CN102660276A - Near ultraviolet stimulated borophosphate white light fluorescent powder and preparation method - Google Patents
Near ultraviolet stimulated borophosphate white light fluorescent powder and preparation method Download PDFInfo
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- CN102660276A CN102660276A CN2012101289467A CN201210128946A CN102660276A CN 102660276 A CN102660276 A CN 102660276A CN 2012101289467 A CN2012101289467 A CN 2012101289467A CN 201210128946 A CN201210128946 A CN 201210128946A CN 102660276 A CN102660276 A CN 102660276A
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- fluorescent powder
- borophosphate
- white light
- near ultraviolet
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Abstract
The invention relates to a single-matrix luminescent material used for a light emitting diode (LED), which outputs strong light under the stimulation of the near ultraviolet, and a preparation method thereof. The single-matrix luminescent material belongs to the field of luminescent materials. The borophosphate white light fluorescent powder has a composition formula of KBa(1-x)Eu<2+>xBP2O8, wherein x is a molar percentage coefficient of EU, which is accounted relatively to Ba, and m is more than 0 and is less than 0.1. The preparation method for the fluorescent powder comprises the following steps of: accurately weighing the raw materials according to a chemical composition formula; after the raw materials are grinded and evenly mixed, firing for 1-4h under the reducing atmosphere at the temperature of 900-1000DEG C; and smashing and screening after cooling to obtain the single-matrix luminescent material. Ray of 400-620nm can be stimulated from the fluorescent powder under the ray of 300-400nm (especially 350-370nm). The near ultraviolet stimulated borophosphate white light fluorescent powder is suitable for a near ultraviolet LED chip and has the characteristics of wide stimulating range, high luminescence luminance, simple and convenient preparation method and the like.
Description
Technical field
The present invention relates to purple light, blue-ray LED is used field of light emitting materials, is specifically related to a kind of boron phosphate luminescent powder that can be excited by near-ultraviolet light LED and preparation method thereof.
Background technology
Light emitting diode (LED) is regarded as the green illumination light source of 21 century because numerous advantages and wide application prospect and markets potential such as energy-saving and environmental protection, green illumination are arranged.Light conversion hysteria LED is the main flow of white-light illuminating development, utilizes blue light InGaN tube core to apply YAG:Ce at present usually
3+Gold-tinted fluorescent material is realized white light LEDs.Yet because this mode synthetic white light is to be formed by the yellow fluorescence of fluorescent material and the blue light of LED, the glow color of device changes with the variation of driving voltage and fluorescent coating thickness, and color reducibility is poor, the low and non-refractory of colour rendering index.For addressing the above problem, people attempt adopting ultraviolet-near ultraviolet, and (350～410nm) InGaN tube cores excite red-green-blue fluorescent material to realize white light LEDs.Yet,, make the luminous efficiency of fluorescent material and color reducibility be a greater impact owing to exist color to absorb again and proportioning regulation and control problem between the mixed fluorescent powder.Single-matrix white fluorescent powder is as the novel fluorescence powder material, because colour stable, color reducibility is good etc., and advantage has become the research focus.But present known single-matrix white fluorescent powder quantity is few, and luminous efficiency is also relatively low, and therefore the suitable near ultraviolet excitated efficient single-matrix white fluorescent powder of development has crucial meaning.
At present, single matrix LED fluorescent material of exciting of near-ultraviolet ray is main with silicate systems still.Kim has reported Ba
3MgSi
2O
8: Eu
2+, Mn
2+And Sr
3MgSi
2O
8: Eu
2+, Mn
2+Etc. a series of single-matrix white fluorescent powders that are suitable near ultraviolet excitation; M subsequently
2MgSi
2O
7: Eu
2+, Dy
3+(M=Ca, Sr), Ca
2MgSi
2O
7: Eu
2+, Mn
2+Be in the news in single-matrix fluorescent material, but this type of silicate substrate fluorescent material synthesis temperature is still higher, luminous efficiency does not reach actual application value as yet.The borophosphate system is one type of novel material system just having found out in recent years, because synthesis temperature is low, thing is mutually easy to control, thereby receives publicity with fluorescence host material as LED.
Summary of the invention
The object of the present invention is to provide a kind of can being excited, the borophosphate white emitting fluorescent powder of emission 400～650nm fluorescence by 300～400nm near ultraviolet LED chip.Another object of the present invention provides the preparation method of above-mentioned borophosphate white emitting fluorescent powder.
The boron phosphate luminescent powder that the present invention proposes is at KBaBP
2O
8Mix Eu in the system
2+, its chemical constitution does
KBa
(1-x)Eu
2+ xBP
2O
8，
Wherein x is the shared molar percentage coefficient of the relative Ba of Eu, 0＜x＜0.1.
Above-mentioned diode is synthetic through high temperature solid-state method with the preparation of fluorescent material, comprises the steps:
(1) presses KBaBP
2O
8Chemical constitution formula prepare burden, be the raw material of potassium element with the oxide compound or the carbonate of potassium, be the raw material of barium element with the oxide compound or the carbonate of barium, with H
3BO
3Being the raw material of boron, is the raw material of phosphoric with primary ammonium phosphate or Secondary ammonium phosphate, is the raw material of europium element with the europiumsesquioxide, obtains initial miscellany;
(2) the above-mentioned initial feed that mixes is behind compressing tablet, 500～700 ℃ of following pre-burnings 2～4 hours;
(3) pulverize after the cooling, grinding is even, and compressing tablet in reducing atmosphere, was calcined 1～3 hour down at 900～1000 ℃ once more, and cooling is after the borophosphate white emitting fluorescent powder is processed in grinding.
Compared with prior art, the present invention has following beneficial effect:
1. the invention provides a kind of synthetic pure phase KBa
(1-x)Eu
2+ xBP
2O
8The preparation method of compound through adopting suitable starting raw material, through solid phase synthesis, can prepare the pure phase of target compound.
2. the non-constant width of the excitation spectrum of fluorescent material of the present invention has strong absorption in 300nm～400nm scope, is applicable to that near ultraviolet LED excites, and is used for white light LED part.
3. fluorescent material of the present invention has strong long wave VISIBLE LIGHT EMISSION, and its emission main peak is positioned at 400nm～620nm and fluorescent material stability is better, and the position and the number of emission peak are tunable.
4. fluorescent material preparation method of the present invention is simple, easy handling.
Description of drawings
Fig. 1 is KBa of the present invention
0.99BP
2O
8: 0.01Eu
2+The room temperature of fluorescent material excites and emmission spectrum figure;
Fig. 2 is KBa of the present invention
0.97BP
2O
8: 0.03Eu
2+The room temperature of fluorescent material excites and emmission spectrum figure;
Fig. 3 is KBa of the present invention
0.94BP
2O
8: 0.06Eu
2+The room temperature of fluorescent material excites and emmission spectrum figure;
Embodiment
Embodiment 1:KBa
0 99BP
2O
8: 0.01Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.0277g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be shaped to the thin slice of Φ 20, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches blue white light.The room temperature of this fluorescent material excites with emmission spectrum sees Fig. 1.
Embodiment 2:KBa
0.98BP
2O
8: 0.02Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.0553g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be pressed into thin slice, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches white light.
Embodiment 3:KBa
0.97BP
2O
8: 0.03Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.0829g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be pressed into thin slice, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches white light.The room temperature of this fluorescent material excites with emmission spectrum sees Fig. 2.
Embodiment 4:KBa
0.96BP
2O
8: 0.04Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.1102g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be pressed into thin slice, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches white light.
Embodiment 5:KBa
0 94BP
2O
8: 0.06Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.1662g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be pressed into thin slice, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches blue white light.The room temperature of this fluorescent material excites with emmission spectrum sees Fig. 3.
Embodiment 6:KBa
0.9BP
2O
8: 0.1Eu
2+The preparation of fluorescent material
Take by weighing salt of wormwood (K respectively
2CO
3) 0.544g, boric acid (H
3BO
3) 0.486g, primary ammonium phosphate (NH
4H
2PO
4) 1.81g, barium carbonate (BaCO
3) 1.55g, europiumsesquioxide (Eu
2O
3) 0.2767g, with above-mentioned raw materials in agate mortar fully ground and mixed evenly after, on tabletting machine, be pressed into thin slice, in the alumina crucible of packing into; 600 ℃ of following calcinations 3 hours, after taking-up is ground then, reinstall in the alumina crucible earlier; Furnace air is caught up with only earlier before the heating through vacuumizing, 900 ℃ of following calcinations 3 hours under carbon monoxide atmosphere then, the cooling back is ground even; Crushing screening, and water again and ethanol wash respectively, finally obtain sample.Sample excites under the 365nm UV-light, mainly launches red white light.
Claims (4)
1. the borophosphate LED fluorescent material that near-ultraviolet ray excites is characterized in that described fluorescent material is with Eu
2+Be activator, concrete chemistry consists of KBa
(1-x)Eu
2+ xBP
2O
8, 0＜x in the formula＜0.1.
2. the white light LEDs that excites by the described near-ultraviolet ray of claim 1 is used boron phosphate luminescent powder; It is characterized in that according to chemical constitution formula, take by weighing the oxide compound or the corresponding salt of K, Ba, B, P and Eu element, behind the even compressing tablet of thorough mixing; 500～700 ℃ of pre-burnings 1～4 hour under air atmosphere earlier; Compressing tablet once more after grinding then, 700～1000 ℃ of sintering are 1～7 hour under reducing atmosphere, obtain boron phosphate luminescent powder.
3. preparation method according to claim 2 is characterized in that: said reducing atmosphere is hydrogen, ammonia, charcoal, carbon monoxide or nitrogen and hydrogen mixed gas.
4. the boron phosphate luminescent powder that excites by the described near-ultraviolet ray of claim 1, its characteristic have strong photoluminescent band in 400～650nm spectral range under 250～450nm optical excitation.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628136A (en) * | 2012-08-23 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Compound lead rubidium borophosphate and non-linear optical crystal of lead rubidium borophosphate, preparation method and applications thereof |
| CN109929554A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate green emitting phosphor and its preparation method and application |
| CN109929553A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate orange red fluorescent powder and its preparation method and application |
| CN109929555A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate white fluorescent powder and its preparation method and application |
| CN110003904A (en) * | 2019-04-04 | 2019-07-12 | 云南大学 | A kind of Ce boron phosphorus doped hydrochlorate ultraviolet fluorescence powder and preparation method thereof |
| CN110003905A (en) * | 2019-04-04 | 2019-07-12 | 云南大学 | A kind of Pr activation borophosphate red fluorescence powder and preparation method thereof |
| CN110003906A (en) * | 2019-02-18 | 2019-07-12 | 云南大学 | A kind of europium boron phosphorus doped hydrochlorate orange-red fluorescence powder and its preparation method and application |
| CN112094645A (en) * | 2020-09-30 | 2020-12-18 | 华南理工大学 | Eu doped2+Blue light fluorescent material, preparation method thereof and white light LED light-emitting device |
| CN114196403A (en) * | 2021-12-28 | 2022-03-18 | 东莞理工学院 | Fluorescent agent and preparation method and application thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628136A (en) * | 2012-08-23 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Compound lead rubidium borophosphate and non-linear optical crystal of lead rubidium borophosphate, preparation method and applications thereof |
| CN103628136B (en) * | 2012-08-23 | 2016-07-06 | 中国科学院新疆理化技术研究所 | Compound boron phosphoric acid rubidium is plumbous and boron phosphoric acid rubidium lead nonlinear optical crystal and preparation method and purposes |
| CN109929554B (en) * | 2018-12-25 | 2021-12-21 | 云南大学 | Boron phosphate green fluorescent powder and preparation method and application thereof |
| CN109929553A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate orange red fluorescent powder and its preparation method and application |
| CN109929555A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate white fluorescent powder and its preparation method and application |
| CN109929554A (en) * | 2018-12-25 | 2019-06-25 | 云南大学 | A kind of borophosphate green emitting phosphor and its preparation method and application |
| CN109929553B (en) * | 2018-12-25 | 2021-12-24 | 云南大学 | Borophosphate orange-red fluorescent powder and preparation method and application thereof |
| CN109929555B (en) * | 2018-12-25 | 2022-01-18 | 云南大学 | White boron phosphate fluorescent powder and preparation method and application thereof |
| CN110003906A (en) * | 2019-02-18 | 2019-07-12 | 云南大学 | A kind of europium boron phosphorus doped hydrochlorate orange-red fluorescence powder and its preparation method and application |
| CN110003904A (en) * | 2019-04-04 | 2019-07-12 | 云南大学 | A kind of Ce boron phosphorus doped hydrochlorate ultraviolet fluorescence powder and preparation method thereof |
| CN110003905A (en) * | 2019-04-04 | 2019-07-12 | 云南大学 | A kind of Pr activation borophosphate red fluorescence powder and preparation method thereof |
| CN112094645A (en) * | 2020-09-30 | 2020-12-18 | 华南理工大学 | Eu doped2+Blue light fluorescent material, preparation method thereof and white light LED light-emitting device |
| CN114196403A (en) * | 2021-12-28 | 2022-03-18 | 东莞理工学院 | Fluorescent agent and preparation method and application thereof |
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Application publication date: 20120912 |