CN104987864A - Layered perovskite red phosphor for white LED and preparation method thereof - Google Patents

Layered perovskite red phosphor for white LED and preparation method thereof Download PDF

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Publication number
CN104987864A
CN104987864A CN201510326166.7A CN201510326166A CN104987864A CN 104987864 A CN104987864 A CN 104987864A CN 201510326166 A CN201510326166 A CN 201510326166A CN 104987864 A CN104987864 A CN 104987864A
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ball
red phosphor
layered perovskite
powder
perovskite red
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张乐
王骋
杨浩
乔学斌
唐定远
沈德元
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Jiangsu Normal University
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Jiangsu Normal University
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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 layered perovskite red phosphor for a white LED and a preparation method thereof. The structural formula of the layered perovskite red phosphor is (A1-xMexBx) 4Ti3O10, wherein A is Ca or Sr, Me is rare earth element Eu or rare earth element Pr, B is Li or Na or K, and x is larger than or equal to 0.005 and smaller than or equal to 0.1. The layered perovskite red phosphor is prepared through a solid phase method. The excitation spectrum of the layered perovskite red phosphor ranges from 350 nm to 400 nm, and the layered perovskite red phosphor can be applied to the white LED and other luminescent material fields; the emission wavelength of the layered perovskite red phosphor is in the red light range of 590 nm to 650 nm, the emission intensity is high, and the color purity and the color rending index are high; raw materials are economical, the technology is simple and controllable, an experimental production period is short, and the layered perovskite red phosphor is high in stability.

Description

A kind of white light LEDs laminated perovskite red fluorescence powder and preparation method thereof
Technical field
The invention belongs to rare earth luminescent material technical field, relate to a kind of white light LEDs laminated perovskite red fluorescence powder and preparation method thereof.
Background technology
White light-emitting diode (white LEDs) is energy-conservation with it, efficient as a kind of New Solid illuminating device, volume is little, pollution-free and can the advantage such as complanation and being applied widely in the field such as flat pannel display, road lighting 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 phosphor emission and chip excite rear remaining blue light to be combined to form white light, red sector transmitting more weak in its spectrum causes its colour rendering index lower, therefore needs to be mixed in fluorescent material with the rouge and powder excited to compensate red emission and to improve light conversion efficiency; Meanwhile, in the red-green-blue fluorescent material that near ultraviolet LED excites, red fluorescence powder used at present as 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, sulfide chemical stability is general, and the pollution that the sulphur gas in use discharged and wider red emission band cause and poor purity of color etc. all limit its application.Therefore, have near ultraviolet to blue light range efficient absorption, there is narrower photoluminescent band and the good red fluorescence powder of environmental stability obtains extensive research, as tungsten hydrochlorate, phosphoric acid salt, vanadate, titanate etc. in red range.
Wherein, titanate matrix has good thermostability and chemical stability.Its stronger luminosity and stable luminescent properties make such material be subject to extensive concern, as CaTiO 3: Pr 3+deng.Its main advantage is embodied in: 1) have extraordinary physical and chemical stability, can stable existence in the packaged material such as epoxy resin or silica gel; 2) in this substrate material, TiO 4 4-there is stronger absorption at near-ultraviolet light wave band (<400nm) in group, can efficient absorption excitation energy pass to rare earth ion and make it luminous; 3) Pr 3+/ Eu 3+the titanate fluorescent powder excitation peak activated, at about 350 ~ 400nm, can coordinate with ultraviolet LED well, and launches stronger pure ruddiness; 4) China's titanium aboundresources, and compared with other tungsten Barbiturates, titanate has obvious price advantage, for the development of rare earth titanium hydrochlorate phosphor material powder provides favourable condition.
Summary of the invention
The object of the invention is the problems such as and poor chemical stability low for existing red fluorescent powder for white radiation LED luminous intensity, and a kind of novel white light LEDs laminated perovskite red fluorescence powder and preparation method thereof is provided.
Technical scheme of the present invention is: at laminated perovskite A 4ti 3o 10: in Me fluorescent material, nonstoichiometry adds charge compensator B +ion, logical charge compensation and stable grade of crystalline phase are used for raising luminous intensity, optimized emission color, its add-on and active ions Me 3+equimolar amount, scope is 0.005≤x≤0.1.It has Ruddlesden-Popper (RP) structure, and the typical structure general formula of the type is Sr n+1ti no 3n+1, belong to the perovskite structure of stratiform, its crystalline structure is SrO layer and TiO 2layer is alternately arranged composition, and as n=1, molecular formula is Sr 2tiO 4, i.e. (SrTiO 3) SrO, be two SrO layers and a TiO 2the square structure that layer is alternately arranged.Of the present invention to as if n=3 time laminated perovskite structure, its molecular formula is A 4ti 3o 10(A=Ca or Sr), i.e. (ATiO 3) 3aO is four AO layers and a TiO 2the square structure that layer is alternately arranged.Compared with during n=1 or 2, the crystalline structure of n=3 has larger unit cell parameters, the rare earth ion Me of its doping 3+(Me=Eu or Pr) replaces A 2+crystal case, can reach higher concentration, forms more, effective luminescence center, thus ensures its higher luminous intensity and luminous efficiency; Meanwhile, in this system, mix charge compensator B simultaneously +ion (B=Li, Na or K), its adding mode is that nonstoichiometry is mixed, and does not take A 2+the stoicheiometry of ion, in ideal, it is present in the interstitial site of larger structure cell with calking form, its add-on and activation ion Me 3+(Me=Eu or Pr) equimolar amount, plays the effect of supporting & stablizing structure and charge compensation.Therefore, ensure that obtained fluorescent material luminous intensity is high, phase purity is good, and it is near ultraviolet or its feature ruddiness of blue-light excited lower transmitting.
Concrete technical scheme of the present invention is: a kind of white light LEDs laminated perovskite red fluorescence powder, it is characterized in that its structural formula is:
(A 1-xMe xB x) 4Ti 3O 10
Wherein, A is the one in Ca or Sr, and Me is the one in rare earth element Eu or Pr, and B is the one in Li, Na or K; 0.005≤x≤0.1.
Present invention also offers the method for above-mentioned white light LEDs laminated perovskite red fluorescence powder, its concrete steps are as follows:
(1) powder metage, ball milling and drying: form (A by laminated perovskite 1-xme xb x) 4ti 3o 10required metallic element molar ratio weighing raw material, be placed in ball grinder, add ball-milling medium simultaneously, put into by ball grinder on ball mill, setting rotational speed of ball-mill is 100 ~ 300r/min, ball milling 6 ~ 15h; Slurry after ball milling is taken out, puts into drying; Wherein material powder: the mass ratio of ball is 1:(1 ~ 3);
(2) calcine: the compound after drying and screening is carried out high-temperature calcination, be incubated 2 ~ 6h calcining at 1300 ~ 1500 DEG C, after furnace cooling to room temperature, namely obtain laminated perovskite red fluorescence powder.
Above-mentioned raw materials A, B metal ion gets the metal carbonate of more than corresponding analytical pure respectively, and Me metal ion gets corresponding metal oxide, and Ti source is commercially available high-purity Ti O 2.
Preferred spheres grinding media is dehydrated alcohol; Dehydrated alcohol and material powder total mass ratio are (2 ~ 4): 1.
The temperature of preferred loft drier is 60 ~ 80 DEG C, and time of drying is 8 ~ 15h.
Abrading-ball in preferred spheres grinding jar is high purity aluminium oxide ball; Ball grinder is high purity aluminium oxide tank.
Beneficial effect:
1. fluorescent material provided by the invention is take titanate as matrix, and its excitation spectrum is within the scope of 350 ~ 400nm, and the emission peak of this and InGaN base near ultraviolet LED chip is very identical, can be used for white light LEDs and other field of light emitting materials.
2. Eu launched by fluorescent material provided by the invention 3+or Pr 3+the feature ruddiness of ion, it occupies the lower position of lattice symmetry in such fluorescent material, and comparatively strong to the absorption of excitation energy, emission wavelength is in 590-650nm red range, and emissive porwer is high, purity of color and color developing good.
3. fluorescent material provided by the invention adopts solid phase method preparation, and raw material economics, technique is simply controlled, tests with short production cycle, good stability.
Accompanying drawing explanation
Fig. 1 is (Ca prepared by example 1 0.995eu 0.005li 0.005) 4ti 3o 10the excitation spectrum of fluorescent material under 615nm monitoring, X-coordinate is wavelength (nm), and ordinate zou is luminous intensity.
Fig. 2 is (Sr prepared by example 2 0.95pr 0.05na 0.05) 4ti 3o 10the emmission spectrum of fluorescent material under 395nm excites, X-coordinate is wavelength (nm), and ordinate zou is luminous intensity.
Fig. 3 is (Sr prepared by example 3 0.9eu 0.1k 0.1) 4ti 3o 10fluorescent material and commercial Y 2o 2the emmission spectrum of S:Eu fluorescent material respectively under 395nm excites, X-coordinate is wavelength (nm), and ordinate zou is luminous intensity.Wherein the red light-emitting intensity of fluorescent material prepared of the present invention is apparently higher than commercial fluorescent material.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but should not limit the scope of the invention with this.The present invention adopts Solid phase synthesis rare earth ion Eu 3+or Pr 3+the formula of 3 specific embodiments of the laminated perovskite red fluorescence powder of ion doping is as shown in table 1.
Table 1
Embodiment 1 #((Ca 0.995eu 0.005li 0.005) 4ti 3o 10):
Form as in table 11 #shown in, concrete preparation method comprises the following steps:
1. weigh, ball mill mixing: weigh pressed powder raw material by the composition in table 1, be placed in high purity aluminium oxide ball grinder, add dehydrated alcohol as ball-milling medium simultaneously, dehydrated alcohol and material powder total mass ratio are 2:1, material powder: the mass ratio=1:3 of ball, are put into by ball grinder on ball mill, setting rotational speed of ball-mill is 200r/min, ball milling 10h.
2. dry: the slurry after ball milling to be taken out, puts into the loft drier of 80 DEG C, dry 8h.
3. calcine: the compound after drying and screening is carried out high-temperature calcination, be incubated 6h calcining at 1300 DEG C, after furnace cooling to room temperature, laminated perovskite red fluorescence powder can be obtained.
4. by obtained ground 200 mesh sieves of product, then with powder compressing machine, its dry-pressing is become thin round plate, carry out performance test.
Test result is as follows:
Process 4. in sample after compressing tablet process carry out fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) test, exciting light spectrogram under monitoring 615nm ruddiness as shown in Figure 1, its excitation peak is positioned at the near ultraviolet region of 364nm, 395nm and the blue region of 465nm, the wherein wide band absorption being emitted as this substrate material of 364nm, excitation intensity is high, strong to the fault tolerance of excitation energy, even if when generation high temperature causes excitation wavelength to change by a small margin during work, still higher absorption intensity can be ensured; Meanwhile, under 395nm excites, phosphor emission is positioned at the feature ruddiness of 594nm and 615nm, and its red light-emitting intensity is commercial Y 2o 21.32 times (the strongest emission peak intensity ratios) of S:Eu fluorescent material.
Embodiment 2 #((Sr 0.95pr 0.05na 0.05) 4ti 3o 10):
Form as in table 12 #shown in, concrete preparation method comprises the following steps:
1. weigh, ball mill mixing: weigh pressed powder raw material by the composition in table 1, be placed in high purity aluminium oxide ball grinder, add dehydrated alcohol as ball-milling medium simultaneously, dehydrated alcohol and material powder total mass ratio are 3:1, material powder: the mass ratio=1:2 of ball, are put into by ball grinder on ball mill, setting rotational speed of ball-mill is 300r/min, ball milling 6h.
2. dry: the slurry after ball milling to be taken out, puts into the loft drier of 60 DEG C, dry 15h.
3. calcine: the compound after drying and screening is carried out high-temperature calcination, be incubated 4h calcining at 1400 DEG C, after furnace cooling to room temperature, laminated perovskite red fluorescence powder can be obtained.
4. by obtained ground 200 mesh sieves of product, then with powder compressing machine, its dry-pressing is become thin round plate, carry out performance test.
Test result is as follows:
Process 4. in sample after compressing tablet process carry out fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) test, as shown in Figure 2, its emission peak is lay respectively at the ruddiness of 613nm and the dark red light of 648nm to utilizing emitted light spectrogram under 395nm excites, is Pr 3+the characteristic emission of ion, its red light-emitting intensity is commercial Y 2o 21.57 (the strongest emission peak intensity ratios) of S:Eu fluorescent material; Separately have bimodal division at 613nm place, show that its red light region is comparatively large, red light color purity improves.
Embodiment 3 #((Sr 0.9eu 0.1k 0.1) 4ti 3o 10):
Form as in table 13 #shown in, concrete preparation method comprises the following steps:
1. weigh, ball mill mixing: weigh pressed powder raw material by the composition in table 1, be placed in high purity aluminium oxide ball grinder, add dehydrated alcohol as ball-milling medium simultaneously, dehydrated alcohol and material powder total mass ratio are 4:1, material powder: the mass ratio=1:1 of ball, are put into by ball grinder on ball mill, setting rotational speed of ball-mill is 100r/min, ball milling 15h.
2. dry: the slurry after ball milling to be taken out, puts into the loft drier of 70 DEG C, dry 10h.
3. calcine: the compound after drying and screening is carried out high-temperature calcination, be incubated 2h calcining at 1500 DEG C, after furnace cooling to room temperature, laminated perovskite red fluorescence powder can be obtained.
4. by obtained ground 200 mesh sieves of product, then with powder compressing machine, its dry-pressing is become thin round plate, carry out performance test.
Test result is as follows:
Process 4. in sample after compressing tablet process carry out fluorescence spectrum (FL3-221, HOROBA, Jobin Yvon, France) test, utilizing emitted light spectrogram under 395nm excites as shown in Figure 3, it launches the broadband ruddiness that main peak splitting is 617nm and 626nm, further illustrate the active ions luminescence that the lower lattice symmetry of this laminated perovskite matrix system causes superiority.And in this system, its doping content can reach 10%, high doping content ensure that high luminous efficiency, and its red light-emitting intensity is commercial Y 2o 22.37 times (the strongest emission peak intensity ratios) of S:Eu fluorescent material.
Above-mentioned example is the present invention's preferably embodiment; but embodiments of the present invention are not by the restriction of above-mentioned example; other are any do not deviate from spirit of the present invention and principle under make amendment, modification, substitute, combine, simplify the substitute mode being equivalence, be included within protection scope of the present invention.

Claims (6)

1. a white light LEDs laminated perovskite red fluorescence powder, is characterized in that its structural formula is:
(A 1-xMe xB x) 4Ti 3O 10
Wherein, A is the one in Ca or Sr, and Me is the one in rare earth element Eu or Pr, and B is the one in Li, Na or K; 0.005≤x≤0.1.
2. prepare a method for white light LEDs laminated perovskite red fluorescence powder as claimed in claim 1, its concrete steps are as follows:
(1) powder metage, ball milling and drying: form (A by laminated perovskite 1-xme xb x) 4ti 3o 10required metallic element molar ratio weighing raw material, be placed in ball grinder, add ball-milling medium simultaneously, put into by ball grinder on ball mill, setting rotational speed of ball-mill is 100 ~ 300r/min, ball milling 6 ~ 15h; Slurry after ball milling is taken out, puts into drying; Wherein material powder: the mass ratio of ball is 1:(1 ~ 3);
(2) calcine: the compound after drying and screening is carried out high-temperature calcination, be incubated 2 ~ 6h calcining at 1300 ~ 1500 DEG C, after furnace cooling, namely obtain laminated perovskite red fluorescence powder.
3. method according to claim 2, is characterized in that: raw material A, B metal ion get corresponding metal carbonate respectively, and Me metal ion gets corresponding metal oxide, and Ti source is high-purity Ti O 2.
4. method according to claim 2, is characterized in that ball-milling medium is dehydrated alcohol; Dehydrated alcohol and material powder total mass ratio are (2 ~ 4): 1.
5. method according to claim 2, it is characterized in that the temperature of loft drier is 60 ~ 80 DEG C, time of drying is 8 ~ 15h.
6. method according to claim 2, is characterized in that the abrading-ball in ball grinder is high purity aluminium oxide ball; Ball grinder is high purity aluminium oxide tank.
CN201510326166.7A 2015-06-12 2015-06-12 Layered perovskite red phosphor for white LED and preparation method thereof Pending CN104987864A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105238399A (en) * 2015-11-19 2016-01-13 中山大学 High-color-purity red light-emitting material and preparation method and application thereof
CN106635017A (en) * 2017-01-06 2017-05-10 江苏师范大学 Titanate-based red fluorescent powder and preparation method thereof
CN106947478A (en) * 2017-02-28 2017-07-14 江苏师范大学 A kind of long-afterglow material that can realize green emitting, preparation method and application
CN107502350A (en) * 2017-08-28 2017-12-22 五邑大学 A kind of praseodymium doped laminated perovskite type red long afterglow luminous material, Its Preparation Method And Use
CN111269718A (en) * 2020-04-02 2020-06-12 常熟理工学院 Composite perovskite type deep red fluorescent powder and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105238399A (en) * 2015-11-19 2016-01-13 中山大学 High-color-purity red light-emitting material and preparation method and application thereof
CN106635017A (en) * 2017-01-06 2017-05-10 江苏师范大学 Titanate-based red fluorescent powder and preparation method thereof
CN106947478A (en) * 2017-02-28 2017-07-14 江苏师范大学 A kind of long-afterglow material that can realize green emitting, preparation method and application
CN106947478B (en) * 2017-02-28 2019-05-24 江苏师范大学 A kind of long-afterglow material can be realized green emitting, preparation method and application
CN107502350A (en) * 2017-08-28 2017-12-22 五邑大学 A kind of praseodymium doped laminated perovskite type red long afterglow luminous material, Its Preparation Method And Use
CN111269718A (en) * 2020-04-02 2020-06-12 常熟理工学院 Composite perovskite type deep red fluorescent powder and preparation method and application thereof
CN111269718B (en) * 2020-04-02 2022-09-23 常熟理工学院 Composite perovskite type deep red fluorescent powder and preparation method and application thereof

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