CN105131953A - Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder - Google Patents

Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder Download PDF

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Publication number
CN105131953A
CN105131953A CN201510568798.4A CN201510568798A CN105131953A CN 105131953 A CN105131953 A CN 105131953A CN 201510568798 A CN201510568798 A CN 201510568798A CN 105131953 A CN105131953 A CN 105131953A
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polysilicate
novel
fluorescent powder
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green fluorescent
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CN105131953B (en
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田跃
崔彩娥
黄平
王磊
冯宁宁
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Taiyuan University of Technology
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Taiyuan University of Technology
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Abstract

The invention belongs to the technical field of light-emitting materials and provides rare earth ion doping novel polysilicate green fluorescent powder for a near ultraviolet stimulated white light LED (light-emitting diode) and a preparation method of the novel polysilicate green fluorescent powder. The chemical expression of the novel polysilicate green fluorescent powder is Na4Sr2Y2(Si2O7)(SiO4)2:Eu<2+>. The preparation method comprises the following steps: weighing quantitative and analytically pure SrCO3, SiO2 and Na2CO3, and spectroscopically pure Y2O3 and Eu2O3 according to stoichiometric ratios of the chemical expression to serve as raw materials, and synthesizing under a CO reduction atmosphere by using a high-temperature solid-phase method. The preparation method is simple and the synthesized novel polysilicate green fluorescent powder has the advantages of strong near ultraviolet absorptivity, high green light emission brightness and good thermal stability. Therefore, the polysilicate is the fluorescent powder with excellent performances and can be widely applied to the fields of illumination of white-light LEDs, display and the like.

Description

A kind of near ultraviolet excited white light LED rare earth ion doped novel polysilicate green emitting phosphor and preparation method thereof
Technical field
The invention belongs to luminescent material technical field, relate to a kind of near ultraviolet excited white light LED rare earth ion doped novel polysilicate green emitting phosphor and preparation method thereof.
Background technology
White light emitting diode (WLED) is the desirable solid-state illumination light source of forth generation because it has the advantage such as energy-saving and environmental protection and long service life and be it is believed that and will finally replaces the lighting sources such as current incandescent light, luminescent lamp.The WLED device of current commercialization mainly adopts semi-conductor GaN base LED chip and YAG:Ce 3+fluorescent powder packaging assembles, and its principle of work is send blue light after LED chip energising, thus excites YAG:Ce 3+fluorescent material obtains gold-tinted, and the blue light be not completely absorbed in hybrid chip thus obtain white light emission.The device luminous efficiency that this assembling mode obtains is the highest, but lacks red color light component due to it, thus causes that device colour rendering index is lower, colour temperature is higher, is unfavorable for interior lighting.In order to overcome above-mentioned shortcoming, near ultraviolet LED Chip Packaging three primary colors fluorescent powder synthesize white light is adopted to be considered to desirable alternative method and commercially to show certain competitive power.Therefore exploitation effectively can be excited by near-ultraviolet light, and the three primary colors fluorescent powder with advantages such as higher quantum yield, excellent heat, chemical stability, low Poison decay and high luminescence quenching temperature is very urgent.
Summary of the invention
The invention provides a kind of near ultraviolet excited white light LED rare earth ion doped novel polysilicate green emitting phosphor and preparation method thereof.This kind of fluorescent material is applicable to the aspect such as white light LEDs, display material.
The rare earth ion doped novel polysilicate green emitting phosphor of near ultraviolet excited white light LED, its chemical expression is as follows: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: Eu 2+; Matrix is Na 4sr 2y 2(Si 2o 7) (SiO 4) 2, its luminescence center adopts Eu 2+adulterate, Eu 2+sr in ionic replacement matrix 2+ion site, its concentration range is 0.3 ~ 10mol%.Select SrCO 3, SiO 2, Na 2cO 3, Y 2o 3and Eu 2o 3as raw material, adopt high temperature solid-state method, prepare under CO reducing atmosphere.Eu 2+the concentration of ion refers to Eu 2+the amount of substance of ion is than upper Eu 2+ion and Na 4sr 2y 2(Si 2o 7) (SiO 4) 2middle Y 3+the amount sum of ionic species.
Further, luminescence center Eu 2+concentration be 3mol%.
The rare earth ion doped novel polysilicate green emitting phosphor of near ultraviolet excited white light LED, preparation method comprises and gets the raw materials ready, grinds, burns till three steps:
1, material preparation step
By the chemical expression Na of a kind of near ultraviolet excited white light LED of the present invention with rare earth ion doped novel polysilicate green emitting phosphor 4sr 2y 2(Si 2o 7) (SiO 4) 2: Eu 2+metering ratio take SrCO 3, SiO 2, Na 2cO 3, Y 2o 3and Eu 2o 3as raw material, wherein Eu 2+the concentration range of ion is 0.3 ~ 10mol%;
2, abrasive material
By the SrCO stoichiometrically taken 3, SiO 2, Na 2cO 3, Y 2o 3and Eu 2o 3put into agate mortar, and add dehydrated alcohol, dehydrated alcohol and raw materials quality are than being 2:1, then grind 2 hours, after all raw material is mixed, finally gained mixture is placed in baking oven at 80 ± 5 DEG C dry 5 hours, by mixture grinding after drying evenly and be loaded in alumina crucible;
3, step is burnt till
The alumina crucible that the rear mixture of dry also grinding is housed is put into high temperature sintering furnace and is warming up to 800 ± 10 DEG C, constant temperature 5 hours, to be cooled to room temperature, taken out and again ground 30 minutes, finally reactant is put into High Temperature Furnaces Heating Apparatus and be warming up to 1200 ± 10 DEG C under CO reducing atmosphere, constant temperature 8 hours, after having reacted, be cooled to after room temperature until High Temperature Furnaces Heating Apparatus, product is taken out.
In whole polysilicate green emitting phosphor preparation process, the first step low-temperature sintering (at 800 ± 10 DEG C constant temperature 5 hours) is crucial, at this temperature, first each raw material reacts and forms simple silicate intermediate product, thus reaction is had clearly direction occurs.If directly rise to 1200 ± 10 DEG C from room temperature, because temperature is higher, each raw material will form other multi-form silicate by oxide compound direct reaction, thus can not obtain the Na of pure phase 4sr 2y 2(Si 2o 7) (SiO 4) 2: Eu 2+fluorescent material.In addition, under CO reducing atmosphere, when temperature is more than 1200 ± 10 DEG C, reaction raw materials will melt, and can not obtain powder body material, if temperature is lower than 1200 ± 10 DEG C, and the polysilicate green emitting phosphor luminosity lower (as shown in Figure 2) obtained.Therefore we select 1200 ± 10 DEG C as the last sintering temperature of polysilicate green emitting phosphor.As shown in Figure 6, the thermostability of prepared polysilicate green emitting phosphor is obviously better than commercial Ba 2siO 4: Eu 2+green emitting phosphor.
The present invention also can make each raw material fully mix by three grindings, and the grinding particularly carried out after high temperature sintering furnace sintering, farthest ensure that the quality of the finished product; Oven temperature in reaction, sintering oven temperature, reduction temperature and corresponding time parameter, fluorescent powder product final production being gone out to have to the advantages such as higher quantum yield, excellent heat, chemical stability, low Poison decay and high luminescence quenching temperature serves crucial effect.
Feature of the present invention is:
(1) novel multi-silicate green emitting phosphor of the present invention is that one can effectively by near ultraviolet excitation, and green luminescence brightness is high, the green emitting phosphor of high color purity;
(2) adopt high temperature solid-state method to prepare this fluor, manufacturing process is simple, easy handling, and suitable batch is produced;
(3) the near ultraviolet excitated novel polysilicate green emitted light-emitting phosphor thermostability that this legal system is standby is high;
(4) satisfied base starting material proportioning is proposed;
(5) propose the doping content scope at optimal luminescent center, experimental result shows, luminescence center Eu 2+doping content be that 3mol% can obtain the maximum product of luminous intensity.
Accompanying drawing explanation
Fig. 1: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: 3mol%Eu 2+the XRD spectra of fluorescent material.
Fig. 2: Na prepared by differing temps 4sr 2y 2(Si 2o 7) (SiO 4) 2: 3mol%Eu 2+the emmission spectrum of fluorescent material.
Fig. 3: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: xeu 2+( x=0.5 ~ 10mol%) excitation spectrum of fluorescent material.
Fig. 4: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: xeu 2+( x=0.5 ~ 10mol%) emmission spectrum of fluorescent material.
Fig. 5: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: 3mol%Eu 2+the chromaticity coordinates of fluorescent material.
Fig. 6: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: 3mol%Eu 2+fluorescent material and commercial Ba 2siO 4: Eu 2+the luminous intensity of fluorescent material and the dependence of temperature.
Embodiment
Embodiment 1
(1) according to stoichiometric ratio, 0.4312gNa is taken 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2and 0.5995gSrCO 3, and put into agate mortar according to this;
(2) in said mixture, add the dehydrated alcohol that quality is raw materials quality 2 times, then grind 2 hours, reactant is mixed;
(3) uniform for grinding mixture is placed in baking oven at 80 ± 5 DEG C dry 5 hours, then obtained mixture is ground again evenly and load in alumina crucible;
(4) alumina crucible of above-mentioned charging feedstock is put into high temperature sintering furnace flat-temperature zone, first high temperature sintering furnace rises to 800 ± 10 DEG C (preferably 800 DEG C) and sinters, constant temperature 5 hours, be cooled to after room temperature until High Temperature Furnaces Heating Apparatus, reaction raw materials is taken out and again grinds 30 minutes, finally ground reactant is put into again High Temperature Furnaces Heating Apparatus to be warming up under CO reducing atmosphere 1200 ± 10 DEG C (preferably 1200 DEG C), constant temperature 8 hours.After having reacted, be cooled to after room temperature until High Temperature Furnaces Heating Apparatus, final product taken out, namely obtains Na of the present invention 4sr 2y 2(Si 2o 7) (SiO 4) 2phosphor host.
Embodiment 2
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5956gSrCO 3and 0.0011gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 0.3mol%Eu 2+fluorescent material.
Embodiment 3
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5950gSrCO 3and 0.0018gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after tested 4sr 2y 2(Si 2o 7) (SiO 4) 2: 0.5mol%Eu 2+fluorescent material.
Embodiment 4
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5944gSrCO 3and 0.0025gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 0.7mol%Eu 2+fluorescent material.
Embodiment 5
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5935gSrCO 3and 0.0035gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 1mol%Eu 2+fluorescent material.
Embodiment 6
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5875gSrCO 3and 0.0106gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 3mol%Eu 2+fluorescent material.
Embodiment 7
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5816gSrCO 3and 0.0176gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 5mol%Eu 2+fluorescent material.
Embodiment 8
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5756gSrCO 3and 0.0246gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 7mol%Eu 2+fluorescent material.
Embodiment 9
According to stoichiometric ratio, take 0.4312gNa 2cO 3, 0.4517gY 2o 3, 0.4807gSiO 2, 0.5667gSrCO 3and 0.0352gEu 2o 3, and put into agate mortar according to this, all the other conditions, with embodiment 1, namely obtain Na of the present invention after testing 4sr 2y 2(Si 2o 7) (SiO 4) 2: 10mol%Eu 2+fluorescent material.

Claims (4)

1. the rare earth ion doped novel polysilicate green emitting phosphor of near ultraviolet excited white light LED, it is characterized in that, its chemical expression is: Na 4sr 2y 2(Si 2o 7) (SiO 4) 2: Eu 2+; Matrix is Na 4sr 2y 2(Si 2o 7) (SiO 4) 2, its luminescence center adopts Eu 2+adulterate, Eu 2+sr in ionic replacement matrix 2+ion site, its concentration range is 0.3 ~ 10mol%.
2. the rare earth ion doped novel polysilicate green emitting phosphor of a kind of near ultraviolet excited white light LED according to claim 1, is characterized in that, luminescence center Eu 2+concentration be 3mol%.
3. a white light LEDs near ultraviolet excitated as claimed in claim 1 preparation method for rare earth ion doped novel polysilicate green emitting phosphor, is characterized in that, comprises getting the raw materials ready, grind, burning till three steps;
Material preparation step comprises the chemical expression Na by fluorescent material 4sr 2y 2(Si 2o 7) (SiO 4) 2: Eu 2+metering ratio take SrCO 3, SiO 2, Na 2cO 3, Y 2o 3and Eu 2o 3as raw material;
Abrasive material step comprises the SrCO that will stoichiometrically take 3, SiO 2, Na 2cO 3, Y 2o 3and Eu 2o 3put into agate mortar, and add dehydrated alcohol, dehydrated alcohol and raw materials quality are than being 2:1, then grind 2 hours, all raw material is mixed, finally gained mixture is placed in baking oven at 80 ± 5 DEG C dry 5 hours, by mixture grinding after drying evenly and be loaded in alumina crucible;
Burning till in step, the alumina crucible that the rear mixture of dry also grinding is housed is put into high temperature sintering furnace and is warming up to 800 ± 10 DEG C, constant temperature 5 hours, to be cooled to room temperature, taken out and again ground 30 minutes, finally reactant put into High Temperature Furnaces Heating Apparatus and be warming up to 1200 ± 10 DEG C under CO reducing atmosphere, constant temperature 8 hours, after having reacted, be cooled to after room temperature until High Temperature Furnaces Heating Apparatus, product is taken out.
4. a kind of near ultraviolet excitated white light LEDs according to claim 3 preparation method of rare earth ion doped novel polysilicate green emitting phosphor, is characterized in that, SrCO 3, SiO 2and Na 2cO 3for analytical pure; Y 2o 3and Eu 2o 3for spectroscopically pure.
CN201510568798.4A 2015-09-09 2015-09-09 A kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphors and preparation method thereof Expired - Fee Related CN105131953B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192610A (en) * 2018-01-12 2018-06-22 南京邮电大学 A kind of ultraviolet light and blue light activated red light flourescent material and its preparation method and application
CN108504352A (en) * 2018-06-07 2018-09-07 东莞理工学院 It is a kind of can be by luminescent material and its preparation method and application that is ultraviolet and near ultraviolet excitated and launching green light
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 (3)

* Cited by examiner, † Cited by third party
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
JP2013185045A (en) * 2012-03-07 2013-09-19 Panasonic Corp Fluorescent substance and light-emitting device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013185045A (en) * 2012-03-07 2013-09-19 Panasonic Corp Fluorescent substance and light-emitting device
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)

* Cited by examiner, † Cited by third party
Title
PINGLU SHI等: "Solid-state reaction preparation and photoluminescence properties of Na2Ba6(Si2O7)(SiO4)2:Eu2+ phosphors", 《MATERIALS RESEARCH BULLETIN》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192610A (en) * 2018-01-12 2018-06-22 南京邮电大学 A kind of ultraviolet light and blue light activated red light flourescent material and its preparation method and application
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
CN108504352A (en) * 2018-06-07 2018-09-07 东莞理工学院 It is a kind of can be by luminescent material and its preparation method and application that is ultraviolet and near ultraviolet excitated and launching green light
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

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