CN106833639A - A kind of white light LEDs phosphate base luminescent material and its preparation method and application - Google Patents
A kind of white light LEDs phosphate base luminescent material and its preparation method and application Download PDFInfo
- Publication number
- CN106833639A CN106833639A CN201610947278.9A CN201610947278A CN106833639A CN 106833639 A CN106833639 A CN 106833639A CN 201610947278 A CN201610947278 A CN 201610947278A CN 106833639 A CN106833639 A CN 106833639A
- Authority
- CN
- China
- Prior art keywords
- compound
- white light
- luminescent material
- carbonate
- light leds
- 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
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 31
- 239000010452 phosphate Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002585 base Substances 0.000 claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052771 Terbium Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 239000010431 corundum Substances 0.000 claims description 11
- 229910001940 europium oxide Inorganic materials 0.000 claims description 11
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 11
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 11
- 239000011656 manganese carbonate Substances 0.000 claims description 11
- 229940093474 manganese carbonate Drugs 0.000 claims description 11
- 235000006748 manganese carbonate Nutrition 0.000 claims description 11
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 11
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- -1 oxalate compound Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 150000003752 zinc compounds Chemical class 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- 150000003438 strontium compounds Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 150000002178 europium compounds Chemical class 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 241001062009 Indigofera Species 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000005284 excitation Effects 0.000 description 17
- 238000000295 emission spectrum Methods 0.000 description 16
- 238000000695 excitation spectrum Methods 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 150000003502 terbium compounds Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to phosphor technical field, a kind of white light LEDs phosphate base luminescent material and its preparation method and application is disclosed.The chemical expression of the material is Sr9‑a‑cZn1‑bA(PO4)7:aEu2+,bMn2+,cTb3+；A is alkali metal Li, Na, K or Rb；A is Eu2+Doping content, 0 ＜ a≤0.1, b is Mn2+Doping content, 0≤b≤0.5, c is Tb3+Doping content, 0≤c≤0.7.Present invention process flow is simple, and synthesis condition is easily realized and controllable, is adapted to large-scale production.Products obtained therefrom of the present invention is applied to black light LED chip, can produce the blue light needed for synthesizing white light, green glow and feux rouges, meets the demand in White-light LED illumination field.
Description
Technical field
The invention belongs to phosphor technical field, more particularly to a kind of white light LEDs phosphate base luminescent material
And its preparation method and application.
Background technology
White light LEDs are a kind of novel green lighting sources, and it has long lifespan, and efficiency is high, small volume, compact conformation, weight
Amount is light, the various features such as energy-conserving and environment-protective.This light source can be widely applied to display screen, instrument, car light, indoor and outdoor lighting etc..Mesh
Preceding white light LEDs are considered as forth generation solid-state illumination light source, will replace traditional lighting source such as fluorescent lamp, incandescent lamp, and
Enjoy wideling popularize for country.
Currently, mainly there is two ways using LED chip synthesis white light：(1) by RGB three-primary color LED chip packages one
Rise.Although the method is efficiently, high cost, heating is serious, is not easy as use time extends each LED chip luminous parameters
Control is consistent.(2) blue-light LED chip is equipped with yellow fluorescent powder (such as YAG:Ce3+), the light that the two sends is white by being formed after mixing
Light.But the white light that this method is obtained causes colour rendering index relatively low due to the missing of red color light component, and colour temperature is higher.(3) using near
Ultraviolet leds chip is excited and feux rouges, green glow, and blue light three primary colours mixed fluorescent powders obtains white light.
Therefore, the fluorescent material suitable for black light LED chip of synthesizing new is for realizing high color rendering index (CRI), low colour temperature
White light is extremely necessary.Phosphate material is due to stable in properties, and raw material is cheap and easy to get, and synthesis condition is gentle, all the time
By the concern and research of numerous scholars.But at present reported suitable for black light LED chip phosphate phosphor simultaneously
Seldom.
The content of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the invention is to provide a kind of white light LEDs phosphorus
Hydrochlorate based luminescent material, the material is applied to the blue light needed near ultraviolet LED chip produces synthesis white light, green glow and feux rouges.
It is still another object of the present invention to provide a kind of above-mentioned white light LEDs preparation method of phosphate base luminescent material.
The method is, by divalent europium, bivalent manganese and a kind of novel phosphoric acid alkali material of trivalent terbium ion doping, to have synthesized and be suitable for
The luminescent material of near ultraviolet LED, realizes blue light, the transmitting of green glow and feux rouges.
A further object of the present invention is to provide the application of above-mentioned white light LEDs phosphate base luminescent material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of white light LEDs phosphate base luminescent material, the chemical expression of the material is Sr9-a-cZn1-bA(PO4)7:
aEu2+,bMn2+,cTb3+；A is alkali metal Li, Na, K or Rb；A is Eu2+Doping content, 0 ＜ a≤0.1, b is Mn2+'s
Doping content, 0≤b≤0.5, c is Tb3+Doping content, 0≤c≤0.7.
The material sends blue and green light and feux rouges under the exciting of blue-light LED chip.
A kind of above-mentioned white light LEDs preparation method of phosphate base luminescent material, including following operating procedure：
(1) raw material is weighed：According to the white light LEDs expression formula of phosphate base luminescent material, weighed according to stoichiometric proportion
Containing strontium compound, zinc compound, alkali metal-containing compound, phosphorus-containing compound, containing europium compound, containing manganese compound and containing terbium
Compound, as raw material；
(2) mixed grinding：Each raw material mixed grinding that will be weighed in step (1) obtains mixture to uniform；
(3) firing process：Gained mixture in step (2) is placed in corundum crucible, is put it into Muffle furnace, in sky
300-500 DEG C is warming up in compression ring border, 2-5 hours is incubated, wait takes out regrinding uniformly after being naturally cooling to room temperature, then
1150-1300 DEG C is warming up in high temperature process furnances, and is passed through weak reducing gas, be calcined 5-8 hours with this understanding；Question response
End naturally cools to room temperature, grinds again, that is, obtain white light LEDs phosphate base luminescent material.
It is the carbonate containing strontium element, nitrate or oxide containing strontium compound that step (1) is described；The zinc compound
It is the carbonate containing Zn-ef ficiency, nitrate, oxalates or oxide；The phosphorus-containing compound is the diammonium hydrogen phosphate of phosphorus element-containing
Or ammonium dihydrogen phosphate；The alkali metal-containing compound is carbonate, nitrate or the oxalate compound of alkali metal containing, wherein alkali
Metal is Li, Na, K or Rb；The element compound containing europium is nitrate or oxide containing europium element；It is described containing manganese compound
It is the carbonate containing manganese element, oxalates, oxide or nitrate；The element compound containing terbium is the nitrate containing terbium element
Or oxide.
Preferably, described is strontium carbonate or strontium nitrate containing strontium compound；The zinc compound is zinc oxalate or zinc oxide；
The phosphorus-containing compound is diammonium hydrogen phosphate or ammonium dihydrogen phosphate；The alkali metal-containing compound is lithium carbonate, sodium carbonate, carbonic acid
Potassium or rubidium carbonate；Described is europium oxide containing europium compound；Described is manganese carbonate or manganese oxalate containing manganese compound；The element containing terbium
Compound is nitrate or oxide containing terbium element.
Step (3) the weak reducing gas be by volume ratio be 90-80%:The nitrogen and hydrogen of 10-20% are mixed
Gas.
Application of the above-mentioned white light LEDs with phosphate base luminescent material in White-light LED illumination field.
Compared with prior art, the present invention has advantages below and beneficial effect：
Present invention obtains a class new E u2+,Mn2+,Tb3+The phosphor of ion doping phosphate matrix, technique
Flow is simple, and building-up process is easily-controllable, and product stability is high；The material can be by near ultraviolet excitation, it is adaptable near ultraviolet LED core
Piece, the blue light needed for producing synthesis white light, green glow and feux rouges.
Brief description of the drawings
Fig. 1 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 1 in the present invention.
Fig. 2 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 2 in the present invention.
Fig. 3 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 3 in the present invention.
Fig. 4 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 5 in the present invention.
Fig. 5 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 6 in the present invention.
Fig. 6 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 7 in the present invention.
Fig. 7 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 8 in the present invention.
Fig. 8 (a) and (b) are respectively the excitation and emission spectras of the luminescent material prepared by embodiment 9 in the present invention.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, lithium carbonate,
Ammonium dihydrogen phosphate, europium oxide and manganese carbonate：Sr8.98Zn0.9Li(PO4)7:0.02Eu2+,0.1Mn2+, it is sufficiently mixed and is ground to uniformly
Afterwards, gained mixture is placed in corundum crucible, is put into Muffle furnace, be warming up to 450 DEG C in air ambient, pre-burning 3 hours,
It is uniform after naturally cool to regrinding is taken out after room temperature, then to put it into and be warming up to 1240 DEG C in tube furnace and be calcined 6 hours,
(volume ratio is N to be passed through weakly reducing atmosphere simultaneously2:H2=80%:20%)；Finally, after it is naturally cooling to room temperature, take out again
Secondary grinding, that is, obtain white light LEDs phosphate base luminescent material.Fig. 1 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 2
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, sodium carbonate,
Ammonium dihydrogen phosphate, europium oxide and manganese carbonate：Sr8.98Zn0.9Na(PO4)7:0.02Eu2+,0.1Mn2+, it is sufficiently mixed and is ground to uniformly
Afterwards, gained mixture is placed in corundum crucible, is put into Muffle furnace, be warming up to 450 DEG C in air ambient, pre-burning 3 hours,
It is uniform after naturally cool to regrinding is taken out after room temperature, then to put it into and be warming up to 1240 DEG C in tube furnace and be calcined 6 hours,
(volume ratio is N to be passed through weakly reducing atmosphere simultaneously2:H2=80%:20%)；Finally, after it is naturally cooling to room temperature, take out again
Secondary grinding, that is, obtain white light LEDs phosphate base luminescent material.Fig. 2 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 3
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, potassium carbonate,
Ammonium dihydrogen phosphate, europium oxide and manganese carbonate：Sr8.98Zn0.9K(PO4)7:0.02Eu2+,0.1Mn2+, it is sufficiently mixed and is ground to uniformly
Afterwards, gained mixture is placed in corundum crucible, is put into Muffle furnace, be warming up to 450 DEG C in air ambient, pre-burning 3 hours,
It is uniform after naturally cool to regrinding is taken out after room temperature, then to put it into and be warming up to 1240 DEG C in tube furnace and be calcined 6 hours,
(volume ratio is N to be passed through weakly reducing atmosphere simultaneously2:H2=80%:20%)；Finally, after it is naturally cooling to room temperature, take out again
Secondary grinding, that is, obtain white light LEDs phosphate base luminescent material.Fig. 3 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 4
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, potassium carbonate,
Ammonium dihydrogen phosphate, europium oxide and manganese carbonate：Sr8.98Zn0.8K(PO4)7:0.02Eu2+,0.2Mn2+, it is sufficiently mixed and is ground to uniformly
Afterwards, gained mixture is placed in corundum crucible, is put into Muffle furnace, be warming up to 400 DEG C in air ambient, pre-burning 4 hours,
It is uniform after naturally cool to regrinding is taken out after room temperature, then to put it into and be warming up to 1285 DEG C in tube furnace and be calcined 6 hours,
(volume ratio is N to be passed through weakly reducing atmosphere simultaneously2:H2=80%:20%)；Finally, after it is naturally cooling to room temperature, take out again
Secondary grinding, that is, obtain white light LEDs phosphate base luminescent material.
Embodiment 5
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, rubidium carbonate,
Ammonium dihydrogen phosphate, europium oxide and manganese carbonate：Sr8.98Zn0.9Rb(PO4)7:0.02Eu2+,0.1Mn2+, it is sufficiently mixed and is ground to uniformly
Afterwards, gained mixture is placed in corundum crucible, is put into Muffle furnace, be warming up to 450 DEG C in air ambient, pre-burning 3 hours,
It is uniform after naturally cool to regrinding is taken out after room temperature, then to put it into and be warming up to 1250 DEG C in tube furnace and be calcined 6 hours,
(volume ratio is N to be passed through weakly reducing atmosphere simultaneously2:H2=80%:20%)；Finally, after it is naturally cooling to room temperature, take out again
Secondary grinding, that is, obtain white light LEDs phosphate base luminescent material.Fig. 4 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 6
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, lithium carbonate,
Ammonium dihydrogen phosphate, europium oxide, manganese carbonate and terbium peroxide：Sr8.95Zn0.8Li(PO4)7:0.02Eu2+,0.2Mn2+,0.03Tb3 +, it is sufficiently mixed after being ground to uniformly, gained mixture is placed in corundum crucible, it is put into Muffle furnace, risen in air ambient
, to 450 DEG C, pre-burning 3 hours is uniform after naturally cool to regrinding is taken out after room temperature, then puts it into liter in tube furnace for temperature
Warm to 1230 DEG C are calcined 6 hours, while being passed through weakly reducing atmosphere, (volume ratio is N2:H2=80%:20%)；Finally, its nature is treated
After being cooled to room temperature, taking-up grinds again, that is, obtain white light LEDs phosphate base luminescent material.Fig. 5 (a) and (b) are respectively this
The excitation and emission spectra figure of luminescent material prepared by embodiment.
Embodiment 7
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, sodium carbonate,
Ammonium dihydrogen phosphate, europium oxide, manganese carbonate and terbium peroxide：Sr8.96Zn0.8Na(PO4)7:0.02Eu2+,0.2Mn2+,0.02Tb3 +, it is sufficiently mixed after being ground to uniformly, gained mixture is placed in corundum crucible, it is put into Muffle furnace, risen in air ambient
, to 450 DEG C, pre-burning 3 hours is uniform after naturally cool to regrinding is taken out after room temperature, then puts it into liter in tube furnace for temperature
Warm to 1240 DEG C are calcined 6 hours, while being passed through weakly reducing atmosphere, (volume ratio is N2:H2=80%:20%)；Finally, its nature is treated
After being cooled to room temperature, taking-up grinds again, that is, obtain white light LEDs phosphate base luminescent material.Fig. 6 (a) and (b) are respectively this
The excitation and emission spectra figure of luminescent material prepared by embodiment.
Embodiment 8
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, potassium carbonate,
Ammonium dihydrogen phosphate, europium oxide, manganese carbonate and terbium peroxide：Sr8.88Zn0.8K(PO4)7:0.02Eu2+,0.2Mn2+,0.1Tb3+,
It is sufficiently mixed after being ground to uniformly, gained mixture is placed in corundum crucible, be put into Muffle furnace, is heated up in air ambient
To 450 DEG C, pre-burning 3 hours is uniform after naturally cool to regrinding is taken out after room temperature, then puts it into intensification in tube furnace
It is calcined 6 hours to 1230 DEG C, while being passed through weakly reducing atmosphere, (volume ratio is N2:H2=80%:20%)；Finally, treat that it drops naturally
After warming to room temperature, taking-up grinds again, that is, obtain white light LEDs phosphate base luminescent material.Fig. 7 (a) and (b) are respectively this reality
Apply the excitation and emission spectra figure of the luminescent material of example preparation.
Embodiment 9
Stoichiometric proportion according to each element in following formula weighs raw material strontium carbonate respectively, zinc oxide, rubidium carbonate,
Ammonium dihydrogen phosphate, europium oxide, manganese carbonate and terbium peroxide：Sr8.96Zn0.8Rb(PO4)7:0.02Eu2+,0.2Mn2+,0.02Tb3 +, it is sufficiently mixed after being ground to uniformly, gained mixture is placed in corundum crucible, it is put into Muffle furnace, risen in air ambient
, to 450 DEG C, pre-burning 3 hours is uniform after naturally cool to regrinding is taken out after room temperature, then puts it into liter in tube furnace for temperature
Warm to 1240 DEG C are calcined 6 hours, while being passed through weakly reducing atmosphere, (volume ratio is N2:H2=80%:20%)；Finally, its nature is treated
After being cooled to room temperature, taking-up grinds again, that is, obtain white light LEDs phosphate base luminescent material.Fig. 8 (a) and (b) are respectively this
The excitation and emission spectra figure of luminescent material prepared by embodiment.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of white light LEDs phosphate base luminescent material, it is characterised in that：The chemical expression of the material is Sr9-a-cZn1-bA
(PO4)7:aEu2+,bMn2+,cTb3+；A is alkali metal Li, Na, K or Rb；A is Eu2+Doping content, 0 ＜ a≤0.1, b
It is Mn2+Doping content, 0≤b≤0.5, c is Tb3+Doping content, 0≤c≤0.7.
2. a kind of white light LEDs phosphate base luminescent material according to claim 1, it is characterised in that：The material is in indigo plant
Blue and green light and feux rouges are sent under the exciting of light LED chip.
3. a kind of white light LEDs according to claim 1 preparation method of phosphate base luminescent material, it is characterised in that bag
Include following operating procedure：
(1) raw material is weighed：According to the white light LEDs expression formula of phosphate base luminescent material, weighed containing strontium according to stoichiometric proportion
Compound, zinc compound, alkali metal-containing compound, phosphorus-containing compound, containing europium compound, containing manganese compound and chemical combination containing terbium
Thing, as raw material；
(2) mixed grinding：Each raw material mixed grinding that will be weighed in step (1) obtains mixture to uniform；
(3) firing process：Gained mixture in step (2) is placed in corundum crucible, is put it into Muffle furnace, in air ring
300-500 DEG C is warming up in border, 2-5 hours is incubated, wait takes out regrinding uniformly after being naturally cooling to room temperature, then in height
1150-1300 DEG C is warming up in warm tube furnace, and is passed through weak reducing gas, be calcined 5-8 hours with this understanding；Question response terminates
Room temperature is naturally cooled to, is ground again, that is, obtain white light LEDs phosphate base luminescent material.
4. a kind of white light LEDs according to claim 3 preparation method of phosphate base luminescent material, it is characterised in that：
It is the carbonate containing strontium element, nitrate or oxide containing strontium compound that step (1) is described；The zinc compound is containing zinc unit
The carbonate of element, nitrate, oxalates or oxide；The phosphorus-containing compound is the diammonium hydrogen phosphate or di(2-ethylhexyl)phosphate of phosphorus element-containing
Hydrogen ammonium；The alkali metal-containing compound is carbonate, nitrate or the oxalate compound of alkali metal containing, and wherein alkali metal is
Li, Na, K or Rb；The element compound containing europium is nitrate or oxide containing europium element；Described is containing manganese containing manganese compound
The carbonate of element, oxalates, oxide or nitrate；The element compound containing terbium is nitrate or oxidation containing terbium element
Thing.
5. a kind of white light LEDs according to claim 4 preparation method of phosphate base luminescent material, it is characterised in that：
Described is strontium carbonate or strontium nitrate containing strontium compound；The zinc compound is zinc oxalate or zinc oxide；The phosphorus-containing compound
It is diammonium hydrogen phosphate or ammonium dihydrogen phosphate；The alkali metal-containing compound is lithium carbonate, sodium carbonate, potassium carbonate or rubidium carbonate；Institute
It is europium oxide to state containing europium compound；Described is manganese carbonate or manganese oxalate containing manganese compound；The element compound containing terbium is containing terbium
The nitrate or oxide of element.
6. a kind of white light LEDs according to claim 3 preparation method of phosphate base luminescent material, it is characterised in that：
Step (3) the weak reducing gas be by volume ratio be 90-80%:The gas that the nitrogen and hydrogen of 10-20% are mixed.
7. a kind of white light LEDs according to claim 1 phosphate base luminescent material in White-light LED illumination field should
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947278.9A CN106833639B (en) | 2016-10-26 | 2016-10-26 | A kind of white light LEDs phosphate base luminescent material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610947278.9A CN106833639B (en) | 2016-10-26 | 2016-10-26 | A kind of white light LEDs phosphate base luminescent material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106833639A true CN106833639A (en) | 2017-06-13 |
| CN106833639B CN106833639B (en) | 2019-04-23 |
Family
ID=59145501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610947278.9A Active CN106833639B (en) | 2016-10-26 | 2016-10-26 | A kind of white light LEDs phosphate base luminescent material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106833639B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893113A (en) * | 2018-08-01 | 2018-11-27 | 陕西师范大学 | A kind of adjustable high thermal stability fluorescent powder of coloration |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498031A (en) * | 2014-11-26 | 2015-04-08 | 中国计量学院 | Phosphate yellow phosphor for white LED, and preparation method thereof |
-
2016
- 2016-10-26 CN CN201610947278.9A patent/CN106833639B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498031A (en) * | 2014-11-26 | 2015-04-08 | 中国计量学院 | Phosphate yellow phosphor for white LED, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XI CHEN ET AL.: "A Highly Efficient White Light (Sr3,Ca,Ba)(PO4)3Cl:Eu2+, Tb3+, Mn2+ Phosphor via Dual Energy Transfers for White Light-Emitting Diodes", 《INORG. CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893113A (en) * | 2018-08-01 | 2018-11-27 | 陕西师范大学 | A kind of adjustable high thermal stability fluorescent powder of coloration |
| CN108893113B (en) * | 2018-08-01 | 2021-06-11 | 陕西师范大学 | Chromaticity-adjustable high-thermal-stability fluorescent powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106833639B (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105038779B (en) | A kind of Eu3+/Eu2+The aluminate multicolor fluorescence material and preparation method of doping | |
| CN102604638A (en) | Eu<3+>-activated phosphate red phosphor powder as well as preparation method and application thereof | |
| CN101402857B (en) | Red luminous material for LED and producing process thereof | |
| CN107189776A (en) | A kind of green silicate long after glow luminous material and preparation method thereof | |
| CN106047341A (en) | Rare earth doped fluorescent powder and synthetic method thereof and application of fluorescent powder in LED devices | |
| CN101307228B (en) | Chlorine-aluminosilicate fluorescent powder and method for preparing same | |
| CN102585812B (en) | Dark red fluorescent powder and preparation method thereof | |
| CN106634997A (en) | Composite phosphate fluorophor and application thereof | |
| CN101857361A (en) | Europium-doped oxyfluoride aluminosilicate luminous glass and preparation method thereof | |
| CN103740364B (en) | A kind of yellow orange-orange red orthosilicate fluorescent material and preparation method thereof | |
| CN101486910A (en) | Green phosphor for white light LED and preparation thereof | |
| CN102703066A (en) | Fluorosilicate fluorescent powder and preparation method thereof | |
| CN105038789A (en) | Single-phase white phosphor and preparation method thereof | |
| JP2017531051A (en) | NASICON structure phosphor and light emitting device including the phosphor | |
| CN103380193B (en) | Fluorophor, its preparation method and light-emitting device | |
| CN108034423B (en) | Mn (manganese)2+Ion-doped silicate red fluorescent powder, preparation method and application | |
| CN106833639B (en) | A kind of white light LEDs phosphate base luminescent material and its preparation method and application | |
| TW201307530A (en) | Aluminate phosphor | |
| CN104910916B (en) | A kind of glow color adjustable New Phosphorus lime stone structure light-emitting material and application thereof | |
| CN104830335A (en) | Europium-doped borate fluorescent powder and preparing method thereof | |
| CN104974756B (en) | Cerium and terbium mono-doped/codoped yttrium sodium phosphate fluorescent powder, and preparation method thereof | |
| CN104804731B (en) | Magnesium silicate potassium blue-green fluorescent powder that a kind of Eu2+ activates and its preparation method and application | |
| CN113201341A (en) | Alkali metal charge compensation type aluminum phosphate red luminescent material and preparation method and application thereof | |
| CN106433623B (en) | A kind of silicon-based nitrogen oxide fluorescent powder and its preparation method and application | |
| TW200927882A (en) | Phosphors and lighting apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |