CN102492427A - White-light luminescent material - Google Patents

White-light luminescent material Download PDF

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Publication number
CN102492427A
CN102492427A CN2011104179464A CN201110417946A CN102492427A CN 102492427 A CN102492427 A CN 102492427A CN 2011104179464 A CN2011104179464 A CN 2011104179464A CN 201110417946 A CN201110417946 A CN 201110417946A CN 102492427 A CN102492427 A CN 102492427A
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white
luminescent material
light
bigger
light luminescent
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王灵利
倪海勇
张秋红
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Guangzhou Research Institute of Non Ferrous Metals
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Guangzhou Research Institute of Non Ferrous Metals
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    • 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

Abstract

The invention discloses a white-light luminescent material. The white-light luminescent material is characterized by showing by a general formula as follows: xN.yM.zP.qS, wherein N is Y2O3 or/and Gd2O3, and x is not smaller than 0.4 and not bigger than 0.5; M is V2O5 or NH4VO3, and y is not smaller than 0 and not bigger than 0.2; P is (NH4)2HPO4, (NH4)H2PO4 or (NH4)3PO4, and z is not smaller than 0.5 and not bigger than 1; S is Dy2O3 and Eu2O3, and q is bigger than 0 and not greater than 0.1, wherein N, M and P form a substrate, and S is an activating ion. The invention discloses a Dy<3+> activating luminescent material, which shows a two-waveband emission combination of blue 483nm and yellow 573nm under the activation of 254mm ultraviolet rays to form the white-light luminescent material, and is doped with Eu<3+> to acquire red 619 nm emission, so that blue light, yellow light and red light can be simultaneously acquired in a substrate, and are combined to be a white-light luminescent material with good colour developing performances.

Description

A kind of white light emitting material
Technical field
The present invention relates to a kind of white-light emitting ceramic.
Background technology
In order to obtain white light, existing electricity-saving lamp, neon light all adopt three basic colors red (Y 2O 3: Eu 3+), blue (BaMgAl 10O 17: Eu 2+), green (CeMgAl 11O 19: Tb 3+) three kinds of luminescent material proportional mixing form.Because the difference of rerum natura, the fluorescent material of three kinds of different substrates is difficult for mixing, and occurs phenomenons such as aberration easily.In addition, blue colour fluorescent powder BaMgAl 10O 17: Eu 2+Thermostability relatively poor, oxidized easily in the process of roasted tube, cause sending the yellow partially light of color, cause aberration.
Dy 3+Activated rare earth vanadium phosphate (Re (P, V) O 4: Dy 3+) under ultraviolet excitation, launch the blue light of 483nm and the gold-tinted of 573nm, can obtain good white light after compound.Adopt the matrix of single-material, the photochromic impure phenomenon that can avoid the three primary colors fluorescent powder skewness to bring as fluorescent material.In addition, the matrix of rare earth vanadium phosphate is comparatively stable, does not have the phenomenon of thermal degradation when.
CN101974334A discloses a kind of mercury lamp with single-phase RE vanadium phosphate white emitting fluorescent powder and preparation method thereof, and its chemical formula does
Figure BSA00000636066100011
Wherein RE is rare earth ion Y 3+, La 3+, Gd 3+, Lu 3+M 1Be alkalimetal ion Li +, Na +, K +M 2Be alkaline earth metal ion Mg 2+, Ca 2+, Sr 2+, Ba 2+0≤n≤4,0≤x≤0.4,0≤y≤0.3,0≤z≤1.Adopt chemical coprecipitation will contain corresponding yin, yang ionic material dissolution and become solution, the throw out that mixes the back generation is through washing, dry, calcining; Or calcining promptly obtains fluorescent material after adopting solid reaction process that raw materials mix is fully ground.This fluorescent material sends the gold-tinted of 573nm and the blue light of 483nm, and mixing can get white light emission.Cooperated-sensitization effect through basic metal and alkaline earth metal ion improves luminous intensity.
CN102002363A discloses a kind of deep UV LED with single-substrate white fluorescent powder and preparation method thereof, and its chemical formula is A NxB xRe 1-x-yP zV 1-zO 4: Dy y 3+, wherein RE is rare earth ion Y 3+, La 3+, Gd 3+, Lu 3+A is alkalimetal ion Li +, Na +, K +B is transition metal ion Zn 2+, Cd 2+0≤n≤4,0≤x≤0.4,0≤y≤0.3,0≤z≤1.This fluorescent material sends the gold-tinted of 573nm and the blue light of 483nm, and mixing can get white light emission.Cooperated-sensitization effect through basic metal and transition metal ion improves luminous intensity, in 250～350nm scope, forms wide strong excitation band.
CN101974334A, CN102002363A is to Re 1-x-yP zV 1-zO 4: Dy y 3+(RE=Y 3+, La 3+, Gd 3+, Lu 3+) under different shooting conditionss the emission white light; Through the doping of basic metal, earth alkali metal and transition metal ion, improve its luminous intensity, but because lack red composition in the white light that the combination of the blue light of the gold-tinted of 573nm and 483nm obtains; Cause its colour rendering index on the low side, color developing is relatively poor.
Zhao Xiaoxia, people such as Xie Yihua ((Y, Gd) (P, V) O 4: Eu 3+The characteristics of luminescence of fluorescent material, luminous journal, 2006,27 (2), 196) reported (Y, Gd) (P, V) O 4: Eu 3+Spectral response curve under VUV and UV excite has been discussed activator Eu 3+Concentration to the influence of luminosity.(Y, Gd) (P, V) O 4: Eu 3+The emission main peak of fluorescent material has purity of color preferably at 619nm.
Above-mentioned Dy 3+The activated white light emitting material improves luminous intensity with basic metal, earth alkali metal or transition metal ion as sensitizing agent, does not appear in the newspapers but its color developing is improved the aspect.
Summary of the invention
The present invention provides a kind of Dy 3+Activate luminescent material, present blue 483nm down 254nm ultraviolet ray excited and launch with yellow 573nm two waveband and be combined to form the luminescent material of white light, and pass through Eu 3+Doping, obtain the emission of red 619nm, improve color developing.
Luminescent material of the present invention can be expressed as with general formula: xN.yM.zP.qS; Wherein N is Y 2O 3Or/and Gd 2O 3, 0.4≤x≤0.5; M is V 2O 5Or NH 4VO 3, 0≤y≤0.2; P is (NH 4) 2HPO 4, (NH 4) H 2PO 4Or (NH 4) 3PO 4, 0.5≤z≤1; S is Dy 2O 3And Eu 2O 3, 0＜q≤0.1; Wherein N, M and P form matrix, and S is active ions.
The optimum proportion of each component of luminescent material of the present invention is 0.4925Y 2O 3, 0.1V 2O 5, 0.8 (NH 4) 2HPO 4, 0.005Dy 2O 3, 0.0025Eu 2O 3
The present invention adopts Dy 3+As active ions, under the exciting of UV-light, launch blue light and gold-tinted.Through adjustment vanadium, phosphorus matrix components, the ratio of adjustment blue light and gold-tinted obtains white light emission.Through co-activation ion Eu 3+Adding, increase red light, obtain blue light, gold-tinted and ruddiness in a kind of matrix simultaneously thereby be implemented in, and be combined into a kind of white light emitting material, have color developing preferably.
Description of drawings
The X-ray diffractogram of Fig. 1 embodiment 1;
The emmission spectrum of Fig. 2 embodiment 1 under ultraviolet ray excited;
Fig. 3 embodiment 1 is at the excitation spectrum of ultraviolet region;
Fig. 4 embodiment 1 chromaticity coordinate figure (X=0.300, Y=0.2453).
Embodiment
V with purity＞99% 2O 5, NH 4VO 3, (NH 4) 2HPO 4, (NH 4) H 2PO 4(NH 4) 3PO 4And the Y of purity＞99.99% 2O 3, Gd 2O 3, Dy 2O 3And Eu 2O 3, press table 1 mixed, batch mixing is 40 hours in encloses container, and the raw material that mixes is placed alumina crucible; Put into High Temperature Furnaces Heating Apparatus, 850 ℃ of insulations 6 hours, furnace cooling was after grinding again; In 1300～1400 ℃ of insulations 12 hours, cooling, broken classification obtained white luminescent material again.
Testing method: use the exciting of Hitachi F-7000 XRF test fluorescent material, emmission spectrum; Use the photoelectric properties of a distant place, Hangzhou photoelectricity PMS-50 ultraviolet-visible-near-infrared spectrum analytical system test fluorescent material.Probe temperature: room temperature.
Relative brightness R%=I Embodiment launches integrated intensity/ I Embodiment 4 emission integrated intensities* 100%
Embodiment sees the following form 1.
The chemical constitution of table 1 embodiment, relative brightness and colour rendering index
Figure BSA00000636066100041
Luminescent properties through embodiment and Comparative Examples relatively can be found out Eu 3+Adding, guaranteeing can effectively to improve Y (P, V) O on the basis of luminous intensity 4: the color developing of Dy, thus make this material have better practicality.

Claims (2)

1. a white light emitting material is characterized in that being expressed as with general formula: xN.yM.zP.qS; Wherein N is Y 2O 3Or/and Gd 2O 3, 0.4≤x≤0.5; M is V 2O 5Or NH 4VO 3, 0≤y≤0.2; P is (NH 4) 2HPO 4, (NH 4) H 2PO 4Or (NH 4) 3PO 4, 0.5≤z≤1; S is Dy 2O 3And Eu 2O 3, 0＜q≤0.1; Wherein N, M and P form matrix, and S is active ions.
2. white light emitting material according to claim 1, the ratio that it is characterized in that each component is 0.4925Y 2O 3, 0.1V 2O 5, 0.8 (NH 4) 2HPO 4, 0.005Dy 2O 3, 0.0025Eu 2O 3
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3555337A (en) * 1968-09-17 1971-01-12 Sylvania Electric Prod Electric discharge device with dysprosium activated yttrium vanadate phosphors
CN1357596A (en) * 2001-12-29 2002-07-10 中国科学院长春应用化学研究所 Prepn of luminous film
US6590333B1 (en) * 1999-10-01 2003-07-08 Hitachi, Ltd. Rare earth phospho-vanadate phosphors, display system and light emitting system
JP2004263088A (en) * 2003-03-03 2004-09-24 Mitsubishi Chemicals Corp Process for producing fluorescent substance
CN1546605A (en) * 2003-12-05 2004-11-17 中国科学院长春光学精密机械与物理研 High color purity rare earth yttrium gadolinium europium vanadophosphoric acid red phosphor and its production method
CN101974334A (en) * 2010-09-25 2011-02-16 西安理工大学 Single-phase rare earth vanadium phosphate white fluorescent powder for mercury lamp and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3555337A (en) * 1968-09-17 1971-01-12 Sylvania Electric Prod Electric discharge device with dysprosium activated yttrium vanadate phosphors
US6590333B1 (en) * 1999-10-01 2003-07-08 Hitachi, Ltd. Rare earth phospho-vanadate phosphors, display system and light emitting system
CN1357596A (en) * 2001-12-29 2002-07-10 中国科学院长春应用化学研究所 Prepn of luminous film
JP2004263088A (en) * 2003-03-03 2004-09-24 Mitsubishi Chemicals Corp Process for producing fluorescent substance
CN1546605A (en) * 2003-12-05 2004-11-17 中国科学院长春光学精密机械与物理研 High color purity rare earth yttrium gadolinium europium vanadophosphoric acid red phosphor and its production method
CN101974334A (en) * 2010-09-25 2011-02-16 西安理工大学 Single-phase rare earth vanadium phosphate white fluorescent powder for mercury lamp and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
《Journal of Nanoparticle Research》 20071207 Hongliang Zhu et al Hydrothermal synthesis and photoluminescent properties of YV1 - xPxO4:Eu3+ (x = 0-1.0) nanophosphors 第1149-1154页 1-2 第10卷, *
HONGLIANG ZHU ET AL: "Hydrothermal synthesis and photoluminescent properties of YV1 - xPxO4:Eu3+ (x = 0-1.0) nanophosphors", 《JOURNAL OF NANOPARTICLE RESEARCH》 *
JIAYUE SUN ET AL: "Synthesis, structure and luminescence properties of Y(V,P)O4:Eu3+,Bi3+ phosphors", 《JOURNAL OF LUMINESCENCE》 *
L. ROBINDRO SINGH ET AL: "Critical view on energy transfer, site symmetry, improvement in luminescence of Eu3+, Dy3+ doped YVO4 by core-shell formation", 《JOURNAL OF APPLIED PHYSICS》 *
SRINIVASU KANCHARLAPALLI, ET AL: "Eu3+ and Dy3+ Doped YPO4 Nanoparticles: Low Temperature Synthesis and Luminescence Studies", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 *
赵晓霞等: "(Y,Gd)(P,V)O4:Eu3+荧光粉的发光特性", 《发光学报》 *

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Application publication date: 20120613