CN107312538A - A kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content - Google Patents

A kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content Download PDF

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CN107312538A
CN107312538A CN201710576444.3A CN201710576444A CN107312538A CN 107312538 A CN107312538 A CN 107312538A CN 201710576444 A CN201710576444 A CN 201710576444A CN 107312538 A CN107312538 A CN 107312538A
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powder
nitrogen
synthetic method
acid
pickling
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CN107312538B (en
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张琳
李万元
鲁路
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BEIJING ZHONGCUN YUJI TECHNOLOGY CO LTD
Xi'an Hongyu Photoelectric Technology Co Ltd
BEIJING YUJI TECHNOLOGY DEVELOPMENT Co
Beijing Yuji Science and Technology Co Ltd
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BEIJING ZHONGCUN YUJI TECHNOLOGY CO LTD
Xi'an Hongyu Photoelectric Technology Co Ltd
BEIJING YUJI TECHNOLOGY DEVELOPMENT Co
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates

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Abstract

The invention discloses a kind of high brightness nitric oxide fluorescent powder Eu of high nitrogen contentxMaSibAlcOdNeSynthetic method, belong to luminescent material technical field.Added by way of europium element raw material is made into alloy with silica flour using Europium Metal, while there is the nitriding step of element silicon, after high temperature is burnt till, with reference to annealing or pickling processes technique, the high high brightness nitric oxide fluorescent powder of nitrogen content can be obtained.The handling process that the present invention is not required to super-pressure can obtain high brightness Eu2+The high nitrogen content nitric oxide fluorescent powder of doping, reduces the cost of installation and maintenance of equipment；And the powder of large-size crystal grain can be obtained, while improving powder brightness, shorten the synthesis cycle of large scale crystal grain powder, reduce production cost；By optimizing to powder surface, the annealing and pickling impurity removal process of reduction matter crystal internal defect and release crystals stress obtain brightness height and the high nitric oxide fluorescent powder of purity, improve the quality of powder.

Description

A kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content
Technical field
The present invention relates to luminescent material technical field, the high brightness nitric oxide fluorescent powder of more particularly to a kind of high nitrogen content Synthetic method.
Background technology
White light LEDs based on solid luminescent principle have efficiency high, brightness height, long lifespan, small volume, safety non-pollution etc. Plurality of advantages, incandescent lamp and the traditional lighting instrument such as fluorescent lamp gradually in substitution life.In illumination, backlight, traffic It is widely used in terms of signal, decoration, instrument and meter, automobile etc..
With the fast development in white light LEDs in recent years and fluorescent material field, current white LED light source mainstream applications are substantially Towards two Main way developing trends：One is the white light LEDs of illumination direction high brightness high color rendering index (CRI)；Two be in display backlight The white light LEDs of direction high brightness wide gamut.Height colour developing white light LEDs acquisition pattern generally uses blue chip and red, green fluorescence group Close or ultraviolet chip and red, green, blue phosphor combination.Also there are two kinds for the implementation method of wide colour gamut white light LEDs, one is to use color The high green powder of purity and rouge and powder encapsulation blue chip, two be that the red, green, blue fluorescent material for exciting excitation high with ultraviolet chip is obtained White light.Therefore, the performance of fluorescent material has decisive influence to the performance of white light LEDs, and it directly affects white LED spectrum, effect Rate, colour temperature, life-span, colour rendering index and gamut range.In fact, brightness of the green powder on white light parts and gamut range influence compared with Greatly, NTSC colour gamut (NTSC) scope of the white light LEDs for example coordinated using blue chip and bloom is only had 70% or so, but collocation β-sialon:Eu2+Green powder and KSF:Mn4+Rouge and powder, its NSTC scope is up to more than 95%.
Application LED green emitting phosphor has silicate, aluminate, sulfide and nitrogen oxides at present.Silicate (BaSr)2SiO4:Eu2+And Ca3Sc2Si3O12:Ce3+Fluorescence spectrum it is wider, the fluorescence excitation of powder is not high.Aluminate SrAl2O4: Eu2+Emission spectrum is also wider, half peak breadth about 80nm, and the fluorescent material has long afterglow property in addition, and inapplicable backlight is shown Field.Sulfide SrGa2S4:Eu2+And ZnS:Cu2+:Al3+Excitation it is higher, but stability is poor, meets water and easily decomposes, to such The application of fluorescent material all considerable restraints.Nitrogen oxide green fluorescent powder Si3-zAlzOzN4-z:Eu2+(β-sialon:Eu2+) Fluorescent peal is adjustable in 520~560nm scopes, and its fluorescence spectrum half-peak breadth changes with z value changes, in 45~80nm it Between, low z values component excitation is high, and the fluorescent material has excellent chemical stability, and temperature is quenched in hyperpyrexia, makes it by wide General concern, and it is more and more applied in backlight display device.Eu2+The nitrogen oxides of the M-sialon series of doping MxSi3-x-y-zAly+zOzN4-2x/3-y/3-z(M is alkaline earth metal cation) equally has excellent chemical stability, good fluorescence Performance, there is good application prospect in illumination and display.Such as Eu2+The Sr of doping3Si13Al3O2N21(M=Sr, x=9/ 19, y=3/19, z=6/19) and Eu2+The Sr of doping14Si61Al13O7N99(M=Sr, x=21/44, y=9/44, z=21/88) Bluish-green --- green fluorescence is photochromic adjustable, Eu2+The Sr of doping2Si7Al3ON13(M=Sr, x=1/2, y=1/2, z=1/4) Orange --- red fluorescence is photochromic adjustable, has in the display index for improving ultraviolet or blue light activated white light LEDs and well should Use prospect.And Eu2+The SrSi of doping9Al19ON31(M=Sr, x=3/29, y=54/29, z=3/29) under ultraviolet excitation, Emission peak is in the wide fluorescence peak of blue region, applied to the white light LEDs of burst of ultraviolel, can make up some existing blue-fluorescences The deficiency of powder.
Because nitrogen content is high in the nitrogen oxides of β-sialon and M-sialon series, need to be introduced by silicon nitride during preparation Silicon source and nitrogen source, and silicon nitride is more stable, reactivity is low.These nitrogen oxides at high temperature could be into phase, and needs Nitrogen atmosphere is protected, and in the case that nitrogen partial pressure is relatively low, is easily decomposed under principal phase high temperature, therefore prepare these fluorescent material at present It is general to use HTHP solid phase method.On the other hand, every kind of powder has needs to consider that its is special in its particularity, preparation process Property, such as Si3-zAlzOzN4-z:Eu2+Centre of luminescence Eu2+Octahedra channel center in Si-Al-O-N solid solution, this original The lattice occupy-place of sub- gap doping way and most light-emitting phosphor centers is very different, and most fluorescent material are hairs Metal ion and occupy-place in light center substitution host lattice.β-sialon:Eu2+This unique lattice occupy-place of the middle centre of luminescence, So that centre of luminescence Eu2+Solid solution capacity it is relatively low, so as to cause the fluorescent brightness of fluorescent material not high.3rd, β-sialon crystal formations belong to It is obvious in the orientation growth of HTHP crystal in hexagonal crystal system, easily produce slender rod shaped crystal morphology, and this Plant pattern unfavorable to powder fluorescence property optimization.In addition, centre of luminescence Eu introducing generally uses Eu3+, in high temperature N2Atmosphere Under, Eu3+The Eu of green light can not be fully converted into2+, this also weakens β-sialon:Eu2+Fluorescent brightness.Using this height β-the sialon of warm high pressure method synthesis:Eu2+Brightness could be improved by needing the subsequent treatment process of a series of complex, such as patent CN102596852A introduces a kind of synthetic method for synthesizing beta Sialon, using 70~150Mpa super-pressure HIP processing, these works Skill considerably increases equipment cost of installation and maintenance.
Therefore, needed for the nitrogen oxides that such nitrogen content is high, preparation process needs high-temperature and high-pressure conditions a kind of simple The synthetic method of effective low equipment requirement.
The content of the invention
In order to overcome the shortcomings of existing process and technology, the invention discloses a kind of high brightness nitrogen oxides of high nitrogen content The synthetic method of fluorescent material.Purpose is to provide a kind of synthetic method being easily controlled, to obtain the nitrogen oxidation that fluorescence intensity is high Thing Fluorescence Fluorescence powder.
The present invention is a kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content, is by Eu2+It is solid-solution in and contains Among the high nitrogen oxides crystalline phase of nitrogen quantity.During the centre of luminescence is introduced, deposited in the form of lower valency rare-earth europium all the time , it is to avoid high-valence state europium source (such as Eu2O3) introduce centre of luminescence Eu2+And cause Eu2+Solid solution capacity it is not high the problem of.Method is First prepared and be easily broken and stable silicon europium alloy with Europium Metal and active silica flour, in this, as europium source, in HTHP N2In, The silicon formation nitrogen oxides network tetrahedron (Si, Al) (O, N) introduced in silicon europium alloy4A part, and europium then aoxidizes generation Eu2+, so as to improve effective centre of luminescence Eu2+Solid solution capacity, and then improve the fluorescence intensity of fluorescent material.On the other hand, by adjusting The selection of whole host lattice raw material and the adjustment of synthesis technique process, can promote fluorescence crystal grain towards the favourable grain form life of fluorescence It is long.Long column shape or the β-sialon of needle-like are easily formed in such as sintering process:Eu2+, it is bigger to obtain crystallite dimension, draw ratio Smaller powder, so as to increase absorption of the powder to exciting light, and then adds the brightness of powder.3rd, pass through rear place A kind of processing approach in science and engineering sequence, including but not limited to annealing, pickling processes, discharges crystals stress, reduces brilliant Volume defect, improves the purity of fluorescence crystalline phase, so as to substantially increase the fluorescence intensity of powder.
The specific of the present invention be using scheme：
A kind of rare earth Eu2+The synthetic method of the high brightness nitric oxide fluorescent powder of doping high nitrogen content, described Eu2+Mix The chemical composition formula of the high brightness nitrogen oxides of miscellaneous high nitrogen content is EuδMaSibAlcOdNe, wherein, M be alkaline-earth metal sun from Son, a >=0；B, c, d, e ＞ 0, e/ (d+e) >=0.5；As a=0, a is worked as in 0.0001 ＜ δ≤0.05>When 0,0.001 ＜ δ/(δ+ A)≤0.15, its synthetic method comprises the following steps：
(1) silicon europium alloy EuSimPreparation section：By europium metal and metallic silicon power in 800~1400 DEG C of high temperature and protection gas Handled under atmosphere, obtain EuSimAlloy block simultaneously carries out being broken into powder, wherein, 0.3≤m≤1.5；
(2) raw material nitridation process：According to the chemical composition of nitrogen oxides, by a certain amount of silica flour, or silica flour and containing aluminium Oxide or nitride, nitrogen treatment is carried out under 1200~1700 DEG C of pressurized nitrogen atmosphere, obtains nitrogenizing silicon bulk, or containing aluminium Nitridation silicon bulk, by block carry out be broken into powder；
(3) high temperature firing process；According to Eu2+Doped nitric oxide chemical composition, the silicon nitride powder that step (2) is obtained End, or the alpha-silicon nitride powders containing aluminium, and the EuSi that aln precipitation or aluminum oxide, step (1) are obtainedmAlloyed powder and necessary Alkaline-earth metal M compounds are uniformly mixed, then by mixed material at a temperature of 1700~2300 DEG C, 0.3~9.8MPa nitrogen gas High temperature is burnt till under atmosphere, will be burnt till acquisition block and is broken into powder, you can obtains Eu2+Doped nitric oxide fluorescent powder；
(4) postprocessing working procedures：Annealing and/or pickling processes comprising fluorescent material；Annealing refers to by step (3) Powder is obtained in the process that heating and calcining is carried out less than firing temperature, pickling processes are in acid solution by the powder after annealed processing The process of dip pickling.
The time of step (1) the high temperature processing is more than 20 minutes, and the protective atmosphere includes blanket of nitrogen, rare gas One or more gaseous mixtures in atmosphere, nitrogen atmosphere.
The temperature of step (1) the high temperature processing is 1000-1200 DEG C；The high-temperature process time is more than 2 hours；It is described Protective atmosphere is argon atmospher.
0.1~the 10Mpa of nitrogen pressure in the step (2), the nitrogen treatment time is not less than 1h, in temperature-rise period In, more than 1000 DEG C heating rates are not higher than 10 DEG C/min.
The raw material of nitridation process is for silica flour and containing aluminum oxide in the step (2), the nitrogen pressure 0.8- 1.0Mpa；In temperature-rise period, more than 1000 DEG C heating rates are not higher than 1-2 DEG C/min；Grain in described broken powder particle Footpath is not more than 300 microns.
High temperature in the step (3) burnt till processing time no less than 30 minutes；The pressure of the pressurized nitrogen is not less than 0.3Mpa。
The pressure of pressurized nitrogen is 0.8-1.0Mpa in the step (3), and the high temperature crushes the middle grain of powder after burning till Footpath is not more than 150 microns.
The alkaline-earth metal M compounds are M oxide, M nitride, M carbonate or M nitrate.
The step (4) annealing temperature is at least below 200 DEG C of firing temperature, and the time of annealing is small no less than 4 When；Step (4) the pickling processes time is no less than 10 minutes.
Described Eu2+The high brightness nitrogen oxides of doping high nitrogen content is M-sialon:Eu2+Chemical composition is (EuM)xSi3-x-y-zAly+zOzN4-2x/3-y/3-z, M is alkaline-earth metal ions, and the ratio between composition (Si, Al)/(O, N) is 0.70~0.95.
The nitrogen oxides (EuM)xSi3-x-y-zAly+zOzN4-2x/3-y/3-zPostprocessing working procedures be pickling processes, through pickling Powder afterwards, then removing acid solution is cleaned with clear water, drying can obtain M-sialon:Eu2+Fluorescent powder；Wherein, acid solution includes Hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mix acid liquor.
The acid solution is hydrochloric acid, and its concentration is 0.5~20wt%, and pickling time is no less than 10 minutes.
Described Eu2+The high brightness nitrogen oxides of doping high nitrogen content is β-sialon:Eu2+, chemical composition is： EusSi3-mAlmOmN4-m, wherein 0 ＜ m≤2, it is 0.70~0.78 to constitute the ratio between (Si, Al)/(O, N).
The nitrogen oxides is β-sialon:Eu2+The postprocessing working procedures of powder include annealing and pickling processes；Annealing The powder that processing refers to step (3) acquisition is made annealing treatment under 1000~1600 DEG C, vacuum or protective atmosphere, wherein, high temperature The time of annealing is no less than 2 hours；Protective atmosphere is to include inert atmosphere, nitrogen, hydrogen, the hydrocarbon gas or their mixing Gas；Powder after pickling, then removing acid solution is cleaned with clear water, drying can obtain β-sialon:Eu2+Fluorescent powder；Wherein, Acid solution includes hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mix acid liquor.
The acid solution is 40wt% hydrofluoric acid and 68wt% nitric acid, its volume ratio 2:The mixed acid of 1 mixing, during the pickling Between be no less than 10 minutes.
Protective atmosphere in the annealing is the mixed atmosphere constituted containing the argon of 10% hydrogen -90%.
Light-emitting phosphor center Eu introducing typically uses Eu2O3, Eu under nitrogen atmosphere3+It is difficult to Restore All into useful Eu2+, Eu3+Presence not only reduce Eu2+Solid solution capacity, and reduce europium concentration quenching europium content.Using conjunction in the present invention Jin Fa, using reduction-state centre of luminescence Eu, prevents Eu to Eu under an inert atmosphere3+Conversion, adds Eu2+Solid solution capacity, improve Powder brightness.On the other hand, silica flour and part aluminum contained compound are used in raw material, increases raw material nitriding process process, rather than Directly use alpha-silicon nitride powders as synthesis material, make the grain growth of the powder of synthesis bigger, crystal draw ratio with small, and then Increase the brightness of powder.3rd, by the postprocessing working procedures of such as annealing or pickling, it can be released crystals stress, subtract Few crystal defect, improves the purity of fluorescence crystalline phase, so as to substantially increase the fluorescence intensity of powder.
The specific preparation method of fluorescent material of the present invention is as follows：
(1) silicon europium alloy preparation section：By Europium Metal and metallic silicon power under 800~1400 DEG C of protective atmospheres at progress Reason, it is EuSi to obtain name compositionmAlloy block.By EuSimAlloy block carries out being broken into powder.Wherein, 0.3≤m≤1.5； Preferably 1150 DEG C of the temperature of high-temperature process；Processing time is no less than 20 minutes, preferably 2 hours；The protective atmosphere includes nitrogen The gaseous mixture of atmosphere, argon atmospher or other rare gas atmosphere, nitrogen atmosphere and above gas, preferably argon atmospher.
(2) raw material nitridation process；According to nitrogen oxides chemical composition, by a certain amount of silica flour, or silica flour and containing aluminium Oxide or nitride, carry out nitrogen treatment under 1200~1700 DEG C of pressurized nitrogen atmosphere, obtain nitrogenizing silicon bulk, or containing aluminium Silicon bulk is nitrogenized, block is carried out to be broken into powder.0.1~the 10Mpa of nitrogen pressure, preferably 0.9Mpa；In temperature-rise period In, more than 1000 DEG C heating rates are not higher than 10 DEG C/min；Processing time is not less than 1h；Particle diameter in described broken powder particle No more than 300 microns.Using silica flour Direct-Nitridation, if under conditions of temperature is not high, silicon powder nitride is slow, nitridation time Long, if improving temperature nitriding temperature, silica flour is easily sintered, in not flowing nitrogen atmosphere inside the part obstruction of top layer via nitride The progress of nitridation increases process complexity, extension firing period, it is necessary to which sintering crush and through repeatedly nitridation.If A certain amount of oxide or nitride containing aluminium are added in the silica flour of nitridation, the oxide or nitride of aluminium are high melting compound, It can prevent that silicon nitride caking is serious, improve nitriding rate.However, the excessive aluminiferous nitride of addition, in depositing containing aluminum oxide Under the conditions, AlN polytypes, the synthesis of unfavorable follow-up powder are easily produced.Therefore, preferably only addition contains alumina to this technique Thing.
(3) high temperature firing process；By the alpha-silicon nitride powders of acquisition, or the alpha-silicon nitride powders containing aluminium, according to nitrogen oxides Chemical composition, by itself and aln precipitation or oxide, EuSimAlloyed powder and other necessary alkaline earth metal compounds are uniformly mixed Close.Then by mixed material, high temperature is burnt till under pressurized nitrogen atmosphere at a temperature of 1700~2300 DEG C, will be burnt till acquisition block and is broken It is broken into powder, you can obtain EuδMaSibAlcOdNeNitric oxide fluorescent powder.Wherein, M is alkaline earth metal cation, a >=0；B, c, D, e ＞ 0, e/ (d+e) >=0.5.As a=0, a is worked as in 0.0001 ＜ δ≤0.05>When 0,0.001 ＜ δ/(δ+a)≤0.15.It is special It is other, β-sialon:Eu2+Chemical composition be：EusSi3-mAlmOmN4-m, wherein 0 ＜ m≤2, composition (Si, Al)/(O, N) it Than for 0.70~0.78.Particularly, for M-sialon:Eu2+Chemical composition is (EuM)xSi3-x-y-zAly+zOzN4-2x/3-y/3-z(M For alkaline-earth metal ions) composition the ratio between (Si, Al)/(O, N) be 0.70~0.95.High temperature sintering processing time is no less than 30 points Clock；The pressure of the pressurized nitrogen is not less than 0.3Mpa, it is contemplated that the raising of pressurized nitrogen pressure, also more tight to equipment requirement Lattice, preferably pressure are 0.9Mpa.The middle particle diameter of the broken powder is not more than 150 microns.
(4) postprocessing working procedures：Including but not limited to a kind for the treatment of process in annealing, pickling processes.At annealing Reason refers to is obtaining powder in the process less than at least 200 DEG C of firing temperature progress heating and calcining by step (3), pickling processes be by The process of powder after annealed processing in acid solution dip pickling.The generation being difficult to avoid that in step (3) high temperature sintering process Some a small amount of impurity, while in shattering process so that plane of crystal and internal generation defect, increase crystals stress, few Amount crystal perfection is destroyed.The influence of these unfavorable factors can be reduced by annealing or pickling processes, powder is improved The brightness of body.
For β-sialon:Eu2+The postprocessing working procedures of powder include annealing and pickling processes.Its anneal i.e. by β- sialon:Eu2+Powder is made annealing treatment under 1200~1600 DEG C, vacuum or protective atmosphere.Wherein, the high temperature anneal Time is no less than 2 hours；Protective atmosphere is to include argon gas or other inert atmospheres, nitrogen, hydrogen, the hydrocarbon gas or their mixing Gas.It is preferred that hydrogen-argon-mixed atmosphere.After annealed processing, powder is optimized, and its brightness is improved largely.At pickling Reason is by the powder after annealed processing in infiltration acid solution after a period of time, then clean with clear water removing acid solution, drying Obtain β-sialon:Eu2+Fluorescent powder；Wherein, acid solution includes hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mixing Acid solution.It is preferred that acid solution is 40wt% hydrofluoric acid and 68wt% nitric acid, its volume ratio 2:The mixed acid of 1 mixing, preferably pickling time No less than 10 minutes.
For Eu2+The nitrogen oxides M of the M-sialon series of dopingxSi3-x-y-zAly+zOzN4-2x/3-y/3-z(M is alkaline earth gold Belonging to cation) postprocessing working procedures of powder are pickling processes, the powder that high temperature firing process is obtained, one in infiltration acid solution After the section time, then clean with clear water and to remove acid solution, drying can obtain M-sialon:Eu2+(M is alkaline earth metal cation) fluorescence Powder.Wherein, acid solution includes hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mix acid liquor.It is preferred that acid solution is hydrochloric acid, 0.5~20wt% of preferred concentration, preferably pickling time are no less than 10 minutes.
Compared with the prior art, specific benefit of the invention：
First, the present invention is introduced into lighting by silicon europium alloy powder stable under first synthesis of air with this lower valency europium source Heart Eu2+, such high brightness Eu can be obtained by being not required to the handling process of super-pressure2+The high nitrogen content nitric oxide fluorescent powder of doping, Reduce the cost of installation and maintenance of equipment.
Second, the silicon nitride raw material containing aluminium is obtained by nitriding process, the powder of large-size crystal grain can be obtained with this, is carried While high powder brightness, shorten the synthesis cycle of large scale crystal grain powder, reduce production cost.
3rd, by optimizing to powder surface, the annealing of reduction matter crystal internal defect and release crystals stress With pickling impurity removal process, brightness height is obtained, the high nitric oxide fluorescent powder of powder purity improves the quality of powder.
Brief description of the drawings
Fig. 1 be embodiment 1 in synthesize Eu2+β-sialon (the Eu of dopingsSi3-mAlmOmN4-m) green emitting phosphor excite and Launching light spectrogram.Wherein s=0.01, m are respectively 0.05,0.1,0.2,0.5,0.8,1.5.
Fig. 2 be in embodiment 2 through high temperature burn till it is broken after obtain β-sialon (EusSi3-mAlmOmN4-m, m=0.1) and powder SEM display figure.
Fig. 3 is the β-sialon (Eu of different process process stages acquisition in embodiment 2sSi3-mAlmOmN4-m, m=0.1) and powder Fluorescence spectrum of the body under 460nm exciting lights, wherein curve 1 are the fluorescence spectrum that powder is obtained after high temperature is burnt till, and curve 2 is warp The powder fluorescence spectrum of annealing, curve 3 is the fluorescence spectrum of the powder through pickling processes.
Fig. 4 be in embodiment 3 through high temperature burn till it is broken after obtain β-sialon (EusSi3-mAlmOmN4-m, m=0.1) and powder SEM display figure.
Fig. 5 is embodiment 2, the and of embodiment 3
The fluorescence spectrum of powder is obtained in reference example 1, wherein curve 1 is β-sialon after the pickling processes of embodiment 2 (EusSi3-mAlmOmN4-m, m=0.1) powder fluorescence spectrum, curve 2 be the pickling processes of embodiment 3 after β-sialon (EusSi3-mAlmOmN4-m, m=0.1) powder fluorescence spectrum, curve 3 is
β-sialon (Eu after the pickling processes of reference example 1sSi3-mAlmOmN4-m, m=0.1) powder fluorescence spectrum
Fig. 6 be embodiment 4 in synthesize Eu2+Doped nitric oxide EuxSr3-xSi13Al3O2N21The transmitting light of green emitting phosphor Spectrogram.Wherein x difference 0.01,0.02,0.05,0.08,0.10,0.15,0.20.
Fig. 7 is the fluorescence spectrum of acquisition powder in embodiment 5, embodiment 6 and reference example 2, and wherein curve 1 is embodiment 5 Eu after high temperature firing process0.08Sr2.92Si13Al3O2N21The fluorescence spectrum of powder, wherein curve 2 is after the pickling processes of embodiment 5 Eu0.08Sr2.92Si13Al3O2N21The fluorescence spectrum of powder, curve 3 is after the pickling processes of embodiment 6 Eu0.08Sr2.92Si13Al3O2N21The fluorescence spectrum of powder, curve 4 is after the pickling processes of reference example 2 Eu0.08Sr2.92Si13Al3O2N21The fluorescence spectrum of powder
Embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1
1. prepared by silicon europium alloy：Raw material 10g Europium Metal blocks are embedded among excessive silica flour, the argon gas gas in alumina crucible By 1150 DEG C of 4h processing under atmosphere, 11.2250g silicon europium alloy blocks are obtained, are crushed and by the sieving of 300m nylon mesh.According to Burn till front and rear mass change, it may be determined that silicon europium alloy name chemical composition is Eu3Si2。
2. raw material is nitrogenized：200g silica flours are placed in cylinder boron nitride crucible (Φ 90mm × 110mm), in 0.9Mpa nitrogen Under pressure atmosphere, the nitrogen treatment 8h at 1500 DEG C.Heat temperature raising speed control is as follows：Room temperature is to 1000 DEG C with 10 DEG C/min Heating, 1000 DEG C to 1200 DEG C are heated up with 2 DEG C/min, and 1200 DEG C to 1350 DEG C, with 1 DEG C/min of heating, 4 are incubated at 1350 DEG C Hour, 1350 DEG C to 1500 DEG C with 1 DEG C/min of heating.Products therefrom is the nitridation silicon bulk of some strength, is ground brokenly It is broken, and by the screening of 150 mesh nylon mesh.
3. high temperature is burnt till：By the silicon nitride powder of acquisition with the aluminium nitride of mass ratio 92.52% and 1.41%, 4.90% oxygen Change aluminium and 1.17% silicon europium alloy powder is uniformly mixed.According to β-sialon:Eu2+Chemical composition EusSi3-mAlmOmN4-m, originally match somebody with somebody S=0.01, m=0.2 than in.The mixed material of sieving is fitted into cylinder boron nitride crucible (Φ 90mm × 110mm), Under 0.9Mpa nitrogen pressure atmosphere, processing 8h is burnt till at 1900 DEG C.The block of gained is ground it is broken, and through 120 mesh Nylon mesh crosses sieve classification, and removing is difficult to broken hard particles.Powder is to obtain β-sialon under collection screen:Eu2+Fluorescent material Body.
4. post-process
Annealing：By the β-sialon of acquisition:Eu2+Fluorescent material loads aluminum oxide Noah's ark (40mm × 40mm × 200mm) In, in tube furnace, in the argon hydrogen gaseous mixture atmosphere containing 10% hydrogen, 1350 DEG C of processing 8h.After being handled through argon hydrogen reduction atmosphere, because Plane of crystal that is broken and causing damage is optimized, and crystals stress is released, and defect is reduced, so that powder is glimmering Luminous intensity is substantially improved.
Pickling processes：β-the sialon for burning till and annealing by HTHP:Eu2+Powder is still containing a certain amount of miscellaneous The AlN polytypes produced in matter, the main silica flour for including failing nitrogenizing and reacting completely, sintering process are, it is necessary to these impurity It is purged.Method is by the β-sialon after annealing:Eu2+Powder 100g, input 300ml hydrofluoric acid (40wt%) and 150ml In nitric acid (68wt%), stir process 2 hours.Then removing acid solution is cleaned with distilled water.Brightness can be obtained after drying and enters one Walk the β-sialon improved:Eu2+Fluorescent material.
Adjust the composition and ratio of mixed material, corresponding adjustment HTHP firing temperature, can obtain the β of different z values- sialon:Eu2+Powder.The difference of z values, the photochromic also difference of fluorescent material.As the difference z values of form 1 raw material proportioning and burn till temperature The fluorescence peak wavelength and full half-peak breadth of degree and acquisition powder under 460nm exciting lights.Fig. 1 is excited and launched for different z values Spectrum.
β-the sialon of form 1, difference z values:Eu2+Raw material mass mixture ratio, firing temperature and fluorescence parameter
Embodiment 2
1. prepared by silicon europium alloy：The Eu in europium source will be used as according to silicon europium alloy preparation technology synthesis in embodiment 13Si2Powder End.
2. raw material is nitrogenized：200g silica flours and 8.71g aluminum oxide are uniformly mixed, cylinder boron nitride crucible (Φ 90mm × In 110mm), under 0.9Mpa nitrogen pressure atmosphere, the nitrogen treatment 8h at 1500 DEG C.Heat temperature raising speed control is as follows：Room Temperature is to 1000 DEG C with 10 DEG C/min of heatings, and 1000 DEG C to 1200 DEG C are heated up with 2 DEG C/min, and 1200 DEG C to 1350 DEG C with 1 DEG C/minute Clock is heated up, and 4 hours are incubated at 1350 DEG C, and 1350 DEG C to 1500 DEG C with 1 DEG C/min of heating.Products therefrom is salic to wrap Silicon bulk is nitrogenized, is ground broken, and by the screening of 150 mesh nylon mesh.
3. high temperature is burnt till：By the salic silicon nitride powder of bag of acquisition with the nitridation of mass ratio 98.36% and 0.47% Aluminium, 1.17% silicon europium alloy powder are uniformly mixed.According to β-sialon:Eu2+Chemical composition EusSi3-mAlmOmN4-m, in this proportioning S=0.01, m=0.1.The mixed material of sieving is fitted into cylinder boron nitride crucible (Φ 90mm × 110mm), in 0.9Mpa nitrogen Under atmospheric pressure atmosphere, processing 8h is burnt till at 1920 DEG C.The block of gained is ground broken and sieved through 120 mesh nylon Sieve classification, removing is difficult to broken hard particles.The crystalline size obtained by this method is larger, and major diameter is smaller, this shape State is the favourable form of powder Fluorescence Increasing.In nitridation process, the silicon nitride of generation is partially oxidized aluminium parcel, high in high temperature Under the conditions of pressure, the aluminum oxide melted first inwardly dissolves silicon nitride so that crystal orientation growth slows down, crystal draw ratio compared with It is small.If Fig. 2 is the scanning electron micrographs of the powder obtained.As curve 1 is the powder in the case where 460nm blue lights are excited in Fig. 3 Fluorescence spectra.
4. post-process
Annealing：It will be annealed in powder such as embodiment 1, after annealing, the fluorescence intensity of powder is big Big lifting.Such as fluorescence spectrum of the curve 2 for the powder after the process in the case where 460nm blue lights are excited in Fig. 3.
Pickling processes：By pickling processes in powder such as embodiment 1, after pickling, the fluorescence intensity of powder is further improved, Such as fluorescence spectrum of the curve 3 for the powder after process in the case where 460nm blue lights are excited in Fig. 3.
The powder obtained if table 2 is powder by different process processing stage the absorptivity under 460nm blue lights are excited, in Quantum efficiency and external quantum efficiency.Wherein, data are obtained by Hitachi's F7000 XRFs and its quantum efficiency test system test .
Form 2, by different process program β-sialon:Eu2+The absorptivity of powder, interior quantum, external quantum efficiency and phase To fluorescence intensity
Embodiment 3
1. prepared by silicon europium alloy：Eu as europium source is prepared according to silicon europium alloy preparation technology in embodiment 13Si2Powder.
2. raw material is nitrogenized：Obtained according to raw material nitriding process in embodiment 1 and alpha-silicon nitride powders are obtained by silicon powder nitride.
3. high temperature is burnt till：Silicon nitride powder will be obtained with the aluminium nitride of mass ratio 95.79% and 0.47%, 2.57% oxidation Aluminium and 1.17% silicon europium alloy powder are uniformly mixed.According to β-sialon:Eu chemical compositions EusSi3-mAlmOmN4-m, in this proportioning S=0.01, m=0.1.The mixed material of sieving is fitted into cylinder boron nitride crucible (Φ 90mm × 110mm), in 0.9Mpa nitrogen Under atmospheric pressure atmosphere, processing 8h is burnt till at 1920 DEG C.The block of gained is ground broken and sieved through 120 mesh nylon Sieve classification, and removing is difficult to broken hard particles.Such as the scanning electron micrographs that Fig. 4 is the powder.The powder of comparison diagram 2 Pattern, it can be seen that the powder that the technique process of embodiment 2 is obtained more disperses, crystalline size is big, and powder microstructure is good.
4. post-process
Annealing：It will be annealed in powder such as embodiment 1.
Pickling processes：It is to be somebody's turn to do as annealing carries out curve 2 in pickling, such as fluorescent powder of acquisition, Fig. 5 in embodiment 1 The fluorescence spectrum of powder.Contrast the fluorescent spectrum curve 1 of the powder in embodiment 2 Jing Guo pickling processes, it can be seen that according to The powder fluorescence intensity that the technique process of embodiment 2 is obtained is higher.
Reference example 1
1. raw material is nitrogenized：200g silica flours and 7.51g aluminum oxide are uniformly mixed, cylinder boron nitride crucible (Φ 90mm × In 110mm), under 0.9Mpa nitrogen pressure atmosphere, the nitrogen treatment 8h at 1500 DEG C.Heat temperature raising speed control is as follows：Room Temperature is to 1000 DEG C with 10 DEG C/min of heatings, and 1000 DEG C to 1200 DEG C are heated up with 2 DEG C/min, and 1200 DEG C to 1350 DEG C with 1 DEG C/minute Clock is heated up, and 4 hours are incubated at 1350 DEG C, and 1350 DEG C to 1500 DEG C with 1 DEG C/min of heating.Products therefrom is salic to wrap Silicon bulk is nitrogenized, is ground broken, and by the screening of 150 mesh nylon mesh.
2. high temperature is burnt till：It will obtain and wrap salic silicon nitride powder with the aluminium nitride of mass ratio 97.51% and 0.75% And 1.75% europium oxide powder is uniformly mixed.And sieve to carry out Task-size Controlling through 120 mesh nylon mesh.According to β-sialon: Eu2+Chemical general formula, EusSi3-mAlmOmN4-m, s=0.01, m=0.1 in this proportioning.The mixed material of sieving is loaded into cylinder nitrogen Change in boron crucible (Φ 90mm × 110mm), under 0.9Mpa nitrogen pressure atmosphere, processing 8h is burnt till at 1920 DEG C.By gained Block be ground broken, and cross sieve classification through 120 mesh nylon mesh, and remove and be difficult to broken hard particles.
3. post-process
Annealing：It will be annealed in powder such as embodiment 1
Pickling processes：It is to be somebody's turn to do as annealing carries out curve 3 in pickling, such as fluorescent powder of acquisition, Fig. 5 in embodiment 1 The fluorescence spectrum of powder.Contrast spectrum can be drawn, compared to using Eu2O3As europium source, silicon europium alloy Eu is used3Si2Powder effect More preferably.β-sialon (the Eu that different process processing is obtained from form 3 threesSi3-mAlmOmN4-m, m=0.1) powder absorption Rate, internal quantum efficiency and external quantum efficiency can also find out, EuSimCompare Eu as europium source effect2O3It is good.
Form 3, embodiment 2 and its absorptivity, interior quantum, external quantum efficiency and the relative fluorescence that contrast all product of reference example Intensity
Embodiment 4
1. prepared by silicon europium alloy：Eu as europium source is prepared according to the silicon europium alloy preparation technology of embodiment 13Si2Powder.
2. raw material is nitrogenized：Obtained according to raw material nitriding process in embodiment 1 and obtained particle diameter by silicon powder nitride and be less than 100 microns Alpha-silicon nitride powders.
3. high temperature is burnt till：By the silicon nitride powder of acquisition with the aluminium nitride of mass ratio 58.68% and 6.60%, 6.56% oxygen Change aluminium, 0.16% silicon europium alloy powder and 28.00% strontium nitride powder uniformly to mix.According to nitrogen oxides EuxSr3- xSi13Al3O2N21Eu contents x=0.08 in chemical composition, this proportioning.The mixed material of sieving is loaded into cylinder boron nitride crucible In (Φ 90mm × 110mm), under 0.9Mpa nitrogen pressure atmosphere, 8h is calcined at 1800 DEG C.The block of gained is ground Worn-off is broken, and crosses sieve classification through 120 mesh nylon mesh, and removing is difficult to broken hard particles.Powder is to obtain Eu under collection screen2+Mix Miscellaneous nitrogen oxides Sr3Si13Al3O2N21Green emitting phosphor.
4. post-process, i.e. pickling processes, high temperature is burnt till to the nitrogen oxides Sr of acquisition3Si13Al3O2N21Fluorescent material powder 100g, puts into the 300ml hydrochloric acid solutions that hydrogen chloride mass ratio is 8%, stir process 2 hours.Then cleaned and removed with distilled water Go acid solution.The nitrogen oxides Sr that brightness is further improved can be obtained after drying3Si13Al3O2N21Fluorescent material.
Adjust the centre of luminescence Eu of mixed material2+Composition and ratio, can obtain the photochromic Sr of different fluorescence3Si13Al3O2N21 Fluorescent material.Such as the Eu of difference Eu content x values in form 4xSr3-xSi13Al3O2N21Raw material proportioning, and handle 8h at 1800 DEG C Fluorescence peak wavelength and full half-peak breadth of the acquisition powder of ground acquisition under 460nm exciting lights.Fig. 6 is the different amounts containing Eu Sr3Si13Al3O2N21The fluorescence spectrum of fluorescent material.
The nitrogen oxides Eu of form 4, difference x valuesxSr3-xSi13Al3O2N21Raw material mass mixture ratio and fluorescence parameter
Embodiment 5
1. prepared by silicon europium alloy：The Eu in europium source will be used as according to silicon europium alloy preparation technology synthesis in embodiment 13Si2Powder End.
2. raw material is nitrogenized：200g silica flours and 16.65g aluminum oxide are uniformly mixed, cylinder boron nitride crucible (Φ 90mm × In 110mm), under 0.9Mpa nitrogen pressure atmosphere, the nitrogen treatment 8h at 1500 DEG C.Heat temperature raising speed control is as follows：Room Temperature is to 1000 DEG C with 10 DEG C/min of heatings, and 1000 DEG C to 1200 DEG C are heated up with 2 DEG C/min, and 1200 DEG C to 1350 DEG C with 1 DEG C/minute Clock is heated up, and 4 hours are incubated at 1350 DEG C, and 1350 DEG C to 1500 DEG C with 1 DEG C/min of heating.Products therefrom is salic to wrap Silicon bulk is nitrogenized, is ground broken, and by the screening of 150 mesh nylon mesh.
3. high temperature is burnt till：By the salic silicon nitride powder of bag of acquisition with the nitridation of mass ratio 61.99% and 6.46% Aluminium, 3.48% aluminum oxide, 1.29% silicon europium alloy powder and 26.78% strontium nitride powder are uniformly mixed.According to nitrogen oxidation Thing EuxSr3-xSi13Al3O2N21Eu contents x=0.08 in chemical composition, this proportioning.The mixed material of sieving is loaded into cylinder nitrogen Change in boron crucible (Φ 90mm × 110mm), under 0.9Mpa nitrogen pressure atmosphere, processing 8h is burnt till at 1800 DEG C.By gained Block be ground broken, and cross sieve classification through 120 mesh nylon mesh, removing is difficult to broken hard particles.Collect minus sieve Body is to obtain Eu2+The nitrogen oxides Sr of doping3Si13Al3O2N21Green emitting phosphor.
4. middle curve 1 is fluorescence spectra of the powder in the case where 460nm blue lights are excited.
Post processing, by pickling processes in powder such as embodiment 4, after pickling, the fluorescence intensity of powder is further improved, such as
Fluorescence spectrum of the middle curve 2 for the powder after post processing in the case where 460nm blue lights are excited.
The powder obtained if table 2 is powder by different process processing stage the absorptivity under 460nm blue lights are excited, in Quantum efficiency and external quantum efficiency.
Form 5, different process stage Sr2.92Eu0.08Si13Al3O2N21The absorption of fluorescent material, inside and outside quantum efficiency and relative Fluorescence intensity
Embodiment 6
1. prepared by silicon europium alloy：Eu as europium source is prepared according to silicon europium alloy preparation technology in embodiment 13Si2Powder.
2. raw material is nitrogenized：Obtained according to raw material nitriding process in embodiment 1 and obtained particle diameter by silicon powder nitride and be less than 100 microns Alpha-silicon nitride powders.
3. high temperature is burnt till：Silicon nitride powder will be obtained with the aluminium nitride of mass ratio 59.20% and 6.47%, 6.44% oxidation Aluminium, 0.81% silicon europium alloy powder and 27.09% strontium nitride powder are uniformly mixed.According to nitrogen oxides EuxSr3- xSi13Al3O2N21Eu contents x=0.08 in chemical composition, this proportioning.The mixed material of sieving is loaded into cylinder boron nitride crucible In (Φ 90mm × 110mm), under 0.9Mpa nitrogen pressure atmosphere, processing 8h is burnt till at 1800 DEG C.The block of gained is entered Row grinding is broken, and crosses sieve classification through 120 mesh nylon mesh, and removing is difficult to broken hard particles.Powder is to obtain under collection screen Obtain Eu2+The nitrogen oxides Sr of doping3Si13Al3O2N21Green emitting phosphor.
4. post-process, by pickling processes in powder such as embodiment 4, after pickling, the fluorescence intensity of powder is further improved, Such as fluorescence spectrum of the curve 3 for the powder after post processing in the case where 460nm blue lights are excited in Fig. 7.
Reference example 2
1. raw material is nitrogenized：According to raw material nitriding process in embodiment 5 obtain by silica flour and aluminum oxide nitrogenize and particle diameter is small In 100 microns of the alpha-silicon nitride powders containing aluminium.
2. high temperature is burnt till：By the salic silicon nitride powder of bag of acquisition with the nitridation of mass ratio 62.24% and 6.65% Aluminium, 3.22% aluminum oxide, 0.83% europium oxide powder and 27.05% strontium nitride powder are uniformly mixed.According to nitrogen oxides EuxSr3-xSi13Al3O2N21Eu contents x=0.08 in chemical composition, this proportioning.The mixed material of sieving is loaded into cylinder nitridation In boron crucible (Φ 90mm × 110mm), under 0.9Mpa nitrogen pressure atmosphere, processing 8h is burnt till at 1800 DEG C.By gained Block is ground broken, and crosses sieve classification through 120 mesh nylon mesh, and removes and be difficult to broken hard particles.Collect minus sieve Body is to obtain Eu2+The nitrogen oxides Sr of doping3Si13Al3O2N21Green emitting phosphor.
3. post-process, by pickling processes in powder such as embodiment 4, after pickling, the fluorescence intensity of powder is further improved, Such as fluorescence spectrum of the curve 4 for the powder after post processing in the case where 460nm blue lights are excited in Fig. 7.Form 6 is respectively embodiment 5, reality Apply example 6, the different process process of reference example 2 and handle obtained Eu0.08Sr2.92Si13Al3O2N21The absorptivity of fluorescent powder, interior quantum Efficiency and external quantum efficiency and relative intensity of fluorescence.
Form 6, embodiment 4 and its absorptivity, interior quantum, external quantum efficiency and the relative fluorescence that contrast all product of reference example Intensity

Claims (16)

1. a kind of rare earth Eu2+The synthetic method of the high brightness nitric oxide fluorescent powder of doping high nitrogen content, described Eu2+Doping is high The chemical composition formula of the high brightness nitrogen oxides of nitrogen content is EuδMaSibAlcOdNe, wherein, M is alkaline earth metal cation, a ≥0；B, c, d, e ＞ 0, e/ (d+e) >=0.5；As a=0, a is worked as in 0.0001 ＜ δ≤0.05>When 0,0.001 ＜ δ/(δ+a)≤ 0.15, its synthetic method comprises the following steps：
(1) silicon europium alloy EuSimPreparation section：Europium metal and metallic silicon power are entered under 800~1400 DEG C of high temperature and protective atmosphere Row processing, obtains EuSimAlloy block simultaneously carries out being broken into powder, wherein, 0.3≤m≤1.5；
(2) raw material nitridation process：According to the chemical composition of nitrogen oxides, by a certain amount of silica flour, or silica flour and the oxygen containing aluminium Compound or nitride, carry out nitrogen treatment under 1200~1700 DEG C of pressurized nitrogen atmosphere, obtain nitrogenizing silicon bulk, or the nitrogen containing aluminium SiClx block, block is carried out to be broken into powder；
(3) high temperature firing process；According to Eu2+Doped nitric oxide chemical composition, the alpha-silicon nitride powders that step (2) is obtained, or Alpha-silicon nitride powders containing aluminium, and the EuSi that aln precipitation or aluminum oxide, step (1) are obtainedmAlloyed powder and necessary alkaline earth Metal M compounds are uniformly mixed, then by mixed material at a temperature of 1700~2300 DEG C, under 0.3~9.8MPa nitrogen atmospheres High temperature is burnt till, and will be burnt till acquisition block and is broken into powder, you can obtains Eu2+Doped nitric oxide fluorescent powder；
(4) postprocessing working procedures：Annealing and/or pickling processes comprising fluorescent material；Annealing refers to be obtained by step (3) Powder is in the process that heating and calcining is carried out less than firing temperature, and pickling processes are to impregnate the powder after annealed processing in acid solution The process of pickling.
2. synthetic method according to claim 1, the time of step (1) the high temperature processing is more than 20 minutes, described Protective atmosphere includes one or more gaseous mixtures in blanket of nitrogen, rare gas atmosphere, nitrogen atmosphere.
3. synthetic method according to claim 2, the temperature of step (1) the high temperature processing is 1000-1200 DEG C； The high-temperature process time is more than 2 hours；The protective atmosphere is argon atmospher.
4. 0.1~the 10Mpa of nitrogen pressure in synthetic method according to claim 1, the step (2), nitridation Processing time is not less than 1h, in temperature-rise period, and more than 1000 DEG C heating rates are not higher than 10 DEG C/min.
5. the raw material of nitridation process is for silica flour and containing alumina in synthetic method according to claim 4, the step (2) Thing, the nitrogen pressure 0.8-1.0Mpa；In temperature-rise period, more than 1000 DEG C heating rates are not higher than 1-2 DEG C/min；Institute Particle diameter is not more than 300 microns in the broken powder particle stated.
6. the high temperature in synthetic method according to claim 1, the step (3) burns till processing time no less than 30 points Clock；The pressure of the pressurized nitrogen is not less than 0.3Mpa.
7. the pressure of pressurized nitrogen is 0.8-1.0Mpa, institute in synthetic method according to claim 6, the step (3) The middle particle diameter for stating broken powder after high temperature is burnt till is not more than 150 microns.
8. synthetic method according to claim 1, the alkaline-earth metal M compounds are M oxide, M nitride, M carbonic acid Salt or M nitrate.
9. synthetic method according to claim 1, the step (4) makes annealing treatment temperature at least below firing temperature 200 DEG C, the time of annealing is no less than 4 hours；Step (4) the pickling processes time is no less than 10 minutes.
10. synthetic method according to claim 1, described Eu2+The high brightness nitrogen oxides of doping high nitrogen content is M- sialon:Eu2+Chemical composition is (EuM)xSi3-x-y-zAly+zOzN4-2x/3-y/3-z, M is alkaline-earth metal ions, composition (Si, Al)/ The ratio between (O, N) is 0.70~0.95.
11. synthetic method according to claim 10, the nitrogen oxides MxSi3-x-y-zAly+zOzN4-2x/3-y/3-zRear place Science and engineering sequence is pickling processes, the powder after pickling, then clean with clear water and to remove acid solution, and drying can obtain M-sialon:Eu2+ Fluorescent powder；Wherein, acid solution includes hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mix acid liquor.
12. synthetic method according to claim 11, the acid solution is hydrochloric acid, its concentration is 0.5~20wt%, during pickling Between be no less than 10 minutes.
13. synthetic method according to claim 1, described Eu2+Adulterate high nitrogen content high brightness nitrogen oxides for β- sialon:Eu2+, chemical composition is：EusSi3-mAlmOmN4-m, wherein 0 ＜ m≤2, it is 0.70 to constitute the ratio between (Si, Al)/(O, N) ~0.78.
14. synthetic method according to claim 13, the nitrogen oxides is β-sialon:Eu2+The post processing work of powder Sequence includes annealing and pickling processes；Annealing refers to the powder of step (3) acquisition at 1000~1600 DEG C, vacuum or protection Made annealing treatment under atmosphere, wherein, the time of the high temperature anneal is no less than 2 hours；Protective atmosphere be include inert atmosphere, Nitrogen, hydrogen, the hydrocarbon gas or their gaseous mixture；Powder after pickling, then removing acid solution is cleaned with clear water, drying can be obtained β-sialon:Eu2+Fluorescent powder；Wherein, acid solution includes hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or their mix acid liquor.
15. synthetic method according to claim 14, the acid solution is 40wt% hydrofluoric acid and 68wt% nitric acid, its volume Than 2:The mixed acid of 1 mixing, the pickling time is no less than 10 minutes.
16. synthetic method according to claim 15, the protective atmosphere in the annealing is containing the argon of 10% hydrogen -90% composition Mixed atmosphere.
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