CN103087712A - Single matrix white phosphor and preparation method thereof - Google Patents

Single matrix white phosphor and preparation method thereof Download PDF

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CN103087712A
CN103087712A CN2013100250731A CN201310025073A CN103087712A CN 103087712 A CN103087712 A CN 103087712A CN 2013100250731 A CN2013100250731 A CN 2013100250731A CN 201310025073 A CN201310025073 A CN 201310025073A CN 103087712 A CN103087712 A CN 103087712A
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powder
fluorescent material
light
preparation
near ultraviolet
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黎学明
徐永燕
李武林
罗彬彬
杨文静
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Chongqing University
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Chongqing University
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Abstract

The invention provides single matrix white phosphor and a preparation method thereof. The chemical expression of the phosphor is (SryBa1-x-y)(MgmZn1-m-p-q)2(PO4)2:xEu,pMn,qTb, wherein x is greater than 0 and less than 0.1; y is greater than 0 and less than 1; m is greater than 0 and less than 1; p is greater than 0 and less than 0.1; and q is greater than 0 and less than 0.1. The phosphor prepared by the method is fine and uniform in granules, can emit red, green and blue bands after being excited by 350-410nm near ultraviolet and can be used for the white LED excited by the near ultraviolet.

Description

Single-matrix white fluorescent powder and preparation method thereof
Technical field
The present invention relates to a kind of fluorescent material and preparation method thereof, particularly a kind of single-matrix white fluorescent powder near ultraviolet excitated white light LEDs and preparation method thereof.
Background technology
Light conversion hysteria white light LEDs has power saving, volume is little, thermal value is low, the life-span is long, response is fast, but the anti-punching of antidetonation, recyclable, pollution-free planar package, easy exploiting becomes the advantages such as compact product, is the new light sources of 21 century most worthy.
Commercialization light conversion hysteria white light LEDs mainly take blue-light LED chip as basic light source, excites yellow fluorescent powder at present, utilizes lens principle that gold-tinted and the blue light of complementation are obtained white light.This method is simple in structure, and manufacture craft requires lower, but the white light LEDs glow color that obtains can be with driving voltage and fluorescent coating variation in thickness, and color reducibility is poor, and colour rendering index is low.Study more light conversion hysteria white light LEDs and excite three kinds of fluorescent material of red, green, blue with high brightness near ultraviolet LED chip, produce the three primary colours light emission, the compound white light that obtains.The white light LEDs glow color that this method obtains only by the decision of fluorescent material proportioning, is more easily realized the white light that glow color is stable, and its luminous efficiency and colour rendering index are all well a lot of than blue chip+yellow fluorescent powder.But owing to having mixed multiple fluorescent material, there are color absorption again, energy waste, proportioning regulation and control and the different problem of rate of ageing between mixture, cause luminous efficiency and color rendition performance to be a greater impact, also increased cost simultaneously.
If adopt the near ultraviolet LED chip, excite the single-matrix fluorescent material with three emission peaks of red, green, blue, it is poor that the method has namely overcome the color reducibility of blue chip+yellow fluorescent powder, the shortcoming that colour rendering index is low, simultaneously owing to only there being single-matrix, can solve again color absorption again between the mixture of near ultraviolet chip+RGB fluorescent material, energy waste, proportioning regulation and control and the equal problem of rate of ageing.
Can be used near ultraviolet excitated single-matrix white fluorescent powder many cases type and the large class of transmission ofenergy type two are arranged at present.For example, (Science Bulletin, 2012, the 57:189-193) CaLaGa of report such as Zhao Wenyu 3O 7: Dy 3+Fluorescent material, and (Journa l of Al loys and Compounds, 2010, the 498:139-142) BaSrMg (PO of report such as Zhan-Chao Wu 4) 2: Eu 2+Just belong to many cases type list substrate fluorescent powder, the emmission spectrum of this class fluorescent material forms white light by blue light and yellow light mix, and because only having a kind of activator, its mixing color is difficulty comparatively.(Materials Science and Engineering B, 2010, the 172:132-135) SrZn of report such as Linghong Yi 2(PO 4) 2: Eu 2+, Mn 2+, (Journal of Al loys and Compounds, 2011, the 509:76-79) Ba such as Zhiping Yang 1-xMg 2-y(PO 4) 2: xEu 2+, yMn 2+, the disclosed Sr of the Chinese patent of application number 200910272541.9 2-mMg 3-nP 4O 15: Eu m 2+, Mn n 2+Homenergic transmission type list substrate fluorescent powder only has blueness, red two luminescence center, and the LED color developing that encapsulation forms is not high; Single substrate fluorescent powder of three activator has the few of report at present, (ACS Appl.Mater.Interfaces, 2012, the 4:296-305) Ca of report such as Guogang Li 4Y 6(SiO 4) 6O:Ce 3+/ Mn 2+/ Tb 3+Fluorescent material, (Inorg.Chem.2011,50, the 7846-7851) BaMg of report such as Wei L ü 2Al 6Si 9O 30: Eu 2+, Tb 3+, Mn 2+Fluorescent material, (Journal of Luminescence, 2011, the 131:2697-2702) Sr of report such as Xi Chen 1.5Ca 0.5SiO 4: Eu 3+, Tb 3+, Eu 2+Fluorescent material, the single substrate fluorescent powder colour rendering index of this class is high, but it mostly is silicate borate matrix, its synthetic method is confined to solid sintering technology more, and preparation temperature is higher, and pattern is inhomogeneous, the fluorescent material particle diameter is larger, need repeatedly ball milling, and ball milling can reduce the luminous intensity of fluorescent material; The single-matrix white fluorescent powder of the disclosed a kind of near ultraviolet excited white light LED of the Chinese patent of application number 201210110827.9, its chemical expression is: NM 1-x-y-zPO 4: xR, yG, zB, wherein N selects free Li, at least a in the group that Na, K form; M selects free Mg, Ca, Sr, at least a in the group that Ba, Zn form; R selects free Mn, at least a in the group that Sm forms; G is Tb; B selects free Ce, at least a in the group that Eu forms, and 0＜x＜0.25,0＜y＜0.25,0＜z＜0.25, and it adopts sol-gel method, the manufacturing process more complicated, preparation cycle is long.
Summary of the invention
The present invention aims to provide a kind of single-matrix white fluorescent powder near ultraviolet excitated white light LEDs and preparation method thereof.
According to the chemical expression of the single-matrix white fluorescent powder of near ultraviolet excited white light LED of the present invention be: (Sr yBa 1-x-y) (Mg mZn 1-m-p-q) 2(PO 4) 2: xEu, pMn, qTb, wherein 0＜x＜0.1,0＜y＜1,0＜m＜1,0＜p＜0.1,0＜q＜0.1.
The preparation method of above-mentioned fluorescent material comprises:
Take respectively oxide compound or the carbonate of Sr, Ba, Mg, Zn, Eu, Tb, Mn by the stoichiometric ratio in described chemical expression, and primary ammonium phosphate;
Above-mentioned oxide compound or carbonate and primary ammonium phosphate are mixed in acetone solvent, grind 30-120min; And
The powder that mixes is being obtained described fluorescent material under reducing atmosphere after 900-1100 ℃ of lower roasting 1-10h.
In another preferred version of the present invention, reducing atmosphere is carbon monoxide, hydrogen or nitrogen/hydrogen gas mixture.
Can launch the bands of a spectrum of three wave bands of red, green, blue after by the 350-410nm near ultraviolet excitation by the fluorescent material of the present invention preparation, thereby three bands of a spectrum stacks have realized white light emission in single-matrix; Fluorescent powder grain by the present invention's preparation is tiny evenly, and synthetic fluorescent material colour rendering index is high, can be used near ultraviolet excitated white light LEDs.
Embodiment
For better explanation the present invention, provide following examples and set forth.It will be appreciated by those skilled in the art that the present invention be not limited to for embodiment.
Embodiment 1
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 1.4760g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 1000 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: Sr 0.975(Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.31,0.36).
Embodiment 2
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 1.4760g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes in carbon monoxide atmosphere in 1000 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: Sr 0.975(Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.31,0.35).
Embodiment 3
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 1.4760g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes in hydrogen atmosphere in 1000 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: Sr 0.975(Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.31,0.36).
Embodiment 4
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 1050 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: (Sr 0.475Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 420nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.33,0.37).
Embodiment 5
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 1100 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: (Sr 0.475Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 420nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.33,0.37).
Embodiment 6
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 60min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 950 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: (Sr 0.475Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 420nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.32,0.37).
Embodiment 7
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0352g, 0.2296g, 0.0749g, above-mentioned substance is mixed in acetone solvent, grind 90min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 950 ℃ of lower roasting 10h.Prepared phosphor molecule formula is: (Sr 0.48Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.02Eu, 0.1Mn, 0.05Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.31,0.36).
Embodiment 8
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0352g, 0.2296g, 0.0749g, above-mentioned substance is mixed in acetone solvent, grind 80min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 1000 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: (Sr 0.48Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.02Eu, 0.1Mn, 0.05Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.31,0.36).
Embodiment 9
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, BaCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 0.7380g, 0.9867g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 70min; With the powder that mixes in hydrogen atmosphere in 1050 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: (Sr 0.475Ba 0.5) (Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 420nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.33,0.37).
Embodiment 10
Take ZnO, Mg (OH) 24MgCO 35H 2O, SrCO 3, NH 4H 2PO 4, Eu 2O 3, MnCO 3, Tb 4O 7Be respectively 1.1066g, 0.6219g, 1.4760g, 2.3006g, 0.0421g, 0.1148g, 0.1498g, above-mentioned substance is mixed in acetone solvent, grind 120min; With the powder that mixes at nitrogen and hydrogen mixture atmosphere (N 2/ H 2Volume ratio is 9:1) in 1000 ℃ of lower roasting 5h.Prepared phosphor molecule formula is: Sr 0.975(Mg 0.3Zn 0.55) 2(PO 4) 2: 0.025Eu, 0.05Mn, 0.1Tb, maximum excitation wavelength can launch 430nm blue light, 543nm green glow and 580nm orange light at 365nm, and its chromaticity coordinates is (0.33,0.36).

Claims (3)

1. the single-matrix white fluorescent powder of a near ultraviolet excited white light LED, its chemical expression is: (Sr yBa 1-x-y) (Mg mZn 1-m-p-q) 2(PO 4) 2: xEu, pMn, qTb, wherein 0＜x＜0.1,0＜y＜1,0＜m＜1,0＜p＜0.1,0＜q＜0.1.
2. method of making fluorescent material claimed in claim 1 comprises:
Take respectively oxide compound or the carbonate of Sr, Ba, Mg, Zn, Eu, Tb, Mn by the stoichiometric ratio in chemical expression claimed in claim 1, and primary ammonium phosphate; And
Above-mentioned oxide compound or carbonate and primary ammonium phosphate are mixed in acetone solvent, grind 30-120min;
The powder that mixes is being obtained described fluorescent material under reducing atmosphere after 900-1100 ℃ of lower roasting 1-10h.
3. method claimed in claim 2, wherein reducing atmosphere is carbon monoxide, hydrogen or nitrogen/hydrogen gas mixture.
CN2013100250731A 2013-01-23 2013-01-23 Single matrix white phosphor and preparation method thereof Pending CN103087712A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103614138A (en) * 2013-11-29 2014-03-05 东北师范大学 Single-matrix white-light-emitting luminescent material suitable for motivating near-ultraviolet LED (light emitting diode) and preparation method of luminescent material
CN106085429A (en) * 2016-07-11 2016-11-09 河北大学 Wide range LED fluorescent powder of a series of Color tunable and preparation method thereof
CN111187622A (en) * 2020-03-03 2020-05-22 淮阴师范学院 Single-matrix phosphate fluorescent powder for white light LED and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101067081A (en) * 2007-06-06 2007-11-07 厦门大学 Phosphor for white light LED with adjustable emitting peak and its prepn process
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101067081A (en) * 2007-06-06 2007-11-07 厦门大学 Phosphor for white light LED with adjustable emitting peak and its prepn process
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

Non-Patent Citations (1)

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Title
ZHAN-CHAO WU ET AL: "A new single-host white-light-emitting BaSrMg(PO4)2:Eu2+ phosphor for white-light-emitting diodes", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 498, 23 March 2010 (2010-03-23), pages 139 - 142 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103614138A (en) * 2013-11-29 2014-03-05 东北师范大学 Single-matrix white-light-emitting luminescent material suitable for motivating near-ultraviolet LED (light emitting diode) and preparation method of luminescent material
CN103614138B (en) * 2013-11-29 2016-07-06 东北师范大学 Luminescent material that the single-matrix white that a kind of applicable black light LED excites is launched and preparation method thereof
CN106085429A (en) * 2016-07-11 2016-11-09 河北大学 Wide range LED fluorescent powder of a series of Color tunable and preparation method thereof
CN111187622A (en) * 2020-03-03 2020-05-22 淮阴师范学院 Single-matrix phosphate fluorescent powder for white light LED and preparation method thereof
CN111187622B (en) * 2020-03-03 2023-10-24 淮阴师范学院 Single matrix phosphate fluorescent powder for white light LED and preparation method thereof

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Application publication date: 20130508