CN106635011A - Trigonal double perovskite red fluorescent powder for white light LED (Light Emitting Diode) and preparation method of trigonal double perovskite red fluorescent powder - Google Patents
Trigonal double perovskite red fluorescent powder for white light LED (Light Emitting Diode) and preparation method of trigonal double perovskite red fluorescent powder Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- 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
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention discloses trigonal double perovskite red fluorescent powder for a white light LED (Light Emitting Diode) and a preparation method of the trigonal double perovskite red fluorescent powder. The trigonal double perovskite red fluorescent powder is prepared from a trigonal crystal system double perovskite component shown as the following formula: A2B2/3MO6:Eu<3+>, wherein A is one of Ba or Sr, B is one of Y, Gd and Lu, and M is one of W and Mo; the trigonal double perovskite red fluorescent powder for the white light LED is prepared by adopting a sol-gel method with ethylenediamine tetraacetic acid (EDTA)-citric acid as a complexing agent. The red fluorescent powder prepared by the preparation method disclosed by the invention takes molybdate and tungstate as a matrix, is provided with a trigonal double perovskite structure, is adjustable in color, and can be effectively excited by ultraviolet light and blue light; the red fluorescent powder is stable, efficient and good in color redenring property and is suitable for the white light LED.
Description
Technical field
The present invention relates to a kind of white light LEDs double-perovskite red fluorescence powder and preparation method thereof, more precisely provides
A kind of double-perovskite of trigonal system, the red fluorescence powder of Color tunable section, belong to rare earth luminescent material technical field.
Background technology
Used as a kind of New Solid illuminating device, white light-emitting diode (LEDs) is with its energy-conservation, efficient, small volume, nothing
Pollution is applied widely with the advantages of can planarizing in fields such as FPD, road lightings.
At present white light LEDs are mainly using InGaN chips (370～410nm) and three primary colors fluorescent powder (red, green, blue) group
Conjunction sends white light.The light that the white light that the system sends simply is sent by fluorescent material is combined, without the beche-de-mer without spike that LED chip sends
With, it is possible to reduce white point with the time drift.But wherein red fluorescence powder system is single, the red fluorescence powder of current commercialization
Mainly Y2O2S:Eu3+.Relative to blue, green fluorescence powder, Y2O2S:Eu3+Be present following prominent defect in fluorescent material, fail so far effectively
Solve, mainly have：It is expensive；400nm or so exciting lights can not effectively be absorbed；Luminosity is blue not as good as commercialization, green fluorescence
The 1/8 of powder；Unstable chemcial property；Service life is short etc., significantly limit its application.For a long time, people try hard to always
New and effective stable red fluorescent powder for white radiation LED is developed, is obtained in that have near ultraviolet to blue light range to it
Efficient absorption, and there is narrower photoluminescent band in red range, mainly there are tungsten hydrochlorate, phosphate, vanadate, titanate at present
Deng.
Wherein relative to other system red fluorescence powders, tungsten silicate system red fluorescence powder has advantage following prominent：
(1) exciting light near 300～400nm can effectively be absorbed；(2) relative luminance is higher；(3) sintering temperature is low, and equipment is simple；
(4) good stability, will not produce under uv irradiation the toxic gases such as sulfide.Tungsten silicate system fluorescent material becomes nearly purple
The excellent host material of outer white light LEDs red light material.
Wherein, the tungsten hydrochlorate with structure of double perovskite causes extensive concern as a kind of new structure type, allusion quotation
Type structure has A2B(Mo/W)O6:Eu3+(A=Sr, Ba, Ca；It is Ca when B=Zn, Mg, Ca, wherein A are different with B)；In order to solve
The symmetry of its doping position is higher and the problems such as cause excitation difference, in patent of invention 201210071449.8 will wherein 2+
The A atoms of divalent, are replaced respectively, such as NaGdMg (W, Mo) O with the atom of+1 valency and+trivalent6:Eu3+Etc. realizing Eu3+Ruddiness
Transmitting；Continue, the employing of patent of invention 201310084960.6 is co-doped with Bi or the scheme of Sm realizes Eu3+The raising of luminous intensity,
Its excitation and luminous intensity are improved, and patent of invention 201510100765.7 is to be co-doped with Li and Mg as sensitization source and carry
For fluxing action, and replace double-perovskite NaGdMgWO6In Gd positions, produce relatively low lattice symmetry, it is ensured that fluorescent material
It is stable, efficiently and high-color rendering.
At present, the fluorescent material of conventional double-perovskite system, often only has single Doping Center, as can only be singly mixed+trivalent
Gd3+Position, can only send monochromatic light；Or the ruddiness that sends of Doping Center or orange light intensity it is weak, such as A2B(Mo/W)O6:Eu3+In ,+
Although divalent A positions or B positions can mix+Eu of trivalent3+, but there is charge unbalance, luminous intensity is low, red light color purity difference.Cause
This, this area can effectively overcome existing fluorescent material shortcoming in the urgent need to developing one kind, with Color tunable section, can be closely ultraviolet
Stable, efficient, the red fluorescence material that colour rendering is good effectively excited with blue light.
The content of the invention
The purpose of the present invention is to improve prior art weak point, there is provided a kind of white light LEDs are red with tripartite's double-perovskite
Fluorescent material and preparation method thereof, its chemical composition formula is
A2B2/3MO6:Eu3+
Wherein, A is the one kind in Ba or Sr, and B is the one kind in Y, Gd, Lu, and M is the one kind in W, Mo.It is double in the structure
Perovskite skeleton is made up of B/M-O octahedrons, and A positions are filled in the multiaspect body space of 12 coordinations.And exist in black light area
O2-Ion is to W/Mo6+The electric charge transfer of ion, forms a strong and wide absorption band, rare earth Eu3+Be incorporated into such material because
The lattice position for occupying different and launch different light.Work as Eu3+Part replaces A positions ion to form (A1-xEux)2B2/3MO6When,
Wherein 0.01≤x≤0.3, based on the orange light (590～595nm) of phosphor emission magnetic dipole transition；Work as Eu3+Part replaces B positions
Ion forms A2(B1-yEuy)2/3MO6When, wherein 0.01≤y≤0.5, the ruddiness of phosphor emission electric dipole transition (610～
Based on 620nm), so as to form Color tunable section, and both of which has higher quantum luminous efficiency (55～70%), and heat is steady
It is qualitative good.
Further, since covalency stronger between W/Mo-O, fluorescent material has higher rare earth ion quenching concentration, therefore has
There is higher doping concentration of rare earth ion, so as to have higher luminous intensity.And then we provide a kind of new with tungsten
Hydrochlorate for matrix, with tripartite's structure of double perovskite, Color tunable section, can closely by ultraviolet and blue light effectively excite it is steady
Good red fluorescence material of fixed, efficient, colour rendering and preparation method thereof.
A kind of white light LEDs proposed by the present invention adopt ethylenediamine tetra-acetic acid with tripartite's double-perovskite red fluorescence powder
(EDTA)-citric acid is prepared for the sol-gal process of complexing agent, and its concrete preparation method is as follows：
(1) raw material：A, B, Eu metal ion chooses respectively the pure metal nitrate of corresponding analysis；Molybdenum source is water-soluble molybdic acid
Ammonium, preferred ammonium heptamolybdate；Tungsten source is water-soluble ammonium tungstate or ammonium metatungstate；
(2) (A is constituted by double-perovskite1-xEux)2B2/3MO6Or A2(B1-yEuy)2/3MO6Required metallic element mol ratio claims
Content of starting materials；
If M is Mo, molybdenum source and ethylenediamine tetra-acetic acid (EDTA) are dissolved in together in ammonia spirit (addition of ammoniacal liquor with
Solute can be dissolved)；By the ammonia spirit of molybdenum source and ethylenediamine tetra-acetic acid (EDTA) and the nitrate of A, B, Eu metal ion
Solution mixes, agitating heating；Then citric acid is added in mixed solution, agitating heating dissolving；It is molten mixing to be adjusted with ammoniacal liquor
Liquid pH is 8～9；
If M is W, during ethylenediamine tetra-acetic acid (EDTA) is dissolved in into ammonia spirit, tungsten source is dissolved in deionized water, respectively
Heating stirring dissolves；The ammonia spirit of ethylenediamine tetra-acetic acid (EDTA) is mixed with the nitrate solution of metal ion afterwards, is stirred
Mix heating；Then citric acid is added into mixed solution, agitating heating dissolving；It is 8～9 to adjust mixed solution PH with ammoniacal liquor, then
Tungsten source solution is added in mixed solution；
Ensure that whole solution system all metal ions total concentration is 0.5～1.0mol/L, whole process stirs add always
Hot (temperature is at 30～50 DEG C)；As the consumption of the citric acid and ethylenediamine tetra-acetic acid (EDTA) of complexing agent, to be respectively A, B, Eu golden
1.0～2.0 times, 0.5～1.5 times of category ion summation；
(3) by the solution for having configured it is closed stirring 0.5～1 hour after break a seal, heat at 50～60 DEG C do not stop stirring 1～
Form colloidal sol within 2 hours；Then heating-up temperature is improved to 70～80 DEG C and is continued stirring, until forming transparent gel；
(4) by 150～180 DEG C of heating of gel, there is combustion reaction, fluffy precursor powder is formed after 3～5 hours；
Again precursor powder is carried out into high temperature pre-burning, pre-burning in 3～6 hours is incubated at 400～600 DEG C；
(5) powder after pre-burning is carried out into high-temperature calcination, the calcining of 6-10 hours is incubated at 900～1200 DEG C.
Beneficial effects of the present invention are：
1., with tungsten hydrochlorate as matrix, its excitation spectrum is in 350- for the red fluorescent powder for white radiation LED that the present invention is provided
In the range of 500nm, near 395nm, 465nm, this sends out with InGaN bases near ultraviolet main excitation peak with blue-light LED chip
Penetrate peak very identical, can be used for white light LEDs and other field of light emitting materials.
2. the fluorescent material transmitting Eu that the present invention is provided3+The feature ruddiness of ion or orange light, it is occupied in the fluorescent material
Different A positions and the lattice position of B positions, launch the light of different wave length, and so as to obtain Color tunable section, launch wavelength is in 590-
In 620nm red ranges, emissive porwer is high, and luminous quantum efficiency is high, and trigonal system, and case is lower to being molded, excitation with
Colour rendering is good.
3. the fluorescent material that the present invention is provided is prepared using sol-gel process, can be in relatively low temperature and shorter insulation
Single-phase tripartite's double-perovskite oxide powder can be obtained under time, rare earth activation ion is capable of achieving on ion or atomic level
Mixing, the test period is short, good stability.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but should not be limited the scope of the invention with this.
The embodiment list of ingredients of table 1
As shown in table 1, the present invention adopts the sol-gal process with citric acid and ethylenediamine tetra-acetic acid (EDTA) as complexing agent
Synthesizing rare-earth ion Eu3+, tripartite's double-perovskite red fluorescence powder is prepared so as to adulterate, M is total metal ion mole in table 1.
Embodiment one：
As 1 in table 1#Shown, concrete preparation method comprises the following steps：
1. the composition pressed in table 1 weighs pressed powder raw material, and EDTA first is dissolved in appropriate ammonia spirit, and tungsten source is dissolved in
In ionized water, heating stirring dissolving；After clarification is completely dissolved, by the ammonia spirit of EDTA and the nitrate solution of metal ion
Mixing, agitating heating；Then citric acid is added in mixed solution, the sealing stirring 20 minutes after citric acid dissolving is finished；
Finally pH value of solution=8 are adjusted with ammoniacal liquor, then tungsten source solution is added in mixed solution；Whole solution system all metal ions
Total concentration is about 1.0mol/L, whole process agitating heating always, and heating-up temperature is 30 DEG C；
2. the solution for having configured is placed on magnetic stirring apparatus, stirring breaks a seal after 40 minutes, heats at 50 DEG C and does not stop
Stirring forms colloidal sol in 1 hour or so；Then heating-up temperature is improved to 70 DEG C and is continued stirring, until forming transparent gel；
3. gel is placed in into 160 DEG C of baking ovens or Muffle stove heat, combustion reaction occurs and more gas is supervened, 3 is little
When after form fluffy precursor powder；After precursor powder is slightly ground, in being put into aluminum oxide porcelain boat, then it is placed in Muffle furnace
400 DEG C of low temperature presinterings, and 4 hours are incubated, then lower the temperature with stove.
4. the powder after pre-burning is ground, in being put in alumina ceramic crucible, carries out 900 DEG C of high-temperature calcinations, insulation 6 is little
When, then lower the temperature with stove.
5. by ground 200 mesh sieve of obtained product, then with powder compressing machine by its dry-pressing into thin round plate, carry out performance
Test.
Test result is as follows：
5. the middle sample Jing after compressing tablet process carries out XRD tests to process, and structure is trigonal system, structure of double perovskite.Enter
Row fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) is tested, and near ultraviolet 395nm sending out for lower powder is excited
Peak is penetrated positioned at 591nm, luminous quantum efficiency is 70%.
Embodiment two：
As 2 in table 1#Shown, concrete preparation method comprises the following steps：
1. the composition pressed in table 1 weighs pressed powder raw material, quantitative EDTA is dissolved in appropriate ammonia spirit first, wolframic acid
Ammonium is dissolved in appropriate amount of deionized water, respectively heating stirring dissolving；After clarification is completely dissolved, by the ammonia spirit and metal of EDTA
The nitrate solution mixing of ion, agitating heating；Then citric acid is added in mixed solution, after citric acid dissolving is finished
Sealing stirring 20 minutes；Finally pH value of solution=9 are adjusted with ammoniacal liquor, then tungsten source solution is added in mixed solution, whole solution
System all metal ions total concentration is about 0.8mol/L, whole process agitating heating always, and heating-up temperature is 40 DEG C；
2. the solution for having configured is placed on magnetic stirring apparatus, stirring breaks a seal after 45 minutes, to heat do not stop at 55 DEG C and stirs
Mix and form colloidal sol in 1.5 hours or so；Then heating-up temperature is improved to 75 DEG C and is continued stirring, until forming transparent gel；
3. gel is placed in into 150 DEG C of baking ovens or Muffle stove heat, combustion reaction occurs and more gas is supervened, 4 is little
When after form fluffy precursor powder；After precursor powder is slightly ground, in being put into aluminum oxide porcelain boat, then it is placed in Muffle furnace
500 DEG C of low temperature presinterings, and 3 hours are incubated, then lower the temperature with stove.
4. the powder after pre-burning is ground, in being put in alumina ceramic crucible, carries out 1000 DEG C of high-temperature calcinations, insulation 6 is little
When, then lower the temperature with stove.
5. by ground 200 mesh sieve of obtained product, you can obtain mixing tripartite's double-perovskite red fluorescence powder of Eu.Then
With powder compressing machine by its dry-pressing into thin round plate, structure and performance test are carried out.
Test result is as follows：5. the middle sample Jing after compressing tablet process carries out XRD tests to process, and structure is trigonal system, double
Perovskite structure.Fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) test is carried out, is swashed near ultraviolet 395nm
The emission peak for giving powder is located at 594nm, and luminous quantum efficiency is 55%.
Embodiment three：
As 3 in table 1#Shown, concrete preparation method comprises the following steps：
1. the composition pressed in table 1 weighs pressed powder raw material, and ammonium molybdate and EDTA are dissolved in appropriate ammonia spirit first,
Heating stirring dissolves；After clarification is completely dissolved, by the ammonia spirit of ammonium molybdate and EDTA and the nitrate solution of metal ion
Mixing, agitating heating；Then citric acid is added in mixed solution, the sealing stirring 20 minutes after citric acid dissolving is finished；
Finally pH value of solution=8.5 are adjusted with ammoniacal liquor, whole solution system all metal ions total concentration is about 0.5mol/L, whole process
Agitating heating always, heating-up temperature is 45 DEG C；
2. the solution for having configured is placed on magnetic stirring apparatus, stirring breaks a seal after 40 minutes, then heats and does not stop stirring 2
Hour or so forms colloidal sol, and heating-up temperature is 55 DEG C；Then heating-up temperature is improved to 75 DEG C and is continued stirring, until forming saturating
Bright gel；
3. gel is placed in into 165 DEG C of baking ovens or Muffle stove heat, combustion reaction occurs and more gas is supervened, 4 is little
When after form fluffy precursor powder；After precursor powder is slightly ground, in being put into aluminum oxide porcelain boat, then it is placed in Muffle furnace
500 DEG C of low temperature presinterings, and 5 hours are incubated, then lower the temperature with stove.
4. the powder after pre-burning is ground, in being put in alumina ceramic crucible, carries out 1000 DEG C of high-temperature calcinations, insulation 9 is little
When, then lower the temperature with stove.
5. by ground 200 mesh sieve of obtained product, then with powder compressing machine by its dry-pressing into thin round plate, carry out structure
And performance test.
Test result is as follows：
5. the middle sample Jing after compressing tablet process carries out XRD tests to process, and structure is trigonal system, structure of double perovskite.Enter
Row fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) is tested, and near ultraviolet 395nm sending out for lower powder is excited
Peak is penetrated positioned at 615nm, luminous quantum efficiency is 65%.
Example IV：
As 4 in table 1#Shown, concrete preparation method comprises the following steps：
1. the composition pressed in table 1 weighs pressed powder raw material, first quantitative ammonium molybdate and EDTA is dissolved in into appropriate ammoniacal liquor
In solution, heating stirring dissolving；After clarification is completely dissolved, by the ammonia spirit of ammonium molybdate and EDTA and the nitric acid of metal ion
Salting liquid mixes, agitating heating；Then citric acid is added in mixed solution, the sealing stirring 20 after citric acid dissolving is finished
Minute；Finally with ammoniacal liquor adjust pH value of solution=9, whole solution system all metal ions total concentration be 1mol/L, whole process
Agitating heating always, heating-up temperature is 50 DEG C；
2. the solution for having configured is placed on magnetic stirring apparatus, stirring breaks a seal after 60 minutes, to heat do not stop at 60 DEG C and stirs
Mix and form colloidal sol in 2 hours or so；Then heating-up temperature is improved to 80 DEG C and is continued stirring, until forming transparent gel；
3. gel is placed in 180 DEG C of baking ovens or Muffle furnace and is heated, combustion reaction occurs and more gas is supervened, 5
Fluffy precursor powder is formed after hour；After precursor powder is slightly ground, in being put into aluminum oxide porcelain boat, then Muffle furnace is placed in
In 600 DEG C of low temperature presinterings, and be incubated 6 hours, then lower the temperature with stove.
4. the powder after pre-burning is ground, in being put in alumina ceramic crucible, carries out 1200 DEG C of high-temperature calcinations, insulation 10 is little
When, then lower the temperature with stove.
5. by ground 200 mesh sieve of obtained product, you can obtain mixing tripartite's double-perovskite red fluorescence powder of Eu.Then
With powder compressing machine by its dry-pressing into thin round plate, structure and performance test are carried out.
Test result is as follows：5. the middle sample Jing after compressing tablet process carries out XRD tests to process, and structure is trigonal system, double
Perovskite structure.Fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) test is carried out, is swashed near ultraviolet 395nm
The emission peak for giving powder is located at 620nm, and luminous quantum efficiency is 61%.
Examples detailed above is the present invention preferably embodiment, but embodiments of the present invention are not limited by examples detailed above
System, other it is any without departing from spirit of the invention and the modification, modification, replacement made under principle, combine, simplify be it is equivalent
Substitute mode, be included within protection scope of the present invention.
Claims (3)
1. a kind of white light LEDs tripartite's double-perovskite red fluorescence powder, it is characterised in that consisting of trigonal system shown in following formula
Double-perovskite component：
A2B2/3MO6:Eu3+
Wherein, A is the one kind in Ba or Sr, and B is the one kind in Y, Gd, Lu, and M is the one kind in W, Mo.Rare earth element Eu3+For red
Photoactivation light emitting ionic, it can partly replace A positions ion to form (A1-xEux)2B2/3MO6, wherein 0.01≤x≤0.3；Also may be used
B positions ion is replaced to form A with part2(B1-yEuy)2/3MO6, wherein 0.01≤y≤0.5.
2. a kind of white light LEDs according to claim 1 tripartite's double-perovskite red fluorescence powder, it is characterised in that described
The host material of tripartite's double-perovskite red fluorescence powder is tungsten, molybdate, and material structure is trigonal system, and doping light emitting ionic is
Eu3+。
3. a kind of white light LEDs preparation method of tripartite's double-perovskite red fluorescence powder, it is characterised in that step is as follows：
(1) raw material：A, B, Eu metal ion chooses respectively the pure metal nitrate of corresponding analysis；Molybdenum source is water-soluble ammonium molybdate,
It is preferred that ammonium heptamolybdate；Tungsten source is water-soluble ammonium tungstate or ammonium metatungstate；
(2) (A is constituted by double-perovskite1-xEux)2B2/3MO6Or A2(B1-yEuy)2/3MO6Required metallic element molar ratio weighing is former
Material；
If M is Mo, molybdenum source and ethylenediamine tetra-acetic acid (EDTA) be dissolved in together in ammonia spirit (addition of ammoniacal liquor is with can be molten
Solution solute)；By the ammonia spirit of molybdenum source and ethylenediamine tetra-acetic acid (EDTA) and the nitrate solution of A, B, Eu metal ion
Mixing, agitating heating；Then citric acid is added in mixed solution, agitating heating dissolving；Mixed solution pH is adjusted with ammoniacal liquor
For 8～9,
If M is W, during ethylenediamine tetra-acetic acid (EDTA) is dissolved in into ammonia spirit, tungsten source is dissolved in deionized water, is heated respectively
Stirring and dissolving；The ammonia spirit of ethylenediamine tetra-acetic acid (EDTA) is mixed with the nitrate solution of metal ion afterwards, stirring adds
Heat；Then citric acid is added into mixed solution, agitating heating dissolving；It is 8～9 to adjust mixed solution PH with ammoniacal liquor, then by tungsten
Source solution is added in mixed solution；
Ensure that whole solution system all metal ions total concentration is 0.5～1.0mol/L, always agitating heating is (warm for whole process
Degree is at 30～50 DEG C)；As the citric acid and ethylenediamine tetra-acetic acid (EDTA) of complexing agent consumption be respectively A, B, Eu metal from
1.0～2.0 times, 0.5～1.5 times of sub- molal quantity summation；
(3) the closed stirring of the solution for having configured is broken a seal after 0.5～1 hour, heats that do not stop stirring 1～2 little at 50～60 DEG C
When form colloidal sol；Then heating-up temperature is improved to 70～80 DEG C and is continued stirring, until forming transparent gel；
(4) by 150～180 DEG C of heating of gel, there is combustion reaction, fluffy precursor powder is formed after 3～5 hours；Again will
Precursor powder carries out high temperature pre-burning, and pre-burning in 3～6 hours is incubated at 400～600 DEG C；
(5) powder after pre-burning is carried out into high-temperature calcination, the calcining of 6-10 hours is incubated at 900～1200 DEG C.
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| CN109021973A (en) * | 2018-06-07 | 2018-12-18 | 江苏师范大学 | A kind of double-perovskite type molybdate red phosphor and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108822844A (en) * | 2018-05-23 | 2018-11-16 | 江苏师范大学 | A kind of high color purity double-perovskite type tungstate red fluorescent powder and preparation method thereof |
| CN109021973A (en) * | 2018-06-07 | 2018-12-18 | 江苏师范大学 | A kind of double-perovskite type molybdate red phosphor and preparation method thereof |
| CN109021973B (en) * | 2018-06-07 | 2021-06-15 | 江苏师范大学 | Double perovskite type molybdate red fluorescent powder and preparation method thereof |
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Application publication date: 20170510 |