CN105602556A - Na/Mn co-doped Sr4Al14O25 red fluorescent powder as well as preparation method and application of Na/Mn co-doped Sr4Al14O25 red fluorescent powder - Google Patents
Na/Mn co-doped Sr4Al14O25 red fluorescent powder as well as preparation method and application of Na/Mn co-doped Sr4Al14O25 red fluorescent powder Download PDFInfo
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- CN105602556A CN105602556A CN201511024435.0A CN201511024435A CN105602556A CN 105602556 A CN105602556 A CN 105602556A CN 201511024435 A CN201511024435 A CN 201511024435A CN 105602556 A CN105602556 A CN 105602556A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/641—Chalcogenides
- C09K11/643—Chalcogenides with alkaline earth metals
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
Abstract
The invention provides Na/Mn co-doped Sr4Al14O25 red fluorescent powder as well as a preparation method and application of the Na/Mn co-doped Sr4Al14O25 red fluorescent powder. The molecular formula of the Na/Mn co-doped Sr4Al14O25 red fluorescent powder is Sr4Al14O25:0.014Mn,xNa,yB, wherein x is a number from 0 to 3.5, but not including zero; y is a number from 0.4 to 0.8. The preparation method of the Na/Mn co-doped Sr4Al14O25 red fluorescent powder comprises the following step of calcining a mixture of strontium carbonate, a compound containing aluminum, manganese carbonate, boric acid and sodium carbonate in the air or an oxygen atmosphere to obtain the red fluorescent powder, wherein the compound containing aluminum is aluminum hydroxide and/or aluminum oxide. The Na/Mn co-doped Sr4Al14O25 red fluorescent powder is more suitable for the mainstream UV-LEDs and LEDs in the market; the half peak width of a peak of the Na/Mn co-doped Sr4Al14O25 red fluorescent powder at 668nm is 38nm, and the strength is similar with peak intensity of commercialized fluorescent powder Sr2Si5N8; a preparation process of the Na/Mn co-doped Sr4Al14O25 red fluorescent powder is simple and the raw materials are cheap; rare earth elements are not used; in a whole flow, no toxic substances are used, and strong-corrosion substances such as acid, alkali and the like are not used.
Description
Technical field
The present invention relates to the Sr that a kind of Na/Mn mixes altogether4Al14O25Red fluorescence powder and preparation method thereof and application, belong toInorganic non-metallic field of light emitting materials.
Background technology
Red fluorescence powder mostly in the market is rare earth doped Nitride phosphor and the fluorine of doped with manganese (Mn) ionCompound fluorescent material, the former doping with rare-earth ions, and the cost compare of rare earth is high, and rare earth price is year after year and goes up andGesture, and the preparation cost of Nitride phosphor is also higher, and condition is harsh, needs high temperature (1600 degree), and nitrogen is highThe condition preparations such as pressure; Latter need to be prepared fluoride fluorescent material by the chemical substance of this high-risk of hydrofluoric acid,And fluoride fluorescent material has the problem of deliquescence, this has all promoted requirement to the environment for use of fluorescent material, has increased simultaneouslyCost, and the glow peak of fluoride fluorescent material too narrow (half-peak breadth 8nm) to be used in meaning in LED illumination limited.Doped with manganese ion (Mn4+) the trial of strontium aluminate (Sr4Al14O25:Mn) red fluorescence powder be just to occur for 2013, the peak position of its stimulated luminescence is 330nm and 450nm two places, radiative peak position is at 653nm and 668nm.But due to its 450nm place excite the excite peak position of peak position far below 330nm, be more suitable for the excitation wave with uviol lampSection, such as being used on UV-LED (ultraviolet LED) or on fluorescent tube, but the preparation cost of UV-LEDHigher, not also the main flow in market, fluorescent lamp is replaced by LED lamp gradually, can be by 450nm so developThe LED fluorescent material that excites of main flow blue chip just become and extremely there is market using value.
Summary of the invention
The object of this invention is to provide the Sr that a kind of Na/Mn mixes altogether4Al14O25Red fluorescence powder and preparation method thereof with shouldWith.
The Sr that Na/Mn provided by the invention mixes altogether4Al14O25Red fluorescence powder, its molecular formula is:Sr4Al14O25: 0.014Mn, xNa, yB, wherein x is the number between 0～3.5, and do not comprise zero, y be 0.4 to 0.8 itBetween number.
In the present invention, molecular formula Sr4Al14O25: 0.014Mn, xNa,, in yB, x specifically can be 0.5,1.0,1.5,2.0,2.5,3.0,3.5 or 0.5～3.5, y specifically can be 0.8; Preferably, x is that 1.5, y is 0.8.
In the present invention, the Sr that described Na/Mn mixes altogether4Al14O25The fluorescence of red fluorescence powder visible yellow color under natural daylightPowder, under blue light or ultraviolet light, red color visible is luminous.
The present invention also provides the preparation method of above-mentioned red fluorescence powder, comprises the steps: by strontium carbonate, containing aluminiumThe mixture of compound, manganese carbonate, boric acid and sodium carbonate in air or oxygen atmosphere, calcine, obtain described rednessFluorescent material;
Wherein, the described compound containing aluminium is aluminium hydroxide and/or aluminium oxide.
In above-mentioned method, the temperature of described calcining can be 1200～1450 DEG C, specifically can be 1400 DEG C;
The time of described calcining can be 2～6h, specifically can be 6h.
In above-mentioned method, described strontium carbonate, described compound containing aluminium, described manganese carbonate, described boric acid, described inThe mixture of sodium carbonate adopts sphere of powder mill to mix or mortar ground and mixed.
In above-mentioned method, strontium element, described containing aluminium element, described manganese carbonate in the compound of aluminium in described strontium carbonateIn middle manganese element, described boric acid, in boron element, described sodium carbonate, the molal weight of sodium element ratio is 4:14:0.014:x:y。
In above-mentioned method, described calcining is carried out in tube furnace or batch-type furnace.
The present invention further provides the application of described red fluorescence powder in preparation LED lamp.
In above-mentioned application, described LED lamp adopts the blue light of 450nm or the ultraviolet excitation of 360～390nm.
The present invention has the following advantages:
(1) Sr of doped with Mn ion in prior art4Al14O25Red fluorescence powder 450nm rate of induced polarization a little less than, thisInvention, by the ion co-doped Na ion of Mn, has realized the strength enhancing of 450nm excitation peak, and 330nm placeExcitation peak also red shift arrived 360nm and make it also be more suitable for UV-LED and the LED for main flow on market.
(2) this fluorescent material in the half-peak breadth at the peak at 668nm place at 38nm, intensity and business-like fluorescent materialSr2Si5N8Peak close by force, there is the value of practical application.
(3) this fluorescent material preparation technology is simple, and in air, 1200 degree all can be prepared to 1450 degree, and raw material is cheap, noUse rare earth element, in whole flow process, there is no noxious material, do not use the strong corrosive materials such as soda acid.
(4) this fluorescent material chemically stable, does not have the problem of hydrolysis, is placed on nondiscolouring in water, has overcome prior artMiddle fluoride is mixed Mn and is easily hydrolyzed the problem of blackening; Under weak acid and weak base environment, can not be corroded, as at ice vinegarAcid was processed with potash can variable color.
Brief description of the drawings
Fig. 1 is red fluorescence powder and the Sr of the Na of different dopings in the embodiment of the present invention 12Si5N8Utilizing emitted light spectrogram.
Fig. 2 is red fluorescence powder and the Sr of the Na of different dopings in the embodiment of the present invention 12Si5N8Exciting light spectrogram;1,2 and 3 peak positions that all refer to 3 contained peaks of each figure in figure.
Fig. 3 is the red fluorescence powder XRD material phase analysis of the Na of different dopings in the embodiment of the present invention 1.
Fig. 4 is that (molecular formula is Sr to red fluorescence powder in the embodiment of the present invention 14Al14O25: 0.014Mn, 1.5Na) encapsulationThe result of test, wherein Fig. 4 (a) is blue chip+Sr4Al14O25: Mn, Na fluorescent material, Fig. 4 (b) is blue lightChip+YAG:Ce+Sr4Al14O25: Mn, Na fluorescent material.
Fig. 5 is the molecular formula Sr of red fluorescence powder in the embodiment of the present invention 14Al14O25: 0.014Mn, 1.5Na, the light of 0.8BSpectrum test result; Wherein Fig. 5 (a) is spectrogram, and Fig. 5 (b) is chromaticity coordinates figure.
Fig. 6 is alternating temperature fluorescence spectrum in the embodiment of the present invention 1 (thermally-stabilised test) figure.
Detailed description of the invention
The experimental technique using in following embodiment if no special instructions, is conventional method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
The Sr that embodiment 1, Na/Mn mix altogether4Al14O25The preparation of red fluorescence powder
According to mole matter of different elements in the molecular formula that will prepare by strontium carbonate (SrCO3), aluminium hydroxide (Al (OH)3)、Manganese carbonate (MnCO3), boric acid (H3BO3) and sodium carbonate (Na2CO3) mix at sphere of powder mill, then in tubular typeStove prepares at 1400 DEG C of calcining 6h the Sr that Na/Mn mixes altogether4Al14O25Red fluorescence powder, its molecular formula is:Sr4Al14O25: 0.014Mn, xNa, yB, wherein x is 0,0.5,1.0,1.5,2.0,2.5,3.0 or 3.5; Y is 0.8.
As shown in Figure 1, be red fluorescence powder and the Sr of the Na of the different dopings of the present invention2Si5N8Utilizing emitted light spectrogram.
As shown in Figure 2, be red fluorescence powder and the Sr of the Na of the different dopings of the present invention2Si5N8Exciting light spectrogram.In Fig. 1, the intensity level that ordinate is normalization, abscissa is the wavelength (nm) of spectrum, from PLEFigure can find out, along with the doping of Na, excitation peak has obtained significant enhancing at 450nm place, proves sample of the present inventionProduct can send red light under the exciting of 450nm. As shown in Figure 2, the Sr that Na/Mn of the present invention mixes altogether4Al14O25RedIn look fluorescent material, excessive Na is unfavorable for that the content of luminous, best Na is x=1.5, and Na/Mn mixes altogetherSr4Al14O25The molecular formula Sr of red fluorescence powder4Al14O25: 0.014Mn, xNa, in yB, preferably x=1.5, y=0.8.
As shown in Figure 3, be XRD material phase analysis of the present invention, nethermost is Sr4Al14O25Standard P DF card(redness), is the XRD collection of illustrative plates of the sample of Na from 0 to 3.5 above, can find out, the principal phase of these samples allSr4Al14O25, still, when the doping content of Na is greater than after 2.0, have a small amount of miscellaneous SrAl2O4Generate mutually.
As shown in Figure 4, be packaging and testing result of the present invention. From Fig. 4 (a), blue chip+Sr4Al14O25:Mn,NaFluorescent material glows; Known blue chip+the YAG:Ce+Sr of Fig. 4 (b)4Al14O25: Mn, Na fluorescent material is sent out warm whiteLight.
In Fig. 5, spectrum test uses XRF F7000, and as shown in Figure 5, effect of the present invention is light intensity and businessFluorescent material intensity is close, and spectrometer tests out the increase along with Na doping, the Changing Pattern of light intensity.
Fig. 6 is alternating temperature fluorescence spectrum of the present invention (thermally-stabilised test), and as shown in Figure 6, Na/Mn of the present invention mixes altogetherSr4Al14O25Red fluorescence powder is in the process of heating, and the light intensity that fluorescent material sends can reduce, with existing fluorescent material toolThere is general character.
Claims (8)
1. the Sr that Na/Mn mixes altogether4Al14O25Red fluorescence powder, its molecular formula is:Sr4Al14O25: 0.014Mn, xNa, yB, wherein x is the number between 0～3.5, and do not comprise zero, y be 0.4 to 0.8 itBetween number.
2. the preparation method of red fluorescence powder claimed in claim 1, comprises the steps: by strontium carbonate, containing aluminiumThe mixture of compound, manganese carbonate, boric acid and sodium carbonate is calcined in air or oxygen atmosphere, obtains described redness glimmeringLight powder;
Wherein, the described compound containing aluminium is aluminium hydroxide and/or aluminium oxide.
3. method according to claim 2, is characterized in that: the temperature of described calcining is 1200～1450 DEG C;
The time of described calcining is 2～6h.
4. according to the method described in any one in claim 1-3, it is characterized in that: described strontium carbonate, described containing aluminiumThe mixture of compound, described manganese carbonate, described boric acid, described sodium carbonate adopt sphere of powder mill to mix or mortar grindsMix.
5. according to the method described in any one in claim 1-4, it is characterized in that: strontium element in described strontium carbonate,Described containing boron element, described sodium carbonate in manganese element, described boric acid in aluminium element, described manganese carbonate in the compound of aluminiumThe molal weight of middle sodium element is than being 4:14:0.014:x:y.
6. according to the method described in any one in claim 1-5, it is characterized in that: described calcining at tube furnace orIn batch-type furnace, carry out.
7. the application of red fluorescence powder claimed in claim 1 in preparation LED lamp.
8. according to the application described in claim 7, it is characterized in that: described LED lamp adopts the blue light of 450nmOr the ultraviolet excitation of 360～390nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190038733A (en) * | 2017-09-29 | 2019-04-09 | 신라대학교 산학협력단 | Barium-yttrium-orthosilicate fluorescent material for white LED |
| CN114045169A (en) * | 2021-11-23 | 2022-02-15 | 光源股份有限公司 | Red fluorescent powder capable of being compounded with LED blue light chip into plant growth lamp and preparation method thereof |
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| CN102286281A (en) * | 2011-09-21 | 2011-12-21 | 合肥工业大学 | Aluminate-based red fluorescent material and preparation method thereof |
| CN102732250A (en) * | 2012-06-27 | 2012-10-17 | 华南理工大学 | Red phosphor and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190038733A (en) * | 2017-09-29 | 2019-04-09 | 신라대학교 산학협력단 | Barium-yttrium-orthosilicate fluorescent material for white LED |
| KR102002695B1 (en) | 2017-09-29 | 2019-10-02 | 신라대학교 산학협력단 | Barium-yttrium-orthosilicate fluorescent material for white LED |
| CN114045169A (en) * | 2021-11-23 | 2022-02-15 | 光源股份有限公司 | Red fluorescent powder capable of being compounded with LED blue light chip into plant growth lamp and preparation method thereof |
| CN114045169B (en) * | 2021-11-23 | 2023-07-25 | 光源股份有限公司 | Red fluorescent powder capable of being compounded with LED blue light chip into plant growth lamp and preparation method thereof |
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