CN109370581A - Green light activated red fluorescence powder and preparation method thereof - Google Patents
Green light activated red fluorescence powder and preparation method thereof Download PDFInfo
- Publication number
- CN109370581A CN109370581A CN201811355470.4A CN201811355470A CN109370581A CN 109370581 A CN109370581 A CN 109370581A CN 201811355470 A CN201811355470 A CN 201811355470A CN 109370581 A CN109370581 A CN 109370581A
- Authority
- CN
- China
- Prior art keywords
- solution
- red fluorescence
- fluorescence powder
- preparation
- powder
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910015667 MoO4 Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 84
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 24
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims description 12
- 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
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 229910052693 Europium Inorganic materials 0.000 abstract description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract description 2
- 238000009877 rendering Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 26
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000295 emission spectrum Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- -1 europium ion Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of green light activated red fluorescence powder and preparation method thereof, which is Ca1‑nMoO4:nEu3+: xSi:yR, wherein R is alkali metal ion, and the range of n is 0.1≤n≤0.6, and the range of x is 0.01≤x≤0.1, and the range of y is 0.1≤y≤0.5.The present invention is with CaCO3‑(NH4)6Mo7O24·4H2O is the host material to glow, europium ion, silicon ion and alkali metal ion is used to adulterate as activator, red fluorescence powder is prepared with sol-gel method, the preparation method of the red fluorescence powder is simple, the red light emitting phosphor being prepared is high-efficient, colour rendering index is high, color saturation is good, colour temperature is stable, can be excited with green light.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly to a kind of green light activated red fluorescence powder and its preparation side
Method.
Background technique
Christian era 1992, first white light LEDs of Nichia company manufacture occurred with commercialized version, and lighting engineering enters
The LED epoch are compared with conventional lighting technology, and LED has following advantage: (1) energy conservation and environmental protection: fluorescent lamp is sent out using mercury vapour
Light, mercury are noxious materials, pollute environment, and LED light is by light-emitting phosphor, and fluorescent powder the inside does not have pollutant, sending
Light does not radiate；(2) durable: the time that incandescent lamp uses is usually 1,000 hours to 2,000 hours, and fluorescent lamp uses
Time is usually 6,000 hours to 10,000 hours, and the time that LED light uses is fluorescent lamp more than 3 times；(3) calorific value and volume
Small: LED lamp bead is small, and chip is smaller, and very thin, can produce different chip, forms beautiful design, reaches market
Change.
In the method that the colour developing rate, color stability, the luminous efficiency that improve fluorescent powder realize white light using fluorescent powder for LED
For be most important, so, research and development high photosynthetic efficiency red fluorescence powder be at this stage break through realize phosphor for white light LED exist
Main task in illumination market.
It realizes in white light LED fluorescent powder, red fluorescence powder accounts for important role, so causing human research's exploitation more
Red fluorescence powder, return before and now it is newly developed, have the host material of 12 big system red fluorescence powders at present.Fluorescence
The synthetic method of powder is mainly include the following types: (1) high temperature solid-state method, (2) sol-gel method, (3) precipitation method；(4) hydrothermal synthesis
Method；(5) combustion method.High temperature solid-state method is easy to operate, but Shortcomings, and calcination temperature is high, and the time is long, if grinding is not filled
Point, the product luminescent properties reacted are poor；In the precipitation method, concentration, pH value, the temperature of solution can all influence sediment
It generates, is not easy to the quality of control fluorescent powder；Hydro-thermal method synthesis temperature is low, and preparation product purity height, morphological rules are not damaged
It is bad, but may be only available for low temperature progress, so its applicability is very restricted；Combustion method is that each material is blended in one
After rising, to put into crucible, put resistance furnace into, be transferred to reactive combustion temperature, mixture is allowed to burn, burning terminates just to obtain product,
The method equipment is simple, and the reaction time is fast, but requires height to ignition temperature, and reaction process risk is high；Sol-gel
Each raw material is mainly mixed into uniform solution by method, and by stirring to get colloidal sol, colloidal sol forms solidifying after drying and evaporation
Glue, gel, which continues drying, will form floc, finally just obtain final product by roasting, sol-gel method can obtain
The even higher product of purity, forms small particle, and maturing temperature is low, preparation process is simple.
Moreover, many LED light are all using ultraviolet excitation at present.The LED light of ultraviolet chip excitation refers to using ultraviolet
The LED chip of wave band as excitation light source, the selection fluorescent powder that excitation wavelength matches therewith can prepare launch it is red green
Blue spectrum.Ultraviolet light emitted energy with higher, therefore this thinking is desirable to excite polychrome glimmering using UV chip
Light powder is compounded to form white light.Major defect existing for the LED light of ultraviolet excitation has, first is that the luminous effect of ultraviolet chip at present
Rate is relatively low, second is that it is still very expensive in the current price of ultraviolet chip, it is unfavorable for largely using；Third is that the light of ultraviolet chip is necessary
Ultraviolet light is removed by the energy absorption of fluorescent powder, to prevent injury of the ultraviolet light to people, especially eyes.
Therefore, it is necessary to research and develop a kind of high green light activated red fluorescence powder of luminous efficiency.
Summary of the invention
Simple, luminous efficiency height, colour rendering index height, excellent colour saturation are prepared the purpose of the present invention is to provide a kind of
Degree, colour temperature are stablized, and green light activated red fluorescence powder can be used.
The technical solution adopted by the present invention is that: a kind of green light activated red fluorescence powder, the red fluorescence powder are Ca1- nMoO4:nEu3+: xSi:yR, wherein R is alkali metal ion, and the range of n is 0.1≤n≤0.6, the range of x be 0.01≤x≤
0.1, y range is 0.1≤y≤0.5.
Preferably, the alkali metal ion is sodium ion, lithium ion or potassium ion.It is furthermore preferred that the alkali metal ion
For lithium ion.
Preferably, the value range of the n is 0.2≤n≤0.3, and the value range of x is 0.02≤x≤0.06, and y's takes
Value range is 0.2≤y≤0.4.
It is furthermore preferred that the value of n is 0.25；The value that the value of x is 0.04, y is 0.25.
Preferably, the launch wavelength coverage area of the red fluorescence powder be 610-630nm, peak wavelength 618nm, more
Preferably, the launch wavelength coverage area of the red fluorescence powder is 615-620nm.
Preferably, the excitation wavelength of the red fluorescence powder is 530-545nm, and wherein the green light excitation of 537nm has the most
Effect.
The present invention also provides the preparation methods of red fluorescence powder, comprising the following steps:
1) calcium carbonate, europium oxide, four Heshui ammonium molybdates, ethyl orthosilicate and alkali metal are stoichiometrically weighed respectively；
2) nitric acid is added into load weighted calcium carbonate, europium oxide and alkali metal respectively, respectively obtains calcium nitrate solution, nitre
Sour europium solution and alkali metal nitric acid solution；Four Heshui ammonium molybdates and the dissolution of citric acid water are respectively obtained into citric acid solution and molybdenum
Acid ammonium solution；The silicon dioxde solution for using water hydrolyzing tetraethoxy orthosilane to obtain concentration as 0.1-0.3g/ml；
3) by calcium nitrate solution, europium nitrate solution, alkali metal nitric acid solution, citric acid solution, silicon dioxde solution and molybdenum
Acid ammonium solution mixing, obtains mixed solution；
4) mixed solution is dried, is sintered and cooled, obtain red fluorescence powder.
Preferably, citric acid can need to add suitable lemon according to material preparation process effect as cosolvent
Acid.
Preferably, in step 4), further include the steps that it is 30-300nm that red fluorescence powder is ground to partial size after cooling.More
Preferably, red fluorescence powder is ground to partial size is 50-200nm, it is furthermore preferred that it is 80- that red fluorescence powder, which is ground to partial size,
100nm。
Particle size is bigger than normal or the scattering less than normal for being all unfavorable for light, to influence luminous efficiency, the present invention selects the partial size to be
The red fluorescence powder of 30-300nm is conducive to light scattering, can significantly improve the luminous efficiency of red fluorescence powder.
Preferably, in step 2), the concentration of citric acid solution is 0.1-1g/mL；The concentration of ammonium molybdate solution is 0.02-
0.2g/mL.It is furthermore preferred that the concentration of citric acid solution is 0.2-0.8g/mL；The concentration of ammonium molybdate solution is 0.03-0.1g/
mL。
Preferably, the concentration of the nitric acid in step 2) is 10%-30%.It is furthermore preferred that the concentration of nitric acid is 25%.
Preferably, in step 4), the concrete operations of drying are: mixed solution is subjected to prebake 3-5h at 70-90 DEG C,
Again at 105-130 DEG C, dry 12-18h, until generating the substance of yellow fluffy.It is furthermore preferred that by mixed solution at 80 DEG C
Prebake 3h is carried out, then at 120 DEG C, dry 15h, until generating the substance of yellow fluffy.
Preferably, in step 4), the concrete operations of sintering are: the substance that drying is obtained is pre-sintered at 400-550 DEG C
3.5-6h；Then it is increased to 600-850 DEG C of sintering 1.5-3h again.It is furthermore preferred that the substance that drying is obtained is pre- at 450-500 DEG C
It is sintered 4-5h；Then it is increased to 700-800 DEG C of sintering 2-3h again.
The present invention also provides red fluorescence powders to be used as application in luminescent material in white light LEDs.
The invention has the advantages that the present invention realizes green light excitation, with CaCO3-(NH4)6Mo7O24·4H2O is to glow
Host material, use europium ion, silicon ion and alkali metal ion as activator adulterate, prepared with sol-gel method luminous
The higher red fluorescence powder of efficiency.The preparation method of the red fluorescence powder is simple, the red light emitting phosphor efficiency being prepared
Height, chromaticity saturation degree are preferable, colour temperature stability is preferable.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare red fluorescence powder emission spectrum (excitation wavelength be respectively 537nm, 395nm and
466nm)；
Fig. 2 is the excitation spectrum of red fluorescence powder prepared by embodiment 1；
Fig. 3 is that the red fluorescence powder of the preparation of embodiment 1 and the emission spectrum of LED commercialization fluorescent powder compare (excitation wavelength
395nm)；
Fig. 4 is that the red fluorescence powder of the preparation of embodiment 1 and the emission spectrum of LED commercialization fluorescent powder compare (excitation wavelength
466nm)；
Fig. 5 is that the red fluorescence powder of the preparation of embodiment 1 and the emission spectrum of LED commercialization fluorescent powder compare (excitation wavelength
537nm)。
Specific embodiment
Green light activated red fluorescence powder in embodiment is prepared using following methods, specifically, comprising the following steps:
(1) raw material are ready to first, find out corresponding relative molecular mass, molecular formula, prepares equation, calculate carbon
Sour calcium, europium oxide, four Heshui ammonium molybdates, ethyl orthosilicate and the corresponding molal weight of alkali metal；
(2) data calculated are good with excel charting, facilitate experiment, using electronic balance weighing raw material,
Will be retained after decimal point by weighing numerical value by three, and calcium carbonate, europium oxide and alkali metal are dissolved with nitric acid respectively, respectively obtain calcium nitrate
Solution, europium nitrate solution and alkali metal nitric acid solution；Four Heshui ammonium molybdates and citric acid are dissolved with water, are respectively obtained concentration and are
The citric acid solution and concentration of 0.1-1g/mL is 0.02-0.2g/mL ammonium molybdate solution；Using water by ethyl orthosilicate (hydrolysis,
Obtain the silicon dioxde solution that concentration is 0.1-0.3g/ml；
(3) respectively calcium nitrate solution, europium nitrate solution, alkali metal nitric acid solution, the citric acid solution, molybdic acid prepared
Ammonium salt solution and silicon dioxde solution mix, and at 60-70 DEG C of temperature, stir 20-60min, so that solution is sufficiently mixed,
Obtain mixed solution；
(4) it puts mixed solution into drying box, temperature is transferred to 70-90 DEG C, carries out prebake 3-5h, it is seen that solution becomes
Glue, then temperature is being increased to 105-130 DEG C, continue dry 12-18h, becomes the substance of yellow fluffy；
(5) yellow substance can be sticked in walls of beaker, it is scraped off at leisure with spoon, puts crucible into, then is put into box
Temperature is transferred to 400-550 DEG C of pre-sintering 3.5-6h, is then increased to 600-850 DEG C of sintering 1.5-3h again by resistance furnace, allows product
Room temperature is naturally rung to, takes out product from chamber type electric resistance furnace, grinding 30 minutes green light activated to get arriving for 30-300nm to partial size
Red fluorescence powder.
Embodiment 1
A kind of green light activated red fluorescence powder Ca0.75MoO4:0.25Eu3+: the preparation method of 0.04Si:0.25Li, packet
Include following steps:
(1) raw material are ready to first, find out corresponding relative molecular mass, molecular formula, prepares equation, calculate carbon
Sour calcium, europium oxide, four Heshui ammonium molybdates, ethyl orthosilicate and the corresponding molal weight of Li；
(2) data calculated are good with excel charting, facilitate experiment, using electronic balance weighing raw material,
Will be retained after decimal point by weighing numerical value by three, and calcium carbonate, europium oxide and Li are dissolved with nitric acid respectively, and it is molten to respectively obtain calcium nitrate
Liquid, europium nitrate solution and lithium nitrate solution；Four Heshui ammonium molybdates and citric acid are dissolved with water, and respectively obtaining concentration is 0.5g/mL
Citric acid solution and concentration be 0.1g/mL ammonium molybdate solution；Using water by teos hydrolysis, obtaining concentration is 0.1-
The silicon dioxde solution of 0.3g/ml；
(3) respectively that calcium nitrate solution, europium nitrate solution, lithium nitrate solution, citric acid solution, the ammonium molybdate prepared is molten
Liquid and silicon dioxde solution mix, and under temperature 60 C, stirring 30min obtains mixing molten so that solution is sufficiently mixed
Liquid；
(4) it puts mixed solution into drying box, temperature is transferred to 80 DEG C, carries out prebake 4h, it is seen that solution becomes gluey,
Temperature is being increased to 120 DEG C again, is continued dry 15h, is become the substance of yellow fluffy；
(5) yellow substance can be sticked in walls of beaker, it is scraped off at leisure with spoon, puts crucible into, then is put into box
Temperature is transferred to 500 DEG C of pre-sintering 5h, is then increased to 800 DEG C of sintering 2.5h again, product is allowed to naturally ring to room temperature by resistance furnace,
Product is taken out from chamber type electric resistance furnace, and grinding 30 minutes to partial size is 30-300nm to get green light activated red fluorescence powder is arrived.
Use the emission spectrum and excitation spectrum of the red fluorescence powder that the test of F-4600 type fluorescence spectrometer is prepared.Its
In, test condition are as follows: it is 2.5nm, scanning speed 1200nm/min, excitation wave that adjusting voltage, which is the corresponding slit width of 400V,
A length of 395nm, 466 and 537nm, Detection wavelength 618nm.
The emission spectrum for the red fluorescence powder that embodiment 1 is prepared is as shown in Figure 1.In 395nm, 466nm and 537nm
Under excitation, for emission peak all in 618nm or so, and in three different excitation wavelength excitations, the luminescent properties showed are different
Sample can excite electromagnetic radiation feux rouges with black light, blue light and green light, but among these, find 537nm green light rate of induced polarization
Ultraviolet light and blue light will be got well, so, which can first can also be gone with ultraviolet light respectively with these three light deexcitations
Blue light is inspired, then blue light inspires green light, and obtained green light deactivates sending feux rouges again.
The 618nm excitation spectrum for the red fluorescence powder that embodiment 1 is prepared is as shown in Figure 2.As shown in Figure 2, red glimmering
There are three excitation peaks for the excitation spectrum of light powder, and one is 395nm, and one is 466nm or so, and one is 537nm or so, and use is ultraviolet
Light and blue light excitation, luminous intensity is similar, but is excited with green light, luminous intensity more 30 or so, and many fluorescent powders are all
With black light deexcitation, invention point is surprised to find that the red fluorescence powder that embodiment 1 is prepared can be excited with green light, and
And luminous strength ratio near ultraviolet is also eager to excel in whatever one does.
Embodiment 2
A kind of green light activated red fluorescence powder Ca0.8MoO4:0.2Eu3+: the preparation method of 0.6Si:0.2Li, including with
Lower step:
(1) raw material are ready to first, find out corresponding relative molecular mass, molecular formula, prepares equation, calculate carbon
Sour calcium, europium oxide, four Heshui ammonium molybdates, ethyl orthosilicate and the corresponding molal weight of Li；
(2) data calculated are good with excel charting, facilitate experiment, using electronic balance weighing raw material,
Will be retained after decimal point by weighing numerical value by three, and calcium carbonate, europium oxide and Li are dissolved with nitric acid respectively, and it is molten to respectively obtain calcium nitrate
Liquid, europium nitrate solution and lithium nitrate solution；Four Heshui ammonium molybdates and citric acid are dissolved with water, and respectively obtaining concentration is 0.4g/mL
Citric acid solution and concentration be 0.08g/mL ammonium molybdate solution；Using water by teos hydrolysis, obtaining concentration is 0.1-
The silicon dioxde solution of 0.3g/ml；
(3) respectively that calcium nitrate solution, europium nitrate solution, lithium nitrate solution, citric acid solution, the ammonium molybdate prepared is molten
Liquid and silicon dioxde solution mix, and under temperature 60 C, stirring 40min obtains mixing molten so that solution is sufficiently mixed
Liquid；
(4) it puts mixed solution into drying box, temperature is transferred to 85 DEG C, carries out prebake 4h, it is seen that solution becomes gluey,
Temperature is being increased to 110 DEG C again, is continued dry 13h, is become the substance of yellow fluffy；
(5) yellow substance can be sticked in walls of beaker, it is scraped off at leisure with spoon, puts crucible into, then is put into box
Temperature is transferred to 450 DEG C of pre-sintering 5h, is then increased to 700 DEG C of sintering 2h again, product is allowed to naturally ring to room temperature by resistance furnace, from
Chamber type electric resistance furnace takes out product, and grinding 30 minutes to partial size is 30-300nm to get green light activated red fluorescence powder is arrived.
Embodiment 2 prepare red fluorescence powder under the excitation of 395nm, 466nm and 537nm, emission peak is all in 618nm
Left and right, and find that 537nm green light rate of induced polarization ultraviolet light and blue light will be got well.
Embodiment 3
A kind of green light activated red fluorescence powder Ca0.7MoO4:0.3Eu3+: the preparation method of 0.05Si:0.4Li, including with
Lower step:
(1) raw material are ready to first, find out corresponding relative molecular mass, molecular formula, prepares equation, calculate carbon
Sour calcium, europium oxide, four Heshui ammonium molybdates, ethyl orthosilicate and the corresponding molal weight of Li；
(2) data calculated are good with excel charting, facilitate experiment, using electronic balance weighing raw material,
Will be retained after decimal point by weighing numerical value by three, and calcium carbonate, europium oxide and Li are dissolved with nitric acid respectively, and it is molten to respectively obtain calcium nitrate
Liquid, europium nitrate solution and lithium nitrate solution；Four Heshui ammonium molybdates and citric acid are dissolved with water, and respectively obtaining concentration is 0.6g/mL
Citric acid solution and concentration be 0.15g/mL ammonium molybdate solution；Using water by teos hydrolysis, obtaining concentration is 0.1-
The silicon dioxde solution of 0.3g/ml；
(3) respectively that calcium nitrate solution, europium nitrate solution, lithium nitrate solution, citric acid solution, the ammonium molybdate prepared is molten
Liquid and silicon dioxde solution mix, and under temperature 70 C, stirring 30min obtains mixing molten so that solution is sufficiently mixed
Liquid；
(4) it puts mixed solution into drying box, temperature is transferred to 90 DEG C, carries out prebake 5h, it is seen that solution becomes gluey,
Temperature is being increased to 120 DEG C again, is continued dry 16h, is become the substance of yellow fluffy；
(5) yellow substance can be sticked in walls of beaker, it is scraped off at leisure with spoon, puts crucible into, then is put into box
Temperature is transferred to 500 DEG C of pre-sintering 6h, is then increased to 800 DEG C of sintering 3h again, product is allowed to naturally ring to room temperature by resistance furnace, from
Chamber type electric resistance furnace takes out product, and grinding 30 minutes to partial size is 30-300nm to get green light activated red fluorescence powder is arrived.
Embodiment 2 prepare red fluorescence powder under the excitation of 395nm, 466nm and 537nm, emission peak is all in 618nm
Left and right, and find that 537nm green light rate of induced polarization ultraviolet light and blue light will be got well.
Embodiment 4
The emission spectrum and LED commercialization powder emission spectrum of red fluorescence powder prepared by embodiment 1 compare.
Wherein, Fig. 3 is that the emission spectrum of red fluorescence powder and LED commercialization fluorescent powder prepared by embodiment 1 compares (excitation wave
Long 395nm)；Fig. 4 is that the red fluorescence powder of the preparation of embodiment 1 and the emission spectrum of LED commercialization fluorescent powder compare (excitation wavelength
466nm)；Fig. 5 is that the red fluorescence powder of the preparation of embodiment 1 and the emission spectrum of LED commercialization fluorescent powder compare (excitation wavelength
537nm)。
From the figure 3, it may be seen that under the near ultraviolet excitation of 395nm, the strong light of red fluorescence powder prepared by discovery embodiment 1
Degree is similar with the luminous intensity of the special red business powder of LED, and high little by little, compares two kinds of fluorescent powders, discovery business
The wave peak width of powder is wider, and the wave peak width of red fluorescence powder prepared by embodiment 1 is narrow and sharp, but, real
The emission peak for applying the red fluorescence powder of the preparation of example 1 appears in 620nm or so, and business powder emission peak is in 615nm or so.
As shown in Figure 4, under the blue light excitation of 466nm, the luminous intensity phase of red fluorescence powder prepared by discovery embodiment 1
The luminous intensity of business powder special red for LED wants low, but be also it is lower, compare two kinds of fluorescent powders, discovery business powder
Wave peak width is wider, and the wave peak width of red fluorescence powder prepared by embodiment 1 is narrow and sharp, and emission peak all exists
618nm or so.
As shown in Figure 5, under the green light excitation of 537nm, the luminous intensity phase of red fluorescence powder prepared by discovery embodiment 1
The luminous intensity of business powder special red for LED is eager to excel very much, and has been higher by 60 or so, compares two kinds of fluorescent powders, is found
The wave peak width of business powder is wider, and the wave peak width of red fluorescence powder prepared by embodiment 1 is narrow and sharp, transmitting
All in 618nm or so, the luminous intensity for the red fluorescence powder that when the same green light with 537nm excites prepared by embodiment 1 is opposite at peak
In the luminous intensity eager to excel in whatever one does 60 or so of business powder, currently, business powder is generally relatively low in green light activated launching efficiency on the market,
Therefore, can be improved rouge and powder has very big reference significance and value in green light activated launching efficiency.
Claims (10)
1. a kind of green light activated red fluorescence powder, which is characterized in that the red fluorescence powder is Ca1-nMoO4:nEu3+:xSi:
YR, wherein R is alkali metal ion, and the range of n is 0.1≤n≤0.6, and the range of x is 0.01≤x≤0.1, and the range of y is 0.1
≤y≤0.5。
2. red fluorescence powder according to claim 1, which is characterized in that the alkali metal ion is sodium ion, lithium ion
Or potassium ion.
3. red fluorescence powder according to claim 1, which is characterized in that the value range of the n is 0.2≤n≤0.3, x
Value range be 0.02≤x≤0.06, the value range of y is 0.2≤y≤0.4.
4. red fluorescence powder according to claim 1, which is characterized in that the launch wavelength of the red fluorescence powder covers model
It encloses for 610-630nm.
5. the preparation method of red fluorescence powder of any of claims 1-4, which comprises the following steps:
1) nitric acid is added into calcium carbonate, europium oxide and alkali metal respectively, respectively obtains calcium nitrate solution, europium nitrate solution and alkali
Metal nitrate solution；Four Heshui ammonium molybdates and the dissolution of citric acid water are respectively obtained into citric acid solution and ammonium molybdate solution；It adopts
Silicon dioxde solution is obtained with hydrolyzing tetraethoxy orthosilane；
2) by calcium nitrate solution, europium nitrate solution, alkali metal nitric acid solution, citric acid solution, silicon dioxde solution and ammonium molybdate
Solution mixing, obtains mixed solution；
3) mixed solution is dried, is sintered and cooled, obtain red fluorescence powder.
6. preparation method according to claim 5, which is characterized in that further include by red fluorescence after cooling in step 3)
Powder is ground to the step of 30-300nm.
7. the preparation method stated according to claim 5, which is characterized in that in step 2), the concentration of citric acid solution is 0.1-1g/
ml；The concentration of ammonium molybdate solution is 0.02-0.2g/ml；The concentration of silicon dioxde solution is 0.1-0.3g/ml.
8. preparation method according to claim 5, which is characterized in that in step 3), the concrete operations of drying are: will mix
Solution carries out prebake 3-5h at 70-90 DEG C, then at 105-130 DEG C, dry 12-18h, until generating the object of yellow fluffy
Matter.
9. preparation method according to claim 5, which is characterized in that in step 3), the concrete operations of sintering are: will dry
Obtained substance is in 400-550 DEG C of pre-sintering 3.5-6h；Then it is increased to 600-850 DEG C of sintering 1.5-3h again.
10. red fluorescence powder of any of claims 1-4 is used as the application in luminescent material in white light LEDs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811355470.4A CN109370581A (en) | 2018-11-14 | 2018-11-14 | Green light activated red fluorescence powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811355470.4A CN109370581A (en) | 2018-11-14 | 2018-11-14 | Green light activated red fluorescence powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109370581A true CN109370581A (en) | 2019-02-22 |
Family
ID=65389064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811355470.4A Pending CN109370581A (en) | 2018-11-14 | 2018-11-14 | Green light activated red fluorescence powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109370581A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698798A (en) * | 2009-10-20 | 2010-04-28 | 中国地质大学（武汉） | High brightness molybdate red phosphor and preparation method thereof |
-
2018
- 2018-11-14 CN CN201811355470.4A patent/CN109370581A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698798A (en) * | 2009-10-20 | 2010-04-28 | 中国地质大学（武汉） | High brightness molybdate red phosphor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| AN XIE等: "Enhancement emission intensity of CaMoO4 : Eu3+, Na+ phosphor via Bi co-doping and Si substitution for application to white LEDs", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Considerable photoluminescence enhancement of LiEu (MoO4) 2 red phosphors via Bi and/or Si doping for white LEDs | |
| WO2009021367A1 (en) | A red phosphor powder used for light emitting diode (led) and its preparing method | |
| CN104868041A (en) | Full-carbon-based quantum dot mixed fluorescent powder LED and preparation method thereof | |
| CN113201342A (en) | Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof | |
| CN105219382A (en) | Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application | |
| CN103113889B (en) | A kind of molybdate red phosphor and preparation method thereof | |
| CN107629794A (en) | A kind of europium ion Eu3+The bismuthino luminescent material of activation, preparation method and application | |
| CN104449720B (en) | Blue colour fluorescent powder based on ultraviolet and near ultraviolet excitation and preparation method thereof | |
| CN107201228A (en) | A kind of Eu3+Ion-activated vanadium silicate material and preparation method and application | |
| CN104830334B (en) | A kind of preparation method and applications of dysprosium doped blue colour fluorescent powder | |
| CN103666471A (en) | Novel method of synthesizing high-performance YAG: Ce fluorescent powder | |
| CN103396798B (en) | A kind of near ultraviolet excitated nitric oxide fluorescent powder and preparation method thereof | |
| CN109370581A (en) | Green light activated red fluorescence powder and preparation method thereof | |
| CN107325813B (en) | Blue-green fluorescent material and preparation method thereof | |
| CN106085430B (en) | A kind of up-conversion phosphor and its preparation method and application | |
| CN108531181A (en) | A kind of rare earth doping fluorescent powder of anti-bombardment and preparation method thereof | |
| CN104927856B (en) | The method that tungstate red fluorescent powder is prepared based on sol-gel combustion method | |
| CN101698798B (en) | High brightness molybdate red phosphor and preparation method thereof | |
| CN105038783B (en) | Additive Mn germanate solid solution red fluorescence powder and preparation method | |
| Guan et al. | Fabrication and luminescent properties of Tb3+ doped double molybdate phosphors | |
| CN106085421A (en) | A kind of Eu3+positive magnesium silicate potassium fluorescent material activated and its preparation method and application | |
| CN107033897A (en) | The tungsten salt luminescent material and synthetic method of a kind of Fluorin doped of near ultraviolet excitation | |
| CN107099291A (en) | It is a kind of can be by the red fluorescence material of near ultraviolet excitation, preparation method and application | |
| CN102002362B (en) | Fluorescent powder for white light LED, preparation method and application thereof | |
| CN106867524B (en) | Preparation and application of alkaline earth aluminate blue fluorescent material |
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 |