CN101693834B - Rare-earth red light-emitting material for converting purple light LED into white light and preparation process thereof - Google Patents

Rare-earth red light-emitting material for converting purple light LED into white light and preparation process thereof Download PDF

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CN101693834B
CN101693834B CN2009102177043A CN200910217704A CN101693834B CN 101693834 B CN101693834 B CN 101693834B CN 2009102177043 A CN2009102177043 A CN 2009102177043A CN 200910217704 A CN200910217704 A CN 200910217704A CN 101693834 B CN101693834 B CN 101693834B
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light
rare
earth
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led
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CN101693834A (en
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张昕彤
刘益春
赵成久
戴鹏鹏
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Northeast Normal University
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Northeast Normal University
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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
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Abstract

The invention relates to a rare-earth red light-emitting material for converting purple light LED into white light and a preparation process thereof, which belong to the technical field of light emission and display and relate to a red light-emitting material and the preparation process thereof. The structural formula of the red light-emitting material includes M4-3a-3b-2c (MoO4) 2: RaRbNc, wherein the M is an alkali metal Li element, the Ra is a rare-earth activator Eu element, the Rb is a rare-earth sensitizer Tb element, and the Nc is a metal sensitizer Pb element. Materials of the structural formula M4-3a-3b-2c (MoO4) 2: RaRbNc are weighed according to percentage by weight; the weighed materials after being grinded and mixed evenly are placed into an aluminum trioxide crucible and sintered for 1-2 hours in a 400-600 DEG C high-temperature furnace; after being cooled, the materials are fetched out, pulverized, placed into the crucible again and sintered for 2-3 hours in 700-1000 DEG C air atmosphere in the high-temperature furnace; after being cooled, the materials are fetched out and pulverized again, and crystalline powders are obtained and can emit bright red light by stimulation of 365 nanometers and a purple light LED. After the crystalline powders are mixed with rare-earth light-emitting materials emitting green and blue light according to a certain proportion, white light can be emitted by coating the crystalline powders onto a purple light LED tube core.

Description

Rare-earth red light-emitting material for converting purple light LED into white light and preparation method
Technical field
The invention belongs to luminous and the technique of display field, relate to a kind of red illuminating material and preparation method thereof.
Background technology
Because the fast development of semi-conductor (LED) technology, white light LEDs are owing to its high light efficiency, plurality of advantages such as high-color rendering, environmental protection, life-span length have become the focus of countries in the world research.It is ripe that the technology of blue-ray LED conversion of white light has been tending towards, and the technology of follow-on LED conversion of white light into purple light is being risen.For the luminous efficiency that further improves LED conversion of white light into purple light, colour rendering index etc.; Make it reach commodity practicability; One side need be improved the purple LED chip technology, and it is red to improve the used rare-earth trichromatic of conversion of white light on the other hand, indigo plant; The improvement of the luminous efficiency of the performance of green luminescent material, particularly red illuminating material, stability improves.Present existing rare-earth activated red illuminating material such as CaS:Eu 3+, SrCaS:Eu 3+, Y 2O 2S:Eu 3+, SrSiO 4: Eu 3+Etc. unstable properties, influence its luminescent properties.At present, at the rare-earth activated red illuminating material of developing, as: the rare-earth activated borate of development such as Zhongshan University, the coloured institute in Beijing, tungstate etc.The present invention relates to one type of novel rare-earth Eu 3+Ion-activated; And mix an amount of molybdate red luminescent material of the coactivated earth alkali metal of sensitizing agent Tb, Pb; Advantages such as this type luminescent material has luminous efficiency height, good stability, color developing is high, synthesis technique is simple are the high efficient luminous materials that can be used for the LED conversion of white light into purple light purposes.
Summary of the invention
The rare-earth red luminous material that LED conversion of white light into purple light of the present invention is used, its structural formula is: M 4-3a-3b-2c(MoO 4) 2: R aR bN c
Technical scheme of the present invention is following:
1. material is chosen: according to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is Li, R aDuring for rare earth Eu element, R bDuring for rare earth Tb element, N cDuring for the metal Pb element, take by weighing the following material of high purity by its weight percent:
Li 2CO 3：5％-40％ Eu 2O 3：7％-45％
MoO 3：40％-65％ Tb 4O 7：0.2％-5％
PbO：0.1％-4％
2. with the above-mentioned material that takes by weighing after grinding is mixed, the alumina crucible of packing into add a cover put into High Temperature Furnaces Heating Apparatus air 400-600 ℃ sintering 1-2 hour.
3. porphyrize is taken out in the cooling back, reinstalls in the alumina crucible and adds a cover, and puts into 700-1000 ℃ of sintering 2-3 of High Temperature Furnaces Heating Apparatus air hour, and cooling is taken out porphyrize and obtained exciting the crystal powder that sends bright red down at 365nm and purple LED.It can be sent white light with being coated on the purple LED tube core after the rare earth luminescent material of greening, blue light mixes by a certain percentage.
LED conversion of white light into purple light of the present invention is with the red illuminating material in the rare-earth trichromatic luminescent material, its structural formula: M 4-3a-3b-2c(MoO 4) 2: R aR bN c, (1) M is a basic metal Li element, R aBe rare-earth activated dose of Eu element, R bBe rare earth sensitizing agent Tb element, N cBe metal sensitizing agent Pb element, span 0.1≤a≤1 of a in (2) structural formula, span 0.01≤b≤0.07 of b, span 0.001≤c≤0.03 of c.
LED conversion of white light into purple light of the present invention is with the red illuminating material advantage in the rare-earth trichromatic luminescent material:
1. rare earth Eu element is an activator, and sensitizing agent is rare earth Tb and metal Pb element, and the luminous efficiency of its activator Eu is significantly improved.
2. high light efficiency, color developing is good, technology is simple.
Description of drawings
Fig. 1 is the novel red fluorescent material of gained after instance 1 high-temperature calcination, at near-ultraviolet light (the red emission spectrogram under exciting of λ=400nm).
Fig. 2 is rare-earth trichromatic green emitting phosphor, blue colour fluorescent powder and red fluorescence powder (instance one) (2: 5: 9) mixing in proportion, and (λ=(chromaticity coordinates is x=0.297, emmission spectrum figure y=0.36) 400nm) to excite following gained white light at near-ultraviolet light.
Embodiment
Instance 1
1. according to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：11.51％ Eu 2O 3：28.70％
Tb 4O 7：0.76％ MoO 3：58.75％
PbO：0.3％
2. with the above-mentioned material that takes by weighing through grinding be mixed even after, the alumina crucible of packing into is added a cover and is put into High Temperature Furnaces Heating Apparatus at air 400 ℃ of sintering 1 hour for the first time.
3. porphyrize is taken out in cooling back, reinstalls to add a cover in the High Temperature Furnaces Heating Apparatus air for the second time 700 ℃ of sintering in the alumina crucible 2 hours, and the crystal powder that porphyrize promptly obtains under ultraviolet 365nm excites with purple LED, sending bright ruddiness is taken out in cooling.
Instance 2
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M was the Li element, Ra was the Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：8.86％ Eu 2O 3：31.8％
MoO 3：57.82％ Tb 4O 7：1.12％
PbO：0.4％
450 ℃ of first sinterings 1 hour, 750 ℃ of sintering 2 hours for the second time, the sintering synthesis step is with instance 1
Instance 3
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：10.95％ Eu 2O 3：28.59％
MoO 3：58.49％ Tb 4O 7：1.52％
PbO：0.45％
450 ℃ of first sintering temperature 2 hours, 800 ℃ of sintering 2 hours for the second time, the sintering synthesis step is with instance 1
Instance 4
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：6.05％ Eu 2O 3：34.74％
MoO 3：56.87％ Tb 4O 7：1.85％
PbO：0.49％
550 ℃ of first sintering temperature 1 hour, 850 ℃ of sintering temperatures 1 hour for the second time, the sintering synthesis step is with instance 1
Instance 5
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：6.93％ MoO 3：56.41％
Eu 2O 3：34.46％ Tb 4O 7：1.46％
PbO：0.74％
600 ℃ of first sintering temperature 2 hours, 850 ℃ of sintering temperatures 3 hours for the second time, the sintering synthesis step is with instance 1
Instance 6
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：15.26％ Eu 2O 3：21.9％
MoO 3：59.75％ Tb 4O 7：2.32％
PbO：0.77％
600 ℃ of first sintering temperature 2 hours, 900 ℃ of sintering temperatures 2 hours for the second time, the sintering synthesis step is with instance 1
Instance 7
According to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is the Li element, R aBe Eu element, R bDuring for the Tb element, N cDuring for the metal Pb element, take by weighing following high purity material by its weight percent:
Li 2CO 3：20.9％ Eu 2O 3：14.97％
Tb 4O 7：0.78％ MoO 3：61.24％
PbO：2.11％
600 ℃ of first sintering temperature 1 hour, 1000 ℃ of sintering temperatures 2 hours for the second time, the sintering synthesis step is with instance 1.

Claims (2)

1. the preparation method of rare-earth red light-emitting material for converting purple light LED into white light is characterized in that concrete steps are following:
1. according to chemical structural formula M 4-3a-3b-2c(MoO 4) 2: R aR bN c, when M is Li, R aDuring for rare earth Eu element, R bDuring for rare earth Tb element, N cDuring for the metal Pb element, take by weighing the following material of high purity by its weight percent:
Li 2CO 3：5％-40％ Eu 2O 3：7％-45％
MoO 3：40％-65％ Tb 4O 7：0.2％-5％
PbO：0.1％-4％，
Span 0.1≤a≤1 of a in the structural formula, span 0.01≤b≤0.07 of b, span 0.001≤c≤0.03 of c;
2. with the above-mentioned material that takes by weighing after grinding is mixed, the alumina crucible of packing into add a cover put into High Temperature Furnaces Heating Apparatus air 400-600 ℃ sintering 1-2 hour;
3. porphyrize is taken out in the cooling back; Reinstall in the alumina crucible and add a cover; Put into 700-1000 ℃ of sintering 2-3 of High Temperature Furnaces Heating Apparatus air hour; Cooling is taken out porphyrize and is obtained exciting the crystal powder that time sends bright red at 365nm and purple LED, and it can be sent white light with being coated on the purple LED tube core after the rare earth luminescent material of greening, blue light mixes by a certain percentage.
2. rare-earth red light-emitting material for converting purple light LED into white light is characterized in that its structural formula is: M 4-3a-3b-2c(MoO 4) 2: R aR bN c, wherein (1) M is a basic metal Li element, R aBe rare-earth activated dose of Eu element, R bBe rare earth sensitizing agent Tb element, N cBe metal sensitizing agent Pb element, span 0.1≤a≤1 of (2) a, span 0.01≤b≤0.07 of b, span 0.001≤c≤0.03 of c.
CN2009102177043A 2009-09-24 2009-09-24 Rare-earth red light-emitting material for converting purple light LED into white light and preparation process thereof Expired - Fee Related CN101693834B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348714A (en) * 2008-09-12 2009-01-21 东北师范大学 Red rare earth luminescent material for purple light LED conversion white light and preparation thereof
CN101402859A (en) * 2008-11-24 2009-04-08 东北师范大学 Rare earth red luminescent material for LED conversion of white light into purple light and production method thereof
US20090134769A1 (en) * 2007-09-14 2009-05-28 Osram Sylvania Inc. Phosphor blend for a compact fluorescent lamp and lamp containing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090134769A1 (en) * 2007-09-14 2009-05-28 Osram Sylvania Inc. Phosphor blend for a compact fluorescent lamp and lamp containing same
CN101348714A (en) * 2008-09-12 2009-01-21 东北师范大学 Red rare earth luminescent material for purple light LED conversion white light and preparation thereof
CN101402859A (en) * 2008-11-24 2009-04-08 东北师范大学 Rare earth red luminescent material for LED conversion of white light into purple light and production method thereof

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