CN100462621C - Luminous diode transmitting white light - Google Patents

Luminous diode transmitting white light Download PDF

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Publication number
CN100462621C
CN100462621C CNB2007100560376A CN200710056037A CN100462621C CN 100462621 C CN100462621 C CN 100462621C CN B2007100560376 A CNB2007100560376 A CN B2007100560376A CN 200710056037 A CN200710056037 A CN 200710056037A CN 100462621 C CN100462621 C CN 100462621C
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light
white light
blue
sio
powder
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CN101118045A (en
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张家骅
郝振东
张霞
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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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 present invention relates to a light emitting diode, in particular to a white light launching light emitting diode blazed by ultraviolet light. The present invention is formed by painting a compound which comprises a green light luminescent powder with a chemical formula of Ba2SiO4:xEu2+ and a blue-orange light luminescent powder with a chemical formula of Ca2P2O7:xEu2+, yMn2+ on the GaN chip of the ultraviolet light, the compound is formed by the weight ratio of the green light luminescent powder to the blue-orange light luminescent powder is equal to 1:1to 3; the Ba2SiO4:xEu2+ formula x is equal to1 to 4 mol percent, the Ca2P2O7:xEu2+, yMn2+ formula x is equal to 1to 10 mol percent, y is equal to 4 to16 molpercent.

Description

The light emitting diode of emission white light
Technical field
The present invention relates to a kind of light emitting diode, particularly a kind of light emitting diode that is suitable for the emission white light of ultraviolet excitation.
Background technology
That white light emitting diode (LED) has is nontoxic, overlong service life (100,000 hours), energy-efficient, all solid state, plurality of advantages such as operating voltage is low, shock resistance and security are good, can be widely used on the various lighting installations, comprise indoor lamp, stop-light, street lamp, automobile taillight, indicator, brake lamp, outdoor ultra-large type screen, display screen and billboard etc., be a kind of environmental protection, energy-conservation green illumination light source, generally believed it is the new light sources that 21 century substitutes the traditional lighting device.
Realize that at present white light LEDs mainly contains two kinds of schemes: 1. the blue led chip is formed white light LEDs with being organically combined by the gold-tinted fluorescent material that blue light effectively excites.The white light of its emission is formed by the gold-tinted of fluorescent material emission and the blue light of tube core emission.2. the black light led chip is launched the fluorescent material combination composition white light LEDs of red, green, blue three primary colours with can effectively being excited by ultraviolet light.But because the white light of scheme in 1. is to be formed by the yellow fluorescence of fluorescent material and the blue light of tube core, the glow color of device can change with the variation of driving voltage and fluorescent coating thickness, and color reducibility is poor, and colour rendering index is lower.
In addition, the white light emitting diode luminous efficiency that this method is made is lower, is generally 60%-80%, and the colour temperature adjustable extent is little, does not satisfy the actual illumination demand.In recent years, the 2. described white light LEDs development that utilizes the black light led chip to launch the combination of red, green, blue three primary colors fluorescent powder with can effectively being excited by ultraviolet light of scheme is rapid.This scheme has many advantages, particularly shows chromaticity matter and choosing at random property, high color rendering index (CRI) Ra〉90, light efficiency is high and select aspects such as the high-efficiency fluorescence body is of a great variety for use.
2006, China researcher has reported a kind of green light fluorescent powder (Mei Zhang, JingWang, Qiuhong Zhang that is suitable near ultraviolet excitation, Weijia Ding, Qiang Su, in press, Mater.Res.Bull. investigation of materials bulletin, 42 volume (1) phases, the 33-39 page or leaf, 2006), its chemical formula is Ba 2SiO 4: Eu 2+, and made green light LED.Also have a kind of Blue Curacao emitting phosphor that is suitable near ultraviolet excitation (W.M.Yen and M.J.Weber, Inorganic Phosphor, (CRC, New York, 2004), Section 4, P.94.), its chemical formula is Ca 2P 2O 7: Eu 2+, Mn 2+
Summary of the invention
The objective of the invention is provides a kind of novel white-light light emitting diode of low colour temperature high color rendering index (CRI) for overcoming the shortcoming that existing white light LEDs exists.
White light emitting diode of the present invention is to be Ba with chemical formula 2SiO 4: xEu 2+Green light fluorescent powder and chemical formula be Ca 2P 2O 7: zEu 2+, yMn 2+The mixture of Blue Curacao emitting phosphor be coated on the ultraviolet light GaN chip and make, this mixture is pressed green light fluorescent powder: Blue Curacao emitting phosphor=1:1～3 weight ratios are formed; Described Ba 2SiO 4: xEu 2+X=1～4mol% in the formula, described Ca 2P 2O 7: zEu 2+, yMn 2+Z=1～10mol% in the formula, y=4～16mol%.
The preparation method of phosphor mixture involved in the present invention is as follows:
1) prepares green light fluorescent powder with high temperature solid-state method
Green light fluorescent powder is the europkium-activated positive barium silicate of divalence, and chemical formula is Ba 2SiO 4: xEu 2+, x=1～4mol% wherein; By this chemical formula metering ratio, take by weighing brium carbonate, silica, europium oxide, the KCl that accounts for chemical formula 0.5～1mol% makees cosolvent, fully mixing is put in the Si-Mo rod Muffle furnace, under the reducing atmosphere, the roast temperature is 1200 ℃-1300 ℃, and the roast time is 3-4 hour.
2) prepare the Blue Curacao emitting phosphor with high temperature solid-state method
The Blue Curacao emitting phosphor is the coactivated calcium pyrophosphate of divalent europium and bivalent manganese, and chemical formula is Ca 2P 2O 7: zEu 2+, yMn 2+, z=1～10mol% wherein, y=4～16mol%; By this chemical formula metering ratio, take by weighing calcium carbonate or calcium monohydrogen phosphate, DAP, manganese carbonate and europium oxide, fully mixing is put in the Si-Mo rod Muffle furnace, and under the reducing atmosphere, the roast temperature is 1200 ℃-1300 ℃, and the roast time is 1-2 hour.
3) above-mentioned green light fluorescent powder that makes and Blue Curacao emitting phosphor are mixed for 1:1～3 by weight.
The white light LEDs that the present invention makes, when forward drive current was 20mA, colour temperature was 5000～6500K that 3797K is better than present commercial white light LEDs; The illuminant colour coordinate is x=0.39, y=0.40; The light efficiency of white light and average colour rendering index are respectively 91m/W and 84%.
Description of drawings
Fig. 1 is embodiment 2 green powder Ba 2SiO 4: 0.03Eu 2+Excitation spectrum (1) and emission spectrum (2), excitation spectrum is very wide bands of a spectrum, mates with the LED purple light.
Fig. 2 is embodiment 5 Blue Curacao powder Ca 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+Excitation spectrum (1,2) and emission spectrum (3), two excitation spectrums are very wide bands of a spectrum, mate with the LED purple light.
Fig. 3 is embodiment 6～8 medium green powder Ba 2SiO 4: 0.03Eu 2+With Blue Curacao powder Ca 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+Weight ratio be the mixed fluorescent powder of 1:1～3 emission spectrum (400nm excites) (a).Be the mixed fluorescent powder of 1:3 and the encapsulation of GaN black light with the weight ratio with green powder and Blue Curacao powder among the embodiment 9, make the emission spectrum (b) of white light LEDs.
The specific embodiment
Embodiment 1: preparation Ba 2SiO 4: xEu 2+, x=1mol% wherein, the formula of embodying is: Ba 2SiO 4: 0.01Eu 2+Take by weighing 392.7066g BaCO by stoichiometric proportion 3, 60.08g SiO 2, 1.76g Eu 2O 3, 0.7456g KCl makees cosolvent, behind the abundant porphyrize mixing of the raw material that takes by weighing, inserts high-purity corundum crucible or platinum crucible, puts into high temperature furnace.At CO or H 2And N 2Under the reducing atmosphere condition, promptly obtained green light fluorescent powder Ba in 4 hours 1300 ℃ of heating 2SiO 4: 0.01Eu 2+
Embodiment 2: preparation Ba 2SiO 4: xEu 2+, x=3mol% wherein, the formula of embodying is: Ba 2SiO 4: 0.03Eu 2+Take by weighing 388.7598g BaCO by stoichiometric proportion 3, 60.08g SiO 2, 5.28g Eu 2O 3, 0.7456g KCl makees cosolvent, behind the abundant porphyrize mixing of the raw material that takes by weighing, inserts high-purity corundum crucible or platinum crucible, puts into high temperature furnace.At CO or H 2And N 2Under the reducing atmosphere condition, promptly obtained green light fluorescent powder Ba in 4 hours 1300 ℃ of heating 2SiO 4: 0.03Eu 2+
Embodiment 3: preparation Ca 2P 2O 7: zEu 2+, yMn 2+, z=4mol% wherein, y=4mol%.Take by weighing 261.12g CaHPO by stoichiometric proportion 4, 10.56g (NH 4) 2HPO 4, 4.598g MnCO 3, 7.04g Eu 2O 3, behind the abundant porphyrize mixing of the raw material that takes by weighing, insert high-purity corundum crucible or platinum crucible, put into high temperature furnace.At CO or H 2And N 2Under the reducing atmosphere condition, promptly obtained orange light phosphor powder Ca in 2 hours 1250 ℃ of heating 2P 2O 7: 0.04Eu 2+, 0.04Mn 2+
Embodiment 4: preparation Ca 2P 2O 7: zEu 2+, yMn 2+, z=4mol% wherein, y=8mol%.Take by weighing 255.68g CaHPO by stoichiometric proportion 4, 15.84g (NH 4) 2HPO 4, 9.196g MnCO 3, 7.04g Eu 2O 3, behind the abundant porphyrize mixing of the raw material that takes by weighing, insert high-purity corundum crucible or platinum crucible, put into high temperature furnace.At CO or H 2And N 2Under the reducing atmosphere condition, promptly obtained orange light phosphor powder Ca in 2 hours 1250 ℃ of heating 2P 2O 7: 0.04Eu 2+, 0.08Mn 2+
Embodiment 5: preparation Ca 2P 2O 7: zEu 2+, yMn 2+, z=4mol% wherein, y=12mol%.Take by weighing 250.24g CaHPO by stoichiometric proportion 4, 21.12g (NH 4) 2HPO 4, 13.794g MnCO 3, 7.04g Eu 2O 3, behind the abundant porphyrize mixing of the raw material that takes by weighing, insert high-purity corundum crucible or platinum crucible, put into high temperature furnace.At CO or H 2And N 2Under the reducing atmosphere condition, promptly obtained orange light phosphor powder Ca in 2 hours 1250 ℃ of heating 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+
Embodiment 6: with green powder (Ba 2SiO 4: 0.03Eu 2+) and Blue Curacao powder (Ca 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+) be that 1:1 evenly mixes with the mass ratio, can obtain white fluorescent powder with ultraviolet leds tube core coupling.
Embodiment 7: with green powder (Ba 2SiO 4: 0.03Eu 2+) and Blue Curacao powder (Ca 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+) be that 1:2 evenly mixes with the mass ratio, can obtain white fluorescent powder with ultraviolet leds tube core coupling.
Embodiment 8: with green powder (Ba 2SiO 4: 0.03Eu 2+) and Blue Curacao powder (Ca 2P 2O 7: 0.04Eu 2+, 0.12Mn 2+) be that 1:3 evenly mixes with the mass ratio, can obtain white fluorescent powder with ultraviolet leds tube core coupling.
Embodiment 9: the white fluorescent powder of embodiment 8 is become white light LEDs with GaN purple light die package, and when forward drive current was 20mA, colour temperature was 3797K; The illuminant colour coordinate is x=0.39, y=0.40; The light efficiency of white light and average colour rendering index are respectively 91m/W and 84%.

Claims (1)

1. light emitting diode of launching white light is characterized in that being is Ba with chemical formula 2SiO 4: xEu 2+Green light fluorescent powder and chemical formula be Ca 2P 2O 7: zEu 2+, yMn 2+The mixture of Blue Curacao emitting phosphor be coated on the ultraviolet light GaN chip and make, this mixture is pressed green light fluorescent powder: Blue Curacao emitting phosphor=1:1～3 weight ratios are formed; Described Ba 2SiO 4: xEu 2+X=1～4mol% in the formula, described Ca 2P 2O 7: zEu 2+, yMn 2+Z=1～10mol% in the formula, y=4～16mol%.
CNB2007100560376A 2007-09-07 2007-09-07 Luminous diode transmitting white light Expired - Fee Related CN100462621C (en)

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CN102720967A (en) * 2012-06-08 2012-10-10 佛山市中昊光电科技有限公司 Color-temperature-adjustable high-color-rendering light source module
JP2014197527A (en) * 2013-03-04 2014-10-16 信越化学工業株式会社 Vehicle direction indicator

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030094893A1 (en) * 2001-09-25 2003-05-22 Patent-Treuhand-Gesellschaft Fur Elektrische Gluhlampen Mbh Illumination unit having at least one LED as light source
CN1197175C (en) * 2000-05-15 2005-04-13 通用电气公司 White light emitting phosphor blend for LCD devices
CN1610465A (en) * 2003-04-09 2005-04-27 株式会社半导体能源研究所 Light emitting element and light emitting device
CN1636259A (en) * 2000-05-15 2005-07-06 通用电气公司 White light emitting phosphor blends for LED devices
CN1705141A (en) * 2004-05-25 2005-12-07 光宝科技股份有限公司 White light illuminator and method for fabricating same
JP2006245003A (en) * 2005-03-02 2006-09-14 Osram Opto Semiconductors Gmbh Electroluminescence device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1197175C (en) * 2000-05-15 2005-04-13 通用电气公司 White light emitting phosphor blend for LCD devices
CN1636259A (en) * 2000-05-15 2005-07-06 通用电气公司 White light emitting phosphor blends for LED devices
US20030094893A1 (en) * 2001-09-25 2003-05-22 Patent-Treuhand-Gesellschaft Fur Elektrische Gluhlampen Mbh Illumination unit having at least one LED as light source
CN1610465A (en) * 2003-04-09 2005-04-27 株式会社半导体能源研究所 Light emitting element and light emitting device
CN1705141A (en) * 2004-05-25 2005-12-07 光宝科技股份有限公司 White light illuminator and method for fabricating same
JP2006245003A (en) * 2005-03-02 2006-09-14 Osram Opto Semiconductors Gmbh Electroluminescence device

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