CN106281317B - 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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CN106281317B
CN106281317B CN201610666337.5A CN201610666337A CN106281317B CN 106281317 B CN106281317 B CN 106281317B CN 201610666337 A CN201610666337 A CN 201610666337A CN 106281317 B CN106281317 B CN 106281317B
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sialon
sintering
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emitting phosphor
green emitting
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CN106281317A (en
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杨志平
王海龙
赵金鑫
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Hubei Ledphor Optoelectronics Technology Co Ltd
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Hubei Ledphor Optoelectronics Technology Co Ltd
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    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
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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 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 the fluorescent powder are 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；The fluorescent powder is formed by two-step sintering, and second of sintering is sintered again after mixing primary sintered material obtained by first sintering with raw material.β-SiAlON:Eu prepared by the present invention2+Green emitting phosphor, particle is uniform, and average grain diameter is big, and luminous intensity is high, has bright prospects in preparing white light LEDs, is more mainly used in liquid crystal display (LCD) of the semiconductor light-emitting apparatus as backlight.Process of the invention is suitable for large-scale industrial production, can be controlled and the β-SiAlON:Eu of realization preparation expectation granularity and the uniformity and the narrow peak of high brightness by the adjusting to raw material proportioning, temperature2+Green emitting phosphor.

Description

A kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor and its preparation Method
Technical field
The present invention relates to a kind of grand type green emitting phosphor of match and preparation method thereof, specifically a kind of high brightness, big Particle size β-SiAlON:Eu2+Green emitting phosphor and preparation method thereof.
Background technique
SiAlON fluorescent powder is a kind of mainly including the nitric oxide fluorescent powder of tetra- kinds of chemical elements of Si, Al, O, N, brilliant Body configuration and Si3N4It is similar.In Si-Al-O-N quaternary system, due to cationic M (Si4+、Al3+) and anion X (N, O) Ratio it is different, the solid solution of formation is also different, mainly there is β-SiAlON, α-SiAlON, O-SiAlON, X-SiAlON and AlN Polytype (8H, 12H, 15R, 21R, 27R etc.).The general formula of β-SiAlON is Si6-ZAlZOZN8-Z, wherein 0 < Z≤4.2, are being scanned Observed under electron microscope to β-SiAlON be typical hexagonal columnar crystal, than β-Si3N4Crystal is coarse, thus it is made 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 powder, with approximation 52nm Narrow spectral width is mainly used in backlight material, i.e. liquid crystal display (LCD).However, β-the SiAlON:Eu being currently known2+It is green The generally existing luminance shortage of color fluorescent powder, particle size be small and the non-uniform problem of granularity.For example, 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 rodlike shape The length of looks only have 4 μm, diameter there was only 0.5 μm；Prepared β-SiAlON:Eu in European patent EP 2664660A12+Green Fluorescent powder, only extremely least a portion of particle can reach 10 μm, and required sintering pressure is 70~200MPa, and technique, equipment are more difficult Control, and post processing mode adds HNO using HF3Nitration mixture carry out pickling, environment, human body are injured larger；For another example document Densificatioon and Microstructure of β-sialon/Nano-size SiC Composites, preparation Granulation uniformity out is poor, granule-morphology is irregular.
β-SiAlON:Eu2+The particle size and size distribution of green emitting phosphor will affect the luminous efficiency of backlight material Therefore it is badly in need of preparing the β-SiAlON:Eu suitable for backlight material of high brightness, bulky grain size with colour developing accuracy2+It is green Color fluorescent powder.
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+The generally existing luminance shortage of green emitting phosphor, particle size are small and granularity is non-uniform asks Topic.
The second object of the present invention is to provide a kind of high brightness, bulky grain size beta-SiAlON:Eu2+The system of green emitting phosphor Preparation Method, to prepare big particle size, even particle size distribution and β-SiAlON:Eu of high brightness2+Green emitting phosphor.
Present invention high brightness to be provided, bulky grain size beta-SiAlON:Eu2+The technical solution of green emitting phosphor is such as Under:
A kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, chemical general formula 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；The fluorescent powder is formed by two-step sintering, and part material is carried out first sintering first, obtains one Secondary sintering feed, then into primary sintered material be added remainder raw material, carry out second of sintering again after mixing.
Preferable scheme is that 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.More preferably scheme 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.
Preferable scheme is that the primary sintered material is mixed with raw material according to 1~10: 1 mass ratio；The double sintering Oxides additive is added in the process.
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 comprising following steps:
A, raw material proportioning: the chemical general formula of the fluorescent powder 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 Raw material is weighed respectively by each element stoichiometric ratio in aforementioned formula under shield, is placed in mortar and is ground, and then crosses 40-200 Mesh is packed into crucible；
The raw material be mixing, Al simple substance or Al compound of Si simple substance or Si compound or both or both mixing, Ga compound and Eu compound；
The Si compound is Si3N4、SiO2At least one of, the Si3N4For α-Si3N4And/or β-Si3N4；It is described Al compound is AlN, Al2O3And AlF3At least one of；The Ga compound is the oxide of Ga；The Eu compound is Eu2O3, at least one of EuN；
B, it is sintered: first by raw material in N2/H2Under mixed atmosphere or in pure N2Atmosphere under carry out it is once sintered, when sintering Between be 1~12h, sintering temperature be 1200 DEG C~2200 DEG C, sintering pressure be 0.01MPa~1.00MPa, obtain primary sintered material； By the cooling taking-up of primary sintered material, after being ground up, sieved, next group raw material is added thereto, and mix the two in mortar It is even, then in pure N2Double sintering is carried out under atmosphere, sintering time is 4~20h, and sintering temperature is 1800 DEG C~2500 DEG C, is burnt Knot pressure power is 0.01MPa~5.00MPa；
Charging mode: BN crucible is placed in high temperature air pressure sintering furnace, is evacuated to 10E-2Pa grades with mechanical pump, molecular pump Not, gas washing twice, opens power supply under low pressure and heats in-furnace temperature to 200-1000 DEG C, main purpose is the water removed in furnace Steam, O2, the substances such as the impurity that easily absorbs in carbon felt, reduce other elements and adulterate influence to the raw material being sintered, then with 0 < inflation rate≤12MPa speed carries out N2Tonifying Qi to furnace pressure Ρ be 0.01MPa-5.00MPa, then carry out heating and Sintering；
C, it anneals: after b step, being cooled to 1000~1200 DEG C, pressure remains unchanged, and then shuts down procedure, naturally cold But it takes out afterwards, gained crosses 40~200 meshes after being sintered abrasive lapping；
D, post-process: after sieving, then through pickling, washing, heat drying to get arrive β-SiAlON:Eu2+Green emitting phosphor；
Pickling: it after sieving, is impregnated with 10.0%-36.5% hydrochloric acid solution and carries out sour processing, every 1h detection is primary, until pH exists 2 do not change；
Washing: after pickling, repeatedly being washed with pure water to cleaning solution pH is 6-7；
It is dry: to use electric drying oven with forced convection heat drying.
Obtained final products can be crushed it using airflow pulverization, according to the different demands of client by column Shape structure is broken into the structure of approximate sphericity, convenient for 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, the once sintered N2/H2Mixed atmosphere is N2∶H2=4~19 : 1 atmosphere.
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 mixing.
In the preparation process in accordance with the present invention, in the double sintering of step b, to adding in the mixture of primary sintered material and raw material Oxygenates auxiliary agent.Preferably, the oxides additive is B2O3、MgO、CaO、Y2O3、ZrO2In any one or a few.
It in the preparation process in accordance with the present invention, need to be with just when primary sintered material is mixed with raw material, oxides additive in step b Beautiful mortar is sufficiently mixed uniformly, and is not sieved after mixing, directly progress double sintering.
β-SiAlON:Eu prepared by the present invention2+Green emitting phosphor, particle is uniform, and average grain 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, process window mouth width, is suitable for large-scale industry Metaplasia produces the β-SiAlON:Eu, it can be achieved that preparation expectation granularity and the uniformity and the narrow peak of high brightness2+Green emitting phosphor.
Detailed description of the invention
Fig. 1 is the made β-SiAlON:Eu of Reference Example 12+The launching light spectrogram of fluorescent powder.
Fig. 2 is the made β-SiAlON:Eu of Reference Example 12+The SEM of fluorescent powder schemes.
Fig. 3 is the made β-SiAlON:Eu of the embodiment of the present invention 322+400 times of optical microscopes of green emitting phosphor.
Fig. 4 is the made β-SiAlON:Eu of the embodiment of the present invention 322+The SEM of green emitting phosphor schemes.
Fig. 5 is the made β-SiAlON:Eu of the embodiment of the present invention 322+The X-ray diffraction analysis figure of green emitting phosphor.
Fig. 6 is the made β-SiAlON:Eu of the embodiment of the present invention 462+The launching light spectrogram of green emitting phosphor.
Specific embodiment
High temperature solid-state method provided by the present invention synthesizes β-SiAlON:Eu2+The chemical general formula of green emitting phosphor is Sia (AlxGa1-x) bOcNd: Eue 2+；
In formula, the source Si is Si powder or corresponding compound, as Si powder, Si3N4、SiO2At least one of, Si3N4For α- Si3N4And/or β-Si3N4；The source Al is Al powder or corresponding compound, as Al powder, AlN, Al2O3And AlF3In at least one Kind；The source Ga is the oxide of Ga, i.e. Ga2O3；Eu compound is Eu2O3, at least one of 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 It tests, 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, using high temperature solid-state method under 10atm pressure, 1900 DEG C of sintering 8h, chemical formula group, which is made, to be become Eu0.00296Si0.41395Al0.01334O0.0044N0.56528Fluorescent powder.
To the carry out electron-microscope scanning of prepared fluorescent powder, and its emission spectrum is detected, as a result respectively such as Fig. 2 and Shown in Fig. 1.
As seen from Figure 1, peak value is located at 530nm, shows green light, as seen from Figure 2, made fluorescent powder grain Diameter is very small, and size distribution is very uneven, and particle diameter (μm) D50 is only 0.8, and size distribution K value is 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 molar ratio α-Si3N4∶AlN∶Al2O3∶ Ga2O3: Eu2O3Weigh at=1.4: 0.08: 0.025: 0.01: 0.03；
Note: weighing for all of above raw material is both needed in glove box N2(water content < 1ppm, oxygen content < are carried out under atmosphere 1ppm)。
(2) the weighed raw material of institute is placed in corundum mortar and grinds 0.5h in one direction, mix well raw material, so 50 meshes are crossed afterwards, are fitted into BN crucible.
(3) once sintered: BN crucible is put into high temperature air pressure sintering furnace, first carry out mechanical pump be pumped to 10Pa hereinafter, It opens molecular pump and is pumped to the 10E-2 order of magnitude, carry out gas washing twice, 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, while being warming up to 1500 DEG C with the speed of 600 DEG C/h, It is warming up to 1800 DEG C again with the speed of 60 DEG C/h to start to be sintered, sintering time 6h, furnace pressure is kept in sintering process In 0.5MPa.
(4) it double sintering: after the cooling taking-up of above-mentioned primary sintered material, ground, cross 50 meshes, once burnt Ramming material adds the raw material of corrresponding quality being uniformly mixed with the mass ratio of primary sintered material according to raw material for 1: 5, and adds B2O3 As auxiliary agent, it is placed in corundum mortar and grinds 0.5h along the same direction, mix well raw material, but sieve (prevents mixed Raw material layering), is fitted into BN crucible, BN crucible is put into high temperature air pressure sintering furnace, first progress mechanical pump be pumped to 10Pa Hereinafter, opening molecular pump is pumped to the 10E-2 order of magnitude, gas washing twice is carried out, and be preheated to 500 DEG C, then filling with 12MPa/h Gas velocity degree is filled with N2(purity 99.999%) to furnace pressure is 2.0MPa, while being warming up to 1500 with the speed of 600 DEG C/h DEG C, then starts to be warming up to 2000 DEG C with the speed of 120 DEG C/h and start to be sintered, sintering time 14h, furnace in sintering process Internal pressure power is maintained at 2.0MPa.
(5) it anneals: after sintering, being cooled to 1200 DEG C using 2h, then shut down procedure, taken out after natural cooling, Gained sintering feed first passes through corundum mortar and is fully ground, and gained abrasive crosses 50 meshes, the product after being sieved.
(6) post-process: the product after sieving is stirred pickling 0.5h first with the hydrochloric acid of 30wt% concentration, recycles It is 6.5 that deionized water, which is washed to cleaning solution pH value, and is placed in electric drying oven with forced convection at 200 DEG C and toasts 2h, obtains finished product β-SiAlON:Eu2+Green emitting phosphor, Grained Requirements finally different according to client are reached more by the broken of airslide disintegrating mill Suitable to require, through EDS test result, gained fluorescent powder chemical formula is Si0.408Al0.006Ga0.011O0.018N0.57: Eu0.007。
Embodiment 2~4
Reference implementation example 1 changes the step N in (three)2/H2The proportion of mixed atmosphere, other process conditions remain unchanged, and survey The brightness of the fixed material after once sintered, the results are shown in Table 1.A defective material in table refers to one obtained after once sintered Secondary sintering feed, corresponding brightness are 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 implementation example 1 only changes the step the once sintered time in (three), and other parameters and condition remain unchanged, and surveys The brightness of the fixed material after once sintered, the results are shown in Table 2.A defective material in table refers to one obtained after once sintered Secondary sintering feed, corresponding brightness are 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 implementation example 7 changes the step the once sintered temperature in (three), and other parameters remain unchanged, and 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
Without using the type of auxiliary agent or change auxiliary agent, once sintered process parameters embodiment 7, other techniques in step (4) Condition is compared with embodiment 1, and with Reference Example 1, the results are shown in Table 4.
Table 4:
Embodiment 22~28
The mass ratio for changing the step raw material and primary sintered material in (four) does not add auxiliary agent, or addition ZrO2Auxiliary agent, He with embodiment 7, the results are shown in Table 5.
Table 5
Embodiment 29~34
Reference implementation example 27 only changes the step the double sintering time in (four), other process conditions remain unchanged, as a result It is shown in Table 6.
Table 6:
Embodiment number β-SiAlON:Eu2+Green emitting phosphor The 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
Electron-microscope scanning and X-ray diffraction analysis are carried out to the preparation-obtained fluorescent powder of the present embodiment 32, as a result as Fig. 3, Shown in Fig. 4 and Fig. 5.
Embodiment 35~39
Reference implementation example 32 only changes the step the double sintering temperature in (four), other process conditions remain unchanged, as a result It is shown in Table 7.
Table 7:
Embodiment number 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
By above-mentioned experiment it is found that as the temperature rises, brightness gradually rises, and when temperature rises to 2500 DEG C, brightness It does not change significantly, but in the case where protecting equipment, improving crucible access times, it is proposed that temperature is burnt to 2300 DEG C.
Embodiment 42~46
Referring to embodiment 1, the doping of Ga element in (one) is changed the step, other conditions remain unchanged, and the results are shown in Table 8.
Table 8:
It can be obtained 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 (4)

1. a kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor, characterized in that the chemical general formula of the fluorescent powder 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≤0.010,0.5≤x≤0.8；The fluorescent powder is formed by two-step sintering, and second sintering is by the Once sintered gained primary sintered material is sintered again after mixing with raw material, and the primary sintered material and raw material are according to 5 ~ 10: 1 Mass ratio mixing, oxides additive is added when being sintered for second, and the oxides additive is B2O3、MgO、CaO、Y2O3、ZrO2 In any one or a few.
2. a kind of high brightness, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, characterized in that including as follows Step:
A, raw material proportioning: the chemical general formula of the fluorescent powder 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≤0.010,0.5≤x≤0.8；N2Atmosphere is protected Raw material is weighed respectively by each element stoichiometric ratio in aforementioned formula under shield, is placed in mortar and is ground, and then crosses 40-200 Mesh is packed into crucible；
The raw material is the mixing of mixing, Al simple substance or Al compound of Si simple substance or Si compound or both or both, Gaization Close object and Eu compound；
The Si compound is Si3N4、SiO2At least one of, the Si3N4For α-Si3N4And/or β-Si3N4；The Alization Closing object is AlN, Al2O3And AlF3At least one of；The Ga compound is the oxide of Ga；The Eu compound is Eu2O3、 At least one of EuN；
B, it is sintered: first by raw material in N2/H2Under mixed atmosphere or in pure N2Atmosphere under carry out once sintered, sintering time 1 ~ 12h, sintering temperature are 1200 DEG C ~ 2200 DEG C, and sintering pressure is 0.01MPa ~ 1.00MPa, obtains primary sintered material；It will once burn Ramming material is cooling to be taken out, and after being ground up, sieved, is added next group raw material thereto, and the mass ratio of the primary sintered material and raw material is 5 ~ 10: 1, and be uniformly mixed the two in mortar, to oxides additive is added in the mixture of primary sintered material and raw material, so Afterwards in pure N2Double sintering is carried out 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, the oxides additive are B2O3、MgO、CaO、Y2O3、ZrO2In any one or a few；
C, it anneals: after b step, being cooled to 1000 ~ 1200 DEG C, pressure remains unchanged, and takes out after natural cooling, gained sintering feed 40 ~ 200 meshes are crossed after grinding；
D, post-process: after sieving, then through pickling, washing, heat drying to get arrive β-SiAlON:Eu2+Green emitting phosphor.
3. high brightness according to claim 2, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, It is characterized in, crucible used is the BN crucible of purity > 99.5%.
4. high brightness according to claim 2, bulky grain size beta-SiAlON:Eu2+The preparation method of green emitting phosphor, It is characterized in, in step b, the once sintered N2/H2Mixed atmosphere is N2∶H2=4 ~ 19: 1 atmosphere.
CN201610666337.5A 2016-08-12 2016-08-12 A kind of high brightness, bulky grain size beta-SiAlON:Eu2+Green emitting phosphor and preparation method thereof Active CN106281317B (en)

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