CN106833639B - 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
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- CN106833639B CN106833639B CN201610947278.9A CN201610947278A CN106833639B CN 106833639 B CN106833639 B CN 106833639B CN 201610947278 A CN201610947278 A CN 201610947278A CN 106833639 B CN106833639 B CN 106833639B
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 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 14
- 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 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 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
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000005286 illumination Methods 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 230000005284 excitation Effects 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 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
- 239000011656 manganese carbonate Substances 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 12
- 235000006748 manganese carbonate Nutrition 0.000 claims description 12
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 12
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 12
- 239000011701 zinc Substances 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 compound [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
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 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
- 150000003438 strontium 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
- 150000003752 zinc 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
- 238000000227 grinding Methods 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
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 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
- 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
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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 compound [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
- NFODKZOKWBFONG-UHFFFAOYSA-N terbium zinc Chemical compound [Zn].[Tb] NFODKZOKWBFONG-UHFFFAOYSA-N 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000000295 emission spectrum Methods 0.000 description 16
- 238000000695 excitation spectrum Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- 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
- 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
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003502 terbium compounds Chemical class 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
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- 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 element Li, Na, K or Rb；A is Eu2+Doping content, 0 < a≤0.1, b Mn2+Doping content, 0≤b≤0.5, c Tb3+Doping content, 0≤c≤0.7.Present invention process process is simple, and synthesis condition is easily realized and controllable, suitable large-scale production.Products obtained therefrom of the present invention is suitable for black light LED chip, and blue light, green light and feux rouges needed for can produce synthesis white light meet the needs of White-light LED illumination field.
Description
Technical field
The invention belongs to phosphor technical field, in particular to a kind of white light LEDs phosphate base luminescent material
And its preparation method and application.
Background technique
White light LEDs are a kind of novel green lighting sources, long with the service life, and efficiency is high, small in size, compact-sized, weight
Amount is light, the various features such as energy conservation and environmental protection.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 lighting light source, will replace traditional lighting source such as fluorescent lamp, incandescent lamp, and
By wideling popularize for country.
Currently, by LED chip synthesis white light there are mainly two types of in the way of: (1) by RGB three-primary color LED chip package one
It rises.Although the method is efficiently, at high cost, fever is serious, is not easy with using the time to extend 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 issues forms white after mixing
Light.But for the white light that this method obtains since the missing of red color light component causes colour rendering index lower, colour temperature is higher.(3) using close
The excitation of ultraviolet leds chip and feux rouges, green light, blue light three primary colours mixed fluorescent powders obtain white light.
Therefore, the fluorescent powder suitable for black light LED chip of synthesizing new is for realizing high color rendering index (CRI), low color temperature
White light be very it is necessary to.Phosphate material is since property is stablized, and raw material is cheap and easy to get, and synthesis condition is mild, all the time
Concern and research by numerous scholars.But the current phosphate phosphor reported suitable for black light LED chip is simultaneously
Seldom.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of white light LEDs phosphorus
Hydrochlorate based luminescent material, the material are suitable for blue light, green light and feux rouges needed near ultraviolet LED chip generates synthesis white light.
A further object of the present invention is to provide a kind of preparation methods of above-mentioned white light LEDs phosphate base luminescent material.
This method is by divalent europium, and bivalent manganese and trivalent terbium ion adulterate a kind of novel phosphoric acid alkali material, synthesized and be suitable for
The luminescent material of near ultraviolet LED realizes blue light, the transmitting of green light and feux rouges.
Another object of the present invention is to provide the application of above-mentioned white light LEDs phosphate base luminescent material.
The purpose of the invention is achieved by the following technical solution:
A kind of white light LEDs phosphate base luminescent material, the chemical expression of the material are Sr9-a-cZn1-bA(PO4)7:
aEu2+,bMn2+,cTb3+；A is alkali metal element Li, Na, K or Rb；A is Eu2+Doping content, 0 < a≤0.1, b Mn2+'s
Doping content, 0≤b≤0.5, c Tb3+Doping content, 0≤c≤0.7.
The material issues blue and green light and feux rouges under the excitation of blue-light LED chip.
A kind of preparation method of above-mentioned white light LEDs phosphate base luminescent material, including following operating procedure:
(1) it weighs raw material: according to the expression formula of white light LEDs phosphate base luminescent material, being weighed according to stoichiometric ratio
Containing strontium compound, zinc compound, alkali metal-containing compound, phosphorus-containing compound, contain europium compound, containing manganese compound and containing terbium
Object is closed, as raw material；
(2) mixed grinding: by each raw material mixed grinding weighed in step (1) to uniform, mixture is obtained；
(3) firing process: gained mixture in step (2) is placed in corundum crucible, is put it into Muffle furnace, in sky
It is warming up to 300-500 DEG C in compression ring border, keeps the temperature 2-5 hours, waiting takes out regrinding uniformly after being naturally cooling to room temperature, then
It is warming up to 1150-1300 DEG C in high temperature process furnances, and is passed through weak reducing gas, is calcined 5-8 hours with this condition；Wait react
Terminate cooled to room temperature, is ground again to get white light LEDs phosphate base luminescent material is arrived.
Step (1) described containing strontium compound is carbonate, nitrate or oxide containing strontium element；The zinc compound
For carbonate, nitrate, oxalates or oxide containing Zn-ef ficiency；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 the nitrate or oxide of the element containing europium；It is described to contain manganese compound
For carbonate, oxalates, oxide or nitrate containing manganese element；The element compound containing terbium is the nitrate of the element containing terbium
Or oxide.
Preferably, the strontium compound that contains is strontium carbonate or strontium nitrate；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；The europium compound that contains is europium oxide；The manganese compound that contains is manganese carbonate or manganese oxalate；The element containing terbium
Compound is the nitrate or oxide of the element containing terbium.
Step (3) the weak reducing gas is mixed by nitrogen and hydrogen that volume ratio is 90-80%:10-20%
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 the following advantages and beneficial effects:
Present invention obtains a kind of new E u2+,Mn2+,Tb3+The phosphor of ion doping phosphate matrix, technique
Process is simple, and synthesis process is easily-controllable, and product stability is high；The material can be suitable near ultraviolet LED core by near ultraviolet excitation
Piece, blue light, green light and feux rouges needed for generating synthesis white light.
Detailed description of the invention
Fig. 1 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 1 in the present invention respectively.
Fig. 2 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 2 in the present invention respectively.
Fig. 3 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 3 in the present invention respectively.
Fig. 4 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 5 in the present invention respectively.
Fig. 5 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 6 in the present invention respectively.
Fig. 6 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 7 in the present invention respectively.
Fig. 7 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 8 in the present invention respectively.
Fig. 8 (a) and (b) are the excitation and emission spectra of luminescent material prepared by embodiment 9 in the present invention respectively.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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 environment, pre-burning 3 hours,
After naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and is warming up to 1240 DEG C of roastings 6 hours,
It is passed through weakly reducing atmosphere (volume ratio N simultaneously2:H2=80%:20%)；Finally, being taken out again after it is naturally cooling to room temperature
It is secondary to grind to get white light LEDs phosphate base luminescent material is arrived.Fig. 1 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 2
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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 environment, pre-burning 3 hours,
After naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and is warming up to 1240 DEG C of roastings 6 hours,
It is passed through weakly reducing atmosphere (volume ratio N simultaneously2:H2=80%:20%)；Finally, being taken out again after it is naturally cooling to room temperature
It is secondary to grind to get white light LEDs phosphate base luminescent material is arrived.Fig. 2 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 3
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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 environment, pre-burning 3 hours,
After naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and is warming up to 1240 DEG C of roastings 6 hours,
It is passed through weakly reducing atmosphere (volume ratio N simultaneously2:H2=80%:20%)；Finally, being taken out again after it is naturally cooling to room temperature
It is secondary to grind to get white light LEDs phosphate base luminescent material is arrived.Fig. 3 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 4
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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 environment, pre-burning 4 hours,
After naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and is warming up to 1285 DEG C of roastings 6 hours,
It is passed through weakly reducing atmosphere (volume ratio N simultaneously2:H2=80%:20%)；Finally, being taken out again after it is naturally cooling to room temperature
It is secondary to grind to get white light LEDs phosphate base luminescent material is arrived.
Embodiment 5
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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 environment, pre-burning 3 hours,
After naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and is warming up to 1250 DEG C of roastings 6 hours,
It is passed through weakly reducing atmosphere (volume ratio N simultaneously2:H2=80%:20%)；Finally, being taken out again after it is naturally cooling to room temperature
It is secondary to grind to get white light LEDs phosphate base luminescent material is arrived.Fig. 4 (a) and (b) are respectively luminous material manufactured in the present embodiment
The excitation and emission spectra figure of material.
Embodiment 6
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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, is put into Muffle furnace, is risen in air environment
Temperature, after naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and rises to 450 DEG C, pre-burning 3 hours
Temperature roasts 6 hours to 1230 DEG C, while being passed through weakly reducing atmosphere (volume ratio N2:H2=80%:20%)；Finally, to its nature
After being cooled to room temperature, taking-up grinds to arrive white light LEDs phosphate base luminescent material again.Fig. 5 (a) and (b) are respectively this
The excitation and emission spectra figure of the luminescent material of embodiment preparation.
Embodiment 7
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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, is put into Muffle furnace, is risen in air environment
Temperature, after naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and rises to 450 DEG C, pre-burning 3 hours
Temperature roasts 6 hours to 1240 DEG C, while being passed through weakly reducing atmosphere (volume ratio N2:H2=80%:20%)；Finally, to its nature
After being cooled to room temperature, taking-up grinds to arrive white light LEDs phosphate base luminescent material again.Fig. 6 (a) and (b) are respectively this
The excitation and emission spectra figure of the luminescent material of embodiment preparation.
Embodiment 8
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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, is put into Muffle furnace, is heated up in air environment
To 450 DEG C, pre-burning 3 hours, after naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and heat up
It is roasted 6 hours to 1230 DEG C, while being passed through weakly reducing atmosphere (volume ratio N2:H2=80%:20%)；Finally, being dropped naturally to it
After warming to room temperature, taking-up grinds to arrive white light LEDs phosphate base luminescent material again.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
Raw material strontium carbonate is weighed respectively according to the stoichiometric ratio of each element in following formula, 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, is put into Muffle furnace, is risen in air environment
Temperature, after naturally cool to regrinding is taken out after room temperature uniformly, then puts it into tube furnace and rises to 450 DEG C, pre-burning 3 hours
Temperature roasts 6 hours to 1240 DEG C, while being passed through weakly reducing atmosphere (volume ratio N2:H2=80%:20%)；Finally, to its nature
After being cooled to room temperature, taking-up grinds to arrive white light LEDs phosphate base luminescent material again.Fig. 8 (a) and (b) are respectively this
The excitation and emission spectra figure of the luminescent material of embodiment preparation.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the 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 element Li, Na, K or Rb；A is Eu2+Doping content, 0 < a≤0.1, b
For Mn2+Doping content, 0≤b≤0.5, c 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 issued under the excitation of light LED chip.
3. a kind of preparation method of white light LEDs phosphate base luminescent material according to claim 1, it is characterised in that packet
Include following operating procedure:
(1) it weighs raw material: according to the expression formula of white light LEDs phosphate base luminescent material, weighing according to stoichiometric ratio containing strontium
Compound, alkali metal-containing compound, phosphorus-containing compound, contains europium compound, contains manganese compound and chemical combination containing terbium zinc compound
Object, as raw material；
(2) mixed grinding: by each raw material mixed grinding weighed in step (1) to uniform, mixture is obtained；
(3) firing process: gained mixture in step (2) is placed in corundum crucible, is put it into Muffle furnace, in air ring
It is warming up to 300-500 DEG C in border, keeps the temperature 2-5 hours, waiting takes out regrinding uniformly after being naturally cooling to room temperature, then in height
It is warming up to 1150-1300 DEG C in warm tube furnace, and is passed through weak reducing gas, is calcined 5-8 hours with this condition；To the end of reacting
Cooled to room temperature is ground again to get white light LEDs phosphate base luminescent material is arrived.
4. a kind of preparation method of white light LEDs phosphate base luminescent material according to claim 3, it is characterised in that:
Step (1) described containing strontium compound is carbonate, nitrate or oxide containing strontium element；The zinc compound is containing zinc member
Carbonate, nitrate, oxalates or the oxide of element；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 the nitrate or oxide of the element containing europium；The manganese compound that contains is containing manganese
Carbonate, oxalates, oxide or the nitrate of element；The element compound containing terbium is nitrate or the oxidation of the element containing terbium
Object.
5. a kind of preparation method of white light LEDs phosphate base luminescent material according to claim 4, it is characterised in that:
The strontium compound that contains is strontium carbonate or strontium nitrate；The zinc compound is zinc oxalate or zinc oxide；The phosphorus-containing compound
For diammonium hydrogen phosphate or ammonium dihydrogen phosphate；The alkali metal-containing compound is lithium carbonate, sodium carbonate, potassium carbonate or rubidium carbonate；Institute
Stating containing europium compound is europium oxide；The manganese compound that contains is manganese carbonate or manganese oxalate；The element compound containing terbium is containing terbium
The nitrate or oxide of element.
6. a kind of preparation method of white light LEDs phosphate base luminescent material according to claim 3, it is characterised in that:
Step (3) the weak reducing gas is by the nitrogen that volume ratio is 90-80%:10-20% and the gas that hydrogen mixes.
7. a kind of white light LEDs phosphate base luminescent material answering in White-light LED illumination field according to claim 1
With.
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| A Highly Efficient White Light (Sr3,Ca,Ba)(PO4)3Cl:Eu2+, Tb3+, Mn2+ Phosphor via Dual Energy Transfers for White Light-Emitting Diodes;Xi Chen et al.;《Inorg. Chem.》;20140331;第53卷;第3441-3448页 |
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