CN102634340A - Red double-perovskite fluorescent powder for white-light LEDs and preparation method of red double-perovskite fluorescent powder - Google Patents
Red double-perovskite fluorescent powder for white-light LEDs and preparation method of red double-perovskite fluorescent powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 39
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- -1 metals ion Chemical class 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000010937 tungsten Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 229910052693 Europium Inorganic materials 0.000 abstract 1
- 229910052777 Praseodymium Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- 238000001228 spectrum Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 241001538234 Nala Species 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910017299 Mo—O Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
Abstract
The invention relates to a red double-perovskite fluorescent powder for white-light LEDs and a preparation method of the red double-perovskite fluorescent powder. The red double-perovskite fluorescent powder is characterized by comprising double-perovskite components shown in the following formula: (AA'1-xMex)MgMO<6>, wherein the A is one of Na or K, the A' is one of La or Gd or composition of the La and the Gd, the M is one of W or Mo or composition of the W and the Mo, the Me is one of rare-earth element Eu or Pr, and the x is larger than or equal to 0.005 and is smaller than or equal to 0.5. The fluorescent powder is prepared by means of sol-gel, single-phase double-perovskite oxide powder can be obtained at the lower temperature and in shorter time, mixing of ions or atoms can be realized by active ions of rare earth, test period is short and stability is fine.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, relate to a kind of white light LEDs with double-perovskite red fluorescence powder and preparation method thereof.
Background technology
White light-emitting diode (white LEDs) but as a kind of novel solid-state illumination device with advantages such as it is energy-conservation, efficient, volume is little, pollution-free and complanations and obtained widespread use in fields such as FPD, road lightings rapidly.
The approach of business-like acquisition white light is that 460nm blue light GaN chip excites Y at present
3Al
5O
12: Ce
3+Yellow fluorescent powder; The gold-tinted of fluorescent material emission and chip excite the remaining blue light in back to be combined to form white light; Red sector emission more weak in its spectrum causes its colour rendering index lower, therefore need in fluorescent material, sneak into the rouge and powder that excites to compensate red emission and improve light conversion efficiency; Simultaneously, in the red-green-blue fluorescent material that near ultraviolet LED excites, at present used red fluorescence powder like CaS:Eu
2+, Y
2O
2S:Eu
3+Deng luminous intensity far below with the BaMgAl that excites
10O
17: Eu
2+Blueness and ZnS:Cu
+, Al
3+Green emitting phosphor.In addition, the sulfide chemicalstability is general, and the sulphur gas that in use discharges and the pollution that the red emission band caused of broad and relatively poor purity of color etc. have all limited its application.Therefore, near ultraviolet have in the blue light range efficient absorption, have narrower photoluminescent band and the good red fluorescence powder of environmental stability has obtained broad research in red range, like tungsten hydrochlorate, phosphoric acid salt, vannadate, titanate etc.
Wherein, the tungsten hydrochlorate absorbs because of it has wide and strong charge migration at ultraviolet-blue wave band, stronger covalency between the W/Mo-O, higher rare earth ion quenching concentration, and become the excellent substrate material of near ultraviolet white light LEDs with red light material, wherein Eu
3+Or Pr
3+Mix the stronger red emission of luminescence center emission that forms in the lattice.Like AMO
4(A=Ca, Sr; M=W, Mo) type, ALn (MO
4)
2(A=Li, Na, K; Ln=lanthanide, Y; M=W, Mo) type, R
2(MoO
4)
3(R=La, Y, Gd) type etc.; But the structure of above tungsten hydrochlorate fluorescent material is MO
4Tetrahedron, and for the launching efficiency that further improves W-O in the tungsten hydrochlorate or Mo-O charge migration band and then obtain stronger red emission, scientists is attempted Eu
3+Be doped to and have the octahedral double-perovskite tungstate of W/Mo-O, prepared a series of Eu
3+Adulterated double-perovskite A
2BMO
6(A=Sr, Ba; B=Ca, Mg; M=W, Mo) dried tangerine peel-red fluorescence powder (Sivakumar V., et al.Electrochemical andSolid-State Letters, 2006,9 (6): H35-H38; Sivakumar V., et al.Journal of Solid State Chemistry.2008,181 (12): 3344-3351; Ye S., et al.Journal of The Electrochemical Society, 2008; 155 (6): J148-J151.Lei F., et al.Journal of Optoelectronics and Advanced Materials, 2008; 10 (1): 158-163.), research shows, Eu
3+Ion has MO at this
6Luminous adjustable in octahedral double-perovskite system, its luminous efficiency is higher than at MO
4In the tetrahedron, be one type of very promising ruddiness light-converting material.
Double-perovskite system (A at above report
2B
IB
IIO
6(B
II=Mo or W)) fluorescence host material in, its A position ion is+alkaline earth metal ion such as the Ca of divalent
2+, Sr
2+, Ba
2+Deng, the symmetry of its structure of double perovskite is stronger, with substrate composed conversion, its structure or cube, four directions or monocline; Under near ultraviolet excitated, Eu
3+It is main in said material, launching orange light basically, Eu
3+The red emission of hypersensitive transition is suppressed, and the intensity of its red emission area is still not enough.
Summary of the invention
The objective of the invention is to existing double-perovskite red fluorescence powder system (A
2B
IB
IIO
6(B
II=Mo or W)) its structural symmetry is strong and cause the red emission problem of lower, and provide a kind of novel white light LEDs to use the double-perovskite red fluorescence powder; Another object of the present invention provides above-mentioned white light LEDs with double-perovskite red fluorescence powder, preparation method thereof.
Technical scheme of the present invention is: in the double-perovskite system 2 A position ions be respectively+A=Na of 1 valency or K and+REE the A '=La or Gd (and combination) combination of 3 valencys (is AA ' MgBO
6(B=Mo or W); Utilization is that the sol-gel method of complexing agent obtains rare earth ion Eu under lower calcining temperature with Hydrocerol A and EDTA
3+Or Pr
3+Even adulterated double-perovskite red fluorescence powder on ion concentration.Because the A position is two different metallic ions; The reduction of crystal structure symmetry is selected to form the more energy pipeline with more doping substitute element; Can further improve and optimize the luminous intensity of red fluorescence powder and improve its emmission spectrum scope, so provide a kind of novel be stable, efficient, fluorescent material that color developing is good matrix, that can be closely effectively excited by ultraviolet and blue light with the tungsten hydrochlorate.
Concrete technical scheme of the present invention is: a kind of white light LEDs is used the double-perovskite red fluorescence powder, it is characterized in that it consists of the double-perovskite component shown in the following formula:
(AA’
1-xMe
x)MgMO
6
Wherein, A is a kind of among Na or the K, and A ' is a kind of or its combination among La or the Gd, and M is a kind of or its combination among W or the Mo; Me is a kind of among REE Eu or the Pr; 0.005≤x≤0.5.
The present invention also provides the method for above-mentioned white light LEDs with the double-perovskite red fluorescence powder, and its concrete steps are following:
(1) choose raw material: A, A ', Me, Mg metals ion are got the above metal nitrate of corresponding analytical pure respectively; The molybdenum source is water-soluble ammonium molybdate, preferred Ammonium Heptamolybdate; The tungsten source is water-soluble ammonium tungstate or ammonium metawolframate;
(2) press double-perovskite form (AA '
1-xMe
x) MgMO
6Required metallic element molar ratio weighing raw material;
When M is Mo, at first molybdenum source and YD 30 (EDTA) are dissolved in (add-on of ammoniacal liquor gets final product can dissolve solute) in the ammonia soln together; Hydrocerol A is dissolved in the deionized water; The ammonia soln of molybdenum source and EDTA is mixed stirring heating with the nitrate soln of A, A ', Me and Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the above-mentioned mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating always;
Perhaps when M is W, at first YD 30 (EDTA) is dissolved in (add-on of ammoniacal liquor gets final product can dissolve solute) in the ammonia soln; Tungsten source and Hydrocerol A are dissolved in the deionized water respectively; The ammonia soln of EDTA is mixed stirring heating with the nitrate soln of A, A ', Me, Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the above-mentioned mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again; At last tungsten source solution is joined in the mixing solutions; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating always;
Perhaps when M is the combination of Mo and W, at first molybdenum source and YD 30 (EDTA) are dissolved in (add-on of ammoniacal liquor gets final product can dissolve solute) in the ammonia soln together; Tungsten source and Hydrocerol A are dissolved in the deionized water respectively; The ammonia soln of molybdenum source and EDTA is mixed stirring heating with the nitrate soln of A, A ', Me, Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again, at last tungsten source solution is joined in the mixing solutions; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating always;
(3) the airtight stirring of the solution that configures was broken a seal after 0.5～1 hour, do not stop to stir 1～2.5 hour formation colloidal sol 50～60 ℃ of heating; Then Heating temperature is increased to 65～75 ℃ and continuation stirring, until forming transparent gel;
(4) transparent gel is continued heating, combustion reactions takes place form fluffy precursor powder; Again the precursor powder was carried out pre-burning in 3～6 hours 500～600 ℃ of insulations;
(5) powder after the pre-burning is incubated 6-8 hour down at 800～1100 ℃ and calcines, promptly obtain the double-perovskite red fluorescence powder.
In the preferred above-mentioned steps (2) whole process always the temperature of stirring heating be 30～50 ℃; Preferred described Hydrocerol A mole dosage is A, A ', Me, Mg metals ion mole number summation 1.0～2.0 times; The EDTA mole dosage is A, A ', Me, Mg metals ion mole number summation 0.5～1.5 times.
Beneficial effect:
1. fluorescent material provided by the invention is for being matrix with the tungsten hydrochlorate; Its excitation spectrum is in the 300-500nm scope; Main excitation peak is near 390nm and 460nm; The emission peak of this and InGaN base near ultraviolet and blue-light LED chip is very identical, can be used for white light LEDs and other field of light emitting materials.
2. fluorescent material emission Eu provided by the invention
3+Or Pr
3+Ionic characteristic ruddiness, it occupies the lower position of lattice symmetry in such fluorescent material, stronger to the absorption of excitation energy, and emission wavelength is in the 590-650nm red range, and emissive porwer is high, and purity of color and color developing are good.
3. fluorescent material provided by the invention adopts the sol-gel method preparation; Can obtain monophasic double-perovskite oxide powder in lower temperature with under than short soaking time; Rare earth activation ion can be realized the mixing on ion or the atomic level, short, good stability of test period.
Description of drawings
Fig. 1 is according to (the NaLa of instance 1 with instance 3 preparations
0.99Eu
0.01) MgMoO
6, (KLa
0.99Pr
0.01) MgWO
6Fluorescent material is the excitation spectrum under 615nm, 606nm monitoring respectively, and X-coordinate is wavelength (nm), and ordinate zou is a luminous intensity.
Fig. 2 is according to instance 1 (a) (NaLa with instance 3 preparations
0.99Eu
0.01) MgMoO
6, (b) (KLa
0.99Pr
0.01) MgWO
6Fluorescent material and (c) commercial Y
2O
2S:Eu fluorescent material is the emmission spectrum under 395nm, 453nm, 395nm excite respectively, and X-coordinate is wavelength (nm), and ordinate zou is a luminous intensity.Wherein the red light-emitting intensity of two kinds of fluorescent materials of the present invention's preparation all is higher than commercial fluorescent material.
Embodiment
Below in conjunction with embodiment the present invention is further described, but should limit protection scope of the present invention with this.
It is the sol-gel method synthesizing rare-earth ion Eu of complexing agent that the present invention adopts with Hydrocerol A and EDTA
3+Or Pr
3+The prescription of 4 specific embodiments of the double-perovskite red fluorescence powder of ion doping is as shown in table 1.
Table 1
Annotate: M is total metals ion molar weight
Embodiment 1
#((NaLa
0.99Eu
0.01) MgMoO
6):
Form as in the table 11
#Shown in, concrete preparation method comprises the following steps:
1. press the composition weighing pressed powder raw material in the table 1, at first ammonium molybdate and EDTA are dissolved in the ammonia soln, Hydrocerol A is dissolved in the deionized water; The ammonia soln of ammonium molybdate and EDTA is mixed stirring heating with the nitrate soln of metals ion; After then consoluet citric acid solution being regulated pH=5 with ammoniacal liquor; It is joined in the mixing solutions, use ammoniacal liquor regulator solution pH=7 at last, whole solution system all metal ions total concn is about 1.0mol/L; Whole process is stirring heating always, and Heating temperature is 35 ℃;
2. the solution that configures is placed on the magnetic stirring apparatus, stir after 40 minutes Kaifeng, do not stop to stir about 2.5 hours 50 ℃ of following heating and form colloidal sol; Then Heating temperature is increased to 70 ℃ and continuation stirring, until forming transparent gel;
3. gel is put and continued heating, combustion reactions takes place form fluffy precursor powder; After precursor powder ground slightly, be put in the aluminum oxide porcelain boat, place 600 ℃ of low temperature presinterings of retort furnace again, and be incubated 4 hours, lower the temperature with stove then.
4. the powder after the pre-burning is ground, be put in the alumina-ceramic crucible, carry out 1000 ℃ of high-temperature calcinations, be incubated 6 hours, lower the temperature with stove then.
5. the product that makes is ground 200 mesh sieves, with powder compressing machine its dry-pressing was become thin plectane then, carried out performance test.
Test result is following:
Process 5. in sample after compressing tablet is handled carry out fluorescence spectrum (FL3-221; HOROBA; Jobin Yvon, France) test, monitoring 615nm ruddiness down excitation spectrum and excite the emmission spectrum of time powder to see Fig. 1 (a) and Fig. 2 (a) respectively near ultraviolet 395nm.
Embodiment 2
#((NaLa
0.5Gd0.48Eu
0.02) MgWO
6):
Form as in the table 12
#Shown in, concrete preparation method comprises the following steps:
1. press the composition weighing pressed powder raw material in the table 1, at first EDTA is dissolved in the ammonia soln, ammonium tungstate and Hydrocerol A are dissolved in the appropriate amount of deionized water, heated and stirred dissolving respectively; The ammonia soln of EDTA is mixed stirring heating with the nitrate soln of metals ion; After then consoluet citric acid solution being regulated pH=6 with ammoniacal liquor, it is joined in the mixing solutions; Regulate mixing solutions pH=8 with ammoniacal liquor at last, and ammonium tungstate solution is added, whole solution system all metal ions total concn is about 1.15mol/L, and whole process is stirring heating always, and Heating temperature is 30 ℃;
2. the solution that configures is placed on the magnetic stirring apparatus, stir after 30 minutes Kaifeng, do not stop to stir about 2 hours 55 ℃ of heating and form colloidal sol; Then Heating temperature is increased to 65 ℃ and continuation stirring, until forming transparent gel;
3. gel is continued heating, take place to form fluffy precursor powder after the combustion reactions; After precursor powder ground slightly, be put in the aluminum oxide porcelain boat, place 500 ℃ of low temperature presinterings of retort furnace again, and be incubated 6 hours, lower the temperature with stove then.
4. the powder after the pre-burning is ground, be put in the alumina-ceramic crucible, carry out 1000 ℃ of high-temperature calcinations, be incubated 6 hours, lower the temperature with stove then.
5. the product that makes is ground 200 mesh sieves, can obtain mixing the double-perovskite red fluorescence powder of Eu.Prepared fluorescent material can send stronger ruddiness.
Embodiment 3
#((KLa
0.99Pr
0.01) MgWO
6):
Form as in the table 13
#Shown in, concrete preparation method comprises the following steps:
1. press the composition weighing pressed powder raw material in the table 1, at first EDTA is dissolved in the ammonia soln, ammonium tungstate and Hydrocerol A are dissolved in the appropriate amount of deionized water, heated and stirred dissolving respectively; The ammonia soln of EDTA is mixed stirring heating with the nitrate soln of metals ion; After then consoluet citric acid solution being regulated pH=7 with ammoniacal liquor, it is joined in the mixing solutions; Use ammoniacal liquor regulator solution pH=7.5 at last, and ammonium tungstate solution is joined in the mixing solutions, whole solution system all metal ions total concn is about 1.25mol/L, and whole process is stirring heating always, and temperature is 30 ℃;
2. the solution that configures is placed on the magnetic stirring apparatus, stir after 30 minutes Kaifeng, do not stop to stir about 2 hours 55 ℃ of heating and form colloidal sol; Then Heating temperature is increased to 65 ℃ and continuation stirring, until forming transparent gel;
3. gel is continued heating, take place to form fluffy precursor powder after the combustion reactions; After precursor powder ground slightly, be put in the aluminum oxide porcelain boat, place 600 ℃ of low temperature presinterings of retort furnace again, and be incubated 4 hours, lower the temperature with stove then.
4. the powder after the pre-burning is ground, be put in the alumina-ceramic crucible, carry out 950 ℃ of high-temperature calcinations, be incubated 8 hours, lower the temperature with stove then.
5. the product that makes is ground 200 mesh sieves, with powder compressing machine its dry-pressing was become thin plectane then, carried out structure and performance test.
Test result is following:
Process 5. in sample after compressing tablet is handled carry out the fluorescence spectrum test, excitation spectrum and blue light 453nm down excites the emmission spectrum of powder to see Fig. 1 (b) and Fig. 2 (b) respectively at monitoring 606nm ruddiness.
Embodiment 4
#((KGd
0.5Pr
0.5) MgMo
0.1W
0.9O
6):
Form as in the table 14
#Shown in, concrete preparation method comprises the following steps:
1. press the composition weighing pressed powder raw material in the table 1, at first molybdenum source and YD 30 (EDTA) are dissolved in the ammonia soln together, tungsten source and Hydrocerol A are dissolved in the deionized water respectively; The ammonia soln of molybdenum source and EDTA is mixed stirring heating with the nitrate soln of metals ion; After then consoluet citric acid solution being regulated pH=7 with ammoniacal liquor, it is joined in the mixing solutions, regulate mixing solutions pH=7 with ammoniacal liquor again, at last tungsten source solution is joined in the mixing solutions; Guarantee that whole solution system all metal ions total concn is 1.25mol/L, whole process is stirring heating always, and temperature is at 40 ℃;
2. the solution that configures is placed on the magnetic stirring apparatus, stir after 30 minutes Kaifeng, do not stop to stir about 2.5 hours 50 ℃ of heating and form colloidal sol; Then Heating temperature is increased to 70 ℃ and continuation stirring, until forming transparent gel;
3. gel is continued heating, take place to form fluffy precursor powder after the combustion reactions; After precursor powder ground slightly, be put in the aluminum oxide porcelain boat, place 600 ℃ of low temperature presinterings of retort furnace again, and be incubated 4 hours, lower the temperature with stove then.
4. the powder after the pre-burning is ground, is put in the alumina-ceramic crucible, carry out 1100 ℃ of high-temperature calcinations,, be incubated 6 hours, lower the temperature with stove then.
5. the product that makes is ground 200 mesh sieves, can obtain mixing the double-perovskite red fluorescence powder of Pr.Prepared fluorescent material can send stronger ruddiness.
Above-mentioned instance is preferred implementation of the present invention; But embodiment of the present invention does not receive the restriction of above-mentioned instance; Other are any not to deviate from modification, the modification made under spirit of the present invention and the principle, substitute, combination, simplify the substitute mode that is equivalence, is included within protection scope of the present invention.
Claims (4)
1. a white light LEDs is used the double-perovskite red fluorescence powder, it is characterized in that it consists of the double-perovskite component shown in the following formula:
(AA’
1-xMe
x)MgMO
6
Wherein, A is a kind of among Na or the K, and A ' is a kind of or its combination among La or the Gd, and M is a kind of or its combination among W or the Mo; Me is a kind of among REE Eu or the Pr; 0.005≤x≤0.5.
2. method for preparing white light LEDs as claimed in claim 1 with the double-perovskite red fluorescence powder, its concrete steps are following:
(1) choose raw material: A, A ', Me, Mg metals ion are got the above metal nitrate of corresponding analytical pure respectively; The molybdenum source is water-soluble ammonium molybdate; The tungsten source is water-soluble ammonium tungstate or ammonium metawolframate;
(2) press double-perovskite form (AA '
1-xMe
x) MgMO
6Required metallic element molar ratio weighing raw material;
When M is Mo, at first be dissolved in molybdenum source and YD 30 (EDTA) in the ammonia soln together; Hydrocerol A is dissolved in the deionized water; The ammonia soln of molybdenum source and EDTA is mixed stirring heating with the nitrate soln of A, A ', Me and Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the above-mentioned mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating always;
Perhaps when M is W, at first YD 30 is dissolved in the ammonia soln; Tungsten source and Hydrocerol A are dissolved in the deionized water respectively; The ammonia soln of EDTA is mixed stirring heating with the nitrate soln of A, A ', Me, Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the above-mentioned mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again; At last tungsten source solution is joined in the mixing solutions; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating always;
Perhaps when M is the combination of Mo and W, at first be dissolved in molybdenum source and YD 30 in the ammonia soln together; Tungsten source and Hydrocerol A are dissolved in the deionized water respectively; The ammonia soln of molybdenum source and EDTA is mixed stirring heating with the nitrate soln of A, A ', Me, Mg metals ion; After then consoluet citric acid solution being regulated pH=5-7 with ammoniacal liquor, it is joined in the mixing solutions, regulate mixing solutions pH=6～8 with ammoniacal liquor again, at last tungsten source solution is joined in the mixing solutions; Controlling whole solution system all metal ions total concn is 1～1.5mol/L; Wherein whole process is stirring heating (temperature is at 30～50 ℃) always;
(3) the airtight stirring of the solution that configures was broken a seal after 0.5～1 hour, do not stop to stir 1～2.5 hour formation colloidal sol 50～60 ℃ of heating; Then Heating temperature is increased to 65～75 ℃ and continuation stirring, until forming transparent gel;
(4) transparent gel is continued heating, combustion reactions takes place form fluffy precursor powder; Again the precursor powder was carried out pre-burning in 3～6 hours 500～600 ℃ of insulations;
(5) powder after the pre-burning is incubated 6-8 hour down at 800～1100 ℃ and calcines, promptly obtain the double-perovskite red fluorescence powder.
3. by the described method of claim 2, it is characterized in that described molybdenum source is an Ammonium Heptamolybdate.
4. by the described method of claim 2, it is characterized in that described Hydrocerol A mole dosage is A, A ', Me, Mg metals ion mole number summation 1.0～2.0 times; The EDTA mole dosage is A, A ', Me, Mg metals ion mole number summation 0.5～1.5 times.
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