CN103146386B - Europium doped lanthanide silicon oxynitride and preparation method thereof - Google Patents
Europium doped lanthanide silicon oxynitride and preparation method thereof Download PDFInfo
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- CN103146386B CN103146386B CN201310082631.8A CN201310082631A CN103146386B CN 103146386 B CN103146386 B CN 103146386B CN 201310082631 A CN201310082631 A CN 201310082631A CN 103146386 B CN103146386 B CN 103146386B
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Abstract
The invention discloses a europium doped lanthanide silicon oxynitride, of which the chemical general formula is La5-5xEu5xSi3O12N, wherein x is more than 0 and less than 0.25. The preparation method comprises the steps of: (a) weighing raw materials: lanthanum trioxide, silicon dioxide, silicon nitride and europium oxide, according to the molar ratio of the chemical formula La5-5xEu5xSi3O12N (x is more than 0 and less than 0.25); (b) ball-milling the raw materials and tabletting; (c) putting tablets into a high temperature furnace, under the nitrogen hydrogen atmosphere, raising the furnace temperature to 1000-1250 DEG C, and sintering for 3-10 hours; (d) turning off a hydrogen source, under the environment of charging nitrogen gas, keeping the high temperature furnace at a pressure of 0.5-1MPa, raising the furnace temperature to 1450-1550 DEG C, and continuously sintering the tablets for 3-10 hours; and (e) ventilating to release the pressure in the furnace to be an ordinary pressure, cooling down the high temperature furnace to room temperature by circulating under the nitrogen-hydrogen mixed atmosphere, taking out the sample tablets, and grinding, thus obtaining a fluorescent material. The fluorescent material prepared by the preparation method is stable in physicochemical property, convenient to control luminescence property, simple in preparation method, and free from environmental pollution, and is applicable to industrialized mass production.
Description
Technical field
The present invention relates to fluorescent material containing in rare earth metal and preparation method thereof, specifically a kind of europium doping group of the lanthanides silica nitrogen compound and preparation method thereof.
Background technology
White light LEDs, because the advantages such as volume is little, energy-saving and environmental protection, long lifetime cause people's extensive concern, is called as lighting source of new generation.At present, White-light LED illumination is mainly realized by light transformation way, excites yellow fluorescent powder by blue chip, and blue, yellow light mix obtains white light, or excite three kinds of fluorescent material of red, green, blue by purple light (or UV-light), red, green-blue light is mixed into white light.For this reason, technician has developed the multiple fluorescent material that can present versicolor visible ray under rayed in constantly studying.
Nitride fluorescent material is because it has nontoxic, not deliquescence and thermostability advantages of higher, becomes one of focus of luminescent material research field in recent years.In nitride, because the bond energy of covalent bond of nitrogen ion is higher, therefore strong, the erosion resistance of its Stability Analysis of Structures, resistance of oxidation, is the good matrix of rare earth doping fluorescent material.La-Si-O-N compound is the one in fluorescent material nitride substrate, its abundant species, and structural formula is various.At present, more existing europiums are entrained in the application that makes the good fluorescent material of luminescent properties in nitride on the market.As CN101434839A discloses a kind of nitric oxide fluorescent powder of mixing europium, the chemical general formula of this fluorescent material is { M
(1-x)eu
x}
asi
bo
cn
dwherein, M is Ba, Sr or Ca, 0<x<1,1.8<a<2.2,4.5<b<5.5,0<c<8,0<d≤8,0<c+d≤8, this material is the fluorescent chemicals that luminous efficiency is good, can glow; Separately there is CN102260502A to disclose a kind of (Ca, Mg) Si
2oN:Eu
2+fluorescent material and preparation method thereof, is that raw material is mixed, is dried, filters, calcines, is pulverized, and makes (Ca, Mg) Si of the green glow that can turn to be yellow
2oN:Eu
2+fluorescent material; And in existing research, also do not find Eu
2+be entrained in La-Si-O-N matrix, preparation can be launched the relevant report of the fluorescent chemicals of blue green light.
Summary of the invention
Object of the present invention is just to provide a kind of europium doping group of the lanthanides silica nitrogen compound and preparation method thereof, with develop a kind of Spectral matching good, with spectrum width, can launch the novel fluorescent material of blue green light.
The object of the invention is to be achieved through the following technical solutions:
A kind of europium doping group of the lanthanides silica nitrogen compound, its chemical general formula is: La
5-5xeu
5xsi
3o
12n, wherein, 0<x<0.25.
Preferred 0<x<0.1 in chemical general formula described in the present invention.
A preparation method for europium doping group of the lanthanides silica nitrogen compound, it comprises the following steps preparation:
(a) according to chemical formula La
5-5xeu
5xsi
3o
12n, wherein mole proportioning raw materials weighing of 0<x<0.25: lanthanum sesquioxide, silicon-dioxide, silicon nitride, europiumsesquioxide;
(b) raw material is carried out to ball milling, the powder after ball milling carries out compressing tablet;
(c) compressing tablet is placed in to High Temperature Furnaces Heating Apparatus, in stove, is filled with nitrogen, hydrogen mixing source of the gas, furnace temperature is risen to 1000～1250 DEG C, sintering 3～10 hours;
(d) turn off hydrogen source gas, under the environment of source of the gas that is filled with nitrogen, the air pressure of High Temperature Furnaces Heating Apparatus maintains under 0.5～1MPa, and furnace temperature rises to 1450～1550 DEG C, and compressing tablet is continued to sintering 3～10 hours;
(e) ventilation makes the pressure in High Temperature Furnaces Heating Apparatus reduce to normal pressure, under the circulation in nitrogen and hydrogen mixture source, makes High Temperature Furnaces Heating Apparatus naturally be down to room temperature, takes out compressing tablet, grinds, and obtains fluorescent material.
Preferred 0<x<0.1 in step of the present invention (a), its x is within the scope of this, and the luminescent properties of the fluorescent material of preparation is relatively stronger.
The described Ball-milling Time of step of the present invention (b) is 1～2 hour, and its ball milling can make reaction raw materials fully mix contact, and Ball-milling Time is too short, and reaction raw materials mixedness is inadequate; Ball-milling Time is oversize, and reaction raw materials is easy to reunite, and is also unfavorable for abundant reaction.
When step of the present invention (b) compressing tablet, pressure is 13～18MPa; Pressure is too little, is unfavorable for reaction; Pressure is too large, easily destroys lattice, and the sample luminous intensity after sintering can be died down.
The described sintering time of step of the present invention (c) preferably 3 hours, can make reaction comparatively abundant, and preparation efficiency is higher.
The described sintering time of step of the present invention (d) preferably 3 hours, can make reaction comparatively abundant, and preparation efficiency is higher.
The air pressure of the described High Temperature Furnaces Heating Apparatus of step of the present invention (d), at 0.5MPa, has the environment of pressure, and raw material reaction degree is better, in the time that air pressure is lower, and bad or reaction times that need to be longer of level of response; Limited by technical qualification, in meeting reaction requirement, institute adds air pressure and is difficult for too high.
Europium doping group of the lanthanides silica nitrogen compound provided by the invention has following characteristics:
(1) fluorescent material grating spectrum of the present invention and La
5si
3o
12n standard card coupling is fine, does not have other dephasigns to exist, and only comprises a kind of urstoff;
(2) excitation spectrum of fluorescent material of the present invention presents wideband spectrum structure, excites the about 340nm of peak position; This fluorescent material can effectively be excited in 250-450nm wavelength region;
(3) emmission spectrum of fluorescent material of the present invention is unimodal wideband spectrum structure, and emmission spectrum frequency band, approximately in 450～650nm scope, is launched the about 510nm of peak position.
In the present invention, europium belongs to the element in group of the lanthanides, Eu
2+be the low price rare earth ion that belongs to abnormal valence state, mix Eu
2+solid chemical compound is all widely used at aspects such as low price rare-earth luminescent material, long after glow luminous material, photostimulated phosphors.But Eu
2+there is stronger reductibility, less stable, Eu in oxide system
2+doped and substituted make lattice that serious distortion occur, and valence state can not stable existence in parent lattice, easily change Eu into
3+.Therefore, affecting in the factor of rare earth valence stability, the selection of substrate material and the method for preparing lattice are vital for the stable ion of rare earth Eu at a low price.The present invention, by specific preparation method, under high-temperature and high-pressure conditions, adopts La-Si-O-N compound as matrix, has reached first Eu
2+the object of stable existence in La (group of the lanthanides)-Si-O-N matrix, has successfully developed the La that can launch blue green light
5si
3o
12n:Eu
2+fluorescent chemicals.
The optical detection of fluorescent chemicals provided by the invention shows to have strong emission peak at 450～650nm wave band, the about 510nm of transmitting peak position, transmitting blue green light; In 250～450nm wavelength region, there is strong excitation peak, excite the about 340nm of peak position, can effectively be excited by purple light or ultraviolet leds chip.
Raw materials of the present invention is simple, Financial cost is low, prepared fluorescent material is nontoxic, be difficult for deliquescence, physicochemical property are stable, luminescent properties is convenient to control, durable in use, environmentally safe; The preparation method that provides is simple, operability is easy to control, it is reproducible to prepare, and is suitable for large-scale industrialization and produces.Fluorescent material of the present invention is applicable to the device of making multiple illumination or indicating system, as: office lighting system, factory illumination system, lighting of home system, roadway lighting system, decorative lightening system, automobile lighting system, telltale lighting system etc.
Brief description of the drawings
Fig. 1 is the powdery diffractometry picture of the fluorescent material that obtains of embodiment 1 provided by the invention.This powder diffraction spectrum and La
5si
3o
12the standard card (JCPDS No.36-0571) of N mates fine.
Fig. 2 is the excitation spectrum of the fluorescent material that obtains of embodiment 1 provided by the invention, and this spectrum presents wideband spectrum structure, excites the about 340nm of peak position, and this fluorescent material can effectively be excited in 250-450nm wavelength region.
Fig. 3 is the emmission spectrum of the fluorescent material that obtains of embodiment 1 provided by the invention, and this emmission spectrum frequency band is approximately in 450-650nm scope, the about 510nm of transmitting peak position.
Embodiment
Embodiment is used for further describing the present invention below, but does not limit in any form the present invention.
Raw material used in embodiment is commercial goods.Wherein: lanthanum sesquioxide, purity > 99.99%; Silicon-dioxide, purity > 99.99%; Silicon nitride, purity > 99.99%; Europiumsesquioxide, purity > 99.99%.
Embodiment 1
Press chemical formula (La
0.95eu
0.05)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.004 grams, powder, SiO
20.8740 gram, powder, Si
3n
40.2265 gram, powder, Eu
2o
30.2846 gram, powder; Mix and be placed in ball mill, ball milling 1 hour, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 15MPa, the about 11mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1250 DEG C, heat preservation sintering 3 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 0.5MPa, is warming up to 1550 DEG C, heat preservation sintering 3 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.Survey its fluorescent powder material diffraction, excite and emmission spectrum, result is as shown in Figure 1, Figure 2 and Figure 3.
Embodiment 2
Press chemical formula (La
0.99eu
0.01)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.002 grams, powder, SiO
20.8385 gram, powder, Si
3n
40.2177 gram, powder, Eu
2o
30.0544 gram, powder; Mix and be placed in ball mill, ball milling 1 hour, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 15MPa, the about 11mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1250 DEG C, heat preservation sintering 3 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 0.5MPa, is warming up to 1450 DEG C, heat preservation sintering 3 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.
Embodiment 3
Press chemical formula (La
0.9eu
0.1)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.0002 grams, powder, SiO
20.9022 gram, powder, Si
3n
40.2390 gram, powder, Eu
2o
30.6000 gram, powder; Mix and be placed in ball mill, ball milling 1 hour, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 15MPa, the about 11mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1250 DEG C, heat preservation sintering 3 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 0.5MPa, is warming up to 1500 DEG C, heat preservation sintering 3 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.
Embodiment 4
Press chemical formula (La
0.85eu
0.15)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.003 grams, powder, SiO
20.9766 gram, powder, Si
3n
40.2532 gram, powder, Eu
2o
30.9533 gram, powder; Mix and be placed in ball mill, ball milling 1.5 hours, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 13MPa, the about 10mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1000 DEG C, heat preservation sintering 5 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 0.8MPa, is warming up to 1450 DEG C, heat preservation sintering 5 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.
Embodiment 5
Press chemical formula (La
0.8eu
0.2)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.004 grams, powder, SiO
21.0375 grams, powder, Si
3n
40.2692 gram, powder, Eu
2o
31.3505 grams, powder; Mix and be placed in ball mill, ball milling 2 hours, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 18MPa, the about 12mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1110 DEG C, heat preservation sintering 10 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 1MPa, is warming up to 1500 DEG C, heat preservation sintering 3 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.
Embodiment 6
Press chemical formula (La
0.75eu
0.25)
5si
3o
12each element mole proportioning raw materials weighing: La in N
2o
35.003 grams, powder, SiO
21.1066 grams, powder, Si
3n
40.2872 gram, powder, Eu
2o
31.8001 grams, powder; Mix and be placed in ball mill, ball milling 1 hour, takes out ball-milled powder, uses tabletting machine compressing tablet, tabletting machine pressure 15MPa, the about 11mm of compressing tablet thickness, diameter 13mm; Print being placed in to High Temperature High Pressure graphite furnace, fully vacuumizing, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, is warming up to 1250 DEG C, heat preservation sintering 3 hours; The hydrogen source gas of breaking, seals other gas source valves, and being filled with high pure nitrogen to pressure in stove is 0.5MPa, is warming up to 1550 DEG C, heat preservation sintering 3 hours; Opening escape pipe valve, pressure drop in stove, to normal pressure, is opened to inlet pipe valve, is that 95:5 passes into nitrogen and hydrogen mixture source by the volume ratio of nitrogen and hydrogen, under the protective atmosphere of nitrogen and hydrogen, will in stove, naturally be down to room temperature; Take out press sheet compression, grind, obtain fluorescent powder material.
Claims (7)
1. a preparation method for europium doping group of the lanthanides silica nitrogen compound, is characterized in that, it comprises the following steps preparation:
(a) according to chemical formula La
5-5xeu
5xsi
3o
12n, wherein mole proportioning raw materials weighing of 0<x<0.25: lanthanum sesquioxide,
Silicon-dioxide, silicon nitride, europiumsesquioxide;
(b) raw material is carried out to ball milling, the powder after ball milling carries out compressing tablet;
(c) compressing tablet is placed in to High Temperature Furnaces Heating Apparatus, in stove, is filled with nitrogen, hydrogen mixing source of the gas, furnace temperature is risen to 1000～1250 DEG C, burn
Tie 3～10 hours;
(d) turn off hydrogen source gas, be filled with under the environment of nitrogen source of the gas, the air pressure of High Temperature Furnaces Heating Apparatus maintains under 0.5～1MPa, stove
Temperature rise to 1450～1550 DEG C, continue sintering 3～10 hours by compressing tablet;
(e) ventilation makes the pressure in High Temperature Furnaces Heating Apparatus reduce to normal pressure, under the circulation of nitrogen, hydrogen mixing source of the gas, High Temperature Furnaces Heating Apparatus is down to naturally
Room temperature, takes out compressing tablet, grinds, and obtains fluorescent material.
2. according to the preparation method of the europium doping group of the lanthanides silica nitrogen compound described in claim 1, it is characterized in that step (a)
Middle 0<x<0.1.
3. according to the preparation method of the europium doping group of the lanthanides silica nitrogen compound described in claim 1, it is characterized in that step (b)
Described Ball-milling Time is 1～2 hour.
4. according to the preparation method of the europium doping group of the lanthanides silica nitrogen compound described in claim 1, it is characterized in that step (b)
When compressing tablet, pressure is 13～18MPa.
5. according to the preparation method of the europium doping group of the lanthanides silica nitrogen compound described in claim 1, it is characterized in that step (c)
Described sintering time is 3 hours.
6. according to the preparation method of the europium doping group of the lanthanides silica nitrogen compound described in claim 1, it is characterized in that step (d)
Described sintering time is 3 hours.
7. the preparation method of europium doping group of the lanthanides silica nitrogen compound according to claim 1, is characterized in that step (d)
The air pressure of described High Temperature Furnaces Heating Apparatus is at 0.5MPa.
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| CN105441078B (en) * | 2014-09-30 | 2017-07-14 | 中国科学院上海硅酸盐研究所 | Rare earth ion Eu2+The Y of doping5Si3O12N fluorescent material and preparation method thereof |
| CN104927858A (en) * | 2015-07-02 | 2015-09-23 | 河北大学 | Nitride fluorescent material capable of emitting green light under excitation of blue light as well as preparation method and application thereof |
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| US20110163322A1 (en) * | 2009-08-10 | 2011-07-07 | Jae Soo Yoo | Phosphor, phosphor manufacturing method, and white light emitting device |
| CN102559184A (en) * | 2011-12-31 | 2012-07-11 | 河北大学 | Silicon-based nitrogen oxide fluorescent powder and preparation method thereof |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110163322A1 (en) * | 2009-08-10 | 2011-07-07 | Jae Soo Yoo | Phosphor, phosphor manufacturing method, and white light emitting device |
| CN102559184A (en) * | 2011-12-31 | 2012-07-11 | 河北大学 | Silicon-based nitrogen oxide fluorescent powder and preparation method thereof |
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