CN105131953B - A kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphors and preparation method thereof - Google Patents
A kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphors and preparation method thereof Download PDFInfo
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- CN105131953B CN105131953B CN201510568798.4A CN201510568798A CN105131953B CN 105131953 B CN105131953 B CN 105131953B CN 201510568798 A CN201510568798 A CN 201510568798A CN 105131953 B CN105131953 B CN 105131953B
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Abstract
The invention belongs to luminescent material technical field, is a kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphors and preparation method thereof.The chemical expression of new polysilicate green fluorescence powder in the present invention is Na4Sr2Y2(Si2O7)(SiO4)2:Eu2+.The preparation method is that the SrCO purer than weighing quantitative analysis is measured by chemical expression3、SiO2、Na2CO3And specpure Y2O3And Eu2O3As raw material, using high temperature solid-state method, synthesize and be made under CO reducing atmospheres.The preparation method of the present invention is simple, and the new polysilicate green emitting phosphor of synthesis has the advantages that near ultraviolet absorbs strong, green emission brightness height and heat endurance is good.Therefore this polysilicate is a kind of fluorescent powder of function admirable, can be widely applied to the fields such as White-light LED illumination, display.
Description
Technical field
The invention belongs to luminescent material technical field, it is related to a kind of near ultraviolet excited white light LED with rare earth ion doped
New polysilicate green emitting phosphor and preparation method thereof.
Background technology
White light emitting diode（WLED）Due to its have the advantages that energy-saving and environmental protection and service life it is long and by it is believed that
It is the preferable solid-state lighting light source of forth generation and the lighting sources such as current incandescent lamp, fluorescent lamp will be finally replaced.It is current commercial
WLED devices mainly use semiconductor GaN base LED chip and YAG:Ce3+Fluorescent powder packaging assembles, its operation principle is
LED chip sends blue light after being powered, so as to excite YAG:Ce3+Fluorescent powder obtains yellow light, and incomplete in hybrid chip
The blue light of absorption is so as to obtain white light emission.The device luminous efficiency highest that this assembling mode obtains, but since it lacks
Red color light component, so as to cause that device colour rendering index is relatively low, colour temperature is higher, is unfavorable for room lighting.In order to overcome disadvantages mentioned above, adopt
It is considered as preferable alternative near ultraviolet LED chip package three primary colors fluorescent powder synthesis white light and commercially shows
Certain competitiveness.Therefore exploitation can effectively be excited by black light, and with higher quantum efficiency, excellent heat, change
The three primary colors fluorescent powder for the advantages that learning stability, low Poison decay and high luminescence queenching temperature is extremely urgent.
The content of the invention
The present invention provides a kind of near ultraviolet excited white light LED with rare earth ion doped new polysilicate green fluorescence
Powder and preparation method thereof.This kind of fluorescent powder is suitable for white light LEDs, display material etc..
A kind of rare earth ion doped new polysilicate green emitting phosphors of near ultraviolet excited white light LED, its chemical table
It is as follows up to formula：Na4Sr2Y2(Si2O7)(SiO4)2:Eu2+；Matrix is Na4Sr2Y2(Si2O7)(SiO4)2, its centre of luminescence uses Eu2 +It is doped, Eu2+Sr in ionic compartmentation matrix2+Ion site, its concentration range are 0.3~10 mol%.Select SrCO3、
SiO2、Na2CO3、Y2O3And Eu2O3As raw material, using high temperature solid-state method, prepared under CO reducing atmospheres.Eu2+The concentration of ion
Refer to Eu2+The amount of the material of ion is than upper Eu2+Ion and Na4Sr2Y2(Si2O7)(SiO4)2Middle Y3+The sum of amount of ionic species.
Further, centre of luminescence Eu2+Concentration be 3mol%.
A kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphor, preparation method
Including stocking up, grinding, burning till three steps：
1st, material preparation step
By a kind of near ultraviolet excited white light LED of the present invention with rare earth ion doped new polysilicate green fluorescence
The chemical expression Na of powder4Sr2Y2(Si2O7)(SiO4)2:Eu2+Metering ratio weigh SrCO3、SiO2、Na2CO3、Y2O3And Eu2O3
As raw material, wherein Eu2+The concentration range of ion is 0.3~10mol%；
2nd, abrasive material
The SrCO that will stoichiometrically weigh3、SiO2、Na2CO3、Y2O3And Eu2O3It is put into agate mortar, and adds nothing
Water-ethanol, absolute ethyl alcohol are 2 with material quality ratio：1,2 hours are then ground, make all raw material after mixing, finally
Gained mixture is placed in baking oven at 80 ± 5 DEG C dry 5 hours, by mixture grinding after drying uniformly and loaded on oxidation
In aluminium crucible；
3rd, step is burnt till
Alumina crucible equipped with mixture after drying and grinding is put into high temperature sintering furnace and is warming up to 800 ± 10 DEG C,
5 hours of constant temperature, after being cooled to room temperature, are drawn off and regrind 30 minutes, finally reactant is put into high temperature furnace
And 1200 ± 10 DEG C are warming up under CO reducing atmospheres, and 8 hours of constant temperature, after the completion of reaction, after high temperature furnace is cooled to room temperature,
Product is taken out.
In whole polysilicate green emitting phosphor preparation process, first step low-temperature sintering（Constant temperature 5 at 800 ± 10 DEG C
Hour）It is crucial, at this temperature, each raw material reacts to form simple silicate intermediate product first, so that reaction has
Direction clearly occurs.If directly rising to 1200 ± 10 DEG C from room temperature, because temperature is higher, each raw material is directly reacted by oxide
Other various forms of silicates will be formed, from the Na for being unable to obtain pure phase4Sr2Y2(Si2O7)(SiO4)2:Eu2+Fluorescence
Powder.In addition, under CO reducing atmospheres, when temperature is more than 1200 ± 10 DEG C, reaction raw materials will melt, it is impossible to obtain powder
Material, if temperature is less than 1200 ± 10 DEG C, obtained polysilicate green emitting phosphor luminosity is relatively low（Such as the institute of attached drawing 2
Show）.Therefore we select 1200 ± 10 DEG C to be used as the last sintering temperature of polysilicate green emitting phosphor.As shown in Figure 6, it is made
The heat endurance of standby polysilicate green emitting phosphor is substantially better than the Ba of commercialization2SiO4:Eu2+Green emitting phosphor.
The present invention can also be sufficiently mixed each raw material by grinding three times, particularly high temperature sintering furnace sintering after institute into
Capable grinding, farthest ensure that the quality of final products；Oven temperature, sintering furnace temperature, reduction temperature in reaction
And corresponding time parameter, go out to have higher quantum efficiency, excellent heat, chemical stability, low glimmering for final production
The fluorescent powder product of the advantages that optical attenuation and high luminescence queenching temperature plays the effect of key.
It is characteristic of the invention that：
（1）New multi-silicate green emitting phosphor of the present invention be one kind can effectively by near ultraviolet excitation, and
Green luminescence brightness is high, the green emitting phosphor of high color purity；
（2）The fluorophor is prepared using high temperature solid-state method, manufacturing process is simple, easily operated, suitable batch production；
（3）Near ultraviolet excitated new polysilicate green emitted light-emitting phosphor heat endurance prepared by this method is high；
（4）It is proposed satisfied base starting material proportioning；
（5）It is proposed the doping concentration scope at optimal luminescent center, test result indicates that, centre of luminescence Eu2+Doping concentration
The product of luminous intensity maximum can be obtained for 3 mol%.
Brief description of the drawings
Fig. 1：Na4Sr2Y2(Si2O7)(SiO4)2:3mol%Eu2+The XRD spectra of fluorescent powder.
Fig. 2：Na prepared by different temperatures4Sr2Y2(Si2O7)(SiO4)2:3mol%Eu2+The emission spectrum of fluorescent powder.
Fig. 3：Na4Sr2Y2(Si2O7)(SiO4)2:xEu2+ (x=0.5~10 mol%) fluorescent powder excitation spectrum.
Fig. 4：Na4Sr2Y2(Si2O7)(SiO4)2:xEu2+ (x=0.5~10 mol%) fluorescent powder emission spectrum.
Fig. 5：Na4Sr2Y2(Si2O7)(SiO4)2:3mol%Eu2+The chromaticity coordinates of fluorescent powder.
Fig. 6：Na4Sr2Y2(Si2O7)(SiO4)2:3mol%Eu2+Fluorescent powder and commercialization Ba2SiO4:Eu2+Fluorescent powder shines
The dependence of intensity and temperature.
Embodiment
Embodiment 1
(1) according to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2And 0.5995g
SrCO3, and be put into according to this in middle agate mortar；
(2) absolute ethyl alcohol that quality is 2 times of material quality is added in said mixture, then grinds 2 hours, is made anti-
Thing is answered to be uniformly mixed；
(3) uniform mixture will be ground and be placed in baking oven at 80 ± 5 DEG C dry 5 hours, then will be resulting mixed
Compound regrinding is uniformly rear to be fitted into alumina crucible；
(4) alumina crucible of above-mentioned charging feedstock is put into high temperature sintering furnace flat-temperature zone, high temperature sintering furnace rises to first
800±10℃（It is preferred that 800 DEG C）It is sintered, when constant temperature 5 is small, after high temperature furnace is cooled to room temperature, reaction raw materials is taken out simultaneously
Regrinding 30 minutes, finally ground reactant is placed again into high temperature furnace and is warming up to 1200 under CO reducing atmospheres ±
10℃（It is preferred that 1200 DEG C）, 8 hours of constant temperature.After the completion of reaction, after high temperature furnace is cooled to room temperature, final product is taken out,
Obtain the Na of the present invention4Sr2Y2(Si2O7)(SiO4)2Phosphor host.
Embodiment 2
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5956g
SrCO3With 0.0011g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:0.3mol%Eu2+Fluorescent powder.
Embodiment 3
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5950g
SrCO3With 0.0018g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after tested with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:0.5mol%Eu2+Fluorescent powder.
Embodiment 4
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5944g
SrCO3With 0.0025g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:0.7mol%Eu2+Fluorescent powder.
Embodiment 5
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5935g
SrCO3With 0.0035g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:1mol%Eu2+Fluorescent powder.
Embodiment 6
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5875g
SrCO3With 0.0106g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:3mol%Eu2+Fluorescent powder.
Embodiment 7
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5816g
SrCO3With 0.0176g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:5mol%Eu2+Fluorescent powder.
Embodiment 8
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5756g
SrCO3With 0.0246g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:7mol%Eu2+Fluorescent powder.
Embodiment 9
According to stoichiometric ratio, 0.4312g Na are weighed2CO3、0.4517g Y2O3、0.4807g SiO2、0.5667g
SrCO3With 0.0352g Eu2O3, and be put into according to this in middle agate mortar, remaining condition obtains this hair after testing with embodiment 1
Bright Na4Sr2Y2(Si2O7)(SiO4)2:10mol%Eu2+Fluorescent powder.
Claims (3)
1. the rare earth ion doped polysilicate green emitting phosphors of a kind of near ultraviolet excited white light LED, it is characterised in that it is changed
Learning expression formula is：Na4Sr2Y2(Si2O7)(SiO4)2:Eu2+；Matrix is Na4Sr2Y2(Si2O7)(SiO4)2, the use of its centre of luminescence
Eu2+It is doped, Eu2+Sr in ionic compartmentation matrix2+Ion site, centre of luminescence Eu2+Concentration be 3 mol%.
A kind of 2. rare earth ion doped polysilicate green fluorescence of near ultraviolet excitated white light LEDs as claimed in claim 1
The preparation method of powder, it is characterised in that including stocking up, grinding, burning till three steps；
Material preparation step includes the chemical expression Na by fluorescent powder4Sr2Y2(Si2O7)(SiO4)2:Eu2+Metering ratio weigh SrCO3、
SiO2、Na2CO3、Y2O3And Eu2O3As raw material；
Abrasive material step includes the SrCO that will stoichiometrically weigh3、SiO2、Na2CO3、Y2O3And Eu2O3It is put into agate mortar,
And absolute ethyl alcohol is added, absolute ethyl alcohol is 2 with material quality ratio：1,2 hours are then ground, make all raw material mixing equal
It is even, gained mixture is finally placed in baking oven at 80 ± 5 DEG C dry 5 hours, by mixture grinding after drying uniformly simultaneously
Loaded in alumina crucible；
In step is burnt till, the alumina crucible equipped with mixture after drying and grinding is put into high temperature sintering furnace and is warming up to
800 ± 10 DEG C, 5 hours of constant temperature, after being cooled to room temperature, are drawn off and regrind 30 minutes, finally put reactant
Enter in high temperature furnace and be warming up to 1200 ± 10 DEG C under CO reducing atmospheres, 8 hours of constant temperature, after the completion of reaction, treat high temperature furnace cooling
But to after room temperature, product is taken out.
A kind of 3. rare earth ion doped polysilicate green of near ultraviolet excitated white light LEDs according to claim 2
The preparation method of fluorescent powder, it is characterised in that SrCO3、SiO2And Na2CO3It is pure to analyze；Y2O3And Eu2O3For spectroscopic pure.
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| CN108192610B (en) * | 2018-01-12 | 2021-03-09 | 南京邮电大学 | Ultraviolet light and blue light excited red light fluorescent material and preparation method and application thereof |
| CN108504352B (en) * | 2018-06-07 | 2021-08-03 | 东莞理工学院 | Luminescent material capable of being excited by ultraviolet and near ultraviolet to emit green light, and preparation method and application thereof |
| CN110041932A (en) * | 2019-05-07 | 2019-07-23 | 中国计量大学 | One plant growth LED light fluorescent powder and preparation method thereof |
| CN112210375A (en) * | 2020-09-24 | 2021-01-12 | 东台市天源光电科技有限公司 | Rare earth doped silicate fluorescent powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8506104B1 (en) * | 2012-03-28 | 2013-08-13 | General Electric Company | Phosphors for LED lamps |
| CN103275718A (en) * | 2013-06-18 | 2013-09-04 | 中国地质大学（北京） | Green light type silicate fluorescent powder and preparation method thereof |
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| JP5795971B2 (en) * | 2012-03-07 | 2015-10-14 | パナソニック株式会社 | Phosphor and light emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8506104B1 (en) * | 2012-03-28 | 2013-08-13 | General Electric Company | Phosphors for LED lamps |
| CN103275718A (en) * | 2013-06-18 | 2013-09-04 | 中国地质大学（北京） | Green light type silicate fluorescent powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Solid-state reaction preparation and photoluminescence properties of Na2Ba6(Si2O7)(SiO4)2:Eu2+ phosphors;Pinglu Shi等;《Materials Research Bulletin》;20141231;第49卷;589-592 * |
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