CN104212449A - Ultraviolet-excited oxynitride red-light fluorescent powder and preparation method thereof - Google Patents

Ultraviolet-excited oxynitride red-light fluorescent powder and preparation method thereof Download PDF

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Publication number
CN104212449A
CN104212449A CN201410433638.4A CN201410433638A CN104212449A CN 104212449 A CN104212449 A CN 104212449A CN 201410433638 A CN201410433638 A CN 201410433638A CN 104212449 A CN104212449 A CN 104212449A
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fluorescent powder
light fluorescent
red light
oxynitride
oxynitride red
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CN201410433638.4A
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CN104212449B (en
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樊先平
万军
乔旭升
王璠
吴一民
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses an ultraviolet-excited oxynitride red-light fluorescent powder of which the chemical formula is Ca2AlSi3O2N5:xSm<3+>, wherein 0.001<=x<=0.1. The ultraviolet-excited oxynitride red-light fluorescent powder is prepared by combination of an in-situ coprecipitation process and an atmosphere reduction nitrizing process. The preparation technique of the oxynitride red-light fluorescent powder is simple, has the advantage of low sintering temperature, can greatly lower the energy consumption, and is suitable for industrial production. The ultraviolet-excited oxynitride red-light fluorescent powder has the advantages of high luminance, ultraviolet radiation resistance, favorable chemical stability and favorable heat stability; the excitation wavelength is 250-350nm, and the fluorescent powder can be effectively excited by the 282nm InAlGaN deep ultraviolet LED (light-emitting diode); and the emission wavelengths are 602nm and 650nm, and thus, the fluorescent powder can be packaged together with the deep ultraviolet LED to implement red light output.

Description

A kind of burst of ultraviolel oxynitride red light fluorescent powder and preparation method thereof
Technical field
The present invention relates to burst of ultraviolel oxynitride red light fluorescent powder being applied to semiconductor lighting and preparation method thereof, belong to technical field of semiconductor illumination.
Background technology
Since the nineties in 20th century, progress along with LED technology, the particularly exploitation of white light LEDs, LED is from special source Application Areas, as large screen display, pilot lamp, Landscape Lighting, backlight etc., step into gradually general lighting, for people's productive life, brought larger facility, improved quality of lighting.Due to overall merits such as LED have high brightness, high color rendering index (CRI), energy-saving and environmental protection, the life-span is long, volume is little, response is fast, reliability is high, radiationless, be therefore considered to after incandescent light, luminescent lamp and high-intensity gas discharge lamp the 4th generation lighting source.
LED, as environment-friendly type a new generation lighting source, mainly refers to white light LEDs.At present, white light LED part is mainly realized white luminous by LED chip excitated fluorescent powder, and therefore, the fluorescent material throwing light on for LED is the focus of studying both at home and abroad always.Nitride/nitric oxide fluorescent powder is due to nitrogen and metal ion bonding power is strong, Stability Analysis of Structures, thereby has the advantages such as good thermostability and physical and chemical stability.Developed polytype rear-earth-doped nitride/nitric oxide fluorescent powder both at home and abroad, but the nitride/nitric oxide fluorescent powder that is applied to LED illumination also exists, red light-emitting efficiency is not high, synthesis condition requires the deficiencies such as harsh.Therefore, nitride/oxynitride red light fluorescent powder of synthesizing high lumineseent efficiency is significant at a lower temperature.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, with low cost, what be applicable to suitability for industrialized production is applied to burst of ultraviolel oxynitride red light fluorescent powder of semiconductor lighting and preparation method thereof.
Burst of ultraviolel oxynitride red light fluorescent powder of the present invention, its chemical formula is Ca 2alSi 3o 2n 5: xSm 3+, 0.001≤x≤0.1 wherein.
The preparation of burst of ultraviolel oxynitride red light fluorescent powder, the method preparation that adopts original position coprecipitation method to combine with atmosphere reduction nitridation method, specifically comprises the steps:
1) according to chemical formula, by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 70 ~ 90 ℃ of constant temperatures, be back to completely to dissolve; Again by Si 3n 4add in above-mentioned solution, continue at 70 ~ 90 ℃ of constant temperature return stirrings 1 ~ 2 hour, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2cO (the NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 70 ~ 90 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol is added in above-mentioned suspension liquid, continues at 70 ~ 90 ℃ of constant temperature return stirrings 1 ~ 2 hour, obtains with Si 3n 4for core, the muriatic urea complex presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 6 ~ 12 hours under 60 ~ 90 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1000 ~ 1500 ℃ of sintering 1 ~ 8 hour, obtain oxynitride red light fluorescent powder.
Above-mentioned reducing atmosphere is NH 3.
The present invention compares with technical background, has following advantage:
The equipment that the present invention uses is simple, in whole preparation process the time short, sintering temperature is low, integral body has significantly reduced energy consumption, is applicable to very much large-scale industrialization and produces.Light-emitting phosphor brightness of the present invention is high, ultraviolet light resistant, chemical stability and Heat stability is good, excitation wavelength is positioned at 250 ~ 350nm scope, the InAlGaN deep ultraviolet LED that can be 282nm by luminescence center wavelength effectively excites, and its emmission spectrum main peak lays respectively at 602nm and 650nm place.This oxynitride red light fluorescent powder by nanoparticle agglomerates form, luminosity is high, ultraviolet light resistant, chemical stability and Heat stability is good, can be packaged together with deep UV (ultraviolet light) LED, realizes ruddiness output.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the oxynitride red light fluorescent powder of embodiment 1 preparation;
Fig. 2 is the transmission electron microscope photo of the oxynitride red light fluorescent powder of embodiment 1 preparation;
Fig. 3 is the X ray diffracting spectrum of the oxynitride red light fluorescent powder of embodiment 1 preparation.
Fig. 4 is excitation spectrum and the emmission spectrum of the oxynitride red light fluorescent powder of embodiment 1 preparation.In figure: curve 1 is the excitation spectrum under 650nm monitoring, curve 2 is the excitation spectrum under 602nm monitoring, and curve 3 is the excitation spectrum under 280nm monitoring.
Embodiment
embodiment 1
1) according to chemical formula Ca 2alSi 3o 2n 5: 0.001Sm 3+by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, nanometer Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 80 ℃ of constant temperatures, is back to completely to dissolve, then by nanometer Si 3n 4add in above-mentioned solution, continue at 80 ℃ of constant temperature return stirrings 2 hours, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2the CO (NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 80 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol be added in above-mentioned suspension liquid, continue at 80 ℃ of constant temperature return stirrings 2 hours, obtain with nanometer Si 3n 4for core, the muriatic urea complex of the take presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 12 hours under 60 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1100 ℃ of sintering 5 hours, obtain oxynitride red light fluorescent powder.
The electron scanning micrograph of this oxynitride red light fluorescent powder is shown in Fig. 1, the fluorescent material making as seen from the figure by being of a size of hundreds of nanometer, particle in irregular shape forms.Fig. 2 is shown in by its transmission electron microscope photo, and the irregular small-particle that shows to form fluorescent material is to be formed by more tiny nanoparticle agglomerates, and the size of nano particle is about 30nm; Fig. 3 is its X ray diffracting spectrum, shows that the nitric oxide fluorescent powder degree of crystallinity making is high.Fig. 4 is excitation spectrum and utilizing emitted light spectrogram, and as seen from the figure, the nitric oxide fluorescent powder that the present invention prepares produces the ruddiness of 602nm and 650nm under the exciting of 280nm light.
embodiment 2
1) according to chemical formula Ca 2alSi 3o 2n 5: 0.005Sm 3+by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, nanometer Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 70 ℃ of constant temperatures, is back to completely to dissolve, then by nanometer Si 3n 4add in above-mentioned solution, continue at 70 ℃ of constant temperature return stirrings 2 hours, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2the CO (NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 70 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol be added in above-mentioned suspension liquid, continue at 70 ℃ of constant temperature return stirrings 2 hours, obtain with nanometer Si 3n 4for core, the muriatic urea complex of the take presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 12 hours under 60 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1000 ℃ of sintering 8 hours, obtain oxynitride red light fluorescent powder.
embodiment 3
1) according to chemical formula Ca 2alSi 3o 2n 5: 0.01Sm 3+by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, nanometer Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 90 ℃ of constant temperatures, is back to completely to dissolve, then by nanometer Si 3n 4add in above-mentioned solution, continue at 90 ℃ of constant temperature return stirrings 1 hour, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2the CO (NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 90 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol be added to fast in above-mentioned suspension liquid, continue at 90 ℃ of constant temperature return stirrings 1 hour, obtain with nanometer Si 3n 4for core, the muriatic urea complex of the take presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 10 hours under 80 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1200 ℃ of sintering 4 hours, obtain oxynitride red light fluorescent powder.
embodiment 4
1) according to chemical formula Ca 2alSi 3o 2n 5: 0.05Sm 3+by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, nanometer Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 85 ℃ of constant temperatures, is back to completely to dissolve, then by nanometer Si 3n 4add in above-mentioned solution, continue at 85 ℃ of constant temperature return stirrings 1.5 hours, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2the CO (NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 85 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol be added to fast in above-mentioned suspension liquid, continue at 85 ℃ of constant temperature return stirrings 1.5 hours, obtain with nanometer Si 3n 4for core, the muriatic urea complex of the take presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 6 hours under 90 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1400 ℃ of sintering 2 hours, obtain oxynitride red light fluorescent powder.
embodiment 5
1) according to chemical formula Ca 2alSi 3o 2n 5: 0.1Sm 3+by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, nanometer Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 80 ℃ of constant temperatures, is back to completely to dissolve, then by nanometer Si 3n 4add in above-mentioned solution, continue at 80 ℃ of constant temperature return stirrings 2 hours, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2the CO (NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 80 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol be added to fast in above-mentioned suspension liquid, continue at 80 ℃ of constant temperature return stirrings 2 hours, obtain with nanometer Si 3n 4for core, the muriatic urea complex of the take presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 9 hours under 80 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1500 ℃ of sintering 1 hour, obtain oxynitride red light fluorescent powder.

Claims (3)

1. a burst of ultraviolel oxynitride red light fluorescent powder, its chemical formula is Ca 2alSi 3o 2n 5: xSm 3+, 0.001≤x≤0.1 wherein.
2. the method for preparation burst of ultraviolel oxynitride red light fluorescent powder claimed in claim 1, is characterized in that comprising the steps:
1) according to chemical formula, by stoichiometric ratio, take CaCl 2, AlCl 36H 2o, Si 3n 4, SmCl 36H 2o, is scattered in three kinds of muriates in above-mentioned raw materials in enough Virahols, stirs and under 70 ~ 90 ℃ of constant temperatures, be back to completely to dissolve; Again by Si 3n 4add in above-mentioned solution, continue at 70 ~ 90 ℃ of constant temperature return stirrings 1 ~ 2 hour, form homodisperse white suspension liquid;
2) taking amount of substance is CaCl 2cO (the NH of 15 times 2) 2, be scattered in enough Virahols, stir and under 70 ~ 90 ℃ of constant temperatures, be back to completely and dissolve; By CO (NH 2) 2aqueous isopropanol is added in above-mentioned suspension liquid, continues at 70 ~ 90 ℃ of constant temperature return stirrings 1 ~ 2 hour, obtains with Si 3n 4for core, the muriatic urea complex presoma throw out that is shell;
3) adopt decompress filter to isolate precipitation, then vacuum-drying 6 ~ 12 hours under 60 ~ 90 ℃ of constant temperatures, dry presoma obtained; By presoma under reducing atmosphere in 1000 ~ 1500 ℃ of sintering 1 ~ 8 hour, obtain oxynitride red light fluorescent powder.
3. the preparation method of burst of ultraviolel oxynitride red light fluorescent powder according to claim 2, is characterized in that described reducing atmosphere is NH 3.
CN201410433638.4A 2014-08-29 2014-08-29 A kind of burst of ultraviolel nitrogen oxides red light fluorescent powder and preparation method thereof Expired - Fee Related CN104212449B (en)

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Publication number Priority date Publication date Assignee Title
CN104876441A (en) * 2015-04-10 2015-09-02 东华大学 Quantum dot glass phosphor powder as well as preparation method and application thereof
CN109628086A (en) * 2018-12-25 2019-04-16 南昌大学 A kind of white light LEDs nitrogen oxides Yellow green fluorescent material and preparation method thereof
CN114316960A (en) * 2016-01-29 2022-04-12 江苏博睿光电有限公司 Nitrogen oxide luminescent particle, preparation method thereof and luminescent device

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104876441A (en) * 2015-04-10 2015-09-02 东华大学 Quantum dot glass phosphor powder as well as preparation method and application thereof
CN114316960A (en) * 2016-01-29 2022-04-12 江苏博睿光电有限公司 Nitrogen oxide luminescent particle, preparation method thereof and luminescent device
CN109628086A (en) * 2018-12-25 2019-04-16 南昌大学 A kind of white light LEDs nitrogen oxides Yellow green fluorescent material and preparation method thereof

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