CN106566530B - Modified sialon fluorescent powder particle and preparation method thereof, sialon phosphor and light-emitting device - Google Patents
Modified sialon fluorescent powder particle and preparation method thereof, sialon phosphor and light-emitting device Download PDFInfo
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- CN106566530B CN106566530B CN201610997570.1A CN201610997570A CN106566530B CN 106566530 B CN106566530 B CN 106566530B CN 201610997570 A CN201610997570 A CN 201610997570A CN 106566530 B CN106566530 B CN 106566530B
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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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
- C09K11/77—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
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The invention relates to a modified sialon fluorescent powder particle and a preparation method thereof, a sialon phosphor and a light-emitting device, wherein the modified sialon fluorescent powder particle has a core-shell structure, and the core structure of the modified sialon fluorescent powder particle is divided into a core-shell layer, a transition layer and a core-shell layer in sequence from the core of the particle to the outer surface by increasing the oxygen content; the main body of the crystal nucleus layer is made of oxynitride materials, the main body of the transition layer is made of oxynitride materials, and the main body of the nucleus outer layer is made of oxide materials or oxynitride materials. The modified sialon phosphor particles and sialon phosphor of the present invention have the advantages of high chemical stability, high ageing resistance, high light attenuation resistance, high light emitting efficiency, etc. and are suitable for various light emitting devices. The preparation method is simple, convenient and reliable, is favorable for improving the chemical and physical stability of the modified sialon fluorescent powder particles and the sialon fluorescent body, and is suitable for industrial mass production and manufacture.
Description
Technical field
The invention belongs to LED fluorescent powder and light emitting device technologies field, more particularly to one kind can by ultraviolet light, purple light or
Modification sialon fluorescent powder particle that blue light effectively excites and preparation method thereof, Sialon fluorophor and luminescent device.
Background technique
In recent years, LCD TV display technology develops rapidly, and the backlight skill as one of the LCD core technology shown
Art has also obtained developing on a large scale very much.LED replaces CCFL to have become generally acknowledged development trend as next-generation LCD backlight technology.
LCD backlight source will become the maximum application market of LED, account for 40% or more of LED total market.
Using LED as LCD backlight, image quality is substantially improved, especially in terms of color saturation.LED
Backlight color domain coverage ratio reaches the 90~100% of NTSC, has compared with the 70~80% of CCFL backlight and is obviously improved, compensates for liquid crystal
Show the insufficient defect of number of colours.In addition, LED backlight light efficiency, response speed, in terms of have compared with CCFL it is significant excellent
Gesture.In addition, the advantage of white light LEDs backlight technology in terms of cost, and this kind of backlight technology is promoted to become the following popular style LED
The optimal case of LCD TV.
Currently, white light LEDs backlight technology is to be combined using green and red fluorescence powder with blue chip.Wherein, red
The general choice of powder is all CaAlSiN3:Eu2+Fluorescent powder, but in the selection of green powder, there are significant differences for selection both domestic and external.
Such as Japanese national Materials Research Laboratories, Mitsubishi Chemical and U.S. Intermatix, enterprise select β-Sialon:Eu2+As
Green powder in phosphor combination, above-mentioned enterprise have grasped the volume production technology of this kind of fluorescent powder, and have started to introduce to the market.Again
β-Sialon:Eu is carried out as domestic scientific research mechanism and fluorescent powder enterprise have also put into a large amount of manpower and financial resources2+The research of fluorescent powder,
And certain progress is obtained, but still in bottleneck period in some key technologies, there are also a distances from application.
Chinese patent application 201010104574.5 discloses a kind of fluorescent powder with core-shell structure and preparation method thereof, the nucleocapsid
Particle made of structure fluorescent powder is coated by different material forms, and the particle ecto-entad is Ln2-xSiO5:xCe、SiO2, M gold
Metal nano-particle.The program is due to introducing SiO2And metal nanoparticle, so that the electric conductivity of fluorescent powder is improved, thus
Luminous intensity with higher, simultaneously as the pattern with almost spherical, so Luminescence Uniformity and the adhesive force with substrate
It is improved.But there is also obvious deficiencies for the program: first is that without reference to the associated performance such as the anti-aging property of fluorescent powder
Parameter, therefore can not prove to also improve anti-aging property while it improves luminous intensity；Second is that preparation method is more multiple
It is miscellaneous, be not suitable for industrialization.
Chinese patent application 201310179866.9 discloses a kind of wideband gradient LED fluorescent powder and preparation method thereof, institute
The individual particle of fluorescent powder is stated from inside to outside successively by crystal structure is identical and three layers or more of fluorescence that chemical constituent is different
Matter composition.Compared with prior art, the fluorescent powder good dispersion of the program, lattice is complete, and bulk density is high, and luminous efficiency is high.
But there is also obvious deficiencies for the program: first is that causing compatibility between layers because the component of every layer of fluorescent powder is different
Property is bad, to influence the stability of fluorescent powder；Second is that preparation method is more complicated, be not suitable for industrialization.
Described in summary, how to overcome the shortcomings of the prior art and have become current LED fluorescent powder and luminescent device skill
One of emphasis problem urgently to be resolved in art field.
Summary of the invention
The purpose of the present invention is provide a kind of modified sialon fluorescent powder particle and its system in order to overcome the deficiencies of the prior art
Preparation Method, Sialon fluorophor and luminescent device, modification sialon fluorescent powder particle of the invention, Sialon fluorophor have chemical stabilization
Property it is good, anti-aging light decay performance is good, luminous efficiency is high the advantages that, be suitable for various luminescent devices.The manufacturing method of the present invention letter
It can lean on, be conducive to the chemistry and physical stability that improve modified sialon fluorescent powder particle, Sialon fluorophor, be suitable for industrialization
Batch production manufacture.
A kind of modified sialon fluorescent powder particle proposed according to the present invention, which is characterized in that the modified sialon fluorescent powder
The structure of particle is core-shell structure, and the nuclear structure of the modified sialon fluorescent powder particle is to be contained from granular core to outer surface with oxygen
Amount is incremented by and is divided into crystal nucleation layer, transition zone and core outer layer；The main body of the crystal nucleation layer is oxymtride material, transition zone
Main body be oxymtride material, the main body of core outer layer is oxide material or oxynitride material；The chemistry of the crystal nucleation layer
Formula is Six-z1Alz1Oz1Ny-z1: r1Eu, the chemical formula of transition zone are Six-z2Alz2Oz2Ny-z2: the chemical formula of r2Eu, core outer layer is
SikAlmOoNn:r3Eu；The chemical formula of the shell of the modified sialon fluorescent powder particle is Sia-cAlcOcNb-c；Wherein；Wherein: x,
Z1, y, r1, z2, r2, k, m, o, n, r3, a, c, b are the atomic percent of respective element, 6 < x≤8,0.1≤z1≤0.3, y=
4x/3,0.001≤r1≤0.1,0.3 < z2≤1,0≤r2≤0.1,0≤k≤3,0≤m≤4,1≤o≤6,0≤n≤4,0≤
R3≤0.1,3≤a < 6,0 < c≤0.3, b=4a/3.
A kind of further preferred scheme of modified sialon fluorescent powder particle proposed by the present invention is:
The transition zone with a thickness of 50-300nm, core outer layer with a thickness of 50nm within, to nitrogen oxidation on the inside of transition zone
The core of matter fluorescent powder particle be crystal nucleation layer, shell with a thickness of 1-100nm.
The content of oxymtride material in the crystal nucleation layer is not less than 90wt%, the nitrogen oxides material in the transition zone
The content of material is not less than 80wt%, and the content of oxide material or oxynitride material is not less than 70wt% in the core outer layer.
The modified sialon fluorescent powder particle excites within the scope of wavelength 300-500nm to be issued appearance wavelength and is located at 500-
The light of 570nm.
A kind of Sialon fluorophor proposed by the present invention, which is characterized in that include any of the above-described one kind proposed by the present invention
It is modified the mixture of sialon fluorescent powder particle, the ratio of modified sialon fluorescent powder particle is not less than 50wt% in the mixture.
The present invention proposes a kind of preparation method of modified sialon fluorescent powder particle, which is characterized in that including following specific step
It is rapid:
Step 1: using the nitride of Si, Al, Eu, oxide or halide as raw material, by chemical general formula Six- z1Alz1Oz1Ny-z1: r1Eu and Sia-cAlcOcNb-c: the stoichiometric ratio of composition weighs required raw material respectively；
Step 2: the weighed raw material of institute in step 1 being uniformly mixed in nitrogen atmosphere or air atmosphere, is respectively formed and changes
Property sialon fluorescent powder particle core and modified sialon fluorescent powder particle shell mixture；
Step 3: condition of the mixture of the core for the modification sialon fluorescent powder particle that step 2 is obtained in high-temperature roasting atmosphere
Lower carry out high-temperature roasting, is then cooled to low-temperature bake temperature, and low-temperature bake is carried out under conditions of low-temperature bake atmosphere, passes through
It is ground up, sieved, obtains the semi-finished product of the core of modified sialon fluorescent powder particle, it is spare；
Step 4: the mixture of the shell for the modification sialon fluorescent powder particle that step 2 is obtained under conditions of calcination atmosphere into
Row high-temperature roasting obtains the semi-finished product of the shell of modified sialon fluorescent powder particle by being ground up, sieved, wash, dry, spare；
Step 5: the semi-finished product of the shell of modification sialon fluorescent powder particle described in step 4 are sprayed or be deposited on step 3 institute
The surface of the semi-finished product of the core for the modification sialon fluorescent powder particle stated, then maturing temperature be 800-1500 DEG C under conditions of into
Row roasting, calcining time 1-12h obtain the finished product of modified sialon fluorescent powder particle.
The present invention proposes that a kind of further preferred scheme of the preparation method of modified sialon fluorescent powder particle is:
The step 3 further include the product after high-temperature roasting is carried out to low-temperature bake after broken, sieving, then it is ground,
Sieving obtains the semi-finished product of the core of modified sialon fluorescent powder particle, spare.
The temperature of high-temperature roasting described in step 3 is 1600-2000 DEG C, and the time of high-temperature roasting is 4-24h, high-temperature roasting
Pressure be 1-20MPa, the atmosphere of high-temperature roasting is that nitrogen atmosphere, the argon-mixed atmosphere of nitrogen, other indifferent gas atmosphere, nitrogen hydrogen are mixed
Closing gas atmosphere or other also Primordial Qi atmosphere, the hydrogen volume percentage composition of the nitrogen and hydrogen mixture is within 50%.
The temperature of low-temperature bake described in step 3 is 200-700 DEG C, and the time of low-temperature bake is 1-24h.
Low-temperature bake atmosphere described in step 3 refers to nitrogen oxygen atmosphere atmosphere or air atmosphere, the nitrogen oxygen atmosphere or sky
The speed that is passed through of gas is 0.1-10L/min, and the oxygen volumn concentration of the nitrogen oxygen atmosphere is within 20%.
Calcination atmosphere described in step 4 refers to the argon-mixed atmosphere of nitrogen atmosphere, nitrogen or other indifferent gas atmosphere；The high temperature
The temperature of roasting is 1600-2000 DEG C, and the time of the high-temperature roasting is 4-24h, and the pressure of roasting is 1-10MPa.
Maturing temperature described in step 5 is 1000-1200 DEG C, calcining time 4-8h.
Spraying described in step 5 or deposition are selected from one of flame-spraying, plasma spraying, Vacuum Deposition and ion plating.
A kind of luminescent device proposed by the present invention, the luminescent device at least contain the LED of hair ultraviolet light, purple light or blue light
Chip and fluorescent powder grain, which is characterized in that the fluorescent powder grain at least uses any of the above-described modification of the present invention
Sialon fluorescent powder particle.
A kind of luminescent device proposed by the present invention, the luminescent device at least contain the LED of hair ultraviolet light, purple light or blue light
Chip and fluorophor, which is characterized in that Sialon fluorophor of the present invention is at least used in the fluorophor.
Realization principle of the invention is: modified sialon fluorescent powder particle proposed by the present invention highlights the knot to its nucleocapsid
Structure design, the structure of center are divided into crystal nucleation layer, transition zone and core outer layer, and cooperate with to become between layers and be connected with chemical bond
The entirety connect.The meval atom composition that mixture is kept in crystal nucleation layer, is conducive to the nucleation of oxymtride material, to ensure
High Efficiency Luminescence；Because of the oxymtride material of transition zone, the oxide material of core outer layer or oxygen nitrogen in modified sialon fluorescent powder particle
Oxygen content in compound material gradually increases, therefore can be effectively reduced transition zone and core outer layer is formed by and is unfavorable for efficiently sending out
The defect of light ensure that luminous efficiency is significantly improved；Compared with Nitrogen ion, the small electronegativity of the radius of oxonium ion is high, interionic
Binding force it is stronger, in the structure of modified sialon fluorescent powder particle from granular core to particle exterior surface passing with oxygen content
Increase, the chemistry and thermal stability of the transition zone and core outer layer that are modified sialon fluorescent powder particle are gradually promoted, so as to modification
The crystal nucleation layer of sialon fluorescent powder particle, which plays, to be effectively protected and shielding action；Meanwhile in the system of modified sialon fluorescent powder particle
During standby, after the deposition shell of core surface, the core-shell structure of chemistry key connection is formed by roasting, while because of the ingredient and core of shell
Ingredient it is approximate, compatibility between the two very well, thus has been obviously improved the light extraction efficiency of modified sialon fluorescent powder particle.Core
The presence of shell also plays protective effect to core in shell structure, so that Eu2+Ion is not easy to be oxidized, and effectively improves modified Sialon
The stability of fluorescent powder grain.Meanwhile the thickness of shell will significantly affect the performance of sialon fluorescent powder particle, the thickness of shell is small by nothing
Method plays the role of being effectively protected, and the thickness of shell will affect greatly the light extraction efficiency of fluorescent powder grain, in view of the present invention to nucleocapsid
Structure design, therefore can effectively improve thermal stability of the modified sialon fluorescent powder particle in LED application environment with it is durable
Property.
Its remarkable advantage is the present invention compared with prior art:
First is that chemical stability is good.The present invention is because of the oxymtride material of transition zone, core in modified sialon fluorescent powder particle
The oxide material of outer layer or the oxygen content in oxynitride material gradually increase, and meet modified sialon fluorescent powder particle matrix
Crystal is needed by the growth being nucleated into molding and compaction process, so that crystal structure is more solid and stablizes, improves modification
The weatherability of sialon fluorescent powder particle；The presence of shell also plays protective effect to core and makes Eu in core-shell structure simultaneously2+Ion
It is not easy to be oxidized, effectively improves the stability of modified sialon fluorescent powder particle.
Second is that anti-aging light decay performance is good.The nuclear structure of modified sialon fluorescent powder particle is divided into crystal nucleation layer, mistake by the present invention
Layer and core outer layer are crossed, is made in the structure of modified sialon fluorescent powder particle from granular core to outer surface with the incremental of oxygen content
Nitrogen ion can more be replaced by obtaining the small oxonium ion of radius ratio Nitrogen ion, to enhance in modified sialon fluorescent powder grain structure
Interionic binding force, so that modified sialon fluorescent powder particle has the high temperature of extremely excellent anti-aging light decay durable
Property.Simultaneously as the crystal nucleation layer of modified sialon fluorescent powder particle is because by the effect of the barrier protection of transition zone and core outer layer, nucleus
Layer is not easily susceptible to the influence of external adverse environment；Meanwhile the presence of shell also plays protective effect to core in core-shell structure, so that
The stability of the centre of luminescence of modified sialon fluorescent powder particle significantly improves.
Third is that luminous efficiency is high.The present invention keeps the meval atom of mixture to form in crystal nucleation layer, is conducive to modified plug
The nucleation of the material of grand fluorescent powder grain, so as to ensure High Efficiency Luminescence；From particle in the structure of modified sialon fluorescent powder particle
The oxygen content of core to outer surface is incremented by, therefore can be effectively reduced transition zone and core outer layer is formed by and is unfavorable for High Efficiency Luminescence
Defect, ensure that luminous efficiency is significantly improved；Simultaneously as the ingredient of shell is approximate with the ingredient of core, compatibility between the two
Property is more preferable, thus has been obviously improved the light extraction efficiency of modified fluorescent powder grain.
Fourth is that applied widely.Modification sialon fluorescent powder particle of the invention is not only suitable for Sialon fluorophor, is also suitable
In the various luminescent devices of manufacture.
Fifth is that manufacturing method is easy to be reliable.The manufacturing method of the present invention is conducive to improve modified sialon fluorescent powder particle, plug
The chemistry and physical stability of grand fluorophor are suitable for industrialized mass production and manufacture.
Detailed description of the invention
Fig. 1 is a kind of the schematic diagram of the section structure of modified sialon fluorescent powder particle proposed by the present invention.
Fig. 2 is the excitation spectrum schematic diagram of embodiment 1-3 and comparative example 1.
Fig. 3 is the emission spectrum schematic diagram of embodiment 1-3 and comparative example 1.
Fig. 4 is the thermal quenching schematic diagram of embodiment 4-6 and comparative example 2.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawings and examples.
In conjunction with Fig. 1, a kind of modified sialon fluorescent powder particle proposed by the present invention, the modified sialon fluorescent powder particle
Structure is core-shell structure, and the nuclear structure of the modified sialon fluorescent powder particle is passing with oxygen content from granular core to outer surface
Increase and is divided into crystal nucleation layer, transition zone and core outer layer；The main body of the crystal nucleation layer is oxymtride material, the main body of transition zone
For oxymtride material, the main body of core outer layer is oxide material or oxynitride material；The chemical formula of the crystal nucleation layer is
Six-z1Alz1Oz1Ny-z1: r1Eu, the chemical formula of transition zone are Six-z2Alz2Oz2Ny-z2: the chemical formula of r2Eu, core outer layer is
SikAlmOoNn:r3Eu；The chemical formula of the shell of the modified sialon fluorescent powder particle is Sia-cAlcOcNb-c；Wherein: x, z1, y,
The atomic percent of r1, z2, r2, k, m, o, n, r3, a, c, b for respective element, 6 < x≤8,0.1≤z1≤0.3, y=4x/3,
0.001≤r1≤0.1,0.3 < z2≤1,0≤r2≤0.1,0≤k≤3,0≤m≤4,1≤o≤6,0≤n≤4,0≤r3≤
0.1,3≤a < 6,0 < c≤0.3, b=4a/3.
A kind of specific embodiment of modified sialon fluorescent powder particle proposed by the present invention, each embodiment is disclosed further below
Involved in modified sialon fluorescent powder particle component and parameter and modified sialon fluorescent powder particle preparation method step
Rapid and condition, meet a kind of modified sialon fluorescent powder particle of aforementioned present invention proposition design scheme and preferred design side
Case.
Embodiment 1.
Weigh Si3N419.366g AlN0.522g, Eu2O3The above raw material is sufficiently mixed by 0.112g in nitrogen atmosphere
1h forms the mixture of core, is fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then nitrogen atmosphere protection under by
1850 DEG C are gradually warming up to, 8h is kept the temperature, then atmosphere pressures 5Mpa is cooled to 350 DEG C, be passed through air with 5L/min speed and carry out
Roasting, calcining time 3h form the semi-finished product of core；Weigh Si3N419.199g, AlN0.801g, by the above raw material in nitrogen gas
It is sufficiently mixed 1h in atmosphere, forms the mixture of shell, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then in nitrogen
It is gradually heated to 1600 DEG C under atmosphere protection, keeps the temperature 6h, atmosphere pressures 2Mpa forms the semi-finished product of shell, by the half of gained shell
Finished product grinding and sieving, being washed out to conductivity is 5.21 μ s/cm, spare after drying.Shell plasma spray is coated in core surface,
Then in 1000 DEG C of heat preservation 5h, modification sialon fluorescent powder finished granule of the invention is obtained.Wherein: the chemistry of the crystal nucleation layer of core
Group becomes Si6.5Al0.2O0.2N8.73: 0.01Eu, the chemical composition of transition zone are Si6.1Al0.6O0.6N8.33: 0.01Eu, with a thickness of
200nm, the chemical composition of core outer layer are Si2Al4O5N3.33: 0.01Eu, with a thickness of 36nm；The chemical formula of shell is
Si4.2Al0.2O0.2N5.67, with a thickness of 50nm.The excitation spectrum and emission spectrum of the modification sialon fluorescent powder particle of embodiment 1
See Fig. 2 and Fig. 3.
Embodiment 2.
Weigh Si3N419.32g, AlN0.565g, EuF3The above raw material is sufficiently mixed 1h by 0.115g in nitrogen atmosphere,
The mixture for forming core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then gradually rises under nitrogen atmosphere protection
Temperature keeps the temperature 8h to 1850 DEG C, then atmosphere pressures 5Mpa is cooled to 350 DEG C, is passed through air with 5L/min speed and is roasted
It burns, calcining time 3h forms the semi-finished product of core；Weigh Si3N419.686g, AlN0.314g, by the above raw material in nitrogen atmosphere
In be sufficiently mixed 1h, form the mixture of shell, be fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then in nitrogen gas
Be gradually heated to 1600 DEG C under atmosphere protection, keep the temperature 6h, atmosphere pressures 2Mpa forms the semi-finished product of shell, by the half of gained shell at
Product grinding and sieving, being washed out to conductivity is 4.88 μ s/cm, spare after drying.Shell plasma spray is coated in core surface, so
Afterwards in 1000 DEG C of heat preservation 5h, modification sialon fluorescent powder finished granule of the invention is obtained.The chemical group of the crystal nucleation layer of its center
As Si7.25Al0.25O0.25N9.25: 0.01Eu, the chemical composition of transition zone are Si6.5AlON9, with a thickness of 120nm, core outer layer
Chemical composition be SiO2, with a thickness of 25nm, the chemical formula of shell is Si5.5Al0.1O0.1N7.37, with a thickness of 80nm.Embodiment 2
Modification sialon fluorescent powder particle excitation spectrum and emission spectrum see Fig. 2 and Fig. 3.
Embodiment 3.
Weigh Si3N419.491g AlN0.358g, EuCl3The above raw material is sufficiently mixed by 0.151g in nitrogen atmosphere
1h forms the mixture of core, is fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then nitrogen atmosphere protection under by
1850 DEG C are gradually warming up to, 8h is kept the temperature, then atmosphere pressures 5Mpa is cooled to 350 DEG C, be passed through air with 5L/min speed and carry out
Roasting, calcining time 3h form the semi-finished product of core；Weigh Si3N419.16g, AlN0.84g, by the above raw material in nitrogen atmosphere
In be sufficiently mixed 1h, form the mixture of shell, be fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then in nitrogen gas
Be gradually heated to 1600 DEG C under atmosphere protection, keep the temperature 6h, atmosphere pressures 2Mpa forms the semi-finished product of shell, by the half of gained shell at
Product grinding and sieving, being washed out to conductivity is 5.85 μ s/cm, spare after drying.Shell plasma spray is coated in core surface, so
Afterwards in 1000 DEG C of heat preservation 5h, modification sialon fluorescent powder finished granule of the invention is obtained.The chemical group of the crystal nucleation layer of its center
As Si7Al0.15O0.15N9.38: 0.01Eu, the chemical composition of transition zone are Si6.75Al0.4O0.4N9.13, with a thickness of 150nm, core
The chemical composition of outer layer is SiO2, with a thickness of 42nm, the chemical formula of shell is Si3.8Al0.2O0.2N5.13, with a thickness of 85nm.It is real
The excitation spectrum and emission spectrum for applying the modification sialon fluorescent powder particle of example 3 are shown in Fig. 2 and Fig. 3.
Comparative example 1.
Weigh Si3N419.292g AlN0.583g, Eu2O3The above raw material is sufficiently mixed by 0.125g in nitrogen atmosphere
1h forms mixture, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then gradually rises under nitrogen atmosphere protection
Temperature keeps the temperature 8h, atmosphere pressures 5Mpa to 1850 DEG C, by gained semi-finished product grinding and sieving, is washed out to conductivity and is
4.62 μ s/cm can be prepared by sialon fluorescent powder finished granule, chemical formula Si after drying5.8Al0.2O0.2N8: 0.01Eu,
Excitation spectrum and emission spectrum are shown in Fig. 2 and Fig. 3.
Sialon fluorescent powder described in modification sialon fluorescent powder particle and comparative example 1 by 1-3 described in above-described embodiment
Luminescent device is respectively prepared in grain, and test result obtains: the luminous intensity and ageing properties of comparative example 1 are below embodiment 1-3, ginseng
It is shown in Table 1.Wherein aging condition are as follows: SMD-2835 type LED lamp bead, 10 × 30mil of chip size, chip wave band 452.5-455nm,
Electric current 150mA, power 0.5W, environmental condition: ambient temperature and moisture.
Table 1
Embodiment 4.
Weigh Si3N419.053g AlN0.445g, Al2O30.184g, Eu2O30.318g, by the above raw material in nitrogen atmosphere
In be sufficiently mixed 2h, form the mixture of core, be fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then in hydrogen
1880 DEG C are gradually heated under the protection for the nitrogen and hydrogen mixture atmosphere that product percentage composition is 10%, keeps the temperature 6h, atmosphere pressures are
Then products therefrom grinding and sieving is gradually heated to 300 DEG C by 8Mpa in air atmosphere, keep the temperature 5h, formed the half of core at
Product；Weigh Si3N4The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms the mixture of shell by 19.603g, AlN0.397g,
It is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, 1800 DEG C are then gradually heated under nitrogen atmosphere protection, heat preservation
10h, atmosphere pressures 1Mpa form the semi-finished product of shell, and the semi-finished product grinding and sieving of gained shell is washed out to conductivity
It is spare after drying for 6.88 μ s/cm.By shell Vacuum Deposition on core surface, then in 1200 DEG C of heat preservation 7h, of the invention change is obtained
Property sialon fluorescent powder finished granule.The chemical composition of the crystal nucleation layer of its center is Si6.76Al0.24O0.24N9.09: 0.03Eu, transition
The chemical composition of layer is Si6.2Al0.8O0.8N8.53: 0.03Eu, with a thickness of 90nm, the chemical composition of core outer layer is Al2O3, thick
Degree is 27nm, and the chemical formula of shell is Si5.2Al0.12O0.12N6.97, with a thickness of 75nm.The modification sialon fluorescent powder of embodiment 4
The thermal quenching figure of grain is shown in Fig. 4.
Embodiment 5.
Weigh Si3N419.011g AlN0.397g, AlF30.271g, EuN0.321g, by the above raw material in nitrogen atmosphere
It is sufficiently mixed 2h, forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then in hydrogen volume
It is gradually heated to 1880 DEG C under the protection for the nitrogen and hydrogen mixture atmosphere that percentage composition is 10%, keeps the temperature 6h, atmosphere pressures 8Mpa,
By products therefrom grinding and sieving, it is then gradually heated to 300 DEG C in air atmosphere, keeps the temperature 5h, forms the semi-finished product of core；Claim
Take Si3N418.969g AlN0.718g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.313g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1800 under nitrogen atmosphere protection
DEG C, 10h is kept the temperature, atmosphere pressures 1Mpa forms the semi-finished product of shell, the semi-finished product grinding and sieving of gained shell is washed out
It is 6.32 μ s/cm to conductivity, it is spare after drying.By shell Vacuum Deposition on core surface, then in 1200 DEG C of heat preservation 7h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6.3Al0.2O0.2N8.47:
0.03Eu, the chemical composition of transition zone are Si6Al0.5O0.5N8.17, with a thickness of 225nm, the chemical composition of core outer layer is
Si3AlO2N3.67, with a thickness of 30nm, the chemical formula of shell is Si4.63Al0.27O0.27N6.26: 0.04Eu, with a thickness of 56nm.It is real
The thermal quenching figure for applying the modification sialon fluorescent powder particle of example 5 is shown in Fig. 4.
Embodiment 6.
Weigh Si3N419.056g SiO20.318g, AlN0.347g, Eu2O30.279g, by the above raw material in nitrogen atmosphere
In be sufficiently mixed 2h, form the mixture of core, be fitted into BN crucible, then by its rapidly move into carbon shirt-circuiting furnace in, then in hydrogen
1880 DEG C are gradually heated under the protection for the nitrogen and hydrogen mixture atmosphere that product percentage composition is 10%, keeps the temperature 6h, atmosphere pressures are
Then products therefrom grinding and sieving is gradually heated to 300 DEG C by 8Mpa in air atmosphere, keep the temperature 5h, formed the half of core at
Product；Weigh Si3N4The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms the mixture of shell by 19.734g, AlN0.266g,
It is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, 1800 DEG C are then gradually heated under nitrogen atmosphere protection, heat preservation
10h, atmosphere pressures 1Mpa form the semi-finished product of shell, and the semi-finished product grinding and sieving of gained shell is washed out to conductivity
It is spare after drying for 5.91 μ s/cm.By shell Vacuum Deposition on core surface, then in 1200 DEG C of heat preservation 7h, of the invention change is obtained
Property sialon fluorescent powder finished granule.The chemical composition of the crystal nucleation layer of its center is Si7.8Al0.16O0.16N10.45: 0.03Eu, transition
The chemical composition of layer is Si7.36Al0.6O0.6N10.01, with a thickness of 290nm, the chemical composition of core outer layer is Al2O3, with a thickness of
48nm, the chemical formula of shell are Si3.9Al0.06O0.06N5.22, with a thickness of 15nm.The modification sialon fluorescent powder particle of embodiment 6
Thermal quenching figure is shown in Fig. 4.
Comparative example 2.
Weigh Si3N418.954 AlN0.43g, Al2O30.178g, EuF30.438g, by the above raw material in nitrogen atmosphere
It is sufficiently mixed 2h, mixture is formed, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then protected in nitrogen atmosphere
Under be gradually heated to 1880 DEG C, gained semi-finished product grinding and sieving is washed out to electricity by heat preservation 6h, atmosphere pressures 8Mpa
Conductance is 4.12 μ s/cm, can be prepared by sialon fluorescent powder finished granule, chemical formula Si after drying5.8Al0.2O0.2N8:
0.03Eu, thermal quenching figure are shown in Fig. 4.
By sialon fluorescent powder particle described in modification sialon fluorescent powder particle described in above-described embodiment 4-6 and comparative example 2
Luminescent device is respectively prepared, test result obtains: the luminous intensity and ageing properties of comparative example 2 are below embodiment 4-6, referring to
Table 2.Wherein aging condition are as follows: SMD-2835 type LED lamp bead, 10 × 30mil of chip size, chip wave band 452.5-455nm, electricity
Flow 150mA, power 0.5W, environmental condition: ambient temperature and moisture.
Table 2
Embodiment 7.
Weigh Si3N419.643g Al2O30.345g, Eu2O3The above raw material is sufficiently mixed by 0.012g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
It is gradually heated to 320 DEG C in the nitrogen oxygen atmosphere atmosphere that volumn concentration is 10%, keeps the temperature 8h, forms the semi-finished product of core；Claim
Take Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.412g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 6.25 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.001Eu,
The chemical composition of transition zone is Si5.8Al0.3O0.3N7.83: 0.001Eu, with a thickness of 110nm, the chemical composition of core outer layer is
SiO2, with a thickness of 30nm, the chemical formula of shell is Si5.1Al0.2O0.2N6.87。
Embodiment 8.
Weigh Si3N419.651g AlN0.287g, Eu2O3The above raw material is sufficiently mixed by 0.062g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
It is gradually heated to 320 DEG C in the nitrogen oxygen atmosphere atmosphere that volumn concentration is 10%, keeps the temperature 8h, forms the semi-finished product of core；Claim
Take Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.412g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 3.88 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.005Eu,
The chemical composition of transition zone is Si5.7Al0.4O0.4N7.73: 0.005Eu, with a thickness of 165nm, the chemical composition of core outer layer is
Si2.5Al1.5O4N3.47, with a thickness of 46nm, the chemical formula of shell is Si5.1Al0.2O0.2N6.87, with a thickness of 58nm.
Embodiment 9.
Weigh Si3N419.531g AlN0.285g, Eu2O3The above raw material is sufficiently mixed by 0.184g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
It is gradually heated to 320 DEG C in the nitrogen oxygen atmosphere atmosphere that volumn concentration is 10%, keeps the temperature 8h, forms the semi-finished product of core；Claim
Take Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.412g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 3.88 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.015Eu,
The chemical composition of transition zone is Si5.75Al0.35O0.35N7.78, with a thickness of 210nm, the chemical composition of core outer layer is SiO2, thick
Degree is 33nm, and the chemical formula of shell is Si5.1Al0.2O0.2N6.87, with a thickness of 75nm.
Embodiment 10.
Weigh Si3N419.236g AlN0.281g, Eu2O3The above raw material is sufficiently mixed by 0.483g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
It is gradually heated to 320 DEG C in the nitrogen oxygen atmosphere atmosphere that volumn concentration is 10%, keeps the temperature 8h, forms the semi-finished product of core；Claim
Take Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.412g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 4.68 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.04Eu,
The chemical composition of transition zone is Si5.68Al0.42O0.42N7.71: 0.038Eu, with a thickness of 267nm, the chemical composition of core outer layer is
SiO2, with a thickness of 38nm, the chemical formula of shell is Si5.1Al0.2O0.2N6.87, with a thickness of 64nm.
Embodiment 11.
Weigh Si3N418.894g AlN0.276g, Eu2O3The above raw material is sufficiently mixed by 0.83g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
It is gradually heated to 320 DEG C in the nitrogen oxygen atmosphere atmosphere that volumn concentration is 10%, keeps the temperature 8h, forms the semi-finished product of core；Claim
Take Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed in nitrogen atmosphere 2h, forms shell by 0.412g
Mixture is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 4.96 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.07Eu,
The chemical composition of transition zone is Si5.78Al0.32O0.32N7.81: 0.065Eu, with a thickness of 78nm, the chemical composition of core outer layer is
Si1.5Al3.2O4N2.53: 0.005Eu, with a thickness of 49nm, the chemical formula of shell is Si5.1Al0.2O0.2N6.87, with a thickness of 70nm.
Embodiment 12.
Weigh Si3N418.564g AlN0.271g, Eu2O3The above raw material is sufficiently mixed by 1.164g in nitrogen atmosphere
2h forms the mixture of core, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then protects in the argon-mixed atmosphere of nitrogen
It is gradually heated to 1900 DEG C under shield, 12h, atmosphere pressures 15Mpa are kept the temperature, by products therefrom grinding and sieving, then in oxygen
Volumn concentration is that 320 DEG C are gradually heated in 10% nitrogen oxygen atmosphere atmosphere, keeps the temperature 8h, forms the semi-finished product of core；It weighs
Si3N419.257g AlN0.331g, Al2O3The above raw material is sufficiently mixed 2h by 0.412g in nitrogen atmosphere, forms the mixed of shell
Material is closed, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, is then gradually heated to 1750 under nitrogen atmosphere protection
DEG C, keep the temperature 9h, atmosphere pressures 5Mpa forms the semi-finished product of shell, by the semi-finished product grinding and sieving of gained shell, be washed out to
Conductivity is 5.06 μ s/cm, spare after drying.By shell flame-spraying on core surface, then in 1100 DEG C of heat preservation 6h, this is obtained
The modification sialon fluorescent powder finished granule of invention.The chemical composition of the crystal nucleation layer of its center is Si6Al0.1O0.1N8.03: 0.1Eu, mistake
The chemical composition for crossing layer is Si5.7Al0.4O0.4N7.73: 0.1Eu, with a thickness of 110nm, the chemical composition of core outer layer is
Si1.5Al2O3N2, with a thickness of 21nm, the chemical formula of shell is Si5.1Al0.2O0.2N6.87, with a thickness of 62nm.
Comparative example 3.
Weigh Si3N418.542g AlN0.275g, Eu2O3The above raw material is sufficiently mixed by 1.183g in nitrogen atmosphere
2h forms mixture, is fitted into BN crucible, then it is moved into carbon shirt-circuiting furnace rapidly, then gradually rises under nitrogen atmosphere protection
Temperature keeps the temperature 12h, atmosphere pressures 15Mpa to 1900 DEG C, by gained semi-finished product grinding and sieving, is washed out to conductivity and is
5.26 μ s/cm can be prepared by sialon fluorescent powder finished granule, chemical formula Si after drying5.9Al0.1O0.1N8:0.1Eu。
By sialon fluorescent powder particle described in modification sialon fluorescent powder particle described in above-described embodiment 7-12 and comparative example 3
Luminescent device is respectively prepared, test result obtains: the luminous intensity and ageing properties of comparative example 3 are below embodiment 7-12, ginseng
It is shown in Table 3.Wherein aging condition are as follows: SMD-2835 type LED lamp bead, 10 × 30mil of chip size, chip wave band 452.5-455nm,
Electric current 150mA, power 0.5W, environmental condition: ambient temperature and moisture.
Table 3
The explanation being not directed in a specific embodiment of the invention belongs to technology well known in the art, can refer to well-known technique
It is implemented.
The present invention achieves satisfied trial effect through validation trial.
The above specific embodiment and embodiment are to a kind of modified sialon fluorescent powder particle proposed by the present invention and its system
The specific support of Preparation Method, Sialon fluorophor and light emitting device technologies thought, this does not limit the scope of protection of the present invention, all
It is any equivalent variations or equivalent change done on the basis of the technical program according to the technical idea provided by the invention,
Still fall within the range of technical solution of the present invention protection.
Claims (15)
1. a kind of modified sialon fluorescent powder particle, which is characterized in that the structure of the modified sialon fluorescent powder particle is nucleocapsid knot
Structure, the nuclear structure of the modified sialon fluorescent powder particle are to be divided into from granular core to outer surface with being incremented by for oxygen content
Crystal nucleation layer, transition zone and core outer layer；The main body of the crystal nucleation layer is oxymtride material, and the main body of transition zone is nitrogen oxides material
Material, the main body of core outer layer are oxide material or oxynitride material；The chemical formula of the crystal nucleation layer is Six-z1Alz1Oz1Ny-z1:
R1Eu, the chemical formula of transition zone are Six-z2Alz2Oz2Ny-z2: r2Eu, the chemical formula of core outer layer are SikAlmOoNn:r3Eu；It is described
The chemical formula of the shell of modified sialon fluorescent powder particle is Sia-cAlcOcNb-c；Wherein: x, z1, y, r1, z2, r2, k, m, o, n, r3,
A, c, b are the atomic percent of respective element, 6 < x≤8,0.1≤z1≤0.3, y=4x/3,0.001≤r1≤0.1,0.3 <
6,0 < c of z2≤1,0≤r2≤0.1,0≤k≤3,0≤m≤4,1≤o≤6,0≤n≤4,0≤r3≤0.1,3≤a <≤
0.3, b=4a/3, in which: k+m+n ≠ 0, and when r2=0, r3=0.
2. a kind of modified sialon fluorescent powder particle according to claim 1, which is characterized in that the transition zone with a thickness of
50-300nm, core outer layer with a thickness of 50nm within, to the core of nitric oxide fluorescent powder particle be crystal nucleation layer on the inside of transition zone,
Shell with a thickness of 1-100nm.
3. a kind of modified sialon fluorescent powder particle according to claim 1, which is characterized in that the nitrogen oxygen in the crystal nucleation layer
The content of compound material is not less than 90wt%, and the content of the oxymtride material in the transition zone is not less than 80wt%, described
The content of oxide material or oxynitride material is not less than 70wt% in core outer layer.
4. a kind of modified sialon fluorescent powder particle according to claim 1, which is characterized in that the modified Sialon fluorescence
Powder particles excite within the scope of wavelength 300-500nm issues the light that appearance wavelength is located at 500-570nm.
5. a kind of Sialon fluorophor, which is characterized in that include modified sialon fluorescent powder of any of claims 1-4
The mixture of grain, the ratio of modified sialon fluorescent powder particle is not less than 50wt% in the mixture.
6. a kind of preparation method of modified sialon fluorescent powder particle according to claim 1, which is characterized in that including as follows
Specific steps:
Step 1: using the nitride of Si, Al, Eu, oxide or halide as raw material, by chemical general formula Six-z1Alz1Oz1Ny-z1:
R1Eu and Sia-cAlcOcNb-c: the stoichiometric ratio of composition weighs required raw material respectively；
Step 2: the weighed raw material of institute in step 1 being uniformly mixed in nitrogen atmosphere or air atmosphere, is respectively formed modified plug
The mixture of the shell of the core of grand fluorescent powder grain and modified sialon fluorescent powder particle；
Step 3: the mixture of the core for the modification sialon fluorescent powder particle that step 2 is obtained under conditions of high-temperature roasting atmosphere into
Then row high-temperature roasting is cooled to low-temperature bake temperature, low-temperature bake is carried out under conditions of low-temperature bake atmosphere, by grinding
Mill, sieving obtain the semi-finished product of the core of modified sialon fluorescent powder particle, spare；
The low-temperature bake atmosphere refers to nitrogen oxygen atmosphere atmosphere or air atmosphere；Step 4: the modification Sialon that step 2 is obtained
The mixture of the shell of fluorescent powder grain carries out high-temperature roasting under conditions of calcination atmosphere, by being ground up, sieved, washing, dry,
The semi-finished product of the shell of modified sialon fluorescent powder particle are obtained, it is spare；
Step 5: the semi-finished product of the shell of modification sialon fluorescent powder particle described in step 4 being sprayed or are deposited on described in step 3
The surface of the semi-finished product of the core of modified sialon fluorescent powder particle, is then roasted under conditions of maturing temperature is 800-1500 DEG C
It burns, calcining time 1-12h obtains the finished product of modified sialon fluorescent powder particle.
7. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that the step
3 further include that the product after high-temperature roasting is carried out to low-temperature bake, then ground, sieving after broken, sieving, obtains modified Sialon
The semi-finished product of the core of fluorescent powder grain, it is spare.
8. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that step 3 institute
The temperature for stating high-temperature roasting is 1600-2000 DEG C, and the time of high-temperature roasting is 4-24h, and the pressure of high-temperature roasting is 1-20MPa,
The atmosphere of high-temperature roasting be nitrogen atmosphere, the argon-mixed atmosphere of nitrogen, other indifferent gas atmosphere, nitrogen and hydrogen mixture atmosphere or it is other also
Primordial Qi atmosphere, the hydrogen volume percentage composition of the nitrogen and hydrogen mixture are within 50%.
9. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that step 3 institute
The temperature for stating low-temperature bake is 200-700 DEG C, and the time of low-temperature bake is 1-24h.
10. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that in step 3
The speed that is passed through of the nitrogen oxygen atmosphere or air is 0.1-10L/min, the oxygen volumn concentration of the nitrogen oxygen atmosphere
Within 20%.
11. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that step 4 institute
It states calcination atmosphere and refers to the argon-mixed atmosphere of nitrogen atmosphere, nitrogen or other indifferent gas atmosphere；The temperature of the high-temperature roasting is
1600-2000 DEG C, the time of the high-temperature roasting is 4-24h, and the pressure of roasting is 1-10MPa.
12. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that step 5 institute
Stating maturing temperature is 1000-1200 DEG C, calcining time 4-8h.
13. a kind of preparation method of modified sialon fluorescent powder particle according to claim 6, which is characterized in that step 5 institute
The spraying stated or deposition are selected from one of flame-spraying, plasma spraying, Vacuum Deposition and ion plating.
14. a kind of luminescent device, the luminescent device at least contains the LED chip and fluorescent powder of hair ultraviolet light, purple light or blue light
Particle, which is characterized in that the fluorescent powder grain at least uses modification sialon fluorescent powder described in claim any one of 1-4
Particle.
15. a kind of luminescent device, the luminescent device at least contains the LED chip and fluorophor of hair ultraviolet light, purple light or blue light,
It is characterized in that, the fluorophor at least uses Sialon fluorophor described in claim 5.
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| CN112897934B (en) * | 2019-11-19 | 2022-05-17 | 吉林建筑大学 | Inorganic vacuum ball and preparation method and application thereof |
| CN113698927B (en) * | 2021-09-22 | 2023-07-11 | 烟台布莱特光电材料有限公司 | Preparation method of alpha-type plug Long Chengse fluorescent powder |
| CN115490508B (en) * | 2022-10-12 | 2023-11-03 | 中国科学院上海光学精密机械研究所 | Composite fluorescent ceramic for white light LD illumination and preparation method thereof |
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