CN106281317A - A kind of high brightness, bulky grain size beta SiAlON:Eu2+green emitting phosphor and preparation method thereof - Google Patents

A kind of high brightness, bulky grain size beta SiAlON:Eu2+green emitting phosphor and preparation method thereof Download PDF

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CN106281317A
CN106281317A CN201610666337.5A CN201610666337A CN106281317A CN 106281317 A CN106281317 A CN 106281317A CN 201610666337 A CN201610666337 A CN 201610666337A CN 106281317 A CN106281317 A CN 106281317A
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sialon
sintering
emitting phosphor
green emitting
high brightness
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CN106281317B (en
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杨志平
王海龙
赵金鑫
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Hebei Ledphor Optoelectronics Technology Co ltd
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Hebei Ledphor Optoelectronics Technology Co ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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 present invention relates to a kind of high brightness, bulky grain size beta SiAlON:Eu2+Green emitting phosphor and preparation method thereof, the chemical general formula of described fluorescent material is Sia(AlxGa1‑x)bOcNd: Eue 2+, in formula, 0.4≤a≤0.5,0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d≤0.664,0 ＜ e≤0.010,0 ＜ x ＜ 1；Described fluorescent material is formed by two-step sintering, and second time sintering be first sintering gained primary sintered material is mixed with raw material after be sintered again.β SiAlON:Eu prepared by the present invention2+Green emitting phosphor, its granule is uniform, and mean diameter is big, and luminous intensity is high, has bright prospects, be more mainly used in the semiconductor light-emitting apparatus liquid crystal display (LCD) as backlight in preparing white light LEDs.The process of the present invention is suitable to large-scale industrial production, can be by regulating proportioning raw materials, temperature control and realize preparation expectation granularity and the uniformity and the β SiAlON:Eu at the narrow peak of high brightness2+Green emitting phosphor.

Description

A kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor and preparation thereof Method
Technical field
The present invention relates to a kind of grand type green emitting phosphor and preparation method thereof of matching, specifically a kind of high brightness, big Particle size β-SiAlON:Eu2+Green emitting phosphor and preparation method thereof.
Background technology
SiAlON fluorescent material is a kind of nitric oxide fluorescent powder mainly including tetra-kinds of chemical elements of Si, Al, O, N, and it is brilliant Body configuration and Si3N4Similar.In Si-Al-O-N quaternary system, due to cation M (Si4+、Al3+) and anion X (N, O) Ratio different, the solid solution of formation is the most different, mainly has β-SiAlON, α-SiAlON, O-SiAlON, X-SiAlON and AlN Polytype (8H, 12H, 15R, 21R, 27R etc.).The formula of β-SiAlON is Si6-ZAlZOZN8-Z, wherein 0 < Z≤4.2, in scanning Observed under electron microscope to β-SiAlON be typical hexagonal columnar crystal, it is than β-Si3N4Crystal is thick, thus its pottery The ductile strength of porcelain body is preferable.
β-SiAlON:Eu2+Green emitting phosphor is a kind of rear-earth-doped β-SiAlON fluorescent material, and it has approximation 52nm's Narrow spectral width, is mainly used in backlight material, i.e. liquid crystal display (LCD).But, the β-SiAlON:Eu being currently known2+Green The problem that color fluorescent material generally exists luminance shortage, particle size is little and granularity is uneven.Such as, document Characterization and properties of green-emittingβ-SiAlON:Eu2+powder phosphors For white light-emitting diodes, wherein prepared β-SiAlON:Eu2+Green emitting phosphor has bar-shaped shape The length of looks only has 4 μm, diameter to only have 0.5 μm；β-SiAlON:Eu prepared in European patent EP 2664660A12+Green glimmering Light powder, the most least a portion of granule can reach 10 μm, and required sintering pressure is 70～200MPa, the most difficult control of technique, equipment Make, and post processing mode uses HF to add HNO3Nitration mixture carry out pickling, environment, human body are all injured bigger；For another example document Densificatioon and Microstructure of β-sialon/Nano-size SiC Composites, it is prepared The granulation uniformity gone out is poor, granule-morphology is irregular.
β-SiAlON:Eu2+The particle size of green emitting phosphor and particle size distribution all can affect the luminous efficiency of backlight material With colour developing accuracy, therefore, it is badly in need of preparing the β-SiAlON:Eu being applicable to backlight material of high brightness, bulky grain size2+Green Color fluorescent material.
Summary of the invention
An object of the present invention is to provide a kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, with Solve existing β-SiAlON:Eu2+Green emitting phosphor generally exists that luminance shortage, particle size be little and uneven the asking of granularity Topic.
The two of the purpose of the present invention are to provide a kind of high brightness, bulky grain size beta-SiAlON:Eu2+The system of green emitting phosphor Preparation Method, to prepare that particle size is big, even particle size distribution and the high β-SiAlON:Eu of brightness2+Green emitting phosphor.
Present invention high brightness to be provided, bulky grain size beta-SiAlON:Eu2+The technical scheme of green emitting phosphor is such as Under:
A kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, its chemical general formula is Sia(AlxGa1-x)bOcNd: Eue 2+, in formula, 0.4≤a≤0.5,0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d≤0.664,0 ＜ e≤ 0.010,0 ＜ x ＜ 1；Described fluorescent material is formed by two-step sintering, first part material is carried out first sintering, obtains once Sintering feed, then in primary sintered material, add the raw material of remainder, carry out second time after mix homogeneously again and sinter.
Preferably scheme is, 0.408≤a≤0.489 in formula, 0.012≤b≤0.02,0.006≤c≤0.02,0.557 ≤ d≤0.664,0.004≤e≤0.010,0.5≤x ＜ 1.The scheme being more highly preferred to is 0.408≤a≤0.489,0.012≤b ≤ 0.02,0.01 ＜ c≤0.02,0.557≤d≤0.664,0.004≤e≤0.008,0.5≤x≤0.8.
Preferably scheme is that described primary sintered material mixes according to the mass ratio of 1～10: 1 with raw material；Described double sintering During add oxides additive.
Present invention high brightness to be provided, bulky grain size beta-SiAlON:Eu2+The technology of green fluorescence powder, preparation method thereof Scheme is as follows:
A kind of high brightness, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, it comprises the steps:
A, proportioning raw materials: the chemical general formula of described fluorescent material is Sia(AlxGa1-x)bOcNd: Eue 2+, in formula, 0.4≤a≤ 0.5,0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d≤0.664,0 ＜ e≤0.010,0 ＜ x ＜ 1；N2Atmosphere is protected Protect down and take raw material by each element chemistry metering score another name in aforementioned formula, be placed in mortar and be ground, then cross 40-200 Mesh sieve, loads crucible；
Described raw material be Si simple substance or Si compound or both mixing, Al simple substance or Al compound or both mixing, Ga compound and Eu compound；
Described Si compound is Si3N4、SiO2In at least one, described Si3N4For α-Si3N4And/or β-Si3N4；Described Al compound is AlN, Al2O3And AlF3In at least one；Described Ga compound is the oxide of Ga；Described Eu compound is Eu2O3, at least one in EuN；
B, sintering: first by raw material at N2/H2Under mixed atmosphere or at pure N2Atmosphere under carry out once sintered, during sintering Between be 1～12h, sintering temperature is 1200 DEG C～2200 DEG C, and sintering pressure is 0.01MPa～1.00MPa, obtains primary sintered material； Primary sintered material cooling is taken out, after grinding, sieving, is added thereto to next group raw material, and in mortar, both is mixed all Even, then at pure N2Carrying out double sintering under atmosphere, sintering time is 4～20h, and sintering temperature is 1800 DEG C～2500 DEG C, burns Knot pressure is 0.01MPa～5.00MPa；
Charging mode: BN crucible is placed in high temperature air pressure sintering furnace, is evacuated to 10E-2Pa level with mechanical pump, molecular pump Not, gas washing twice, under low pressure power-on heating in-furnace temperature is to 200-1000 DEG C, and its main purpose is to remove the water in stove Steam, O2, the material such as the impurity that easily absorbs in carbon felt, reduce the impact of other element dopings raw material on being sintered, then with 0 The speed of ＜ inflation rate≤12MPa carries out N2QI invigorating is 0.01MPa-5.00MPa to furnace pressure Ρ, then carries out a liter gentleness Sintering；
C, annealing: after b step, be cooled to 1000～1200 DEG C, and pressure keeps constant, then shuts down procedure, the coldest Taking out the most afterwards, gained sintering feed crosses 40～200 mesh sieves after grinding；
D, post processing: after sieving, then through pickling, washing, heat drying, i.e. obtain β-SiAlON:Eu2+Green emitting phosphor；
Pickling: after sieving, soaks with 10.0%-36.5% hydrochloric acid solution and carries out acid treatment, and every 1h detects once, exists to pH 2 do not change；
Washing: after pickling terminates, repeatedly wash with pure water to cleaning mixture pH be 6-7；
It is dried: use electric drying oven with forced convection heat drying.
The final products obtained can use airflow pulverization to crush it, by post according to the different demands of client Shape structure is broken into the structure of approximate sphericity, it is simple to encapsulation.
In the preparation process in accordance with the present invention, crucible used is the BN crucible of purity ＞ 99.5%.
In the preparation process in accordance with the present invention, in step b, described once sintered N2/H2Mixed atmosphere is N2∶H2=4～19 : the atmosphere of 1.
In the preparation process in accordance with the present invention, in the double sintering of step b, primary sintered material and raw material are according to 1～10: 1 Mass ratio mixes.
In the preparation process in accordance with the present invention, in the double sintering of step b, add in primary sintered material with the compound of raw material Oxygenates auxiliary agent.Preferably, described oxides additive is B2O3、MgO、CaO、Y2O3、ZrO2In any one or a few.
In the preparation process in accordance with the present invention, when in step b, primary sintered material mixes with raw material, oxides additive, need to be with just Beautiful mortar is sufficiently mixed uniformly, and does not sieves after mixing, directly carries out double sintering.
β-SiAlON:Eu prepared by the present invention2+Green emitting phosphor, its granule is uniform, and mean diameter is big, luminous intensity Height, not only has broad application prospects in preparing white light LEDs, is more mainly used in semiconductor light-emitting apparatus as backlight Liquid crystal display (LCD).
Operation is simple for present invention process method, raw materials used cheap, and process window width is suitable to large-scale industry Metaplasia is produced, and can realize preparation expectation granularity and the uniformity and the β-SiAlON:Eu at the narrow peak of high brightness2+Green emitting phosphor.
Accompanying drawing explanation
Fig. 1 is Reference Example 1 made β-SiAlON:Eu2+The emission spectrum figure of fluorescent material.
Fig. 2 is Reference Example 1 made β-SiAlON:Eu2+The SEM figure of fluorescent material.
Fig. 3 is the embodiment of the present invention 32 made β-SiAlON:Eu2+400 times of optical microscope of green emitting phosphor.
Fig. 4 is the embodiment of the present invention 32 made β-SiAlON:Eu2+The SEM figure of green emitting phosphor.
Fig. 5 is the embodiment of the present invention 32 made β-SiAlON:Eu2+The X-ray diffraction analysis figure of green emitting phosphor.
Fig. 6 is the embodiment of the present invention 46 made β-SiAlON:Eu2+The emission spectrum figure of green emitting phosphor.
Detailed description of the invention
High temperature solid-state method provided by the present invention synthesis β-SiAlON:Eu2+The chemical general formula of green emitting phosphor is Sia (AlxGa1-x)bOcNd: Eue 2+；
In formula, Si source is Si powder or corresponding compound, is Si powder, Si3N4、SiO2In at least one, Si3N4For α- Si3N4And/or β-Si3N4；Al source is Al powder or corresponding compound, is Al powder, AlN, Al2O3And AlF3In at least one Kind；Ga source is the oxide of Ga, i.e. Ga2O3；Eu compound is Eu2O3, at least one in EuN；
In formula, 0.4≤a≤0.5,0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d≤0.664,0 ＜ e≤ 0.010,0 ＜ x ＜ 1.
Reference Example 1
According to document " Characterization and properties of green-emitting β-SiAlON: Eu2+Powder phosphors for white light-emitting diodes " disclosed in method to carry out repeatability real Test, specific as follows:
With Eu2+As the excitation center of β-SiAlON phosphor, 94.77%Si by mass percentage3N4, 2.68% AlN, 2.55%Eu2O3, use high temperature solid-state method under 10atm pressure, 1900 DEG C of sintering 8h, prepared chemical formula consists of Eu0.00296Si0.41395Al0.01334O0.0044N0.56528Fluorescent material.
The electron-microscope scanning that carries out to prepared fluorescent material, and its emission spectrum is detected, result respectively such as Fig. 2 and Shown in Fig. 1.
As seen from Figure 1, its peak value is positioned at 530nm, aobvious green light, as seen from Figure 2, and made fluorescent powder grain Diameter is the least, and particle size distribution is the most uneven, and its particle diameter (μm) D50 is only 0.8, particle size distribution K value up to 2.03.
Embodiment 1
β-SiAlON:Eu2+The preparation of green emitting phosphor:
(1) with α-Si3N4、AlN、Al2O3、Ga2O3、Eu2O3For raw material, according to mol ratio α-Si3N4∶AlN∶Al2O3∶ Ga2O3: Eu2O3Weigh at=1.4: 0.08: 0.025: 0.01: 0.03；
Note: weighing of all above raw material is both needed at glove box N2(water content ＜ 1ppm, oxygen content ＜ is carried out under atmosphere 1ppm)。
(2) raw material weighed is placed in corundum mortar grinds 0.5h in one direction, make raw material fully mix, so Rear mistake 50 mesh sieve, loads in BN crucible.
(3) once sintered: BN crucible to be put in high temperature air pressure sintering furnace, first carry out mechanical pump and be pumped to below 10Pa, Open molecular pump and be pumped to the 10E-2 order of magnitude, carry out twice gas washing, and be preheated to 500 DEG C, then with the inflation speed of 12MPa/h Degree is filled with N2: H2The atmosphere of=9:1 ratio to furnace pressure is 0.5MPa, is warming up to 1500 DEG C with the speed of 600 DEG C/h simultaneously, Being warming up to 1800 DEG C with the speed of 60 DEG C/h again and proceed by sintering, sintering time is 6h, and in sintering process, furnace pressure keeps At 0.5MPa.
(4) double sintering: after the cooling of above-mentioned primary sintered material is taken out, be ground, cross 50 mesh sieves, once burnt Ramming material, is 1: 5 raw material mixed homogeneously adding respective quality according to raw material and the mass ratio of primary sintered material, and adds B2O3 As auxiliary agent, it is placed in corundum mortar and grinds 0.5h along same direction, make raw material fully mix, but screen cloth (prevents mixed Raw material layering), load in BN crucible, BN crucible put in high temperature air pressure sintering furnace, first carry out mechanical pump and be pumped to 10Pa Hereinafter, open molecular pump and be pumped to the 10E-2 order of magnitude, carry out twice gas washing, and be preheated to 500 DEG C, then filling with 12MPa/h Gas speed is filled with N2(purity 99.999%) to furnace pressure is 2.0MPa, is warming up to 1500 DEG C with the speed of 600 DEG C/h simultaneously, Starting to be warming up to 2000 DEG C with the speed of 120 DEG C/h again and proceed by sintering, sintering time is 14h, and in sintering process, stove is intrinsic pressure Power is maintained at 2.0MPa.
(5) annealing: after terminating, utilize 2h to be cooled to 1200 DEG C, then shut down procedure, takes out after natural cooling, Gained sintering feed first passes through corundum mortar and is fully ground, and 50 mesh sieves crossed by gained abrasive, the product after being sieved.
(6) post processing: the product after sieving is stirred pickling 0.5h first with the hydrochloric acid of 30wt% concentration, recycling It is 6.5 that deionized water is washed to cleaning mixture pH value, and is placed in electric drying oven with forced convection and toasts 2h at 200 DEG C, obtains finished product β-SiAlON:Eu2+Green emitting phosphor, finally according to the Grained Requirements that client is different, crushing by jet mill, reaches more Suitably requirement, through EDS test result, gained fluorescent material chemical formula is Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007。
Embodiment 2～4
Reference example 1, changes N in step (three)2/H2The proportioning of mixed atmosphere, other process conditions keep constant, survey The brightness of fixed material after once sintered, the results are shown in Table 1.A defective material in table refers to obtained after once sintered Secondary sintering feed, corresponding brightness is also the brightness of primary sintered material.
Table 1:
Embodiment β-SiAlON:Eu2+Green emitting phosphor H2:N2 Brightness
Embodiment 1 One defective material 1:9 43.2
Embodiment 2 One defective material 1:19 32.5
Embodiment 3 One defective material 1:4 12.5
Embodiment 4 One defective material Pure N2 23.4
Embodiment 5～9
Reference example 1, only changes the once sintered time in step (three), other parameters and condition and keeps constant, survey The brightness of fixed material after once sintered, the results are shown in Table 2.A defective material in table refers to obtained after once sintered Secondary sintering feed, corresponding brightness is also the brightness of primary sintered material.
Table 2:
Embodiment β-SiAlON:Eu2+Green emitting phosphor Once sintered time (h) Brightness
Embodiment 1 One defective material 6 43.2
Embodiment 5 One defective material 1 5.6
Embodiment 6 One defective material 4 23.5
Embodiment 7 One defective material 8 44.1
Embodiment 8 One defective material 10 32.5
Embodiment 9 One defective material 12 30.8
Embodiment 10～14
Reference example 7, changes the once sintered temperature in step (three), and other parameters keep constant, the results are shown in Table 3. A defective material in table refers to the primary sintered material obtained after once sintered, and corresponding brightness is also the bright of primary sintered material Degree.
Table 3:
Embodiment β-SiAlON:Eu2+Green emitting phosphor Once sintered temperature (DEG C) Brightness
Embodiment 7 One defective material 1800 44.1
Embodiment 10 One defective material 1200 7.8
Embodiment 11 One defective material 1400 15.4
Embodiment 12 One defective material 1600 34.2
Embodiment 13 One defective material 2000 39.2
Embodiment 14 One defective material 2200 36.1
Embodiment 15～21
Step (four) does not make used additives or changes the kind of auxiliary agent, once sintered process parameters embodiment 7, other techniques Condition is with embodiment 1, and contrasts with Reference Example 1, the results are shown in Table 4.
Table 4:
Embodiment 22～28
Change raw material and the mass ratio of primary sintered material in step (four), without auxiliary agent, or add ZrO2Auxiliary agent, its He all with embodiment 7, the results are shown in Table 5.
Table 5
Embodiment 29～34
Reference example 27, only changes the double sintering time in step (four), and other process conditions keep constant, result It is shown in Table 6.
Table 6:
Embodiment is numbered β-SiAlON:Eu2+Green emitting phosphor Double sintering time (h) Brightness
Embodiment 27 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 14 78.3
Embodiment 29 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 4 26.2
Embodiment 30 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 8 38.5
Embodiment 31 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 12 64.2
Embodiment 32 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 16 72.2
Embodiment 33 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 18 71.8
Embodiment 34 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 20 65.2
Fluorescent material preparation-obtained to the present embodiment 32 carries out electron-microscope scanning and X-ray diffraction analysis, result such as Fig. 3, Shown in Fig. 4 and Fig. 5.
Embodiment 35～39
Reference example 32, only changes the double sintering temperature in step (four), and other process conditions keep constant, result It is shown in Table 7.
Table 7:
Embodiment is numbered β-SiAlON:Eu2+Green emitting phosphor Double sintering temperature (DEG C) Brightness
Embodiment 32 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2000 72.2
Embodiment 35 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 1800 54.6
Embodiment 36 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 1900 59.3
Embodiment 37 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2100 73.8
Embodiment 38 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2200 76.2
Embodiment 39 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2300 78.9
Embodiment 40 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2400 77.3
Embodiment 41 Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007 2500 76.9
From above-mentioned experiment, along with the rising of temperature, brightness gradually rises, and when temperature rises to 2500 DEG C, brightness is also Do not change significantly, but in the case of protection equipment, raising crucible access times, it is proposed that temperature is burnt to 2300 DEG C.
Embodiment 42～46
With reference to embodiment 1, changing the doping of Ga element in step (), other conditions keep constant, the results are shown in Table 8.
Table 8:
Can be drawn by above-mentioned experimental data, the Ga element of doped portion on Al element case, can increase its β-SiAlON: Eu2+The brightness of green emitting phosphor final product, and doping needs ＜ 0.005, and >=0.002, the emission spectrum of embodiment 46 is shown in Fig. 6.

Claims (10)

1. a high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, is characterized in that, the chemical general formula of this fluorescent material For Sia(AlxGa1-x)bOcNd: Eue 2+, in formula, 0.4≤a≤0.5,0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d ≤ 0.664,0 ＜ e≤0.010,0 ＜ x ＜ 1；Described fluorescent material forms through two-step sintering, and second time sintering is by for the first time Sintering gained primary sintered material is sintered after mixing with raw material again.
High brightness the most according to claim 1, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, is characterized in that, institute State 0.5≤x ＜ 1 in chemical general formula.
High brightness the most according to claim 1, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, is characterized in that, institute State primary sintered material to mix according to the mass ratio of 1 ~ 10: 1 with raw material.
High brightness the most according to claim 1, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, is characterized in that, Oxides additive is added during second time sintering.
5. a high brightness, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, is characterized in that, including as follows Step:
A, proportioning raw materials: the chemical general formula of described fluorescent material is Sia(AlxGa1-x)bOcNd: Eue 2+, in formula, 0.4≤a≤0.5, 0.01≤b≤0.02,0.006≤c≤0.02,0.47 ＜ d≤0.664,0 ＜ e≤0.010,0 ＜ x ＜ 1；N2Under atmosphere protection Take raw material by each element chemistry metering score another name in aforementioned formula, be placed in mortar and be ground, then cross 40-200 mesh sieve, Load crucible；
Described raw material is Si simple substance or Si compound or both mixing, Al simple substance or Al compound or both mixing, Gaization Compound and Eu compound；
Described Si compound is Si3N4、SiO2In at least one, described Si3N4For α-Si3N4And/or β-Si3N4；Described Alization Compound is AlN, Al2O3And AlF3In at least one；Described Ga compound is the oxide of Ga；Described Eu compound is Eu2O3、 At least one in EuN；
B, sintering: first by raw material at N2/H2Under mixed atmosphere or at pure N2Atmosphere under carry out once sintered, sintering time is 1 ~ 12h, sintering temperature is 1200 DEG C ~ 2200 DEG C, and sintering pressure is 0.01MPa ~ 1.00MPa, obtains primary sintered material；To once burn Ramming material cooling is taken out, and after grinding, sieving, is added thereto to next group raw material, and in mortar will both mix homogeneously, then exist Pure N2Carrying out double sintering under atmosphere, sintering time is 4 ~ 20h, and sintering temperature is 1800 DEG C ~ 2500 DEG C, and sintering pressure is 0.01MPa~5.00MPa；
C, annealing: after b step, be cooled to 1000 ~ 1200 DEG C, and pressure keeps constant, takes out, gained sintering feed after natural cooling 40 ~ 200 mesh sieves are crossed after grinding；
D, post processing: after sieving, then through pickling, washing, heat drying, i.e. obtain β-SiAlON:Eu2+Green emitting phosphor.
High brightness the most according to claim 5, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, its Feature is, crucible used is the BN crucible of purity ＞ 99.5%.
High brightness the most according to claim 5, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, its Feature is, in step b, and described once sintered N2/H2Mixed atmosphere is N2∶H2The atmosphere of=4 ~ 19: 1.
High brightness the most according to claim 5, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, its Feature is, in the double sintering of step b, primary sintered material mixes according to the mass ratio of 1 ~ 10: 1 with raw material.
High brightness the most according to claim 5, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, its Feature is, in the double sintering of step b, adds oxides additive in the primary sintered material compound with raw material.
High brightness the most according to claim 9, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, It is characterized in that, described oxides additive is B2O3、MgO、CaO、Y2O3、ZrO2In any one or a few.
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