efficiency of fluorescent material, and sintering temperature can be reduced, control the size of granule, make the distributed components of granule.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of LED fluorescent powder: described LED fluorescent powder is through Al3+The modified molybdenum hydrochlorate fluorescent material that doping vario-property prepares, its formula is Ca0.95-xAlxTb0.02Eu0.03MoO4, wherein x=0.02～0.1；More excellent, x=0.06.
A kind of method preparing LED fluorescent powder as above, comprises the following steps:
(1) get the raw materials ready: respectively by CaCl2、Na2MoO4·2H2O and AlCl3·6H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
(2) precipitation: stoichiometrically formula ratio measures CaCl2、AlCl3、EuCl3And TbCl3Solution, is mixed into solution A, and the pH value using NaOH solution regulation solution A is 1～3, stirs；Then by Na2MoO4Adding in solution A, continue stirring 60～90min, mixing speed is 400～600 rpm, it is thus achieved that precipitate；By changing Al3+The luminous efficiency of the doping of ion (2%～10%, mol ratio) regulation fluorescent material, and make different components precipitate by regulation pH value simultaneously, it is thus achieved that the predecessor that component is homogeneous；
(3) precipitated product cleaning and be dried: the precipitate deionized water eccentric cleaning that step (2) is obtained 3 ~ 5 times, put in drying baker be dried；
(4) sintering of desciccate: the product that step (3) is dried is put into box high temperature sintering furnace roasting；
(5) sample grinds: by the sample grind into powder after step (4) roasting, prepares LED fluorescent powder.
Centrifugal speed described in step (3) is 6000～8000 rpm, and centrifugal rear baking temperature is 80 ~ 90 DEG C, and drying time is 10-12h.
Sintering temperature described in step (4) is 700～900 DEG C, and the time is 2-4h, and sintering atmosphere is air.
LED fluorescent powder grain diameter obtained by step (5) is 1～2.5 μm, and quantum yield is 45%～85%.
The beneficial effects of the present invention is:
(1) abundant raw material used by the present invention, environmental protection, cheap, reduce the production cost of fluorescent material；The technique and the equipment that are used are simple, it is easy to implementing, easy and simple to handle, preparation process does not has harmful gas to produce；And by regulation pH value in the preparation process of fluorescent material, thus raw material can precipitate simultaneously, it is thus achieved that the presoma that component is homogeneous；
(2) by introducing Al in molybdate fluorescent material system3+, to modulate the localised crystal field around rare earth activation ion, improve the luminous efficiency of fluorescent material, even particle size distribution, size is controlled；And change Al by (2%～10%) within the specific limits3+The doping of ion, can effectively regulate the luminous efficiency of fluorescent material, prepare the fluorescent material that luminous efficiency is different according to actual needs.
Accompanying drawing explanation
Fig. 1 is emission spectrum and the sample luminous photo of the fluorescent material of embodiment 1 preparation；
Fig. 2 is the stereoscan photograph of the fluorescent material of embodiment 1 preparation.
Detailed description of the invention
Present invention the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
Embodiment
1
Fluorescent material formula is: Ca0.89Al0.06Tb0.02Eu0.03MoO4, its preparation process comprises the following steps:
1) the most respectively by CaCl2、Na2MoO4·2H2O and AlCl3·6H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
2) example 89:6:3:2 measures CaCl the most in molar ratio2、AlCl3、EuCl3And TbCl3Being mixed into solution A, the pH value using NaOH solution regulation solution A is 2, uses magnetic stirrer；By Na2MoO4Add and solution A is formed precipitation, continue magnetic agitation 60min；By the precipitate deionized water eccentric cleaning that obtains 3 times, centrifugal speed is 7000
Rpm, puts into 80 DEG C of dry 12h in drying baker；
3) finally dry sample is put into 900 DEG C of sintering 2h in box high temperature sintering furnace, is ground after cooling obtaining fluorescent material.
Al3+Doping be 6%, obtained fluorescent powder grain mean diameter is 1.5 μm, and quantum yield is 85%.
Embodiment
2
Fluorescent material formula is: Ca0.85Al0.1Tb0.02Eu0.03MoO4, its preparation process comprises the following steps:
1) the most respectively by CaCl2、Na2MoO4·2H2O and AlCl3·6H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
2) example 85:10:3:2 measures CaCl the most in molar ratio2、AlCl3、EuCl3And TbCl3Being mixed into solution A, the pH value using NaOH solution regulation solution A is 3, uses magnetic stirrer；By Na2MoO4Add and solution A is formed precipitation, continue magnetic agitation 90min；By the precipitate deionized water eccentric cleaning that obtains 5 times, centrifugal speed is 6000
Rpm, puts into 90 DEG C of dry 10h in drying baker；
3) finally dry sample is put into 700 DEG C of sintering 4h in box high temperature sintering furnace, is ground after cooling obtaining fluorescent material.
Al3+Doping be 10%, obtained mean particle size is 1.5 μm, and quantum yield is 53%.
Embodiment 3
Fluorescent material formula is: Ca0.93Al0.02Tb0.02Eu0.03MoO4, its preparation process comprises the following steps:
1) the most respectively by CaCl2、Na2MoO4·2H2O and AlCl3·6H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
2) example 93:2:3:2 measures CaCl the most in molar ratio2、AlCl3、EuCl3And TbCl3Being mixed into solution A, the pH value using NaOH solution regulation solution A is 3, uses magnetic stirrer；By Na2MoO4Add and solution A is formed precipitation, continue magnetic agitation 90min；By the precipitate deionized water eccentric cleaning that obtains 5 times, centrifugal speed is 6000
Rpm, puts into 90 DEG C of dry 10h in drying baker；
3) finally dry sample is put into 700 DEG C of sintering 4h in box high temperature sintering furnace, is ground after cooling obtaining fluorescent material.
Al3+Doping be 2%, obtained mean particle size is 1.5 μm, and quantum yield is 45%.
Comparative example
1
Fluorescent material formula is: Ca0.95Tb0.02Eu0.03MoO4, its preparation process comprises the following steps:
1) first by CaCl2、Na2MoO4·2H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
2) example 95:3:2 measures CaCl the most in molar ratio2、EuCl3And TbCl3Being mixed into solution A, the pH value using NaOH solution regulation solution A is 1, uses magnetic stirrer；By Na2MoO4Add and solution A is formed precipitation, continue magnetic agitation 75min；By the precipitate deionized water eccentric cleaning that obtains 4 times, centrifugal speed is 8000
Rpm, puts into 85 DEG C of dry 11h in drying baker, for the sample of undoped p Al；
3) finally dry sample is put into 800 DEG C of sintering 3h in box high temperature sintering furnace, is ground after cooling obtaining fluorescent material；
Al3+Doping be 0%, obtained mean particle size is 1.5 μm, and quantum yield is 30%.
From the Comparative result of the result of embodiment 1-3 Yu comparative example 1, work as Al3+Doping when being 2% ~ 10%, the quantum yield of obtained fluorescent material is 45% ~ 85%, with comparative example 1 do not mix Al sample compared with (quantum yield is 30%), quantum yield is significantly improved, and illustrates that Al doping is the effective means improving light-emitting phosphor performance；More preferably, Al is worked as3+Doping when being 6%, quantum yield is 85%, and obtained light-emitting phosphor efficiency is best.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (6)
1. a LED fluorescent powder, it is characterised in that: described LED fluorescent powder is through Al3+The molybdate fluorescent material that doping vario-property prepares, its formula is Ca0.95-xAlxTb0.02Eu0.03MoO4, wherein x=0.02～0.1.
LED fluorescent powder the most according to claim 1, it is characterised in that: x=0.06 in described LED fluorescent powder.
3. the method preparing LED fluorescent powder as claimed in claim 1, it is characterised in that: comprise the following steps:
(1) get the raw materials ready: respectively by CaCl2、Na2MoO4·2H2O and AlCl3·6H2O makes the aqueous solution of 1mol/L, by Eu2O3And Tb3O4It is dissolved in concentrated hydrochloric acid respectively and is configured to the EuCl of 0.1mol/L3And TbCl3Solution；
(2) precipitation: stoichiometrically formula ratio measures CaCl2、AlCl3、EuCl3And TbCl3Solution, is mixed into solution A, and the pH value using NaOH solution regulation solution A is 1～3, stirs；Then by Na2MoO4Adding in solution A, continue stirring 60～90min, mixing speed is 400～600 rpm, prepares precipitate；
(3) cleaning of precipitated product and being dried: the precipitate deionized water eccentric cleaning 3 ~ 5 times step (2) prepared, puts in drying baker and is dried；
(4) sintering of desciccate: the product that step (3) is dried is put into box high temperature sintering furnace roasting；
(5) sample grinds: by the sample grind into powder after step (4) roasting, prepares LED fluorescent powder.
The preparation method of LED fluorescent powder the most according to claim 3, it is characterised in that: the centrifugal speed described in step (3) is 6000～8000 rpm, and centrifugal rear baking temperature is 80 ~ 90 DEG C, and drying time is 10-12h.
The preparation method of LED fluorescent powder the most according to claim 3, it is characterised in that: the sintering temperature described in step (4) is 700～900 DEG C, and the time is 2-4 h, and sintering atmosphere is air.
The preparation method of LED fluorescent powder the most according to claim 3, it is characterised in that: the LED fluorescent powder grain diameter obtained by step (5) is 1～2.5 μm, and quantum yield is 45%～85%.
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| CN101270282B (en) * | 2008-05-15 | 2012-04-25 | 沈阳化工学院 | Rare earth red fluorescent powder for light emitting diode and preparation method thereof |
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