CN106047341A - Rare earth doped fluorescent powder and synthetic method thereof and application of fluorescent powder in LED devices - Google Patents
Rare earth doped fluorescent powder and synthetic method thereof and application of fluorescent powder in LED devices Download PDFInfo
- Publication number
- CN106047341A CN106047341A CN201610384438.3A CN201610384438A CN106047341A CN 106047341 A CN106047341 A CN 106047341A CN 201610384438 A CN201610384438 A CN 201610384438A CN 106047341 A CN106047341 A CN 106047341A
- Authority
- CN
- China
- Prior art keywords
- oxide
- rare earth
- carbonate
- fluorescent powder
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7735—Germanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses rare earth doped fluorescent powder and a synthetic method thereof and application of the fluorescent powder in LED devices, and belongs to the technical field of luminescent materials. The general chemical formula of the fluorescent powder is MS[2-y]AyO[2+y]N[2-y-4z/3]Cz:Rx. According to the compound, C<4-> is substituted for N<3->, due to the fact that the electronegativity of C is smaller than that of N, the electron cloud expansion effect of the C<4-> is more obvious than that of the N<3->, after doping is conducted, rare earth ion 5d energy level splitting is increased, Stokes shift can change, and fluorescence parameters such as fluorescent peal and full half-peak width of the powder change. By adjusting generation of the above-mentioned doped ions, fluorescent powder with different fluorescent light colors and quantum efficiency can be obtained. The invention further discloses the application of the fluorescent powder in the field of LED devices. The fluorescent powder is applied to white LED light fixtures or light-emitting components which take blue LED or purple LED as a light source and can help to increase the color rendering indexes of the devices.
Description
Technical field
The present invention relates to luminescent material technical field, particularly to a kind of rare earth doping fluorescent powder and synthetic method, and
Application on the led device.
Background technology
It is little, right that the white light LEDs using chemiluminescence has low power consuming, high electro-optical efficiency, long-life, high brightness, volume
The plurality of advantages such as environmental nonpollution, response are fast, being considered to replace the traditional lighting instrument such as electric filament lamp and fluorescent lamp becomes and has province concurrently
Electricity and the new lighting source of environmental protection, be widely used in illumination, traffic signal, backlight, laser, communication, automobile, instrument instrument
The various lighting fields such as table, plant culture, decoration.
Fluorescent material has decisive role in solid-state illumination LED technology, and its performance determines the luminous light of white light LEDs
The critical technical parameters such as spectrum, luminous efficiency, color rendering index, colour temperature and service life.Current LED commonly uses white light implementation and is
InGaN chip sends blue light and excites YAG:Ce3+The blue light making its gold-tinted sent and chip pass through is combined into white light.Due to this kind
The white light color rendering index that method obtains is the highest, it is difficult to more than 80.Obtain the LED white light of high color rendering index (CRI), usually through blue chip
The blue light that excitated red fluorescent powder and green emitting phosphor make the two light sent pass through with chip again is combined into white light, or passes through
Ultraviolet chip excitated red fluorescent powder, green emitting phosphor and blue colour fluorescent powder make the recovery synthesis white light that three sends.If it addition,
Expect to obtain the white light of more high color rendering index (CRI) (more than 95), in addition to red, green, blue three-color phosphor, bluish-green, yellow or orange glimmering
Light powder is also needs.Therefore, it is thus achieved that luminous efficiency is high, good and good heat stability the multicolor phosphor of chemical stability becomes
Obtain high color rendering index (CRI), the essential condition of the most high-power white-light LED with high color rendering index lamp.
Currently used and exploitation is more for Hydrargyri Oxydum Rubrum, green powder and bloom, and the exploitation photochromic for other fluorescence is less, especially
It it is bluish-green powder.Patent CN103242834A discloses a kind of rear-earth-doped Sr4Al14O25The fluorescent material of strontium aluminate, but this powder is only capable of
Just there is stronger fluorescence under ultraviolet light, and its long afterglow qualities limits its application on LED.The silicate of Eu doping
Ba5Si8O21(emission peak 480nm) and BaSi2O5(emission peak 505nm) also can launch blue green light under ultraviolet excitation, but due to
The stability of silicate is limited, and this fluorescent material is applied in actual package and is out of favour.The oxygen fluoride Sr of Ce doping3AlO4F exists
Excite bimodal respectively at 460nm and 502nm under ultraviolet excitation, and this fluorescent material has higher quantum efficiency, but
This fluorescent material is also due to heat stability is the most excellent makes it use to be restricted.
The method preparing nitric oxide fluorescent powder at present mainly has solid phase method, microwave method, vapour phase reduction nitriding.Microwave method
Raw material should not obtain and poisonous, and carrying cost is high.Before vapour phase reduction nitriding need to use the preparation of organic/inorganic solution finely dispersed
Driving body, cost of material is high, is easily introduced impurity in complex process and building-up process.Also researcher is had to be incited somebody to action by plasma discharging (SPS)
It is used in the study on the synthesis of such fluorescent material, though the method is applied more ripe in ceramic post sintering, but makes in powder body synthesis
Easily make powder sintering in bulk by the method, shattering process is substantially reduced the fluorescence intensity of powder body, quantum efficiency and fluorescence steady
Qualitative fluorescence property such as grade, the method synthesizes the most immature in fluorescent powder.
It is true that solid phase method is the method commonly used in current fluorescent material commercial production, the method technique is simple and easy to control
System, and easily accomplish scale production.But its defect is the method synthesis easily produces impurity phase, it is thus achieved that powder body produces group
Poly-, broken reunion reduces the fluorescence property of fluorescent material.Therefore, the optimization side of the fluorescence property of this system fluorescent material a kind of is developed
Method, under conditions of keeping volume production, to improve luminous efficiency, the fluorescence property increasing fluorescent material is necessary.
White light is made up of the mixing of multiple monochromatic light, and common white light LEDs passes through ultraviolet LED or blue LED die with glimmering
Light powder combines, and the light light unabsorbed with chip that fluorescent material emits after absorbing the light that chip sends mixes and obtains white
Light.In order to improve the display index of White LED, it is desirable to obtain the white light of the most full spectrum as far as possible, except using common Huang
Outside color, redness and green emitting phosphor, the most colorful fluorescent material is also used in high display index LED component.Therefore, having must
The fluorescent material of special color to be developed, special fluorescence peak spike length is in 470～520nm blue green light fluorescent material.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention discloses a kind of rear-earth-doped MS2-yAyO2+yN2-y-4z/3Cz:
RxFluorescent material, and provide synthetic method and the application on the led device thereof of this fluorescent material, it is therefore intended that exploitation efficient stable
Fluorescent material, and by simple and easy to control and can the process conditions of volume production, it is thus achieved that luminous efficiency can be improved, increase fluorescent material
The synthetic method of fluorescence property so that obtain powder body and be conducive to improving further the color rendering index of LED component.
First purpose of the present invention, the present invention passes through Design of Chemical Composition and technology controlling and process, successfully C is mixed MS2- yAyO2+yN2-y: among R, it is thus achieved that rare earth mixes MS2-yAyO2+yN2-y-4z/3Cz:RxFluorescent material, uses C4-Replace N3-, due to C relatively N electronegativity
Less, C4-Compare N3-electron cloud bulking effect become apparent from, make rare earth ion 5d engery level cracking aggravate after incorporation, stoke
This displacement increases, and Fluorescent peal red shift, half-peak breadth broadens, thus obtains this system fluorescent material of more high emission wavelength.
Due to the successful incorporation of C, to mutually replacing and the crystal structure that causes between rear-earth-doped and alkaline-earth metal ions
Defect plays the effect of correction so that while improving fluorescence emission peak wavelength, it is possible to the heat stability optimization to fluorescent material.
Second object of the present invention is to provide the preparation method of above-mentioned fluorescent material.
Third object of the present invention is the white light LED part solving to provide display index excellent.Especially with indigo plant
Color LED or ultraviolet LED are as the White LED of the excitation source of fluorescent material.While ensureing the heat stability of fluorescent material, and energy
Enough realize the fluorescent material that industrial scale produces.
Utilize the rear-earth-doped MS that the present invention synthesizes2-yAyO2+yN2-y-4z/3CzNitric oxide fluorescent powder has chemical stability
Height, luminous efficiency is high, excitation energy low (blue light can effectively excite), emission spectrum width, and luminous efficiency is high, thermodynamic property
Good, hot-quenching temperature of going out is high.By adjusting ratio and the ratio of S/A of Mg, Ca, Sr, Ba, it is possible to obtain bluish-green-yellowish green-orange-yellow
Fluorescent material.This fluorescent material is suitable for the white LED lamp of high color rendering index (CRI), including the encapsulation of high-power LED lamp.
The technical solution adopted in the present invention is:
A kind of rare earth doping fluorescent powder, its molecular formula is MS2-yAyO2+yN2-y-4z/3Cz:Rx, wherein in M=Mg, Ca, Sr, Ba
One or more, S is one or more in Si, Ge, and A is Al, one or more in Ga, and R is in rare earth ion
Planting or multiple, 0.001≤x≤0.2,0≤y≤0.8,0 < z≤0.1, O represent oxygen atom, and N represents nitrogen-atoms, and it is former that C represents carbon
Son.
Preferably: 0.001≤x≤0.1,0≤y≤0.1,0 < z≤0.05.
Preferably: (Ca1-t-m-n-xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3Cz, wherein Re ' is trivalent rare earth ions Ce3 +、La3+、Pr3+、Sm3+、Tb3+、Dy3+In one or more, L is alkali metal ion Li+、Na+, K+In one or more, 0≤
M, n, t≤1,0.001≤x≤0.1.
Preferably: (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3Cz, wherein Re is bivalent rare earth ion Eu2+、Yb2 +、Sm2+In one or more, 0≤m, n, t≤1,0.001≤x≤0.1.
Described S is Si or Si Yu Ge combination, and A is the combination of Al or Al Yu Ga, and Re is Eu2+。
Preferably t=0, y=0.
The transmitting boundary of described fluorescent material is 460nm～580nm, and fluorescence emission peak wavelength is between 470～520nm.
The preparation method of above-mentioned fluorescent material, uses a step nitriding or two step nitridings to prepare,
A described step nitriding is the carbonate measuring raw material M according to molecular formula, the oxide of S and S nitride, A oxygen
Compound, R oxide, carbon containing simple substance or carbonaceous organic material, some mix with additive synthesis, grind gained fluorescent material after nitridation calcining
Body；
The step of described two step nitridings is to measure the carbonate of raw material M, the oxide of S, A oxidation according to molecular formula
Presoma is obtained, with S nitride after being ground by presoma after thing, R oxide and carbon containing simple substance or carbonaceous organic material mixed calcining
And additive synthesis mixing, carry out nitridation calcining the most again, also can obtain fluorescent powder；
Or measure the carbonate of raw material M, the oxide of S, A oxide and the mixing of R oxide according to molecular formula to forge
Presoma is obtained, with S nitride, carbon containing simple substance or carbonaceous organic material and additive synthesis mixing after being ground by presoma, so after burning
After again carry out nitridation calcining, also can obtain fluorescent powder.
Described carbon containing simple substance is activated carbon powder or graphite powder, or carbonaceous organic material is sucrose, glucose or maltose.
The carbonate of M, S nitride, S oxide, R oxide, A oxide, be stoichiometrically (1.8～2.2):
(0.8～1.2): 1:(0.001～0.1): (0～0.8), auxiliary agent press quality proportioning, its content be raw material sum 0.2%～
10%.
Described auxiliary agent is the one in fluoride, chloride, carbonate, phosphate, borate, oxide, boric acid or several
Kind.
Described fluoride comprises lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), calcium fluoride
(CaF2), Afluon (Asta) (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminium fluoride (AlF3)。
Described chloride comprises lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), chlorination
Calcium (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl), aluminum chloride
(AlCl3)。
Described carbonate comprises lithium carbonate (Li2CO3), sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate
(Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg(OH)2·5H2O)。
Described phosphate is including but not limited to lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid
Caesium (Cs3PO4), magnesium phosphate (Mg3(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3
(PO4)2), disodium-hydrogen (Na2HPO4), magnesium hydrogen phosphate (MgHPO4), calcium hydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4)、
Barium hydrogen phosphate (BaHPO4), lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), phosphorus
Acid dihydride magnesium (Mg (H2PO4)2), dalcium biphosphate (Ca (H2PO4)2)。
Described borate comprises Lithium biborate (Li3BO3), sodium borate (Na3BO3), "Antifungin". (MgB2O4)。
Described oxide comprises magnesium oxide (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), Scia (Sc2O3), oxidation
Yttrium (Y2O3)。
Wherein after nitridation calcining, then it is cooled to room temperature with the rate of temperature fall of 2～20 DEG C/min, obtains fluorescent material or block
Body, is placed in grinding grinding by block or ball is clayed into power and i.e. be can get target product.
Wherein nitridation calcination process is to be in protective atmosphere calcining 2～20 hours at a temperature of 1250～1600 DEG C.
Wherein obtaining the calcination process of presoma is that to be in protective atmosphere calcining 0.5～10 at 1000～1400 DEG C little
Time.
Described protective atmosphere is one or more in argon, nitrogen, argon hydrogen gaseous mixture, nitrogen and hydrogen mixture or ammonia.
The application in LED component of the above-mentioned fluorescent material.
The chip emission peak wavelength scope of described LED component is between 200nm～520nm.
The compound C of the present invention4-Replace N3-, owing to C is less compared with N electronegativity, C4-Compare N3-electron cloud bulking effect
Becoming apparent from, make rare earth ion 5d engery level cracking aggravate after incorporation, Stokes shift also can change, the fluorescence of powder body
The fluorescence parameter such as peak position, full half-peak breadth changes.Therefore, by adjusting the generation of above-mentioned dopant ion, it is possible to obtain different
The fluorescent material of fluorescence light normal complexion quantum efficiency.
Adjust alkaline-earth metal kind and ratio, can effectively adjust the fluorescence spectrum of powder body, it is thus achieved that the fluorescence of different colourities
Powder.This system belongs to silica-based nitrogen oxides, Si-N and Si-O forms spatial network result, by doped and substituted, such as Ge4+Replace
Si4+, Al-O (or Ga-O) replaces Si-N, changes the lattice paprmeter of crystal, thus changes the coordination ring of luminescent center ion
Border, causes change and the change of electron cloud effect of centre of luminescence engery level cracking, and then makes to obtain the fluorescence spectrum of powder body, send out
The parameters such as light efficiency change.
The concrete preparation method of fluorescent material of the present invention is as follows:
Above-mentioned MS2-yAyO2+yN2-y-4z/3CzFluorescent material, a step nitriding comprises the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion is by alkaline earth metal carbonate, silicon nitride, germanium nitride, dioxy
SiClx, germanium dioxide, rare earth oxide, aluminium oxide and alkali carbonate and carbon dust proportioning, additive synthesis press quality proportioning,
Its content is above-mentioned alkaline earth metal carbonate, silicon nitride, germanium nitride, silicon dioxide, germanium dioxide, rare earth oxide, aluminium oxide
With alkali carbonate and the 0.5%～10% of carbon dust quality sum.Then mix homogeneously, obtains raw material mixed-powder.
(2) raw material mixed-powder is placed in crucible, under protective atmosphere, crucible is imposed the heating rate of 3～30 DEG C
It is warming up to 1250～1600 DEG C, after being incubated 2～20 hours, is then cooled to room temperature with the rate of temperature fall of 2～20 DEG C/min, obtains
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent material or block.Powder body or block are placed in grinding grinding or ball grinds
End gets final product the MS of desired particle size2-yAyO2+yN2-y-4z/3Cz:RxOxynitride fluorescent powder.
By such scheme, (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion is joined
During than raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide): rare earth oxygen
Compound: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～0.8): (0～
0.1) proportioning.
By such scheme, (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometry
During than proportioning raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide): dilute
Soil oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～0.8):
(0～0.1), for keeping the amount proportioning of charge balance, alkali carbonate and rare earth ion Re ' same substance.
By such scheme, in step (1), additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), fluorination
Caesium (CsF), calcium fluoride (CaF2), Afluon (Asta) (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminium fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl), aluminum chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O), lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate
(Mg3(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium hydrogen phosphate (MgHPO4), calcium hydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), Magnesium biphosphate (Mg
(H2PO4)2), dalcium biphosphate (Ca (H2PO4)2), Lithium biborate (Li3BO3), sodium borate (Na3BO3), "Antifungin". (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), Scia (Sc2O3), yittrium oxide (Y2O3) any one or a few.Excellent
Elect potassium carbonate as.
By such scheme, in step (1), the uniform method of batch mixing is to grind in mortar or ball milling in ball mill.
By such scheme, described in step (2), crucible is alumina crucible, molybdenum crucible or tungsten crucible.
By such scheme, described in step (2), protective atmosphere is inert atmosphere or reducing atmosphere.
By such scheme, described in step (2), protective atmosphere is high pure nitrogen, high-purity argon gas, nitrogen and argon gaseous mixture,
Nitrogen and hydrogen mixed gas, argon and hydrogen mixed gas.
Above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent material, two step nitridings comprise the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion by alkaline earth metal carbonate, silicon dioxide, germanium dioxide,
Rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate proportioning, additive synthesis is by quality proportioning, and its content is above-mentioned alkali
Earth metal carbonate, silicon dioxide, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate quality sum
0.5%～10%.Then by alkaline earth metal carbonate, silicon dioxide, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and
Alkali carbonate proportioning salt mix homogeneously, i.e. preliminary mixed-powder；
(2) preliminary mixing raw material is placed in crucible, under protective atmosphere, crucible imposes the heating rate intensification of 3～30 DEG C
To 1000～1400 DEG C, after insulation 0.5～10h is fully decomposed, then it is cooled to room temperature with the rate of temperature fall of 2～20 DEG C/min,
Obtain presoma, wear into powder body by mixed for presoma, it is thus achieved that presoma powder body.
(3) by presoma powder body and silicon nitride, germanium nitride and additive synthesis with content proportioning described in step (1), uniformly
Mixing, obtains two step mixed-powders；
(4) two step mixed-powders are placed in crucible, under protective atmosphere, crucible are imposed the heating rate of 3～30 DEG C
It is warming up to 1250～1600 DEG C, after being incubated 2～20 hours, is then cooled to room temperature with the rate of temperature fall of 2～20 DEG C/min, obtains
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent material or block.Fluorescent powder or block are placed in grinding grinding or ball milling
Become powder can obtain the MS of desired particle size2-yAyO2+yN2-y-4z/3Cz:RxFluorescent material.
By such scheme, with (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion
During proportioning raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide): rare earth
Oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～0.8): (0
～0.1) proportioning.
By such scheme, with (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzChemistry meter
When amount is than proportioning raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide):
Rare earth oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～
0.8): (0～0.1), for keeping the amount proportioning of charge balance, alkali carbonate and rare earth ion Re ' same substance.
By such scheme, in step (1), additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), fluorination
Caesium (CsF), calcium fluoride (CaF2), Afluon (Asta) (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminium fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl) aluminum chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O, lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate (Mg3
(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium hydrogen phosphate (MgHPO4), calcium hydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), Magnesium biphosphate (Mg
(H2PO4)2), dalcium biphosphate (Ca (H2PO4)2), Lithium biborate (Li3BO3), sodium borate (Na3BO3), "Antifungin". (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), Scia (Sc2O3), yittrium oxide (Y2O3) any one or a few.Excellent
Elect potassium carbonate as.
By such scheme, in step (1) and (3), the uniform method of batch mixing is to grind in mortar or ball milling in ball mill.
By such scheme, described in step (2) and (4), crucible is alumina crucible, molybdenum crucible or tungsten crucible.
By such scheme, described in step (2) and (4), protective atmosphere is inert atmosphere or reducing atmosphere.
By such scheme, described in step (2) and (4), protective atmosphere is high pure nitrogen, and high-purity argon gas, nitrogen and argon are mixed
Close gas, nitrogen and hydrogen mixed gas, argon and hydrogen mixed gas.
Above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent material, two step nitriding the second realize comprising the following steps that
(1) according to chemical formula (Ca1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzOr (Ca1-t-m-n- 2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion reduced lyes earth metal carbonate, silicon dioxide, titanium dioxide
Germanium, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate, additive synthesis is by quality proportioning, and its content is above-mentioned alkaline earth
Metal carbonate, silicon dioxide, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and alkali carbonate quality sum
0.1%～10%.Then by alkaline earth metal carbonate, silicon dioxide, germanium dioxide, rare earth oxide, aluminium oxide, gallium oxide and
Alkali carbonate and additive synthesis mix homogeneously, obtain and tentatively mix raw material；
(2) preliminary mixing raw material is placed in crucible, under protective atmosphere, crucible imposes the heating rate intensification of 3～30 DEG C
To 1000～1400 DEG C, after being incubated abundant decomposition in 0.5～10 hour, then it is cooled to room with the rate of temperature fall of 2～20 DEG C/min
Temperature, then obtains presoma powder body or block, is ground into the powder of desired particle size, it is thus achieved that precursor powder.
(3) precursor powder and silicon nitride, germanium nitride grinding or ball milling are uniformly mixed, obtain two step mixed-powders；
(4) two step mixed-powders are placed in crucible, under protective atmosphere, crucible are imposed the heating rate of 3～30 DEG C
It is warming up to 1250～1600 DEG C, after being incubated 2～20 hours, is then cooled to room temperature with the rate of temperature fall of 2～20 DEG C/min, obtains
Rear-earth-doped MS2-yAyO2+yN2-y-4z/3CzFluorescent material or block.Powder body or block are placed in grinding grinding or ball is clayed into power
I.e. can get the MS of desired particle size2-yAyO2+yN2-y-4z/3Cz:RxFluorescent material.
By such scheme, with (Ca in step (1)1-t-m-n-xMgtSrmBanRex)S2-yAyO2+yN2-y-4z/3CzStoichiometric proportion
During proportioning raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide): rare earth
Oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～0.8): (0
～0.1) proportioning.
By such scheme, with (Ca in step (1)1-t-m-n-2xMgtSrmBanRe’xLx)S2-yAyO2+yN2-y-4z/3CzChemistry meter
When amount is than proportioning raw material, proportioning raw materials is alkaline earth metal carbonate: (silicon nitride+germanium nitride): (silicon dioxide+germanium dioxide):
Rare earth oxide: (aluminium oxide+gallium oxide): carbon dust is (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～
0.8): (0～0.1), for keeping the amount proportioning of charge balance, alkali carbonate and rare earth ion Re ' same substance.
By such scheme, in step (1), additive synthesis is lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), fluorination
Caesium (CsF), calcium fluoride (CaF2), Afluon (Asta) (MgF2), strontium fluoride (SrF2), barium fluoride (BaF2), ammonium fluoride (NH4F), aluminium fluoride
(AlF3), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), calcium chloride (CaCl2), magnesium chloride
(MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), ammonium chloride (NH4Cl) aluminum chloride (AlCl3), lithium carbonate (Li2CO3)、
Sodium carbonate (Na2CO3), potassium carbonate (K2CO3), cesium carbonate (Cs2CO3), magnesium carbonate (MgCO3), basic magnesium carbonate (4MgCO3·Mg
(OH)2·5H2O, lithium phosphate (Li3PO4), sodium phosphate (Na3PO4), potassium phosphate (K3PO4), phosphoric acid caesium (Cs3PO4), magnesium phosphate (Mg3
(PO4)2), calcium phosphate (Ca3(PO4)2), strontium phosphate (Sr3(PO4)2), barium phosphate (Ba3(PO4)2), disodium-hydrogen
(Na2HPO4), magnesium hydrogen phosphate (MgHPO4), calcium hydrogen phosphate (CaHPO4), strontium monophosphate (SrHPO4), barium hydrogen phosphate (BaHPO4)、
Lithium dihydrogen phosphate (LiH2PO4), sodium dihydrogen phosphate (NaH2PO4), potassium dihydrogen phosphate (KH2PO4), Magnesium biphosphate (Mg
(H2PO4)2), dalcium biphosphate (Ca (H2PO4)2), Lithium biborate (Li3BO3), sodium borate (Na3BO3), "Antifungin". (MgB2O4), oxygen
Change magnesium (MgO), zinc oxide (ZnO), aluminium oxide (Al2O3), Scia (Sc2O3), yittrium oxide (Y2O3) any one or a few.Excellent
Elect potassium carbonate as.
By such scheme, in step (1) and (3), the uniform method of batch mixing is to grind in mortar or ball milling in ball mill.
By such scheme, described in step (2) and (4), crucible is alumina crucible, molybdenum crucible or tungsten crucible.
By such scheme, described in step (2) and (4), protective atmosphere is inert atmosphere or reducing atmosphere.
By such scheme, described in step (2) and (4), protective atmosphere is high pure nitrogen, and high-purity argon gas, nitrogen and argon are mixed
Close gas, nitrogen and hydrogen mixed gas, argon and hydrogen mixed gas.
The implementation method of above-mentioned illuminating device is:
The LED adhesive of encapsulation includes but not limited to silicones, and comprises above-mentioned rear-earth-doped MS2-yAyO2+yN2-y-4z/ 3Cz:RxThe fluorescent material of fluorescent material is as the composition that mainly comprises of encapsulating compound, encapsulation blue light or UV LED chip, it is thus achieved that white light LEDs
Device.
Compared with prior art, the invention has the beneficial effects as follows:
First, present invention process is simple, and especially one step nitriding shortens synthesis cycle, and easily realizes technique metaplasia
Produce；
Second, by adjusting kind and the content of additive synthesis, the crystallite dimension of powder body, degree of crystallinity, crystalline substance can be controlled flexibly
Lattice integrity and grain morphology.
3rd, the present invention prepares rear-earth-doped MS2-yAyO2+yN2-y-4z/3Cz:RxThe excitation wavelength range of fluorescent material is
250～520nm, excitation wavelength range width, fluorescence intensity is high, all can use on UV LED chip or blue chip.
4th, the present invention prepares rear-earth-doped MS2-yAyO2+yN2-y-4z/3Cz:RxFluorescent material and other color fluorescence powder,
Specifically with green powder, bloom, Hydrargyri Oxydum Rubrum hybrid package blue light or UV LED chip, easily obtain the white light LEDs that display index is excellent
Device.
Accompanying drawing explanation
Fig. 1 is (Ba in embodiment one0.993-m-nSrmCanEu0.007)Si2O2N1.996C0.003Excitation and emission spectra figure.
Wherein curve 1 is m=0.1, n=0；Curve 2 is m=0.2, n=0；Curve 3 is m=0, n=0.1；Curve 4 is m=0, n=
0.4；Curve 5 is m=0.05, n=0.05；Curve 6 is m=0.1, n=0.1.
Fig. 2 is the excitation and emission spectra of gained sample in embodiment two and reference example one.
Fig. 3 is gained Sample Scan ultramicroscope display figure in embodiment two.
Fig. 4 is the scanning electron microscope display figure of institute's sample in embodiment three.
Fig. 5 is gained sample and LuAG:Ce in embodiment two3+Green powder and (SrCa) AlSiN3:Eu2+Encapsulation blue-ray LED core
Spectrogram before and after sheet 100W module group aging.
Fig. 6 is X-ray diffraction (XRD) figure of gained sample in embodiment four.
Fig. 7 is that in embodiment four, the fluorescence spectrum of gained sample varies with temperature figure
Fig. 8 is gained sample heat stability testing result in embodiment four and reference example two.
Fig. 9 is the particle size distribution figure of gained sample in embodiment four.
Figure 10 is the basic structure of white light LED part in embodiment seven, reference example three and reference example four.Transmitted wave is a length of
The InGaN blue chip 1 of 460nm, it embeds in the groove 6 in lighttight encapsulating structure 10.Chip 1 one end is straight with electrode 3
Connecing connected, the other end is connected with electrode 4 through wire 2.Filling with encapsulating compound 5 in groove 6, encapsulating compound is with fluorescent material 7 and glue
For mainly comprising.Fluorescent material 7 comprises middle rare earth of the present invention doping MS2-yAyO2+yN2-y-4z/3Cz:RxForm with other fluorescent material.Recessed
The wall 8 of groove 6 has high reflection, with the light reflecting chip and fluorescent material sends.9 is that high printing opacity protects mould.
Figure 11 is the spectrum of white light LEDs in embodiment seven and reference example three.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment one
Reaction raw materials 35.24g brium carbonate, 2.96g strontium carbonate, 0g calcium carbonate, 5.64g silicon dioxide, 15.24g silicon nitride,
0.24g europium oxide and 0.01g high purity graphite powder are placed in ground and mixed 30min in ceramic mortar and obtain mixture, by mixture mistake
Load in alumina crucible after 100 mesh sieves and calcine in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen gaseous mixture
(hydrogen content 10%), throughput is 0.3L/min, is warming up to 1490 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours,
Room temperature is cooled to the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.Products therefrom through the most ground 120 mesh sieves,
I.e. can get blue-green fluorescent powder (BaSr) Si2O2N1.996C0.003:Eu2+.In Fig. 1, curve 1 is for being somebody's turn to do (BaSr)
Si2O2N1.996C0.003:Eu2+Excitation and emission spectra.
Adjust brium carbonate, strontium carbonate, the proportioning of calcium carbonate, Different Alkali metal substituted aeruginous yellow fluorescence can be obtained
Powder.
Form 1 lists the composition quality of different proportion of composing.
The form 1, (Ba of different m, n value0.993‐m‐nSrmCanEu0.007)Si2O2N1.996C0.003Quality proportioning
Embodiment two
Reaction raw materials 64.68g brium carbonate, 9.31g silicon dioxide, 25.14g silicon nitride, 0.40g europium oxide, 1.12g carbonic acid
Potassium and 0.015g high purity graphite powder are placed in ground and mixed 30min in ceramic mortar and obtain mixture, after mixture is crossed 100 mesh sieves
Load in alumina crucible and calcine in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen gaseous mixture (hydrogen content
10%), throughput is 0.3L/min, is warming up to 1510 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours, with 10 DEG C/min
Rate of temperature fall be cooled to 700 DEG C after cool to room temperature with the furnace.Products therefrom is through the most ground 120 mesh sieves, i.e. available blue
Green emitting phosphor BaSi2O2N1.996C0.003:Eu2+.In Fig. 2, curve 2 is the excitation and emission spectra of this sample, contrasts reference example one
Spectrum, it can be seen that doped portion C replaces, and fluorescence spectrum red shift, fluorescence emission peak wavelength moves to long-wave band.This sample of Fig. 3
Scanning electron microscope display figure.Comparative example three is it can be seen that adding assistant crystal growth is the most regular.Fig. 5 is this sample
And LuAG:Ce3+Green powder and (SrCa) AlSiN3:Eu2+Spectrogram before and after encapsulation blue-light LED chip 100W module group aging.
Reference example one
Reaction raw materials 64.68g brium carbonate, 9.31g silicon dioxide, 25.14g silicon nitride, 0.40g europium oxide, 1.12g carbonic acid
Potassium is placed in ground and mixed 30min in ceramic mortar and obtains mixture, mixture is crossed load after 100 mesh sieves in alumina crucible
Horizontal pipe furnace is calcined.Being passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%) in calcination process, throughput is
0.3L/min, is warming up to 1510 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours, lowers the temperature with the rate of temperature fall of 10 DEG C/min
Room temperature is cooled to the furnace after 700 DEG C.Products therefrom, through the most ground 120 mesh sieves, i.e. can get blue-green fluorescent powder
(BaEu)Si2O2N2.In Fig. 2, curve 1 is the excitation and emission spectra of this sample.
Embodiment three
Reaction raw materials 64.68g brium carbonate, 9.31g silicon dioxide, 25.14g silicon nitride, 0.40g europium oxide and 0.015g are high
Pure graphite is placed in ground and mixed 30min in ceramic mortar and obtains mixture, loads alumina crucible after mixture is crossed 100 mesh sieves
In calcine in horizontal pipe furnace.Being passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%) in calcination process, throughput is
0.3L/min, is warming up to 1510 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours, lowers the temperature with the rate of temperature fall of 10 DEG C/min
Room temperature is cooled to the furnace after 700 DEG C.Products therefrom ground mistake 120 mesh sieve, i.e. can get blue-green fluorescent powder (BaEu)
Si2O2N1.996C0.003。
It Fig. 4 is the scanning electron microscope display figure of this sample.
Embodiment four
Reaction raw materials 130.64g brium carbonate, 18.83g silicon dioxide, it is mixed that 0.82g europium oxide is placed in ceramic mortar grinding
Close 30min and obtain mixture, load in alumina crucible after mixture is crossed 100 mesh sieves and calcine in horizontal pipe furnace.
Being passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%) in calcination process, throughput is 0.2L/min, with the intensification of 8 DEG C/min
Ramp, to 1190 DEG C, after being incubated 2 hours, cools to room temperature with the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Products therefrom, through the most ground 100 mesh sieves, i.e. obtains precursor powder.By 120g precursor powder, 50.33g silicon nitride,
1.55g potassium carbonate and 0.03g high purity graphite are placed in ground and mixed 30min in ceramic mortar and obtain mixture, and mixture is crossed 100
Load in alumina crucible after mesh sieve and calcine in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen gaseous mixture (hydrogen
Gas content 10%), throughput is 0.3L/min, is warming up to 1450 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours, with 10
DEG C/rate of temperature fall of min cools to room temperature with the furnace after being cooled to 700 DEG C.Products therefrom, through the most ground 120 mesh sieves, also may be used
Obtain the blue-green fluorescent powder of Eu doping.Fig. 6 is X-ray diffraction (XRD) collection of illustrative plates of this sample.Fig. 7 is this fluorescent spectrum
Vary with temperature figure.Fig. 8 curve 1 is the thermally-stabilised test result of this sample, and in contrast reference example two, the sample heat of undoped p C is steady
Qualitative test result, doping C heat stability when more than 200 DEG C optimizes substantially.
Fig. 9 is the particle size distribution chart of this sample, and particle size distribution shows can well control grain size and granule chi
Very little distribution.
Reference example two
Reaction raw materials 130.64g brium carbonate, 18.83g silicon dioxide, it is mixed that 0.82g europium oxide is placed in ceramic mortar grinding
Close 30min and obtain mixture, load in alumina crucible after mixture is crossed 100 mesh sieves and calcine in horizontal pipe furnace.
Being passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%) in calcination process, throughput is 0.2L/min, with the intensification of 8 DEG C/min
Ramp, to 1190 DEG C, after being incubated 2 hours, cools to room temperature with the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Products therefrom, through the most ground 100 mesh sieves, i.e. obtains precursor powder.By 120g precursor powder, 50.33g silicon nitride,
1.55g potassium carbonate is placed in ground and mixed 30min in ceramic mortar and obtains mixture, loads oxidation after mixture is crossed 100 mesh sieves
Aluminum crucible is calcined in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%), gas
Flow is 0.3L/min, is warming up to 1450 DEG C with the heating rate of 8 DEG C/min, after being incubated 8 hours, with the cooling speed of 10 DEG C/min
Rate cools to room temperature with the furnace after being cooled to 700 DEG C.Products therefrom, through the most ground 120 mesh sieves, also can get the indigo plant of Eu doping
Green emitting phosphor BaSi2O2N2:Eu2+.In Fig. 8, curve 2 is the thermally-stabilised test result of this sample.
Embodiment five
Reaction raw materials 39.07g brium carbonate, 5.74g silicon dioxide, 13.68g silicon nitride, 0.21g germanium dioxide, 0.51g oxygen
Change aluminum, 0.35g europium oxide and 0.005g high purity graphite powder are placed in ground and mixed 30min in ceramic mortar and obtain mixture, will be mixed
Compound loads in alumina crucible after crossing 100 mesh sieves to be calcined in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen
Gaseous mixture (hydrogen content 10%), throughput is 0.3L/min, is warming up to 1450 DEG C with the heating rate of 8 DEG C/min, and insulation 8 is little
Shi Hou, cools to room temperature with the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.Products therefrom ground mistake 120 mesh sieve,
I.e. can get bottle green fluorescent material (BaEu) (SiGe)1.95Al0.05O2.05N1.95C0.003。
Embodiment six
Reaction raw materials 38.64g brium carbonate, 0.30g strontium carbonate, 6.02g silicon dioxide, 0.19g gallium oxide, 0.10g aoxidize
Aluminum, 0.35g europium oxide are placed in ground and mixed 30min in ceramic mortar and obtain mixture, load oxygen after mixture is crossed 100 mesh sieves
Change in aluminum crucible and calcine in horizontal pipe furnace.Calcination process is passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%),
Throughput is 0.2L/min, is warming up to 1150 DEG C with the heating rate of 8 DEG C/min, after being incubated 2 hours, with the cooling of 10 DEG C/min
Speed cools to room temperature with the furnace after being cooled to 700 DEG C.Products therefrom, through the most ground 100 mesh sieves, i.e. obtains precursor powder.
35g precursor powder, 13.28g silicon nitride, 0.014g high purity graphite powder and 0.283g LiF are placed in ceramic mortar grinding mixed
Close 30min and obtain mixture, load in alumina crucible after mixture is crossed 100 mesh sieves and calcine in horizontal pipe furnace.
Being passed through nitrogen-hydrogen gaseous mixture (hydrogen content 10%) in calcination process, throughput is 0.3L/min, with the intensification of 8 DEG C/min
Ramp, to 1400 DEG C, after being incubated 8 hours, cools to room temperature with the furnace after being cooled to 700 DEG C with the rate of temperature fall of 10 DEG C/min.
Products therefrom, through the most ground 120 mesh sieves, also can get bottle green fluorescent material (BaSr) Si of Eu doping1.98(AlGa)0.02O2.02N1.972C0.006:Eu2+。
Form 2 shows that the chemical composition of sample in doping synthetic example and synthetic method and auxiliary agent select.
Form 2, embodiment overview
Embodiment seven
Fluorescent material (the emission peak λ that will be obtained by the synthetic method of embodiment twoem=501nm) and LuAG:Ce3+Green powder
(emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm) weigh with mass ratio 3.3:1.9:2.4,
With fluorescent material: glue=0.13:0.87 mass, than proportioning, uniformly after mixing, encapsulates InGaN blue chip (λex=460nm), warp
After some glue, baking, pressing mold, separation, obtain comprising the high display White-light LED illumination device of this invention fluorescent powder packaging.
Figure 10 is the basic structure of this encapsulation white light LED part.The InGaN blue chip 1 of a length of 460nm of transmitted wave, its
Embed in the groove 6 in lighttight encapsulating structure 10.Chip 1 one end is joined directly together with electrode 3, and the other end is through wire 2 and electricity
Pole 4 is connected.Filling with encapsulating compound 5 in groove 6, encapsulating compound is with fluorescent material 7 and glue for mainly comprising.Fluorescent material 7 comprises this
Invention middle rare earth doping MS2-yAyO2+yN2-y-4z/3Cz:RxForm with other fluorescent material.The wall 8 of groove 6 has high reflection, with
The light that reflection chip and fluorescent material send.9 is that high printing opacity protects mould.
In Figure 11,501N# is added to use the spectrum of this fluorescent powder packaging white light LEDs, and in form 3,501N# is added to use
15 kinds of color rendering indexs of this fluorescent material.
Reference example three
Use LuAG:Ce3+Green powder (emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm)
Weighing with mass ratio 2.1:2.4, with fluorescent material: glue=0.12:0.88 mass is than proportioning, uniformly after mixing, encapsulation InGaN is blue
Optical chip (λex=460nm), after a glue, baking, pressing mold, separation, the high display obtaining comprising this invention fluorescent powder packaging is white
Light LED illumination device.Figure 10 is the basic structure of this encapsulation white light LED part.Figure 11 is not added with for not using the present invention
The spectrum of fluorescent powder packaging white light LEDs.Form 3 is not added with 15 kinds of color rendering indexs for using this fluorescent material.Comparative example
White light LED part is obtained, it is found that the display index using the white light LEDs of the fluorescent powder packaging of present invention acquisition is exhausted in seven
Major part improves, and average display index promotes, and represents saturated blue colors display index R12 and is obviously improved.
Reference example four
Fluorescent material (the emission peak λ obtained with reference to the synthetic method of example oneem=500nm) and LuAG:Ce3+Green powder
(emission peak λem=525nm) and (SrCa) AlSiN3:Eu2+(emission peak λem=628nm) weigh with mass ratio 3.2:1.9:2.3,
With fluorescent material: glue=0.13:0.87 mass, than proportioning, uniformly after mixing, encapsulates InGaN blue chip (λex=460nm), warp
After some glue, baking, pressing mold, separation, obtain comprising the high display White-light LED illumination device of this invention fluorescent powder packaging.Figure 10 is
The basic structure of this encapsulation white light LED part.In form 3,500N# is added to 15 kinds of display indexes of this encapsulation white light LEDs.Right
Display exponent data than 501N#, it can be seen that the display index overwhelming majority adding 501N# sample is improved, particularly
It is common display index (R1～R8).
Form 3, use the present invention and do not use the present invention and LuAG:Ce3+Green powder and (SrCa) AlSiN3:Eu2+Hydrargyri Oxydum Rubrum seals
Dress white light LEDs display index contrast
| R1 | R2 | R3 | R4 | R5 | R6 | R7 | R8 | R9 | R10 | R11 | R12 | R13 | R14 | R15 | |
| 501N# adds | 96 | 97 | 99 | 98 | 96 | 95 | 98 | 96 | 89 | 96 | 96 | 81 | 96 | 98 | 92 |
| 500N# adds | 95 | 96 | 98 | 98 | 95 | 94 | 98 | 96 | 88 | 95 | 96 | 81 | 95 | 98 | 93 |
| It is not added with | 96 | 98 | 95 | 95 | 95 | 93 | 97 | 95 | 87 | 93 | 96 | 71 | 98 | 97 | 96 |
Claims (18)
1. a rare earth doping fluorescent powder, its molecular formula is MS2-yAyO2+yN2-y-4z/3Cz:Rx, wherein in M=Mg, Ca, Sr, Ba
One or more, S is one or more in Si, Ge, and A is Al, one or more in Ga, and R is the one in rare earth ion
Or multiple, 0.001≤x≤0.2,0≤y≤0.8,0 < z≤0.1, O represent oxygen atom, and N represents nitrogen-atoms, and C represents carbon atom.
Rare earth doping fluorescent powder the most according to claim 1, wherein 0.001≤x≤0.1,0≤y≤0.1,0 < z≤
0.05。
Rare earth doping fluorescent powder the most according to claim 1, wherein molecular formula is (Ca1-t-m-n-xMgtSrmBanRe’xLx)
S2-yAyO2+yN2-y-4z/3Cz, wherein Re ' is trivalent rare earth ions Ce3+、La3+、Pr3+、Sm3+、Tb3+、Dy3+In one or many
Kind, L is alkali metal ion Li+、Na+, K+In one or more, 0≤m, n, t≤1,0.001≤x≤0.1.
Rare earth doping fluorescent powder the most according to claim 1, wherein molecular formula (Ca1-t-m-n-xMgtSrmBanRex)S2- yAyO2+yN2-y-4z/3Cz, wherein Re is bivalent rare earth ion Eu2+、Yb2+、Sm2+In one or more, 0≤m, n, t≤1,
0.001≤x≤0.1。
5., according to the rare earth doping fluorescent powder described in claim 3 or 4, wherein molecular formula S is Si or Si Yu Ge combination, and A is Al
Or the combination of Al Yu Ga, Re is Eu2+。
Rare earth doping fluorescent powder the most according to claim 5, wherein t=0, y=0.
7., according to the arbitrary described rare earth doping fluorescent powder of claim 1-6, the transmitting boundary of fluorescent material is 460nm～580nm,
Fluorescence emission peak wavelength is between 470～520nm.
8. the preparation method of the arbitrary described rare earth doping fluorescent powder of claim 1-7, uses a step nitriding or the nitridation of two steps
Method prepares,
A described step nitriding is the carbonate measuring M according to molecular formula, the oxide of S and S nitride, A oxide, rare earth
Element oxide, carbon containing simple substance or carbonaceous organic material, some mix with additive synthesis, grind gained fluorescent material after nitridation calcining
Body；
The step of described two step nitridings is to measure the carbonate of M, the oxide of S, A oxide, R oxide according to molecular formula
And obtain presoma after carbon containing simple substance or carbonaceous organic material mixed calcining, after being ground by presoma and S nitride and additive synthesis
Mixing, carries out nitridation calcining the most again, also can obtain fluorescent powder；
Or measure the carbonate of M, the oxide of S, A oxide and rare earth oxide mixed calcining according to molecular formula
After obtain presoma, will presoma grind after and S nitride, carbon containing simple substance or carbonaceous organic material and additive synthesis mixing, then
Carry out nitridation calcining again, also can obtain fluorescent powder.
Preparation method the most according to claim 1, described carbon containing simple substance is activated carbon powder or graphite powder, and carbonaceous organic material is
Sucrose, glucose or maltose.
Preparation method the most according to claim 8, the wherein carbonate of M, S nitride, S oxide, R oxide, A oxygen
Compound, is stoichiometrically (1.8～2.2): (0.8～1.2): 1:(0.001～0.1): (0～0.8), auxiliary agent is joined by quality
Ratio, its content is the carbonate of M, the oxide of S and S nitride, A oxide, rare earth oxide, carbon containing simple substance or carbon containing
The 0.2%～10% of Organic substance summation.
11. preparation methoies according to claim 8, described auxiliary agent is fluoride, chloride, carbonate, phosphate, boric acid
One or more in salt, oxide, boric acid.
12. preparation methoies according to claim 11, described fluoride comprises lithium fluoride, sodium fluoride, potassium fluoride, fluorination
Caesium, calcium fluoride, Afluon (Asta), strontium fluoride, barium fluoride, ammonium fluoride, aluminium fluoride；
Described chloride comprises lithium chloride, sodium chloride, potassium chloride, cesium chloride, calcium chloride, magnesium chloride, strontium chloride, barium chloride, chlorine
Change ammonium, aluminum chloride；
Described carbonate comprises lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, basic magnesium carbonate；
Described phosphate comprises lithium phosphate, sodium phosphate, potassium phosphate, phosphoric acid caesium, magnesium phosphate, calcium phosphate, strontium phosphate, barium phosphate, phosphorus
Acid one hydrogen sodium, magnesium hydrogen phosphate, calcium hydrogen phosphate, strontium monophosphate, barium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, biphosphate
Potassium, Magnesium biphosphate, dalcium biphosphate；
Described borate comprises Lithium biborate, sodium borate, "Antifungin".；
Described oxide comprises magnesium oxide, zinc oxide, aluminium oxide, Scia, yittrium oxide.
13. preparation methoies according to claim 8, wherein after nitridation calcining, cool down with the rate of temperature fall of 2～20 DEG C/min
To room temperature, obtain fluorescent material or block, block is placed in grinding grinding or ball is clayed into power and i.e. be can get target product.
14. preparation methoies according to claim 8, wherein nitridation calcination process is to locate at a temperature of 1250～1600 DEG C
Calcine 2～20 hours in protective atmosphere.
15. preparation methoies according to claim 8, the calcination process wherein obtaining presoma is at 1000～1400 DEG C
It is in protective atmosphere calcining 2～10 hours.
16. according to the preparation method described in claims 14 or 15, and described protective atmosphere is argon, nitrogen, argon hydrogen gaseous mixture, nitrogen
One or more in hydrogen gaseous mixture or ammonia.
The application in LED component of the 17. claim 1-7 arbitrary described rare earth doping fluorescent powder.
18. application according to claim 17, the chip emission peak wavelength scope of described LED component at 200nm～
Between 520nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610384438.3A CN106047341B (en) | 2016-06-02 | 2016-06-02 | A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610384438.3A CN106047341B (en) | 2016-06-02 | 2016-06-02 | A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106047341A true CN106047341A (en) | 2016-10-26 |
| CN106047341B CN106047341B (en) | 2019-01-22 |
Family
ID=57173025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610384438.3A Active CN106047341B (en) | 2016-06-02 | 2016-06-02 | A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106047341B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312538A (en) * | 2017-07-14 | 2017-11-03 | 北京宇极科技发展有限公司 | A kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content |
| WO2019109867A1 (en) * | 2017-12-06 | 2019-06-13 | 佛山市国星光电股份有限公司 | White led device and manufacturing method thereof, and led lamp |
| CN111073645A (en) * | 2019-12-28 | 2020-04-28 | 中国科学院长春光学精密机械与物理研究所 | Broadband fluorescent powder, preparation method thereof, application of broadband fluorescent powder and light-emitting device |
| CN111909590A (en) * | 2020-08-14 | 2020-11-10 | 段晓静 | Preparation method of antirust flame-retardant fluorescent paint |
| CN113607699A (en) * | 2021-07-30 | 2021-11-05 | 中钞印制技术研究院有限公司 | Luminescent product, authenticity detection method and system, anti-counterfeiting element and anti-counterfeiting article |
| CN113604221A (en) * | 2021-07-30 | 2021-11-05 | 中钞印制技术研究院有限公司 | Luminescent material, authenticity detection method and system thereof, anti-counterfeiting element and anti-counterfeiting article |
| CN114084880A (en) * | 2021-10-19 | 2022-02-25 | 中国科学院福建物质结构研究所 | K3Sc3(PO4)(PO3F)2F5Compound, nonlinear optical crystal and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917978A (en) * | 2010-05-14 | 2013-02-06 | 渲染材料公司 | Carbonitride based phosphors and light emitting devices using the same |
| CN102939355A (en) * | 2010-05-14 | 2013-02-20 | 渲染材料公司 | Oxycarbonitride phosphors and light emitting devices using the same |
| CN103305215A (en) * | 2012-03-08 | 2013-09-18 | 株式会社东芝 | Phosphors and method for producing thereof |
| WO2015135888A1 (en) * | 2014-03-13 | 2015-09-17 | Koninklijke Philips N.V. | Supertetrahedron phosphor for solid-state lighting |
| CN105018080A (en) * | 2015-07-23 | 2015-11-04 | 北京宇极科技发展有限公司 | Method for preparing high-efficiency phosphor powder |
-
2016
- 2016-06-02 CN CN201610384438.3A patent/CN106047341B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917978A (en) * | 2010-05-14 | 2013-02-06 | 渲染材料公司 | Carbonitride based phosphors and light emitting devices using the same |
| CN102939355A (en) * | 2010-05-14 | 2013-02-20 | 渲染材料公司 | Oxycarbonitride phosphors and light emitting devices using the same |
| CN103305215A (en) * | 2012-03-08 | 2013-09-18 | 株式会社东芝 | Phosphors and method for producing thereof |
| WO2015135888A1 (en) * | 2014-03-13 | 2015-09-17 | Koninklijke Philips N.V. | Supertetrahedron phosphor for solid-state lighting |
| CN105018080A (en) * | 2015-07-23 | 2015-11-04 | 北京宇极科技发展有限公司 | Method for preparing high-efficiency phosphor powder |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312538A (en) * | 2017-07-14 | 2017-11-03 | 北京宇极科技发展有限公司 | A kind of synthetic method of the high brightness nitric oxide fluorescent powder of high nitrogen content |
| CN107312538B (en) * | 2017-07-14 | 2020-05-22 | 北京宇极科技发展有限公司 | Synthetic method of high-nitrogen-content high-brightness nitrogen oxide fluorescent powder |
| WO2019109867A1 (en) * | 2017-12-06 | 2019-06-13 | 佛山市国星光电股份有限公司 | White led device and manufacturing method thereof, and led lamp |
| CN111073645A (en) * | 2019-12-28 | 2020-04-28 | 中国科学院长春光学精密机械与物理研究所 | Broadband fluorescent powder, preparation method thereof, application of broadband fluorescent powder and light-emitting device |
| CN111073645B (en) * | 2019-12-28 | 2021-03-19 | 中国科学院长春光学精密机械与物理研究所 | Broadband fluorescent powder, preparation method thereof, application of broadband fluorescent powder and light-emitting device |
| CN111909590A (en) * | 2020-08-14 | 2020-11-10 | 段晓静 | Preparation method of antirust flame-retardant fluorescent paint |
| CN113607699A (en) * | 2021-07-30 | 2021-11-05 | 中钞印制技术研究院有限公司 | Luminescent product, authenticity detection method and system, anti-counterfeiting element and anti-counterfeiting article |
| CN113604221A (en) * | 2021-07-30 | 2021-11-05 | 中钞印制技术研究院有限公司 | Luminescent material, authenticity detection method and system thereof, anti-counterfeiting element and anti-counterfeiting article |
| CN114084880A (en) * | 2021-10-19 | 2022-02-25 | 中国科学院福建物质结构研究所 | K3Sc3(PO4)(PO3F)2F5Compound, nonlinear optical crystal and preparation method and application thereof |
| CN114084880B (en) * | 2021-10-19 | 2023-05-09 | 中国科学院福建物质结构研究所 | K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compound, nonlinear optical crystal, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106047341B (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106047341B (en) | A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device | |
| KR100969836B1 (en) | Phosphor and light emission appliance using phosphor | |
| JP4362625B2 (en) | Method for manufacturing phosphor | |
| CN103881706A (en) | Nitrogen oxide fluorescent powder, preparation method thereof and luminescent device containing the fluorescent powder | |
| WO2011094937A1 (en) | Terbium doped phosphate-based green luminescent material and preparation method thereof | |
| CN101307228B (en) | Chlorine-aluminosilicate fluorescent powder and method for preparing same | |
| CN103045267B (en) | Nitride fluorescent powder and preparation method thereof, luminescent device containing fluorescent powder | |
| CN104962286A (en) | Garnet-structure multiphase fluorescent material and preparation method thereof | |
| JP5563542B2 (en) | Aluminate compound phosphor | |
| CN103184048B (en) | Composite fluorescent material and preparation method thereof | |
| Sun et al. | A novel reddish-orange-emitting phosphor Ca3Gd7 (PO4)(SiO4) 5O2: Sm3+ for white light-emitting diodes | |
| CN107163934B (en) | Quadrivalent manganese ion doped fluorine aluminum oxide lithium red fluorescent powder and preparation method thereof | |
| CN113549458B (en) | High-color-rendering trivalent Eu ion-doped red fluorescent material based on apatite structure and preparation method thereof | |
| CN112920801B (en) | Red light fluorescent powder material and preparation method thereof | |
| CN105820817B (en) | A kind of scandate green emitting phosphor and preparation method thereof | |
| CN101560392A (en) | Stable aluminate-based phosphor powder, preparing method and application thereof | |
| CN102994075A (en) | Silicon-based nitrogen oxide green phosphor | |
| CN110272740B (en) | Zero-doped rare earth borate red fluorescent powder, preparation and application thereof in L ED field | |
| CN113999671A (en) | Fluorescent powder for lighting display white light LED and preparation and application thereof | |
| CN113201341A (en) | Alkali metal charge compensation type aluminum phosphate red luminescent material and preparation method and application thereof | |
| CN106867524B (en) | A kind of preparation and application of alkaline earth aluminate blue fluorescent material | |
| CN104804742B (en) | Red fluorescent powder for white light LED and preparation method thereof | |
| WO2014091776A1 (en) | Phosphor, method for producing same, and light emitting device | |
| CN110591712A (en) | Single-matrix multicolor fluorescent powder for ultraviolet LED and preparation method thereof | |
| CN103184047A (en) | A group of compound fluorescent materials and a preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |