CN103382390A - Phosphate fluorescent powder used for white light LED and its preparation - Google Patents
Phosphate fluorescent powder used for white light LED and its preparation Download PDFInfo
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- CN103382390A CN103382390A CN2013102895098A CN201310289509A CN103382390A CN 103382390 A CN103382390 A CN 103382390A CN 2013102895098 A CN2013102895098 A CN 2013102895098A CN 201310289509 A CN201310289509 A CN 201310289509A CN 103382390 A CN103382390 A CN 103382390A
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Abstract
The invention discloses a fluorescent powder able to realize blue-green visible light emission under ultraviolet/near ultraviolet excitation and a preparation technology thereof. The fluorescent powder provided in the invention takes phosphate as a matrix and is doped with Eu<2+> ions. With a chemical expression of Eux<2+>:Ca3-x(PO4)2 (with x being greater than or equal to 0.005 and smaller than or equal to 0.21), the fluorescent powder is prepared by: weighing reagents CaCO3(A.R.), NH4H2PO4(A.R.), and Eu2O3 (greater than or equal to 99.99%) according to the chemical expression, adding a proper amount of C2H5OH (anhydrous ethanol), grinding them uniformly, placing the mixture into a tube furnace with an introduced reduction atmosphere, and carrying out high temperature sintering. By adjusting the fluorescent powder doped ion concentration, the light emitted by the fluorescent powder can be adjusted from blue to green under the excitation of 250-420nm ultraviolet/near ultraviolet. The light-emitting quantum efficiency of a sample can realize 56.7%. And the material is expected to be used for white light LED excited by ultraviolet/near ultraviolet.
Description
Technical field
The present invention relates to the solid luminescent material field, especially relate to white light LEDs with ultraviolet/near ultraviolet excitated fluorescent material and preparation technology thereof.
Background technology
Solid state lighting, especially solid white-light illuminating have the characteristics such as economize on electricity, pollution-free, long lifetime, are the new generation of semiconductor light sources that substitutes conventional incandescent and luminescent lamp.Common commercial white light LEDs is by blue light GaN chip and mixes Ce at present
3+Yttrium aluminum garnet (YAG) fluorescent powder packaging make together, fluorescent material is mixed in epoxy resin and is coated on chip.The blue light part that the GaN chip sends is absorbed by fluorescent material, make it be excited to send gold-tinted, and the yellow light mix that unabsorbed blue light and fluorescent material send just obtains white light.Lack the ruddiness composition because the white light LEDs that obtains is whole, cause its colour rendering index on the low side, colour temperature is higher.For fear of these problems, can obtain by the mode that adopts ultraviolet/near-ultraviolet light LED chip to apply manifold color-emitting fluorescent material.At this moment, ultraviolet/near-ultraviolet light that chip sends is absorbed fully by fluorescent material, makes the light of the multiple different colours of fluorescent material stimulated emission, obtains white light after mixing.Therefore, exploitation can produce the fluorescent material of manifold color-emitting under ultraviolet/near ultraviolet excitation, be current research and development focus.
Phosphoric acid salt is with its physics and chemistry stability and Heat stability is good and be widely adopted matrix as luminescent material.At present, white light LEDs is with the research of the green glow phosphate phosphor of ultraviolet/near ultraviolet excitated with to use be mainly with Tb
3+For activator (as flat in document 1 Yang Zhi, Ma Xin, Song Zhaofeng. LiSrPO
4: Tb
3+The preparation of fluorescent material and the characteristics of luminescence, luminous journal, 2010,31 (2): 185-188; Document 2 Yang Zhi are flat, Wang Shaoli, Yang Guangwei. green emitting phosphor NaCaPO
4: Tb
3+Preparation and the characteristics of luminescence, luminous journal, 2008,29 (1): 81-83; Document 3 Yang Zhi are flat, Ma Shuyuan, Yu Hongwei. green emitting phosphor Zn
2Ca (PO
4)
2: Tb
3+Preparation and luminescent properties research, functional materials, 2010,41 (7): 1228-1231.), due to Tb
3+Luminously belong to the 4f-4f forbidden transition, emission band is narrow, the green glow composition is replenished not enough.On the other hand, and the emission wavelength of the present phosphoric acid salt blue powder that obtains general ultraviolet region partially (as document 4 Yong-Kwang Kim, Sungho Choi, Ha-Kyun Jung. Photoluminescence properties of Eu
2+And Mn
2+-activated BaMgP
2O
7As a potential red phosphor for white-emission, J. Lumin 2010,130:60 – 64; Document 5 Yu-Sheng Tang, Shu-Fen Hu, Chun Che Lin, Nitin C. Bagkar, and Ru-Shi Liu, Thermally stable luminescence of KSrPO
4: Eu
2+Phosphor for white light UV light-emitting diodes, 2007,90:151108.).And employing Eu
2+Indigo plant-green light fluorescent powder for activator obtains can replenish blue light ingredient, can replenish the green glow composition again, thereby be expected to for ultraviolet/near ultraviolet excitated white light LEDs.
Based on above-mentioned consideration, we have developed a kind of novel rare-earth Eu
2+The Ca of doping
3(PO
4)
2Fluorescent material.This calcium phosphate matrix belongs to orthohormbic structure, and its lattice parameter is a=15.22, b=20.71, c=9.19.Eu
2+Enter lattice, be subject to the effect of crystal field, the strong indigo plant-green glow (wavelength region is 400-600nm) of emission under ultraviolet/near ultraviolet excitation.The high luminous quantum efficiency that obtains at present can reach 56.7%, is expected for ultraviolet/near ultraviolet excitated white light LEDs.
Summary of the invention
The present invention proposes a kind of Eu
2+The Ca of doping
3(PO
4)
2Component and preparation technology thereof, purpose is to prepare stable performance, can realizes indigo plant-green luminous phosphor material powder under ultraviolet/near ultraviolet excitation.
The white light LEDs phosphate phosphor of the present invention's preparation, its chemical expression is Eu
x 2+: Ca
3-x(PO
4)
2(0.005≤x≤0.21), crystal phase structure are the quadrature phase.
Fluorescent material can effectively be excited between 250-420nm as mentioned above, the indigo plant-green glow between emission 400-600nm.
The present invention adopts and is prepared as follows technique: powder raw material is mixed according to certain component proportion, add appropriate ethanol to grind 30-45 minute, then dried by the fire 2-5 minute in 60 ℃ of baking ovens, take out and ground again approximately 10-15 minute, dried by the fire 5-10 minute in 60 ℃ of baking ovens again, ground 5-10 minute after taking out, then be placed in square crucible, insert and be connected with 5%H
2-95%N
2Tube type resistance furnace in, be warming up to 1350-1450 ℃ with stove and carry out sintering, and the insulation 6-9 hour; At last, furnace cooling obtains our sample.
Adopt above component and preparation technology, successfully obtained the fluorescent material sample, it has following structure and luminescence feature: fluorescent material matrix is quadrature Ca mutually
3(PO
4)
2, the Eu of doping
2+Enter in lattice, thereby produce strong luminescence under ultraviolet/near ultraviolet excitation.Raw materials cost in this preparation process is cheap, good reproducibility, and preparation technology is simple.
Change Eu
2+The doping content of ion, under 250-420nm ultraviolet/near ultraviolet excitation, the luminous of fluorescent material can change to green glow from blue light; Therefore, by controlling rear-earth-doped concentration, can realize the regulation and control to such light-emitting phosphor color.
Fluorescent material preparation technology of the present invention is simple, with low cost, and nontoxic pollution-free has good physics, chemical stability and thermal stability, is expected to be applied to white light LED part.
Description of drawings
Fig. 1 is different Eu
2+Doping content sample xEu
2+: Ca
3-x(PO
4)
2The X-ray diffraction spectrogram;
Fig. 2 is different Eu
2+Doping content sample xEu
2+: Ca
3-x(PO
4)
2Excitation and emission spectra figure; Wherein excitation wavelength is 365nm, and the emission wavelength of monitoring is 490nm.
Fig. 3 is 0.05Eu
2+: Ca
2.95(PO
4)
2Exciting and emission spectrum of fluorescent material sample and reference sample, illustration are the partial enlarged drawings of emission spectrum; The luminous quantum efficiency that calculates (QY) is marked in figure.
Adopt the crystalline structure of Rigaku RIGAKU – DMAX2500 X-ray polycrystalline diffractometer specimen; Adopt fluorescent emission/excitation spectrum and the quantum yield of the Edinburgh FS920 of company fluorescence spectrophotometer (band integrating sphere) specimen.
Embodiment
Example 1: with analytically pure CaCO
3, NH
4H
2PO
4With purity be 99.99% Eu
2O
3Powder is pressed 2.95CaCO
3: 2NH
4H
2PO
4: 0.025Eu
2O
3The proportioning accurate weighing of (mol ratio) is placed in agate mortar, adds appropriate ethanol to grind after 30 minutes, makes it even mixing; Dried by the fire in 60 ℃ of baking ovens approximately 2 minutes and be placed on, after taking-up, ground in mortar approximately 15 minutes, then dried by the fire 10 minutes in 60 ℃ of baking ovens, after taking out, grinding is 10 minutes, then is placed in square crucible, is being connected with 5%H
2-95%N
2The high temperature tubular resistor furnace of temperature programmed control in be heated to 1400 ℃, be incubated after 8 hours, furnace cooling obtains sample.According to X-ray diffraction analysis result (as shown in x=0.05 in Fig. 1), the fluorescent material that obtains is pure quadrature phase Ca
3(PO
4)
2It excites and emission spectrum (as shown in x=0.05 in Fig. 2) illustrates that it can effectively be excited in ultraviolet/near ultraviolet region, thus the emission blue green light; It excites the lower bright blue green light that shown at the 365nm ultraviolet lamp.The luminous quantum efficiency of this fluorescent material sample can reach for 56.7% (as shown in Figure 3).
By above-mentioned preparation method, keep NH
4H
2PO
4Amount constant, regulate CaCO
3And Eu
2O
3Mol ratio we also obtained the 0.0025Eu that adulterates respectively
2O
3, 0.005Eu
2O
3, 0.015Eu
2O
3, 0.045Eu
2O
3, 0.075Eu
2O
3, 0.105Eu
2O
3The fluorescent material sample.This series samples is under ultraviolet/near ultraviolet excitation of 250-420nm, and glow color can change to green by blueness.
Example 2: with analytically pure CaCO
3, NH
4H
2PO
4With purity be 99.99% Eu
2O
3Powder is pressed 2.99CaCO
3: 2NH
4H
2PO
4: 0.005Eu
2O
3The proportioning accurate weighing of (mol ratio) is placed in agate mortar, adds appropriate ethanol to grind after 35 minutes, makes it even mixing; Dried by the fire in 60 ℃ of baking ovens approximately 5 minutes and be placed on, after taking-up, ground in mortar approximately 10 minutes, then dried by the fire 8 minutes in 60 ℃ of baking ovens, after taking out, grinding is 5 minutes, then is placed in square crucible, is being connected with 5%H
2-95%N
2The high temperature tubular resistor furnace of temperature programmed control in be heated to 1450 ℃, be incubated after 6 hours, furnace cooling obtains sample.According to the X-ray diffraction analysis result, the fluorescent material that obtains is pure quadrature phase Ca
3(PO
4)
2It excites with emission spectrum and illustrates that it can effectively be excited in ultraviolet/near ultraviolet region, and the emission blue light.
Example 3: with analytically pure CaCO
3, NH
4H
2PO
4With purity be 99.99% Eu
2O
3Powder is pressed 2.91CaCO
3: 2NH
4H
2PO
4: 0.045Eu
2O
3The proportioning accurate weighing of (mol ratio) is placed in agate mortar, adds appropriate ethanol to grind after 45 minutes, makes it even mixing; Dried by the fire in 60 ℃ of baking ovens approximately 3 minutes and be placed on, after taking-up, ground in mortar approximately 12 minutes, then dried by the fire 5 minutes in 60 ℃ of baking ovens, after taking out, grinding is 7 minutes, then is placed in square crucible, is being connected with 5%H
2-95%N
2The high temperature tubular resistor furnace of temperature programmed control in be heated to 1350 ℃, be incubated after 9 hours, furnace cooling obtains sample.According to the X-ray diffraction analysis result, the fluorescent material that obtains is pure quadrature phase Ca
3(PO
4)
2It excites with emission spectrum and illustrates that it can effectively be excited in ultraviolet/near ultraviolet region, and the emission blue green light.
Claims (3)
1. white light LEDs phosphate phosphor, its chemical expression is Eu
x 2+: Ca
3-x(PO
4)
2, 0.005≤x≤0.21 wherein, crystal phase structure is the quadrature phase.
2. fluorescent material according to claim 1, it is characterized in that: described fluorescent material is effectively excited between 250nm-420nm, the indigo plant-green glow between emission 400nm-600nm.
3. the preparation method of the described fluorescent material of claim 1 comprises the following steps:
(1) Ca in molar ratio
2+: (PO
4)
3: Eu
2+=3-x:2:x takes raw material powder CaCO
3, NH
4H
2PO
4, Eu
2O
3,0.005≤x≤0.21 wherein; Grind evenly, obtain compound;
(2) the gained compound is inserted be connected with 5%H
2-95%N
2Tube type resistance furnace in, be warming up to 1350-1450 ℃ with stove and carry out sintering, and the insulation 6-9 hour, cooling rear grinding obtains described fluorescent material.
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| CN201310289509.8A CN103382390B (en) | 2013-07-11 | 2013-07-11 | A kind of white light LEDs phosphate phosphor and its preparation |
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| CN201310289509.8A CN103382390B (en) | 2013-07-11 | 2013-07-11 | A kind of white light LEDs phosphate phosphor and its preparation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315994A (en) * | 2014-07-29 | 2016-02-10 | 湖南师范大学 | Alkaline-earth phosphate fluorescent powder and preparation method therefor |
| CN109054836A (en) * | 2018-09-28 | 2018-12-21 | 苏州鼎安科技有限公司 | A kind of two-phase tricalcium phosphate white fluorescent powder and its in-situ synthetic method and purposes |
| CN115109590A (en) * | 2022-07-12 | 2022-09-27 | 中国科学院长春应用化学研究所 | Phosphor and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100468789C (en) * | 2002-02-15 | 2009-03-11 | 三菱化学株式会社 | Light emitting device and illuminating device using it |
| JP2010215717A (en) * | 2009-03-13 | 2010-09-30 | National Institute Of Advanced Industrial Science & Technology | Illuminant and method for producing the illuminant |
| CN102167976A (en) * | 2010-02-26 | 2011-08-31 | 海洋王照明科技股份有限公司 | Fluo phosphate green luminescent material and method for preparing same |
| CN102618272A (en) * | 2012-03-16 | 2012-08-01 | 武汉工程大学 | Phosphate red luminescent material and preparation method thereof |
-
2013
- 2013-07-11 CN CN201310289509.8A patent/CN103382390B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100468789C (en) * | 2002-02-15 | 2009-03-11 | 三菱化学株式会社 | Light emitting device and illuminating device using it |
| JP2010215717A (en) * | 2009-03-13 | 2010-09-30 | National Institute Of Advanced Industrial Science & Technology | Illuminant and method for producing the illuminant |
| CN102167976A (en) * | 2010-02-26 | 2011-08-31 | 海洋王照明科技股份有限公司 | Fluo phosphate green luminescent material and method for preparing same |
| CN102618272A (en) * | 2012-03-16 | 2012-08-01 | 武汉工程大学 | Phosphate red luminescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YINQUN LI等: "Color Point Tuning by Partial Ba2+ Substitution of Ca2+ in (Ca1-xBax)3(PO4)2 Phosphor for White Light Emitting Diodes", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315994A (en) * | 2014-07-29 | 2016-02-10 | 湖南师范大学 | Alkaline-earth phosphate fluorescent powder and preparation method therefor |
| CN109054836A (en) * | 2018-09-28 | 2018-12-21 | 苏州鼎安科技有限公司 | A kind of two-phase tricalcium phosphate white fluorescent powder and its in-situ synthetic method and purposes |
| CN115109590A (en) * | 2022-07-12 | 2022-09-27 | 中国科学院长春应用化学研究所 | Phosphor and application thereof |
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| CN103382390B (en) | 2017-07-18 |
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