CN105331361B - A kind of β SiAlON: Eu2+Green emitting phosphor and its synthetic method - Google Patents
A kind of β SiAlON: Eu2+Green emitting phosphor and its synthetic method Download PDFInfo
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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
- C09K11/77—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
Abstract
The invention provides a kind of bar-shaped β SiAlON of new strip:Eu2+Green emitting phosphor, its chemical general formula is EuxSiaAlbOcNd, 0.003≤x≤0.030,4.0 ＜ a ＜ 5.2,0.10 ＜ b ＜ 0.3,0.04≤c ＜ 0.1,5.6≤d ＜ 7.2 in formula.The invention also discloses the preparation technology of the fluorescent material, the technique is using the mixture of the halide of any one in Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga and Ce or two or more any halide as fluxing agent, using Segmented heating heating mode, stage one：Room temperature ~ T1, T1 is 1400 ~ 1600 DEG C, 5 DEG C/min ＜ heating rate≤10 DEG C/min；Stage two：T1 ~ T2, T2 are 1850 DEG C ~ 2000 DEG C, 0 DEG C/min ＜ heating rate≤5 DEG C/min；Reach after T2,8 ~ 12h is incubated at a temperature of T2.Made phosphor emission spike length has stronger green emission at 530 ~ 540nm, and half-peak breadth can be controlled in 50~55nm, and diameter of particle is uniform, good luminous performance, and excitation is high, and the method technique of the present invention is simple, low for equipment requirements.
Description
Technical field
The present invention relates to fluorescent material, specifically a kind of β-SiAlON: Eu2+Green emitting phosphor and its synthetic method.
Background technology
Since 1990s, the tremendous development of LED technology gets over the application in the fields such as its white light LEDs, LED backlight
Come more deep and extensive.
White light LEDs have the advantages that low energy consumption, high efficiency, pollution-free, long lifespan relative to conventional lighting technology, civilian
Future is optimistic in terms of illumination.In LED illumination technology, fluorescent material is one of its key technology and raw material.Current white light LEDs are commonly used
Green emitting phosphor be mainly sulfide base fluorescent powder (such as ZnS:Cu,Al、SrGa2S4:Eu2+), this kind of fluorescent material Yin Qipu
All over luminous efficiency is low, poor chemical stability, easy deliquescence, and the problems such as the sulfide gas harmful to human body and environment can be produced and
It is restricted its application.
In LED backlight field, current market mainstream trend is still the backlight mode of concrete-cored of fluorescent material, and it is used green
Color fluorescent material is mainly the aluminates system (YAG systems, LuAG systems) of broad band and the silicate systems of narrow band.YAG aluminium
Silicate system is mainly yellowish green powder, and the half-peak breadth of its spectrum is in 106nm or so, and excitation is relatively low, is extremely difficult to NTSC standard value
Requirement；LuAG aluminates systems, same brightness is higher, and half-peak breadth is wider (FWHM=106nm), and color saturation is low, its
Granule density is larger, mixes and easily occurs the phenomenon of sedimentation layering when glue matches somebody with somebody powder, influences light-emitting uniformity, and cost of material is higher.
Although being 65nm or so and silicate systems half-peak breadth is narrower, there is the system high heat fade and moisture to decay in itself,
It is appropriate only for the display product of some low sides.Therefore, study that new matrix is stable and synthesis condition be simply adapted to white light LEDs,
LED backlight, which is shown, just seems particularly necessary with green emitting phosphor.
In recent years, rear-earth-doped new oxynitride, Nitride systems light-converting material with its good stability and
Reliability causes the extensive concern of researcher.Rear-earth-doped Sialon has the spectroscopy performance of uniqueness, with excellent light
Conversion efficiency, is a kind of LED light transition material with applications well prospect, thus receives the extensive concern of researcher and grind
Study carefully.
Naoto Hirosaki in 2005 et al. are in " the article delivered on APPLIED PHYSICS LETTERS "
《Characterization and properties of green-emittingβ-SiAlON:Eu2+powder
phosphors for white light-emitting diodes》Using conventional high-temperature Solid phase synthesis β-SiAlON:Eu2+
Fluorescent material, technique is simple, and it is 4 μm that it, which tests sample particle length, and particle diameter is only 0.5 μm；Hua Yang in 2014 et al.
Delivered on " J.AM.Ceram.Soc " magazine《Eu-Dopedβ-SiAlON Phosphors:Template-Assistant
Low Temperature synthesis,Dual Band Emission,and High-Thermal Stability》Pass through
Low Temperature Solid-Phase synthesis obtains laboratory sample, and its fine particle is more, and shaped granule is few, and most thick particle diameter is only 0.7 μm；China
Patent CN102701745B prepares the β-SiAlON of submicrometer structure by carbon thermal reduction-sol-gal process, and particle diameter is only
0.3~0.5 μm.European patent EP 2570400A1 and EP2662430A1 prepare β-SiAlON there is provided one kind:Eu2+Fluorescent material
Process, pass through the techniques, the final sample particle uniformity of acquisition such as heat treatment, strong acid (hydrofluoric acid adds nitric acid) acid treatment
Difference, particle diameter are short, particle diameter D50=5~6 μm, and integrated artistic is complicated, and long flow path, operation has certain danger, energy
Consumption is high, and production cost is high.
Existing β-the SiAlON it can be seen from the above document:Eu2+In green emitting phosphor solid sintering technology, low temperature
The product particle diameter that sintering is obtained is respectively less than 1 μm, and granule-morphology is uneven, has a strong impact on brightness, the light efficiency of fluorescent material；And adopt
The preparation method introduced with European patent EP 2570400A1, although result in slightly coarse grained β-SiAlON:Eu2+Green is glimmering
Light powder, particle diameter D50=5~6 μm, but integrated artistic are complicated, long flow path, and operation has certain danger, and high energy consumption is raw
Produce cost high.
The content of the invention
The invention aims to provide the β-SiAlON that a kind of pattern rule, size uniform, particle diameter are thicker:Eu2+Fluorescence
Powder, at the same also provide good operability, the efficient synthesis of environment-friendly fluorescent material.
The present invention is realizes that the technical scheme that object above is used is as follows：
The invention provides a kind of β-SiAlON:Eu2+Green emitting phosphor, its chemical general formula is EuxSiaAlbOcNd, in formula
0.003≤x≤0.030,4.0 ＜ a ＜ 5.2,0.10 ＜ b ＜ 0.3,0.04≤c ＜ 0.1,5.6≤d ＜ 7.2.
Present invention also offers a kind of β-SiAlON:Eu2+The preparation method of green emitting phosphor, it comprises the following steps：
(1) chemical general formula of the fluorescent material is EuxSiaAlbOcNd, 0.003≤x≤0.030,4.0 ＜ a ＜ 5.2 in formula,
0.10 ＜ b ＜ 0.3,0.04≤c ＜ 0.1,5.6≤d ＜ 7.2；
(2)N2Under atmosphere protection, by general formula E uxSiaAlbOcNdMiddle each element stoichiometric proportion weighs raw material respectively, then
Fluxing agent is added, mixed material is obtained；
Raw material accounts for 94-99.9wt% in the mixed material, and fluxing agent accounts for 0.1-6wt%；
The raw material is Si3N4、AlN、Al2O3And Eu2O3, the Si3N4For α-Si3N4And/or β-Si3N4；It is described fluxing
Agent is halide；
(3) mixed material is placed in ball mill mixing device, it is dry-mixed, then sieve, load crucible, be then placed in high temperature air pressure
In sintering furnace, furnace pressure is evacuated to less than 10Pa, N is then charged with2, it is 0.75~0.85MPa, Ran Houjia to furnace pressure
Heat heating；
The heating up process is divided into two stages, is specially：
Stage one：Room temperature~T1, T1 is 1400~1600 DEG C, 5 DEG C/min ＜ heating rate≤10 DEG C/min；Heat up herein
Stage, furnace pressure raises with temperature and rises to 1.0MPa；
Stage two：T1~T2, T2 are 1850 DEG C~2000 DEG C, 0 DEG C/min ＜ heating rate≤5 DEG C/min；Reach after T2,
8~12h is incubated at a temperature of T2；Maintain the pressure of 1.0MPa in stove constant in this phase process；
(4) after step (3), room temperature is naturally cooling to, is sieved after products therefrom grinding, it is then dense using 36~38wt%
The hydrochloric acid of degree carries out acid treatment, then it is 6~7 to be washed to cleaning solution pH, and then heating, drying, produces β-SiAlON:Eu2+Green is glimmering
Light powder.
In the method for the present invention, in step (2), the Si3N4Preferably α-Si3N4Or α-Si3N4With β-Si3N4Mixing
Thing, the α-Si3N4With β-Si3N4Mixture in α-Si3N4Ratio is more than 95%.
In the method for the present invention, the preferred scheme of step (3) is：Mixed material is placed in ball mill mixing device, it is dry-mixed
0.5h, then crosses 50~100 mesh sieves, loads crucible, is then placed in high temperature air pressure sintering furnace, and it is 0 to be evacuated to furnace pressure
~10Pa, is then charged with N2Gas to furnace pressure is 0.75~0.85MPa, then heat temperature raising；
The heating up process is divided into two stages, is specially：
Stage one：Room temperature~T1, T1 is 1400~1600 DEG C, 5 DEG C/min ＜ heating rate≤10 DEG C/min；Heat up herein
Stage, furnace pressure raises with temperature and rises to 1.0MPa；
Stage two：T1~T2, T2 are 1850 DEG C~2000 DEG C, 0 DEG C/min ＜ heating rate≤5 DEG C/min；Reach after T2,
8~12h is incubated at a temperature of T2；Maintain the pressure of 1.0MPa in stove constant in this phase process.
In the method for the present invention, the halide is any one in Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga and Ce
Halide or two or more any halide mixture.
It is preferred that scheme be that in method of the invention, contained halogen is fluorine, chlorine or iodine in the halide.
Specifically, the halide is at least one of following compounds：LiCl、NaCl、KCl、MgCl2、CaCl2、
SrCl2、BaCl2、AlCl3、GaCl3、CeCl3、LiF、NaF、KF、MgF2、CaF2、SrF2、BaF2、AlF3、GaF3、 CeF3、LiI、
NaI、KI、MgI2、CaI2、SrI2、BaI2、AlI3、GaI3、CeI3.Wherein, preferably：KF、 CeF3、NaI、BaF2、SrF2、
CaCl2、LiF、NaF、AlF3、MgF2、CaF2、GaF3、KI。
In the method for the present invention, the preferred scheme of step (4) is：After step (3), room temperature, gained production are naturally cooling to
50~100 mesh sieves are crossed after thing grinding, then acid treatment are carried out using the hydrochloric acid of 36~38wt% concentration, then be washed to cleaning solution pH
For 6~7, then heating, drying, produces β-SiAlON:Eu2+Green emitting phosphor.
The scheme being more highly preferred to is, in method of the invention, and the concentration of the hydrochloric acid is 36wt%, and the mode of acid treatment is
2~3h of stirring and pickling.
It is preferred that, in method of the invention, the heating rate in step (3) stage two is 1 DEG C/min, and T2 is 1900-2000
DEG C, soaking time is 10h.Most preferably T2=1950 DEG C.
The invention provides a kind of bar-shaped β-SiAlON of new strip:Eu2+Green emitting phosphor, it arrives blue light (280 ultraviolet
~480 nm) in the range of effectively excited, its emission peak wavelength has stronger green emission at 530~540nm, and half-peak breadth can
To control in 50~55nm, diameter of particle is uniform, good luminous performance, and excitation is high, in white light LEDs field, wide colour gamut and high color
Purity LED backlight field has broad application prospects.
Operation is simple for the inventive method, is raw material using common cheap compound, using specific high temperature solid-state
The method of sintering, is prepared for the fluorescent material product that a kind of particle is uniform, diameter is big, relative luminance is high, is a kind of potential white
Light LED, backlight, which are shown, uses fluorescent material；And the method technique of the present invention is simple, low for equipment requirements, without being heat-treated
Technique, and post processing need not using hydrofluoric acid and nitric acid mixed acid solution, reduce the danger of production, improve production can
Operability, it is energy-saving, it is environment-friendly, production cost is effectively reduced, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the β-SiAlON of the embodiment of the present invention 38:Eu2+The launching light spectrogram of fluorescent material.
Fig. 2 is the β-SiAlON of the embodiment of the present invention 38:Eu2+The SEM figures of fluorescent material.
Fig. 3 is the β-SiAlON in patent EP2570400A1 Reference Examples 3:Eu2+The SEM figures of fluorescent material.
Embodiment
β-SiAlON provided by the present invention:Eu2+The chemical general formula of fluorescent material is that chemical general formula is EuxSiaAlbOcNd, formula
In 0.003≤x≤0.030,4.0 ＜ a ＜ 5.2,0.10 ＜ b ＜ 0.3,0.04≤c ＜ 0.1,5.6≤d ＜ 7.2.
β-SiAlON in the present invention are described in detail with specific embodiment below:Eu2+The preparation method of green emitting phosphor, and it is right
The pattern and luminescent properties of prepared fluorescent material are evaluated.
The raw materials used present invention is purchased in market obtains.The pressure being previously mentioned in the present invention is absolute pressure.
Embodiment 1：β-SiAlON:Eu2+The preparation of fluorescent material
(1) according to general formula E u0.011Si4.8Al0.21O0.067N6.573Middle each element stoichiometric proportion calculate and weigh raw material (α-
Si3N4(oxygen content ＜ 2.0%), AlN (3N grades, oxygen content=0.8wt%), Eu2O3Powder (5N grades), Al2O3(4N grades)), so
After weigh and add fluxing agent (LiCl), obtain mixed material：
α-Si3N4、AlN、Eu2O3、Al2O3With LiCl according to 93.8wt%, 3.6wt%, 0.8wt%, 0.6wt%,
1.2wt% proportioning is weighed；
Wherein ɑ-Si3N4, AlN and Eu2O3Need the N in glove box2(H is weighed under gas shielded environment2O content≤1ppm,
O2Content≤1ppm)；
(2) by the α-Si weighed3N4、AlN、Eu2O3、Al2O3It is placed in LiCl in ball mill mixing device, dry-mixed 0.5h, so
100 mesh sieves are crossed afterwards；
After sieving, be placed in BN crucibles, be then placed in high temperature air pressure sintering furnace, be first evacuated to 0.07Pa, after be filled with
N2Gas is to 0.8MPa, then begins to warm up heating：
Stage 1：The temperature in crucible is first made by room temperature to T1 (T1=1500 DEG C) with 10 DEG C/min heating rate；
In this temperature rise period, air pressure furnace pressure rises to 1.0MPa with the rise of temperature；
Stage 2：1.0MPa pressure is maintained, starts with 3 DEG C/min heating rate, is warming up to T2 (T2=1950 DEG C) simultaneously
Maintain this temperature 10h；
(3) room temperature is naturally cooling to after step (2), products therefrom is ground and crosses 100 mesh sieves, then utilizes quality
The hydrochloric acid of percent concentration 36% is stirred pickling 2h, is then handled its pH value to 6 using deionized water washing and (washed
It is 6), most after at 100 DEG C, to obtain finished product fluorescent material after baking 2h, its chemical general formula is after testing to cleaning solution pH value
Eu0.011Si4.8Al0.21O0.067N6.573。
Embodiment 2-20
Change the species (being specifically shown in Table 1) of fluxing agent, other process conditions are same as Example 1.
Embodiment 21-26
Feed change is matched, and prepares the fluorescent material (being specifically shown in Table 2) that different elements are constituted, other process conditions with implementation
Example 17 is identical.
Embodiment 27-29, comparative example 1,2
Changing sintering temperature, (i.e. 3) T2 is specifically shown in Table, other process conditions are identical with embodiment 17.
Embodiment 30-31, comparative example 3,4
Change soaking time (being specifically shown in Table 4), other process conditions are identical with embodiment 17.
Embodiment 32-37, comparative example 5,6
Raw material major ingredient α-Si3N4、AlN、Eu2O3、Al2O3Constant with respect to major ingredient proportioning, the ratio for only changing fluxing agent is (specific
It is shown in Table 5), other process conditions are identical with embodiment 17.
Embodiment 38：
(1) according to general formula E u0.011Si4.8Al0.21O0.067N6.573Middle each element stoichiometric proportion calculate and weigh raw material (α-
Si3N4(oxygen content ＜ 2.0%), AlN (3N grades, oxygen content=0.8wt%), Eu2O3Powder (5N grades), Al2O3(4N grades)), so
After weigh and add fluxing agent (LiCl), obtain mixed material：
α-Si3N4、AlN、Eu2O3、Al2O3And CeF3According to 93.04wt%, 3.57wt%, 0.79wt%, 0.6wt%,
2wt% proportioning is weighed (raw material proportioning is identical with embodiment 33)；
Wherein ɑ-Si3N4, AlN and Eu2O3Need the N in glove box2(H is weighed under gas shielded environment2O content≤1ppm,
O2Content≤1ppm)；
(2) by the α-Si weighed3N4、AlN、Eu2O3、Al2O3And CeF3It is placed in ball mill mixing device, dry-mixed 0.5h, so
100 mesh sieves are crossed afterwards；
After sieving, be placed in BN crucibles, be then placed in high temperature air pressure sintering furnace, be first evacuated to 0.07Pa, after be filled with
N2Gas is to 0.8MPa, then begins to warm up heating：
Stage 1：The temperature in crucible is first made by room temperature to T1 (T1=1500 DEG C) with 10 DEG C/min heating rate；
In this temperature rise period, air pressure furnace pressure rises to 1.0MPa with the rise of temperature；
Stage 2：1.0MPa pressure is maintained, starts with 1 DEG C/min heating rate, is warming up to T2 (T2=1950 DEG C) simultaneously
Maintain this temperature 10h；
(3) room temperature is naturally cooling to after step (2), products therefrom is ground and crosses 100 mesh sieves, then utilizes quality
The hydrochloric acid of percent concentration 36% is stirred pickling 2h, is then handled its pH value to 6 using deionized water washing and (washed
It is 6), most after at 100 DEG C, to obtain finished product fluorescent material after baking 2h, its chemical general formula is after testing to cleaning solution pH value
Eu0.011Si4.8Al0.21O0.067N6.573。
Embodiment 39-42, comparative example 7
The programming rate of change stage 2 (being specifically shown in Table 6), other process conditions are identical with embodiment 38.
Reference Example 1
Repeated experiment is carried out according to patent document EP2570400A1 embodiment 5 (Experiment 5)
According to 95.4wt%, 3.1wt%, 0.7wt%, 0.8wt% proportioning weighs Si3N4, AlN, Al2O3, Eu2O3, thing
Expect 1kg, through the dry-mixed 0.5h of V-type blender, cross 100 mesh sieves；Material loads 9 (internal diameter 8cm, high 8cm) BN crucibles, places into
(inner wall size 51/31cm, high 20cm) graphite with cover, is put into high temperature air pressure sintering furnace, in N2Under environment, pressure is
0.9MPa, 2000 DEG C of high temperature sintering 10h, after by hand breaking, cross 100 mesh sieves；Sample is under inert gas Ar, normal pressure after broken
1450 DEG C of sintering 8h are heat-treated, and 325 mesh sieves are crossed afterwards；Sample is through V after heat treatment50% (v/v) hydrofluoric acid：V70% (v/v) nitric acid=1:1 mixes
Acid solution processing, until supernatant is changed into bright green from dark green, washes, dries afterwards；Sample after acid treatment is immersed into six inclined phosphorus
Sour sodium removes supernatant as the solution of dispersant after sedimentation, until supernatant is transparent, filtering precipitate, washout goes to disperse
Agent, is dried to obtain formula for Si6-zAlzOzN8-z：Eu2+Fluorescent material.
Relative luminance, D50, K value to the fluorescent material prepared by above example 1-42, comparative example 1-7 and Reference Example 1
((D90-D10)/D50 values) is detected, as a result as follows.
(1) to the relative luminance of the fluorescent material prepared by the fluorescent material prepared by 1-20 of the embodiment of the present invention and Reference Example 1
Detected, and count its D50 value and K values, as a result such as table 1 below.
Table 1：
In terms of the data of table 1, using the β-SiAlON type fluorescent material prepared by the inventive method, its particle diameter D50 values
Bigger, relative luminance is also higher, the fluorescent material prepared by the overall method better than Reference Example 1, and particularly, of the invention is used
Method with CeF3As (embodiment 17) during fluxing agent, gained particle diameter is maximum, and its diameter D50 is relatively bright up to 10.1 μm
Degree also highest, the fluorescent material relative to Reference Example 1 has and significantly lifted.
(2) to the relative luminance and D50 of the fluorescent material prepared by 21-26 of the embodiment of the present invention and particle uniformity
((D90-D10)/D50) is detected, and compared with embodiment 17, as a result such as table 2.
Table 2：
It can be seen from the data of table 2 at equal process conditions, the diameter of the fluorescent powder grain of different component proportioning
With relative luminance kept stable, and overall it is better than Reference Example and comparative example.
(3) to the relative luminance and particle diameter of the fluorescent material prepared by 27-29 of the embodiment of the present invention, comparative example 1,2
D50 and particle uniformity ((D90-D10)/D50) detected, and compared with embodiment 17, as a result such as table 3.
Table 3：
Sintering temperature is can be seen that from the data of table 3 to have a significant effect to the particle of product, it is made glimmering at 1800 DEG C
Light powder particles diameter, relative luminance and particle uniformity are than less desirable.At 1850-1950 DEG C, made fluorescent material is in particle
All it is improved on diameter D50, relative luminance and particle uniformity, and maximum is reached in 1950 DEG C of particle diameter D50 and brightness
Value, in the range of 2000-2200 DEG C, temperature is too high to cause grain crystalline to be deteriorated, and particle diameter attenuates, and the rise of K values is prepared
Obtained fluorescent material relative luminance reduction, preferably 1950 DEG C of sintering temperature.
(4) to the relative luminance and D50 and particle of the fluorescent material prepared by 30-31 of the embodiment of the present invention, comparative example 3,4
Uniformity ((D90-D10)/D50) detected, and compared with embodiment 17, as a result such as table 4.
Table 4：
Soaking time is can be seen that from the data of table 4 also to have a significant effect to the granular grows of product, soaking time is 6h
When, made fluorescent material powder particle diameter is very small, and its D50 is only 2.2 μm, and relative luminance and particle uniformity are all very not yet
It is good, it is impossible to meet demand.When soaking time is 8h, diameter of particle is significantly increased, and relative luminance and particle uniformity are also more preferable, is protected
When the warm time is 10h, particle diameter and brightness all reach peak, with the extension of time, when soaking time is 12-13h, by
Particle diameter is caused to reduce in sintering time extension, particle agglomeration phenomenon, particle brightness reduction, soaking time occurs in the reduction of K values
In 8-12h particle diameters D50 and brightness value preferably, prioritizing selection soaking time is obtained in 10h or so in actual production
Fluorescent powder grain particle diameter is maximum, relative luminance also highest.
(5) to the relative luminance and D50 and particle of the fluorescent material prepared by 32-37 of the embodiment of the present invention, comparative example 5,6
Uniformity ((D90-D10)/D50) detected, and compared with embodiment 17, as a result such as table 5.
Table 5：
| Embodiment | Nitric oxide fluorescent powder | It is fluxing | Fluxing agent | Relatively | D50 | (D90-D10 |
| Agent | Amount | Brightness | (μm) | )/D50 | ||
| Comparative example 5 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 0 | 82.7 | 5.8 | 1.27 |
| Embodiment 32 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 0.1wt% | 86.4 | 6.5 | 0.92 |
| Embodiment 17 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 1.2wt% | 105.6 | 10.1 | 0.74 |
| Embodiment 33 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 2.0wt% | 110.3 | 10.5 | 0.72 |
| Embodiment 34 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 3.0wt% | 102.1 | 9.8 | 0.73 |
| Embodiment 35 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 4.0wt% | 96.4 | 8.7 | 0.71 |
| Embodiment 36 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 5.0wt% | 90.4 | 7.8 | 0.70 |
| Embodiment 37 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 6.0wt% | 84.5 | 6.2 | 0.70 |
| Comparative example 6 | Eu0.011Si4.8Al0.21O0.067N6.573 | CeF3 | 7.0wt% | 72.4 | 3.5 | 0.65 |
By the data of table 5, under the process conditions selected by the present invention, fluxing agent CeF3Addition to the diameter of particle and
Brightness has an impact, and its addition effect in the range of 1.2-3.0wt% is preferably, overall to be better than prior art (Reference Example 1).
(6) it is equal to the relative luminance and D50 and particle of the fluorescent material prepared by 38-41 of the embodiment of the present invention, comparative example 7
Even property ((D90-D10)/D50) detected, and compared with embodiment 33, as a result such as table 6.
Table 6：
In 1500 DEG C~1950 DEG C temperature ranges it can be seen from the data of table 6, heating rate is to fluorescent powder grain diameter
And relative luminance has a significant effect, the fluorescent powder grain particle diameter that heating rate is obtained in the range of 1-3 DEG C/min is maximum, brightness
Also highest, heating rate is more than particle diameter and relative luminance after 5 DEG C/min and all declined.
Electron-microscope scanning is carried out to fluorescent material prepared by the embodiment of the present invention 38, as a result as shown in Figure 2.Prepared by Reference Example 1
Fluorescent material SEM scanning results such as Fig. 3.Comparison diagram 2 and Fig. 3 are understood using the fluorescent powder grain prepared by the method for the present invention also more
Plus it is uniform, pattern is more regular.
The emission spectrum of the fluorescent material of the preparation of the embodiment of the present invention 38 is detected, as a result as shown in Figure 1.Can by Fig. 1
Know, the transmitting peak-to-peak value of fluorescent material prepared by the embodiment of the present invention 38 (is in 535nm or so, and with narrow half-peak breadth
53.2nm), with good excitation and brightness, good luminescence property.
(7) fluorescent material prepared by embodiment 1-42, after testing, its half-peak breadth fluctuation range within 50-55nm,
Emission peak has stronger green emission at 530-540nm, and diameter of particle is uniform, and good luminous performance, excitation is high.
Claims (4)
1. a kind of β-SiAlON: Eu2+The preparation method of green emitting phosphor, it is characterised in that comprise the following steps：
(1) chemical general formula of the fluorescent material is EuxSiaAlbOcNd, 0.003≤x≤0.030,4.0 ＜ a ＜ 5.2,0.10 in formula
＜ b ＜ 0.3,0.04≤c ＜ 0.1,5.6≤d ＜ 7.2；
(2)N2Under atmosphere protection, by general formula E uxSiaAlbOcNdMiddle each element stoichiometric proportion weighs raw material respectively, then adds
Fluxing agent, obtains mixed material；
Raw material accounts for 94-99.9wt% in the mixed material, and fluxing agent accounts for 0.1-6wt%；
The raw material is Si3N4、AlN、Al2O3And Eu2O3, the Si3N4For α-Si3N4And/or β-Si3N4；The fluxing agent is
Halide；
(3) mixed material is placed in ball mill mixing device, dry-mixed 0.5h, then crosses 50 ~ 100 mesh sieves, loaded crucible, be then placed in
In high temperature air pressure sintering furnace, furnace pressure is evacuated to less than 10Pa, N is then charged with2Gas, to furnace pressure be 0.75~
0.85MPa, then heat temperature raising；
The heating up process is divided into two stages, is specially：
Stage one：Room temperature~T1, T1 is 1400~1600 DEG C, 5 DEG C/min ＜ heating rate≤10 DEG C/min；Heat up herein rank
Section, furnace pressure raises with temperature and rises to 1.0MPa；
Stage two：T1~T2, T2 are 1850 DEG C~2000 DEG C, 0 DEG C/min ＜ heating rate≤5 DEG C/min；Reach after T2, in T2
At a temperature of be incubated 8~12h；Maintain the pressure of 1.0MPa in stove constant in this phase process；
(4) after step (3), room temperature is naturally cooling to, is sieved after products therefrom grinding, then using 36~38wt% concentration
Hydrochloric acid carries out acid treatment, then it is 6~7 to be washed to cleaning solution pH, and then heating, drying, produces β-SiAlON:Eu2+Green fluorescence
Powder.
2. β-SiAlON: Eu according to claim 12+The preparation method of green emitting phosphor, it is characterised in that the halogenation
Thing is the halide of any one or two or more any halogen in Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga and Ce
The mixture of compound.
3. β-SiAlON: Eu according to claim 22+The preparation method of green emitting phosphor, it is characterised in that the halogenation
Contained halogen is fluorine, chlorine or iodine in thing.
4. β-SiAlON: Eu according to claim 12+The preparation method of green emitting phosphor, it is characterised in that the hydrochloric acid
Concentration be 36wt%, the mode of acid treatment is 2~3h of stirring and pickling.
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