CN101284990B - White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof - Google Patents
White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof Download PDFInfo
- Publication number
- CN101284990B CN101284990B CN2008100385812A CN200810038581A CN101284990B CN 101284990 B CN101284990 B CN 101284990B CN 2008100385812 A CN2008100385812 A CN 2008100385812A CN 200810038581 A CN200810038581 A CN 200810038581A CN 101284990 B CN101284990 B CN 101284990B
- Authority
- CN
- China
- Prior art keywords
- equal
- white light
- less
- alkali metal
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the rare earth luminescent material technical field, and in particular relates to alkaline earth metal phosphosilicate white light-emitting phosphor and a method for making the same. The composition of the phosphor is expressed as BaaSrbCac(PO4)x(SiO4)y:Eud, Mne, wherein a is more than or equal to 3.9 and less than 9; b is more than or equal to 0 and less than or equal to 3; c is more than 0.1 and less than or equal to 1; d is more than 0.01 and less than or equal to 0.1; e is more than 0.01 and less than or equal to 0.1; x is more than 1 and less than or equal to 4; y is more than or equal to 0.1 and less than or equal to 2. Along with the change of composition, the excitation wavelength range of the phosphor is ultraviolet or purple light (lambda exc=300-410 nm). The phosphor emits white light under 365 nm excitation; the color temperature of the white light can be adjusted between 4000 and 10000 K, and the color rendering index Ra is between 78 and 88. The phosphor can be used as a single-matrix luminescent material for white LED excited by ultraviolet purple light chips.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, be specifically related to the coactivated earth alkali metal silicophosphate of a kind of divalent europium and bivalent manganese single-matrix white light emitting phosphor and preparation method thereof.
Background technology
White light LEDs (photodiode) is compared with traditional lighting source, have energy-conservation, efficient, volume is little, the life-span is long, advantages such as response speed is fast, driving voltage is low, anti-vibration receive the extensive concern of countries in the world.Say have two kinds of methods can obtain White LED light source at technical standpoint.A kind of is with three kinds of monochromatic LED combination results of red, green, blue white light; Second kind is to mix with other luminescent materials of LED de excitation to form white light, promptly cooperates the fluorescent material of jaundice light with blue-ray LED, or with three kinds of fluorescent material of near ultraviolet LED de excitation red, green, blue.The method of three kinds of monochromatic LED combination results of red, green, blue white light have the efficient height, can the dynamic conditioning colour temperature, advantage such as color developing is good; But the forward voltage of three kinds of color LED is different with light output; To keep characteristic also inequality for their temperature profile and light in addition, and it must possess optical output signal sample circuit feedback function, dynamically controls; The coordinate of the chroma point of the white light that sends with toilet remains unchanged, thereby having relatively high expectations to circuit layout.See from present development trend,, utilize the optical excitation fluorescent material of LED emission and mix the method that forms white light, all be superior to first method in second method aspect feasibility, practicality and the commercialization with led chip and phosphor combination.Carry out in the scheme of light conversion at two kinds of use fluorescent material; The white light LEDs that near ultraviolet purple light chip excites is because the white light color is fluorescent coating decision, so photochromic stable aspect is better than the combination of blue chip and yellow fluorescent powder in color quality, photochromic consistence and the working process.The white light LEDs that near ultraviolet purple light chip excites can use in mixture of red, green, the Huang dichromatism or red, green, blue three primary colors fluorescent powder to make, and also can use single-matrix white emission fluorescent material.Owing to have color absorption again, energy waste, proportioning regulation and control and rate of ageing different problems between mixture, cause luminous efficiency and colour rendering index etc. to be a greater impact.Therefore developing the single-matrix white emitting phosphor has certain advantage.Patent of the present invention promptly provide a kind of can be by ultraviolet purple light and the single-matrix white that excites emitting phosphor.
Summary of the invention
The object of the present invention is to provide a kind of can be by ultraviolet purple light excited, single-matrix white light emitting phosphor and preparation method thereof.
White light emitting phosphor provided by the invention is a kind of divalent europium and the coactivated earth alkali metal silicophosphate of bivalent manganese single-matrix white light emitting phosphor, and its moity can be by following chemical formulation: Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3,0.1＜c≤1,0.01＜d≤0.1,0.01＜e≤0.1,1＜x≤4,0.1＜y≤2 wherein.
The preparation method of above-mentioned divalent europium provided by the invention and the coactivated earth alkali metal silicophosphate of bivalent manganese single-matrix white light emitting phosphor may further comprise the steps:
(1) batching is pressed chemical formula Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3 wherein; 0.1＜c≤1,0.01＜d≤0.1,0.01＜e≤0.1; 1＜x≤4,0.1＜y≤2 take by weighing barium carbonate, lime carbonate, Strontium carbonate powder, silicon-dioxide, europiumsesquioxide, Secondary ammonium phosphate, the manganous carbonate of requirement; Take by weighing the fusing assistant that accounts for chemical formula 0.5%～5% quality again, with the abundant mixing of these components;
(2) sintering, with the said mixture corundum crucible of packing into, and to place High Temperature Furnaces Heating Apparatus sintering, atmosphere be air, and sintering temperature is 800～1400 ℃, and sintering time is 3～10 hours;
(3) reduction, with sinter pyroprocessing under reducing atmosphere, treatment temp is 1100～1350 ℃, the treatment time is 3～5 hours;
(4) washing, oven dry drops to room temperature in reducing atmosphere, sinter is broken, with 70～85 ℃ of deionized water wash, dries under 120～150 ℃ of temperature, promptly obtains required product.
Among the present invention, described fusing assistant is SrF
2, BaF
2, NH
4HF
2, SrCl
2, BaCl
2, NH
4Cl, H
3BO
3In one or more, its consumption is 0.5%～5%, preferred 2～3% of a fluorescent material chemical formula quality.
Can obtain having chemical formula Ba according to the present invention
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
eFluorescent material; This fluorescent material can (300～410nm) effectively excite, and are replaced and P/Si Eu when the Mn concentration change by Sr with matrix positively charged ion Ba by ultraviolet purple light; Sintering temperature and change of program; Not only excitation spectrum can change, and 365nm excites down colour temperature modulation between 4000～11000K of emission white light, and colour rendering index Ra changes between 78～88.Therefore, can fluorescent material of the present invention be used as the luminescent material of the white light LEDs that the ultraviolet purple light chip excites.
Table 1 part divalent europium of the present invention and the coactivated earth alkali metal silicophosphate of bivalent manganese luminescent properties (365nm excites).
Description of drawings
Fig. 1 is Ba of the present invention
5.9Ca (PO
4)
2(SiO
4)
2: Eu
0.06Mn
0.04The exciting light spectrogram of fluorescent material (465nm monitoring).
Fig. 2 is Ba of the present invention
5.9Ca (PO
4)
2(SiO
4)
2: Eu
0.06Mn
0.04Emmission spectrum figure under fluorescent material 365nm excites.
Embodiment
With the preferred embodiment that present invention will be described in detail with reference to the accompanying.It is obvious that for the person of ordinary skill of the art: under the situation that does not deviate from essence of the present invention and scope, can therefrom carry out various improvement and variation.Thereby improvement of the present invention and the variation within the scope that is in accompanying claims and equivalent thereof contained in the present invention.
Hereinafter will be explained the specific embodiments of essence according to the present invention about europkium-activated earth alkali metal silicophosphate fluorescent material preparation method.
At first, take by weighing high purity reagent barium carbonate (BaCO
3), lime carbonate (CaCO
3), Strontium carbonate powder (SrCO
3), silicon-dioxide (SiO
2), europiumsesquioxide (Eu
2O
3), Secondary ammonium phosphate ((NH
4)
2HPO
4), manganous carbonate (MnCO
3).Wherein, the negatively charged ion total amount is excessive 3～5%, and the concentration of Eu is 0.02～0.10 mole in every mole of fluorescent material, and more excellent is 0.05～0.8, and the concentration of Mn is 0.02～0.10 mole in every mole of fluorescent material, and more excellent is 0.05～0.8.Take by weighing the fusing assistant that accounts for chemical formula 0.5%～5% quality again, more excellent is the fusing assistant of Chemical formula 2～3% quality.They were ground 2～3 hours with a little absolute ethyl alcohol in mortar, make its abundant mixing.
Afterwards, the dry and corundum crucible of packing into, compacting with said mixture, and place High Temperature Furnaces Heating Apparatus; In 800-1400 ℃ of sintering 3-10 hour; Also can adopt temperature programming agglomerating mode, be warmed up to 800-900 ℃, keep 1～5 hour like speed with 8～12 ℃/min; Speed with 8～12 ℃/min is warmed up to 1300～1400 ℃ then, keeps 2～5 hours.The cooling back is taken out and is broken, and the former crucible of packing into is then at H
2/ N
2Reduction (H
2Volume content 5～10%) 1100～1350 ℃ were reduced 3～5 hours in.Cool to room temperature in the reduction atmosphere; With above-mentioned sinter from High Temperature Furnaces Heating Apparatus, take out, broken again; With 80 ℃ of left and right sides deionized water wash three times (3L water/kg powder), 120～150 ℃ of baking oven bakings promptly got required divalent europium in 6～10 hours and activate earth alkali metal silicophosphate fluorescent material.
Embodiment:
In order to guarantee accuracy, earlier agents useful for same was handled 8 hours in 120 ℃ of baking ovens.Take by weighing the reagent and the fusing assistant of aequum and add a little absolute ethyl alcohol by chemical formula, in mortar, ground 3 hours, make its abundant mixing.Drying and pack into corundum crucible and compacting then.Sintering 2 hours and 3 hours respectively in 800 ℃ and the 1350 ℃ of air in sintering oven is then at 1300 ℃ of H
2/ N
2(H in the reducing atmosphere
2Account for 10%) reduced 3-5 hour.After dropping to room temperature in the reducing atmosphere, taking-up from High Temperature Furnaces Heating Apparatus, fragmentation, washing, baking promptly get required product.
Use method for preparing and have chemical formula Ba
5.9Ca (PO
4)
2(SiO
4)
2: Eu
0.06Mn
0.04The excitation spectrum of fluorescent material is shown in figure l.As can be seen from the figure, this powder has very wide and stronger excitation spectrum in 300～410nm scope, explains that this fluorescent material can be used for long wave ultraviolet, purple LED chip to make white LED light source.The emmission spectrum of this fluorescent material under 365nm excites is as shown in Figure 2.As can be seen from the figure, this fluorescent material respectively has an emission band in bluish-green district and orange red district, thereby is combined into white light, and colour temperature is 5435K, colour rendering index Ra=80.1.
That uses method for preparing has a chemical formula Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3,0.1＜c≤1 wherein; 0.01 the europium manganese co-activation earth alkali metal silicophosphate fluorescent material of＜d≤0.1,0.01＜e≤0.1,1＜x≤4,0.1＜y≤2; Along with the matrix cation type (Ba, Sr, Ca) with the variation of concentration, Eu; Mn concentration and ratio change, and 365nm excites the colour temperature of the white light of being sent out between 4000～11000K, to change, and colour rendering index Ra can change between 78～88, and the luminescent properties of part fluorescent material under 365nm excites is summarised in the table 1.
Table 1 part europium manganese co-activation earth alkali metal silicophosphate luminescent properties (365nm excites)
Claims (5)
1. an earth alkali metal silicophosphate white light emitting phosphor is characterized in that moity is by following chemical formulation: Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3,0.1＜c≤1,0.01＜d≤0.1,0.01＜e≤0.1,1＜x≤4,0.1＜y≤2 wherein.
2. earth alkali metal silicophosphate white light emitting phosphor according to claim 1 is characterized in that this fluorescent material can be by ultraviolet purple light excited, and 365nm excites down the white light colour temperature of emission between 4000～10000K, and colour rendering index Ra is between 78～88.
3. the preparation method of earth alkali metal silicophosphate white light emitting phosphor as claimed in claim 1 is characterized in that concrete steps are following:
(1) batching is pressed chemical formula Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3 wherein; 0.1＜c≤1,0.01＜d≤0.1,0.01＜e≤0.1; 1＜x≤4,0,1＜y≤2; Take by weighing barium carbonate, lime carbonate, Strontium carbonate powder, silicon-dioxide, europiumsesquioxide, Secondary ammonium phosphate, the manganous carbonate of requirement, take by weighing the fusing assistant that accounts for chemical formula 0.5%～5% quality again, with the abundant mixing of these components;
(2) sintering, with the said mixture corundum crucible of packing into, and to place High Temperature Furnaces Heating Apparatus sintering, atmosphere be air, and sintering temperature is 800～1400 ℃, and sintering time is 3～10 hours;
(3) reduction, with sinter pyroprocessing under reducing atmosphere, treatment temp is 1100～1350 ℃, the treatment time is 3～5 hours;
(4) washing, oven dry drops to room temperature in reducing atmosphere, sinter is broken, with 70～85 ℃ of deionized water wash, dries under 120～150 ℃ of temperature, promptly obtains required product.
4. preparation method according to claim 3 is characterized in that described fusing assistant is SrF
2, BaF
2, NH
4HF
2, SrCl
2, BaCl
2, NH
4Cl, H
3BO
3In one or more.
5. preparation method according to claim 3 is characterized in that sintering process adopts temperature-programmed mode: be warmed up to 800 ℃-900 ℃ with 8～12 ℃/min temperature rise rate, kept 1～5 hour; Be warmed up to 1300 ℃～1400 ℃ with 8～12 ℃/min temperature rise rate again, kept 2～5 hours; Reduction process is at H
2And N
2Carry out in the mixed atmosphere, in the mixed atmosphere, H
2Account for the 5-10% volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100385812A CN101284990B (en) | 2008-06-05 | 2008-06-05 | White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100385812A CN101284990B (en) | 2008-06-05 | 2008-06-05 | White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101284990A CN101284990A (en) | 2008-10-15 |
| CN101284990B true CN101284990B (en) | 2012-11-21 |
Family
ID=40057404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100385812A Expired - Fee Related CN101284990B (en) | 2008-06-05 | 2008-06-05 | White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101284990B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140346A (en) * | 2010-01-29 | 2011-08-03 | 大连路明发光科技股份有限公司 | Eu<2+> activated wlkeite luminescent material and preparation method thereof |
| DE102010045368A1 (en) * | 2010-09-14 | 2012-03-15 | Merck Patent Gmbh | Silicophosphate phosphors |
| CN102492422A (en) * | 2011-12-12 | 2012-06-13 | 苏州大学 | Green emitting phosphor for white-light LEDs and preparation method thereof |
| JP2015514830A (en) * | 2012-03-29 | 2015-05-21 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Metal nanoparticle-doped luminescent material and preparation method thereof |
| CN102643644A (en) * | 2012-04-16 | 2012-08-22 | 重庆大学 | Light emitting diode (LED) fluorescent powder with single matrix white light excited by near ultraviolet and preparation method thereof |
| CN102643647B (en) * | 2012-05-04 | 2014-07-16 | 苏州大学 | Eu3+ activated rear earth silicon phosphate fluorescent powder and preparing method and application thereof |
| CN102911663B (en) * | 2012-09-29 | 2014-09-10 | 浙江工业大学 | White light phosphor powder using calcium carbonate as only substrate and preparation method thereof |
| CN103740370A (en) * | 2013-12-11 | 2014-04-23 | 中国地质大学（北京） | Apatite-structure fluorescent powder capable of exciting blue green light and preparation method thereof |
| CN107459991B (en) * | 2017-07-25 | 2020-06-26 | 中国计量大学 | Phosphate three-primary-color fluorescent powder for white light LED and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729267A (en) * | 2002-12-20 | 2006-02-01 | 丰田合成株式会社 | Phosphor and optical device using same |
| CN101029231A (en) * | 2007-01-11 | 2007-09-05 | 复旦大学 | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production |
| CN101077973A (en) * | 2006-05-26 | 2007-11-28 | 大连路明发光科技股份有限公司 | Silicate luminescent material, preparation method thereof and luminescent device using the same |
-
2008
- 2008-06-05 CN CN2008100385812A patent/CN101284990B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729267A (en) * | 2002-12-20 | 2006-02-01 | 丰田合成株式会社 | Phosphor and optical device using same |
| CN101077973A (en) * | 2006-05-26 | 2007-11-28 | 大连路明发光科技股份有限公司 | Silicate luminescent material, preparation method thereof and luminescent device using the same |
| CN101029231A (en) * | 2007-01-11 | 2007-09-05 | 复旦大学 | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101284990A (en) | 2008-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101284990B (en) | White luminous emission fluorescent powder of alkali metal phosphosilicate and preparation method thereof | |
| JP5926302B2 (en) | Novel silicate yellow-green phosphor | |
| KR100632144B1 (en) | Novel silicate-based yellow-green phosphors | |
| TWI363793B (en) | ||
| CN101134895B (en) | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same | |
| CN103237867B (en) | Borophosphate phosphor and light source | |
| CN101238195A (en) | Silicate-based orange phosphors | |
| CN101029231A (en) | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production | |
| CN102559179B (en) | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof | |
| CN101597493A (en) | A kind of alkaline-earth metal silicophosphate fluorescent material and manufacture method and application | |
| CN101126023B (en) | Silicate substrate luminescent material with multiple emission peak, preparation method thereof and luminescent device using the same | |
| CN102732251A (en) | Single-phase white light phosphor for near-ultraviolet light excitation and preparation method thereof | |
| CN107129805B (en) | Europium ion doped silicate white light fluorescent powder and preparation method thereof | |
| CN100383988C (en) | White light LED and light converting luminophore | |
| CN101130690B (en) | Bivalence europium enabled alkaline earth metal silicate fluorescent powder and method of producing the same | |
| CN108728088B (en) | Europium ion excited silicate white light fluorescent powder and preparation method thereof | |
| CN100427566C (en) | Alkaline-earth metal silicate fluorescent powder and its preparation method and application | |
| CN102181284A (en) | Ultraviolet excited or near ultraviolet excited borate fluorescent powder and preparation method thereof | |
| CN101473013B (en) | Thulium-containing fluorescent substance for white light emitting diode and manufacturing method thereof | |
| CN101270282B (en) | Rare earth red fluorescent powder for light emitting diode and preparation method thereof | |
| CN101880526B (en) | Blue-green silicate luminescent material | |
| CN103087712A (en) | Single matrix white phosphor and preparation method thereof | |
| CN103937494B (en) | A kind of single-substrate white fluorescent powder and preparation method thereof | |
| CN101230271B (en) | Red-light fluorescent powder for LED and method for making same | |
| CN114316982B (en) | Red phosphor powder of sulfur phosphate, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121121 Termination date: 20150605 |
|
| EXPY | Termination of patent right or utility model |