CN102181285B - Silica nitride fluorescent powder and preparation method thereof - Google Patents

Silica nitride fluorescent powder and preparation method thereof Download PDF

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CN102181285B
CN102181285B CN2011100560141A CN201110056014A CN102181285B CN 102181285 B CN102181285 B CN 102181285B CN 2011100560141 A CN2011100560141 A CN 2011100560141A CN 201110056014 A CN201110056014 A CN 201110056014A CN 102181285 B CN102181285 B CN 102181285B
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fluorescent powder
nitride
powder
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silica nitride
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CN102181285A (en
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徐鑫
唐家业
黄凯
杨秀芳
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University of Science and Technology of China USTC
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Abstract

The invention provides a silica nitride fluorescent powder. A general formula of the fluorescent powder is BaeCfDgSi3+a(Al, Ga, In) 3+bO4+cN5+d, wherein a is more than -2 and less than 2; b is more than -2 and less than 2; c is more than -2 and less than 2; d is more than -2 and less than 2; f is not less than 0 and not more than 0.30; g is not less than 0 and not more than 0.5; the sum of 2e+fvC+gvD is 2; e is more than 0; vC and vD represent valence states of C and D; C is a light emitting center of one or more elements selected from Ce (Cerium), Pr (praseodymium), Nd (Neodymium), Sm (Samarium), Eu (Europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Mn (Manganese), Cr (Chromium), Bi (Bismuth), Pb (Plumbum) and Fe (Ferrum); and D is a mixture of one or more elements selected from alkaline-earth metals and Zn (Zinc) except for Ba (Barium). The silica nitride fluorescent powder provided by the invention has the advantages of small brightness reduction while being exposed in an excitation source, excellent conversion efficiency to blue light or near ultraviolet, excellent color purity, thermal stability, high chemical stability, small and uniform crystallite dimension, low calcining temperature, simple process, easiness for continuous industrial production and broad industrial application prospect.

Description

A kind of silica nitride fluorescent powder and preparation method thereof
Technical field
The present invention relates to the phosphor field, be specifically related to a kind of silica nitride fluorescent powder and preparation method thereof.
Background technology
With traditional lighting engineering, compare, white light-emitting diodes (White Light Emitting Diodes, WLED) lighting engineering has its significant advantage: photodiode has the advantages such as volume is little, thermal value is low, current consumption is low, the life-span is long, speed of response is fast, environmental protection, but planar package and be easy to the advantages such as lightening.Wherein, the white light LEDs of near ultraviolet and blue-light excited (360nm-450nm) is at automotive lighting, backlight and being widely used in other electronicss.And novel plasma flat-panel display (Plasma Display Panel, PDP) has that volume is little, weight is lighter, without X-radiation, brightness is high, color reducibility good, gray scale is abundant, to advantages such as vertiginous picture fast response times.More lighting display technology using also comprises three-color fluorescent lamp, fluorescent display tube (VFD), field-emitter display (FED), cathode ray tube (CRT) etc.
The performance of above illuminated displays part depends on many factors, wherein for the fluorescent material of light conversion, has also played the part of an important role.For any one purposes wherein, in order to make light-emitting phosphor, need to provide the energy of excitated fluorescent powder to fluorescent material, comprise that electron rays, vacuum ultraviolet ray, ultraviolet ray are so that visible ray, under the exciting of the excitaton source that these energy are provided, fluorescent material sends visible rays.
The fluorescent material kind is more, silicate fluorescent powder, phosphate phosphor, aluminate fluorescent powder, sulphide fluorescent material etc. are arranged, fluorescent material is in the situation that be exposed to for a long time the problem that excitaton source has brightness to reduce, its application is restricted, and therefore needs to explore brightness and reduces novel fluorescence powder material little, stable performance.
Summary of the invention
The problem that the present invention solves is to provide a kind of silica nitride fluorescent powder, has high thermostability and chemical stability, and light conversion efficiency is high.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of silica nitride fluorescent powder, general formula is: Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d, wherein-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0≤f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, Fe, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn.
As preferably, the general formula of described silica nitride fluorescent powder is: Ba 1-f-gc fd gsi 3(Al, Ga, In) 3o 4n 5, 0≤f≤0.30,0≤g≤0.5; C is the luminescence center that is selected from one or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, Fe, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and metallic element.
As preferably, its basic structure is by BaSi 3al 3o 4n 5the monoclinic crystal structure formed, its crystallization phases, in using the XRD diffraction test that CuK α is x-ray source, has diffraction peak at following three 2 θ: 24.3 °-26.3 °, 30.7 °-32.7 °, 35.6 °-37.6 °.
As preferably, described Si can partly be replaced by Ge or B.
As preferably, the luminescence center of described C at least containing a kind of element in Ce, Sm, Eu or Yb.
As preferably, in fluorescence spectrum, maximum emission wavelength is 460nm-500nm, and in excitation spectrum, the maximum excitation wavelength is 240nm-420nm, at vacuum ultraviolet-excited middle maximum excitation wavelength, is 140nm-155nm.
As preferably, in fluorescence spectrum, maximum emission wavelength is 400nm-440nm, and in excitation spectrum, the maximum excitation wavelength is 250nm-370nm.
As preferably, in fluorescence spectrum, maximum emission wavelength is 300nm-550nm, and in excitation spectrum, the maximum excitation wavelength is 650nm-740nm.
A kind of preparation method of silica nitride fluorescent powder comprises the following steps:
1) according to chemical expression Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d, calculate each raw material consumption according to each element ratio, in formula-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0≤f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, Fe, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn;
Each raw material is: barium oxide maybe can be converted into one or more containing barium compounds in barytic barium carbonate or barium oxalate, containing Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, one or more simple substance in Fe, oxide compound, nitride maybe can be converted into the compound of oxide compound or nitride, containing one or more simple substance in the alkaline-earth metal beyond Ba and Zn, oxide compound, nitride maybe can be converted into the compound of oxide compound or nitride, oxide compound containing Si, nitride maybe can be converted into the compound of oxide compound or nitride,
2) above-mentioned various raw materials are mixed, under reducing atmosphere, mixture is heated to l400 ℃～1600 ℃ and carries out roasting, insulation 2h～40h, naturally cool to room temperature;
3) powder obtained after roasting being crushed to particle diameter is below 10 μ m.
As preferably, described 2) Raw also comprises that oxide compound, nitride containing Ge or B maybe can be converted into the compound of oxide compound or nitride.
As preferably, described 2), after will above-mentioned various raw materials mixing in, also add fusing assistant H 3bO 3or BaF 2.
As preferably, described 2) in, above-mentioned various raw materials being mixed to mixing device used is V-Mixer, shaking apparatus, ball mill, oscillatory type ball mill.
As preferably, described 2), after will above-mentioned various raw materials mixing in, mixture be contained in boron nitride, silicon nitride, tungsten, molybdenum or aluminum oxide and has in the crucible of low reactivity.
As preferably, described 2), after will above-mentioned various raw materials in mixing, the accumulation relative density is controlled at 20%-40%.
As preferably, described 2) in, reducing atmosphere is one or more mixed atmospheres in nitrogen, hydrogen or ammonia.
As preferably, the pressure of described reducing atmosphere is more than 1atm.
As preferably, described 2) in, by blend heated speed, be 1 ℃/min-10 ℃/min.
As preferably, described 2) continuous oven or batch furnace that the stove that in, roasting is used is metallic resistance hot type, graphite resistance hot type or Si-Mo rod resistive heating type.
A kind of containing fluorescent powder composition, comprise silica nitride fluorescent powder noted earlier, and the weight percentage that described silica nitride fluorescent powder accounts for described containing fluorescent powder composition is more than 25%.
A kind of illuminating device, comprise illuminating source and described silica nitride fluorescent powder, and described illuminating device is white LED lamp or three-color fluorescent lamp.
As preferably, described illuminating source is the LED that emission wavelength is 320nm-470nm.
A kind of image display device, comprise excitaton source and described silica nitride fluorescent powder, and described image display device is a kind of in fluorescent display tube, field-emitter display, plasma display, cathode tube, high definition television.
As preferably, described excitaton source is a kind of in electron rays, electric field, vacuum ultraviolet ray or ultraviolet ray.
A kind of silica nitride fluorescent powder provided by the invention, adopting new silicon oxynitride is substrate material, while being exposed to excitaton source for a long time, brightness reduces little, efficiency of conversion excellence and purity of color excellence to blue light or near-ultraviolet light, thermostability and chemical stability are high, but the erosion of withstand high temperatures and sour environment, grain-size is little and even, is the fluorescent material of high characteristic; And with general silicon-based oxynitride, to compare sintering temperature low, and technique is simple, is easy to industrialization and produces continuously, has wide prospects for commercial application.By using this silica nitride fluorescent powder to reach the containing fluorescent powder composition containing silica nitride fluorescent powder, can obtain the light-emitting device of high-level efficiency and high characteristic, as illuminating device and image display device.
The accompanying drawing explanation
The XRD spectra that Fig. 1 is the embodiment of the present invention 1 gained powder;
The excitation and emission spectra figure that Fig. 2 is the embodiment of the present invention 1 gained powder;
The excitation and emission spectra figure that Fig. 3 is the embodiment of the present invention 2 gained powders;
The excitation and emission spectra figure that Fig. 4 is the embodiment of the present invention 3 gained powders;
The excitation and emission spectra figure that Fig. 5 is the embodiment of the present invention 4 gained powders;
The excitation and emission spectra figure that Fig. 6 is the embodiment of the present invention 5 gained powders;
The excitation and emission spectra figure that Fig. 7 is the embodiment of the present invention 6 gained powders;
The excitation and emission spectra figure that Fig. 8 is the embodiment of the present invention 7 gained powders;
The excitation and emission spectra figure that Fig. 9 is the embodiment of the present invention 8 gained powders;
The excitation and emission spectra figure that Figure 10 is the embodiment of the present invention 9 gained powders;
The excitation and emission spectra figure that Figure 11 is the embodiment of the present invention 10 gained powders;
The excitation and emission spectra figure that Figure 12 is the embodiment of the present invention 11 gained powders;
The excitation and emission spectra figure that Figure 13 is the embodiment of the present invention 12 gained powders;
The excitation and emission spectra figure that Figure 14 is the embodiment of the present invention 13 gained powders.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The inventor has carried out for a long time, has goed deep into and systematic research for the characteristics of luminescence of rear-earth-doped baric sial base oxynitride and rare earth ion, in conjunction with alpha-siaion and beta-type sialon powder in the past, find a kind of brand-new fluorescent material with good luminous efficiency of the unknown up to now, its general formula is: Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d, wherein-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0≤f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, Fe, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn.
Preferred general formula is: Ba 1-f-gc fd gsi 3(Al, Ga, In) 3o 4n 5, element and the footmark of each letter representative are the same.
General formula is Ba 1-f-gc fd gsi 3(Al, Ga, In) 3o 4n 5the basic structure of fluorescent material be by BaE 3al 3o 4n 5the monoclinic crystal structure formed, by a certain amount of Eu that adulterates 2+and other light emitting ionic, acquisition can be by electron rays (FED, CRT use), vacuum ultraviolet (VUV) (PDP uses), ultraviolet (three-color fluorescent lamp is used), and the new and effective fluorescent material of near ultraviolet and blue-light excited (LED uses), compare with general fluorescent material, shown high luminous efficiency, long-time light decay is also smaller under excitaton source.Al-O, Si-N, Al-N, the Si-O tetrahedron is by the synthetic three-dimensional framework configuration of certain spatial group, and the Ba atom is distributed in these three-dimensional framework configurations.Al wherein can part be replaced by other trivalent element, and Ba also can part be replaced by other metal ions, and part Si-O key and Al-N key can carry out mutual replacement to a certain degree simultaneously, and therefore the general formula of the actual fluorescent material formed is as previously shown: Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d.In the XRD diffraction test that crystallization phases with base material of this basic structure is x-ray source at use CuK α, at following three 2 θ, there is diffraction peak: 24.3 °-26.3 °, 30.7 °-32.7 °, 35.6 °-37.6 °.
Light emitting ionic is (as Eu 2+) doping position generally replace Ba 2+position, doping is relatively and Ba 2+, molar fraction can change between 0%-30%, preferably has the doping scope of high brightness between 1%-20%, and selected light emitting ionic can be rare earth ion and Mn 2+, Cr 3+, Bi 3+deng, can be also the combination of above-mentioned light emitting ionic.Fluorescent material of the present invention, along with the composition difference that forms fluorescent material, excitation spectrum and emmission spectrum are also different, by aptly it being carried out to the reasonable combination selection, can at random set the fluorescent material with various luminescent spectrums for.
Wherein Si can partly be replaced by Ge or B, and preferably crystalline phase is by BaSi 3al 3o 4n 5single-phase solid molten formation, and but in the scope that does not reduce performance, also can be formed by the mixture with other crystallization phases or noncrystalline phase.
C is preferably the luminescence center of one or more elements that at least contain Ce, also can be the luminescence center of one or more elements that at least contain Sm, also can be the luminescence center of one or more elements that at least contain Eu, also can be the luminescence center of one or more elements that at least contain Yb.
Due to C doped with a lot of different situations, therefore the fluorescent material of preparing fluorescence spectrum, excitation spectrum and vacuum ultraviolet-excited in there is different wavelength regions, in fluorescence spectrum, maximum emission wavelength is 460nm-500nm, in excitation spectrum, the maximum excitation wavelength is 240nm-420nm, at vacuum ultraviolet-excited middle maximum excitation wavelength, is 140nm-155nm; Perhaps in fluorescence spectrum, maximum emission wavelength is 400nm-440nm, and in excitation spectrum, the maximum excitation wavelength is 250nm-370nm; Perhaps in fluorescence spectrum, maximum emission wavelength is 300nm-550nm, and in excitation spectrum, the maximum excitation wavelength is 650nm-740nm.
For singly mixing Eu 2+fluorescent material, can obtain the blue colour fluorescent powder that maximum emission wavelength is 450nm-500nm, its excitation spectrum can be vacuum ultraviolet (VUV) wave band 140nm-160nm and ultraviolet-visible optical band 220nm-420nm on a large scale.
The present invention also provides a kind of preparation method of fluorescent material, comprises the following steps:
1) according to chemical expression Ba ec fd ge 3+a(Al, Ga, In) 3+bo 4+cn 5+d, calculate each raw material consumption according to each element ratio, in formula-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0≤f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, Fe, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn.
Each raw material is: barium oxide maybe can be converted into one or more containing barium compounds in barytic barium carbonate or barium oxalate, containing Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn, Cr, Bi, Pb, one or more simple substance in Fe, oxide compound, nitride maybe can be converted into the compound of oxide compound or nitride, containing one or more simple substance in the alkaline-earth metal beyond Ba and Zn, oxide compound, nitride maybe can be converted into the compound of oxide compound or nitride, oxide compound containing Si, nitride maybe can be converted into the compound of oxide compound or nitride as selected silicon nitride, silicon-dioxide or pure silicon powder, can also select the oxide compound containing Ge or B, nitride maybe can be converted into the compound of oxide compound or nitride, part Si is replaced by Ge or B.
In order to make various raw materials fully disperse contact in reaction process, finally make at high temperature abundant reactive crystallization of reactant, by after above-mentioned various raw materials mixing, also add fusing assistant H as preferred 3bO 3or BaF 2.
2) above-mentioned various raw materials are mixed, can adopt dry type to mix or remove after wet mixing the method for desolventizing in the inert solvent substantially do not reacted with each composition of raw material.
During mixing, mixing device used can use V-Mixer, shaking apparatus, ball mill, oscillatory type ball mill, after mixing, mixture can be contained in boron nitride, silicon nitride, tungsten, molybdenum or aluminum oxide and have in the crucible of low reactivity.Pile up relative density and be controlled at 20%-40%.Tap density too hour, cause the solid phase diffusion distance because the contact area between material powder is too little, or there is no suitable diffusion path and make solid state reaction be difficult to carry out fully, may leave in a large number to the very little impurity phase of luminescent properties contribution, on the other hand, when tap density is too large, resulting fluorescent material easily forms hard agglomeration, not only need long pulverising step, and easily reduce the luminous efficiency of fluorescent material and increase the possibility of introducing impurity.
Under reducing atmosphere, mixture is heated to l400 ℃～1600 ℃ and carries out roasting after mixing, insulation 2h～40h, naturally cool to room temperature.
Reducing atmosphere is one or more mixed atmospheres in nitrogen, hydrogen or ammonia, preferably contains nitrogen, and the pressure of reducing atmosphere is more than 1atm.
The speed of preferably take is added thermal bake-out to mixture as 1 ℃/min-10 ℃/min, can use continuous oven or the batch furnace of metallic resistance hot type, graphite resistance hot type or Si-Mo rod resistive heating type, preferably mixture is heated to l450 ℃～1600 ℃ and carry out roasting.Sintering temperature is too low, is difficult to carry out solid state reaction and can not synthesizes required fluorescent material, and synthetic fluorescent material also has poor crystal property, thereby affects luminous intensity; And sintering temperature is too high, resulting fluorescent material easily forms hard agglomeration, and the decomposition of even can volatilizing, also can have influence on luminescent properties, under the prerequisite that reasonably sintering temperature can reach full growth at crystal grain, suppresses the generation of hard agglomeration.
3) powder obtained after roasting being crushed to particle diameter is below 10 μ m.Can pass through industrial pulverizer commonly used, as ball mill etc., pulverized, preferred powder is broken to 0.1-5 μ m, because when granularity is too large, the mobility of powder and dispersed variation and while forming light-emitting device luminous intensity inhomogeneous, when particle diameter becomes 0.1 μ m or more hour, lip-deep defect proportion increases, and can cause luminous intensity to reduce.
The present invention also provides a kind of containing fluorescent powder composition, comprises silica nitride fluorescent powder provided by the invention, and the weight percentage that silica nitride fluorescent powder accounts for this containing fluorescent powder composition is more than 25%.
The present invention also provides a kind of illuminating device, comprises illuminating source and silica nitride fluorescent powder, and illuminating device is white LED lamp or three-color fluorescent lamp.This illuminating source is the LED that emission wavelength is 320nm-470nm.
Can use illuminating source and containing fluorescent powder composition provided by the invention to prepare illuminating device, except selecting separately phosphor combination of the present invention, can also and there is fluorescent material the use of other characteristics of luminescence, form the illuminating device of expectation color.For example, the ultraviolet LED luminescent device of 330-420nm and by this wavelength, excited after can send the green emitting phosphor of 520-570nm wavelength, the red fluorescence powder that can send 570-700nm light and doping Eu of the present invention 2+baAl 3si 3o 4n 5combination, can obtain the white light LEDs of high color rendering index (CRI), green emitting phosphor, can be used the BaMgAl of doping Eu or Mn 10o 17, or the SrSi of doping Eu 2n 2o 2, red fluorescence powder, can use the doping Eu Y 2o 3or the CaAlSiN of doping Eu 3.
The present invention also provides a kind of image display device, comprise excitaton source and silica nitride fluorescent powder, use containing fluorescent powder composition provided by the invention to get final product, image display device is a kind of in fluorescent display tube (VFD), field-emitter display (FED), plasma display (PDP), cathode ray tube (CRT), high definition television (HDTV).This excitaton source is a kind of in electron rays, electric field, vacuum ultraviolet ray or ultraviolet ray.As vacuum ultraviolet ray, the ultraviolet-visible light of 220～420nm, the electron rays that can use 100～190nm excited containing fluorescent powder composition of the present invention.
The concrete preparation process of silica nitride fluorescent powder provided by the invention is as follows, the experimental technique used in following embodiment if no special instructions, is ordinary method, material used, reagent, reducing gas etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1
Form Ba according to chemical formula 0.85eu 0.15si 3al 3o 4n 5, take 2.6560gBaCO 3, 1.7536gSi 3n 4, 0.3168gEu 2o 3, 0.4968gAlN, 1.2186gAl 2o 3initial powder, and add 0.1288gH 3bO 3as fusing assistant, jointly put into the silicon-dioxide mortar and fully grind 20 minutes, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, and purpose is in order to reduce oxygen content, then passes into and mixes the mobile N that reducing gas is 99.999% in purity 2/ NH 3in (its volume ratio is 10:1) ambiance, heat-up rate with 10 ℃/min is warmed up to 800 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 5 ℃/min, be incubated 4 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 10 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder passes through to measure its excitation-emission spectral characterization, and compares with business BAM blue powder.Fig. 1 means the XRD figure spectrum of gained fluorescent material, and it is one single-phase, at 24.3-26.3 °, and 30.7-32.7 °, 35.6-37.6 °.Have three strong peaks, for different light emitting ionic doping, and the replacement of other ions is admittedly molten, and the position of diffraction peak and intensity have skew to a certain degree.Fig. 2 has shown (little figure is the fluorescence spectrum of sample under vacuum ultraviolet (VUV)), gained fluorescent material can be excited by the wide band from vacuum ultraviolet (VUV) and near ultraviolet to blue light, send bright blue light, centre wavelength is 474nm, higher by 20% than business BAM blue powder exciting with emissive porwer of blue wave band.
Embodiment 2
Form Ba according to chemical formula 0.95ce 0.05si 3al 3o 4n 5, take 2.2345gBa (NO 3) 2, 0.9139gAl 2o 3, 0.3726gAlN, 1.3151gSi 3n 4, 0.0775gCeO 2initial powder, jointly put into the silicon nitride mortar and fully grind 20 minutes, and various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, the BN crucible is packed in plumbago crucible, finally plumbago crucible is put into to vacuum carbon tube furnace, at first carry out vacuum pumping, then pass into purity and be 99.999% mobile N 2gas, heat-up rate with 4 ℃/min is warmed up to 800 ℃, and then be warmed up to 1200 ℃ with the temperature rise rate of 6 ℃/min, the temperature rise rate of last 5 ℃/min is warmed up to 1600 ℃ of insulations 8 hours, then naturally cool to room temperature after being cooled to 1200 ℃ with the speed of cooling of 5 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization.As shown in Figure 3, gained fluorescent material can be excited by the wide band from the near ultraviolet to the blue light, sends bright blue light, and the center emission wavelength is at 437nm.Can realize different blue light emittings by Eu and Ce element, for the purity of color of condition blue light, there is important effect.
Embodiment 3
Form Ba according to chemical formula 0.94sm 0.06si 3al 3o 4n 5, take 2.2109gBa (NO 3) 2, 0.9139gAl 2o 3, 0.3726gAlN, 1.3151gSi 3n 4, 0.0942gSm 2o 3, and add 0.0244gNH 4cl makees fusing assistant, jointly puts into the silicon nitride mortar and fully grinds 20 minutes, and various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, and purpose is in order to reduce oxygen content, then passes into and mixes the mobile N that reducing gas is 99.999% in purity 2/ H 2in (its volume ratio is 95:5) ambiance, heat-up rate with 10 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization, as shown in Figure 4, gained fluorescent material can by from the near ultraviolet to the blue light until have very strong wide band to excite to green light band, send bright ruddiness, centre wavelength is 699nm.It should be noted that especially powder has very strong exciting at blue wave band, the red fluorescence powder that can be used as gallium nitride based LED improves the purity of color of white light.
Embodiment 4
Form Ba according to chemical formula 0.95yb 0.05si 3al 3o 4n 5, take 2.2580gBa (NO 3) 2, 0.9139gAl 2o 3, 0.3726gAlN, 1.3151gSi 3n 4, 0.0709gYb 2o 3, and with the BaF of 5at% mark 2replace Ba (NO as the Ba source 3) 2as fusing assistant, jointly put into the silicon nitride mortar and fully grind 20 minutes, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, and purpose is in order to reduce oxygen content, then passes into and mixes the mobile N that reducing gas is 99.999% in purity 2/ NH 3in (its volume ratio is 20:1) ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 4 ℃/min, be incubated 4 hours, then naturally cool to room temperature after being cooled to 800 ° of C with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization, and as shown in Figure 5, gained fluorescent material can be excited by the wide band from the near ultraviolet to the blue light, sends bright green glow, and centre wavelength is 535nm.Sample is noticeable especially exciting of blue wave band, and in view of the thermostability of sample excellence, the green emitting phosphor that can be used as white light LEDs is used.
Embodiment 5
Form Ba according to chemical formula 0.98mn 0.02si 3al 3o 4n 5, take 1.7405gBaCO 3, 0.0207gMnCO 3, 0.9139gAl 2o 3, 1.3151gSi 3n 4, the 0.3726gAlN initial powder, jointly put into agate mortar and fully grind 20 minutes, and various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile N that reducing gas is 99.999% in purity 2/ NH 3in (its volume ratio is 4:1) ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1600 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization, and as shown in Figure 6, gained fluorescent material can be excited by the wide band from the near ultraviolet to the blue light, at 370nm and 440nm, sends bright blue light.
Embodiment 6
Form Ba according to chemical formula 0.8eu 0.15sm 0.05si 3al 3o 4n 5, take 2.5089gBa (NO 3) 2, 0.3168g Eu 2o 3, 0.0942gSm 2o 3, 1.2186gAl 2o 3, 1.7536gSi 3n 4, 0.4968gAlN, and add BaF according to the 2at% that Ba accounts for total Ba source 2, jointly put into agate mortar and fully grind 20 minutes as initial powder as fusing assistant, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile N that reducing gas is 99.999% in purity 2/ NH 3in (its volume ratio is 5:1) ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization, and as shown in Figure 7, gained fluorescent material can be excited by the wide band from the near ultraviolet to the blue light, sends bright blue light and ruddiness, and centre wavelength is respectively 467nm and 699nm.The fluorescent material obtained, under the exciting of identical near ultraviolet or blue light, can have the emission peak of blue light and ruddiness simultaneously, is adding that the green emitting phosphor with similar excitation spectrum is (as BaSi 3al 3o 4n 5: Yb 2+green emitting phosphor), can realize white light.
Embodiment 7
Form Ba according to chemical formula 0.55sr 0.4eu 0.15si 3al 3o 4n 5, take 0.3168g Eu 2o 3, 1.2186gAl 2o 3, 1.7536gSi 3n 4, 0.4968gAlN, 1.0656gBaCO 3and 0.7086gSrCO 3as initial powder, jointly put into the silicon nitride mortar and fully grind 20 minutes, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization (Fig. 8).Experiment showed, by regulating the ratio of alkaline earth element Ba and Sr, can make emission wavelength fluctuate in the 470nm-475nm scope, for the regulation and control that realize emission wavelength, there is positive effect.
Embodiment 8
Form Ba according to chemical formula 0.55ca 0.4eu 0.15si 3al 3o 4n 5, take 0.3168g Eu 2o 3, 1.2186gAl 2o 3, 1.7536gSi 3n 4, 0.4968gAlN, 1.0656gBaCO 3and 0.4804gSrCO 3as initial powder, jointly put into the silicon nitride mortar and fully grind 20 minutes, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1500 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization (Fig. 9).Experiment showed, by regulating the ratio of alkaline earth element Ba and Ca, can make emission wavelength fluctuate in the 470nm-530nm scope, can suitably reduce the synthetic temperature of powder and the regulation and control that realize emission wavelength simultaneously, for industrial production, there is positive effect.
Embodiment 9
Form Ba according to chemical formula 0.55zn 0.2eu 0.15si 3al 3o 4n 5, take 0.3168g Eu 2o 3, 1.2186gAl 2o 3, 1.7536gSi 3n 4, 0.4968gAlN, 1.0656gBaCO 3, jointly put into the silicon nitride mortar and fully grind 20 minutes as initial powder with 0.1954gZnO, various raw materials are fully mixed.Mixed powder is put into to the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1550 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization (Figure 10).Experiment showed, by regulating the ratio of element Zn in crystal, can make emission wavelength and luminous intensity fluctuate within the specific limits, can play the effect of the purity of color of regulating fluorescent material.
Embodiment 10
Form Ba according to chemical formula 0.85eu 0.15si 3al 2ga 1o 4n 5, take 0.1584g Eu 2o 3, 0.3059gAl 2o 3, 0.8714gSi 3n 4, 0.2459gAlN, 1.0064gBaCO 3and 0.5623gGa 2o 3as initial powder, jointly put into agate jar and fully grind 20 hours, various raw materials are fully mixed.Will be mixed powder put into the BN crucible after drying, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1500 ℃ with the temperature rise rate of 4 ℃/min, be incubated 4 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization (Figure 11).Experimental results show that, by regulating element al and the ratio of Ga in crystal, can make the peak value of emission wavelength move in 470nm-480nm, the adjustment of realization in blue wave band, adjusting to the purity of color of fluorescent material plays a positive role, on the other hand, mixing of Ga can make the synthesis temperature of powder greatly reduce, and for the synthetic cost that reduces powder also tool, has certain effect.
Embodiment 11
Form Ba according to chemical formula 0.85eu 0.15si 3al 2inO 4n 5the preparation powder, take 0.1584gEu 2o 3, 0.3059gAl 2o 3, 0.8714gSi 3n 4, 0.2459gAlN, 1.0064gBaCO 3and 0.8329gIn 2o 3as initial powder, jointly put into the silicon nitride mortar and fully grind 40 minutes, various raw materials are fully mixed.Various raw materials are fully mixed.Will be mixed powder put into the BN crucible after drying, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1500 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization (Figure 12).Experiment showed, by regulating element al and the ratio of In in crystal, can make the peak value of emission wavelength move in 470-480nm, realize the adjustment in blue wave band, the adjusting of the purity of color of fluorescent material is played a positive role; On the other hand, mixing of In can make the synthesis temperature of powder greatly reduce, and for the synthetic cost that reduces powder also tool, has certain effect.
Embodiment 12
Form Ba according to chemical formula 0.85eu 0.15si 3-xge xo 4n 5, get x=0.5, according to chemical formula Ba 0.85eu 0.15si 2.5ge 0.5o 4n 5the preparation powder, take 0.1584g Eu 2o 3, 0.4062gAl 2o 3, 0.7014gSi 3n 4, 0.4098gAlN, 1.0064gBaCO 3and 0.3139gGeO 2as initial powder, jointly put into the silicon nitride mortar and fully grind 40 minutes, various raw materials are fully mixed.Various raw materials are fully mixed.Will be mixed powder put into the BN crucible after drying, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile N that reducing gas is 99.999% in purity 2in ambiance, heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1500 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization.Mixing of Ge can replace the position of Si in lattice, and the content of regulating within the specific limits Ge simultaneously can change the wavelength of the emmission spectrum of matrix.Experiment showed, under the exciting of UV-light, powder has very strong emission in the wider spectral range of 450-500nm.
Embodiment 13
Form Ba according to chemical formula 0.85eu 0.15si 3-xb xal 3o 4+3/2xn 5-4/3x, get x=0.3, according to chemical formula Ba 0.85eu 0.15si 2.6b 0.4al 3o 4.45n 4.6the preparation powder, take 0.1584g Eu 2o 3, 0.6093gAl 2o 3, 0.7295gSi 3n 4, 0.2459gAlN, 1.0064gBaCO 3and 0.1113gH 3bO 3as initial powder, jointly put into the silicon nitride mortar and fully grind 40 minutes, various raw materials are fully mixed.Various raw materials are fully mixed.After being dried, mixed powder puts into the BN crucible, pile up relative density about 30%, then cover unsealed top cover, put into the corundum tube furnace, High Temperature Furnaces Heating Apparatus is carried out to vacuum pumping, then pass into and mix the mobile NH that reducing gas is 99.999% in purity 3and N 2in the mixed atmosphere of (volume ratio 1:4), heat-up rate with 5 ℃/min is warmed up to 1000 ℃, and then be warmed up to 1500 ℃ with the temperature rise rate of 4 ℃/min, be incubated 6 hours, then naturally cool to room temperature after being cooled to 800 ℃ with the speed of cooling of 4 ℃/min, be placed in mortar after the powder obtained is taken out and grind powdered and obtain required fluorescent material.The fluorescence conversion performance of powder is by measuring its excitation-emission spectral characterization.Not experiment showed, because the valency between Si and B does not mate the charge unbalance caused and can be regulated by the O of self and the ratio of N in crystalline structure.Gained fluorescent material can be excited by the wide band from vacuum ultraviolet (VUV) and near ultraviolet to blue light, sends bright blue light, and centre wavelength is 472nm, higher by 20% than business BAM blue powder exciting with emissive porwer of blue wave band.
Above a kind of silica nitride fluorescent powder provided by the present invention and preparation method thereof is described in detail.Applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.

Claims (21)

1. a silica nitride fluorescent powder, is characterized in that, general formula is: Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d, wherein-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0<f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Sm, Eu, Yb and Mn, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn.
2. silica nitride fluorescent powder according to claim 1, is characterized in that, general formula is: Ba 1-f-gc fd gsi 3(Al, Ga, In) 3o 4n 5, 0<f≤0.30,0≤g≤0.5; C is the luminescence center that is selected from one or more elements in Sm, Eu, Yb and Mn, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn.
3. silica nitride fluorescent powder according to claim 2, is characterized in that, its basic structure is by BaSi 3al 3o 4n 5the monoclinic crystal structure formed, its crystallization phases, in using the XRD diffraction test that CuK α is x-ray source, has diffraction peak at following three 2 θ: 24.3 °-26.3 °, 30.7 °-32.7 °, 35.6 °-37.6 °.
4. according to the described silica nitride fluorescent powder of any one in claims 1 to 3, it is characterized in that, described Si can partly be replaced by Ge or B.
5. according to the described silica nitride fluorescent powder of any one in claims 1 to 3, it is characterized in that, in fluorescence spectrum, maximum emission wavelength is 460nm-500nm, and in excitation spectrum, the maximum excitation wavelength is 240nm-420nm, at vacuum ultraviolet-excited middle maximum excitation wavelength, is 140nm-155nm.
6. according to the described silica nitride fluorescent powder of any one in claims 1 to 3, it is characterized in that, in fluorescence spectrum, maximum emission wavelength is 400nm-440nm, and in excitation spectrum, the maximum excitation wavelength is 250nm-370nm.
7. the preparation method of a silica nitride fluorescent powder, is characterized in that, comprises the following steps:
1) according to chemical expression Ba ec fd gsi 3+a(Al, Ga, In) 3+bo 4+cn 5+d, calculate each raw material consumption according to each element ratio, in formula-2<a<2 ,-2<b<2 ,-2<c<2 ,-2<d<2,0<f≤0.30,0≤g≤0.5,2e+f ν c+ g ν d=2, e>0, ν c, ν drepresent C, the valence state of D; C is the luminescence center that is selected from one or more elements in Ce, Sm, Eu, Yb and Mn, the mixture that D is one or more elements in alkaline-earth metal beyond Ba and Zn;
Each raw material is: barium oxide maybe can be converted into one or more containing barium compounds in barytic barium carbonate or barium oxalate, maybe can be converted into the compound of oxide compound or nitride containing one or more simple substance, oxide compound, nitride in Ce, Sm, Eu, Yb and Mn, maybe can be converted into the compound of oxide compound or nitride containing one or more simple substance, oxide compound, nitride in the alkaline-earth metal beyond Ba and Zn, the oxide compound, the nitride that contain Si maybe can be converted into the compound of oxide compound or nitride;
2) above-mentioned various raw materials are mixed, under reducing atmosphere, mixture is heated to l400 ℃～1600 ℃ and carries out roasting, insulation 2h～40h, naturally cool to room temperature;
3) powder obtained after roasting being crushed to particle diameter is below 10 μ m.
8. preparation method according to claim 7, is characterized in that, described 2) Raw also comprises that oxide compound, nitride containing Ge or B maybe can be converted into the compound of oxide compound or nitride.
9. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) middle by after above-mentioned various raw materials mixing, also add fusing assistant H 3bO 3or BaF 2.
10. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) in above-mentioned various raw materials are mixed to mixing device used is V-Mixer, shaking apparatus or ball mill.
11. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) middle by after above-mentioned various raw materials mixing, mixture is contained in boron nitride, silicon nitride, tungsten, molybdenum or aluminum oxide and has in the crucible of low reactivity.
12. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) middle by after above-mentioned various raw materials mixing, pile up relative density and be controlled at 20%-40%.
13. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) in reducing atmosphere be one or more mixed atmospheres in hydrogen or ammonia.
14. preparation method according to claim 13, is characterized in that, the pressure of described reducing atmosphere is more than 1atm.
15. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) in by blend heated speed, be 1 ℃/min-10 ℃/min.
16. according to the described preparation method of claim 7 or 8, it is characterized in that described 2) in the stove that uses of roasting be metallic resistance hot type, graphite resistance hot type or Si-Mo rod resistive heating type continuous oven or batch furnace.
17. a containing fluorescent powder composition, is characterized in that, comprises the described silica nitride fluorescent powder of any one in claim 1 to 6, the weight percentage that described silica nitride fluorescent powder accounts for described containing fluorescent powder composition is more than 25%.
18. an illuminating device, is characterized in that, comprises the described silica nitride fluorescent powder of any one in illuminating source and claim 1 to 6, described illuminating device is white LED lamp or three-color fluorescent lamp.
19. illuminating device according to claim 18, is characterized in that, described illuminating source is the LED that emission wavelength is 320nm-470nm.
A 20. image display device, it is characterized in that, comprise the described silica nitride fluorescent powder of any one in excitaton source and claim 1 to 6, described image display device is a kind of in fluorescent display tube, field-emitter display, plasma display, cathode tube, high definition television.
21. image display device according to claim 20, is characterized in that, described excitaton source is a kind of in electron rays, electric field, vacuum ultraviolet ray or ultraviolet ray.
CN2011100560141A 2011-03-08 2011-03-08 Silica nitride fluorescent powder and preparation method thereof Expired - Fee Related CN102181285B (en)

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