CN107880885A - Carbuncle type aluminosilicate fluorescent powder and preparation method thereof and the luminescent device for including it - Google Patents
Carbuncle type aluminosilicate fluorescent powder and preparation method thereof and the luminescent device for including it Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 206010007247 Carbuncle Diseases 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 78
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000002223 garnet Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 238000012805 post-processing Methods 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 8
- 238000000695 excitation spectrum Methods 0.000 description 8
- 229910003443 lutetium oxide Inorganic materials 0.000 description 8
- 238000009877 rendering Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 229910019064 Mg-Si Inorganic materials 0.000 description 6
- 229910019406 Mg—Si Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 229910018173 Al—Al Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 rare earth ion Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005090 crystal field Methods 0.000 description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910017113 AlSi2 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 241001025261 Neoraja caerulea Species 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of carbuncle type aluminosilicate fluorescent powder is disclosed, chemical formula is:(Lu1‑x‑yLnxCey)aMgbAlcSidOe, wherein, 1.8≤a≤2.2,1.8≤b≤2.1,1.8≤c≤2.2,1.8≤d≤2.1,11.8≤e≤12.2, one or more kinds of combinations according to arbitrary proportion in Ln Sc, Y, Gd, La, 0≤x≤0.15,0<y≤0.08.Fluorescent material prepared by the present invention has the crystal structure of yttrium-aluminium-garnet, and can be excited by light of the wavelength less than 520nm, and emission peak is 560nm to 590nm visible ray.In addition, also disclose the preparation method of the fluorescent material and include its luminescent device.
Description
Technical field
The invention belongs to rare earth luminescent material field, is related to a kind of carbuncle type fluorescent material and preparation method thereof and comprising it
Luminescent device, can strongly be excited by purple light-blue light more particularly, to one kind and produce relative YAG:Ce3+Emission peak red shift
The carbuncle type aluminosilicate fluorescent powder of Huang-orange light and preparation method thereof and include its luminescent device.
Background technology
In recent years, white light LEDs are extensively paid close attention to and studied by people, because it has low efficiency height, operating voltage, long lifespan, dirt
Contaminate the advantages of other conventional light sources such as small, stability is high institute is incomparable.The preparation skill of technical most ripe white light LEDs at present
Art is the light transformation approach of fluorescent material coating, and therefore, the performance of fluorescent material plays vital effect to white light LEDs performance.
Blue-light LED chip coats YAG:Ce3+Bloom, because it has the advantages that efficiency high, prepares that simple, cost is cheap, and
By extensive use.However, its transmitting in red light region is insufficient, cause its colour rendering index relatively low (Ra≤78), colour temperature higher
(CCT >=4500K), can not meet the needs of high-quality illumination.The warm white that colour temperature is relatively low, colour rendering index is high can be produced in order to manufacture
Light LED is general using in YAG:Ce3+Such as (Sr, Ca) S is mixed into yellow fluorescent powder:Eu2+、CaAlSiN3:Eu2+Etc. can be blue
Light activated sulfide or nitride substrate red fluorescence powder, this method can overcome the disadvantages that YAG:Ce3+This insufficient problem of feux rouges,
But these rouge and powder also have the problem of respective, it is allowed to that extensive use can not be able to, such as:Sulfide stability is poor and gives environment
Bring sulphur pollution;Nitride synthesis condition is harsh, and it is high to prepare cost.Therefore, new and effective, suitable white light LEDs are developed
Orange fluorescent powder has particularly important meaning.
Due to stronger crystal field strength, and preparation process is simple, and garnet structure matrix is to explore synthesis new
Had been attached great importance during type orange fluorescent powder.2006, Setlur et al. transmitting main peaks by Solid phase synthesis
In 605nm or so new garnet structure Lu2CaMg2Si3O12:Ce3+Fluorescent material (non-patent literature 1).It is with blue-ray LED core
After piece is packaged, although reducing colour temperature, however, unfortunately colour rendering index is relatively low (76), and the quantum of the fluorescent material
Efficiency (about 60%) is not also high.In addition, Katelnikovas et al. is in YAG:Ce3+On the basis of pass through Mg-Si and substitute Al-Al
Method has synthesized transmitting main peak about in 600nm or so new Y3Mg2AlSi2O12:Ce3+Fluorescent material (non-patent literature 2), can
To compensate YAG:Ce3+The deficiency of red light region, still, its thermal quenching performance are relatively poor, from practical application gap.Separately
Outside, Pan Zaifa et al. is in YAG:Ce3+On the basis of by Mg-Si substitute Al-Al and Mg-Si to substitute Y-Al, synthesized new orange
Color Y2Mg2Al2Si2O12:Ce3+Fluorescent material (non-patent literature 3), although colour rendering index is improved, there is also thermal quenching performance
The defects of relatively poor and quantum efficiency is relatively low.For improving thermal quenching performance this problem, Wang Yuhua et al. in LuAG:Ce3+
On the basis of by Mg-Si substitute Al-Al synthesized a thermal quenching performance Lu higher than commercial bloom3MgAl3SiO12:Ce3+
Bloom (non-patent literature 4), although the fluorescent material is with respect to LuAG:Ce3+Red shift is successfully realized, emission peak wavelength is located at
560nm or so, yet with red shift insufficient amplitude, matched with blue chip caused by white light to still have colour temperature higher (about
5500K) this problem.Patent document 1-4 also describes the fluorescent material with garnet structure, however, these fluorescent material are same
Above mentioned problem more or less be present.
It would therefore be highly desirable to finding one kind can be excited, with respect to YAG strongly by purple light-blue-light LED chip:Ce3+Red shift and with compared with
The aobvious yellow-orange color aluminosilicate fluorescent powder referred to of height.
Non-patent literature 1:Anant A.Setlur, Chemistry of Materials, 2006,18 (14):3314-
3322;
Non-patent literature 2:Katelnikovas A, Journal of Luminescence, 2009,129 (11):1356-
1361;
Non-patent literature 3:Pan Z, RscAdvances, 2014,5 (13):9489-9496:
Non-patent literature 4:Shi Y, Dalton Transactions, 2014,44 (4):1775-1781;
Patent document 1:The A1 of United States Patent (USP) US 2006/0284196;
Patent document 2:CN 104212455 A;
Patent document 3:CN 104212458 A;
Patent document 4:WO 2010/043287 A1.
The content of the invention
In view of the shortcomings of the prior art, be to provide one kind can be strong by purple light-blue-light LED chip for an object of the present invention
It is strong to excite and emission peak is 560nm to adjustable yellow-orange color aluminosilicate fluorescent powder between 590nm.
The second object of the present invention is to provide a kind of preparation method of above-mentioned carbuncle type aluminosilicate fluorescent powder, the party
Method is simple and easy.
The third object of the present invention is to provide a kind of luminescent device for including above-mentioned carbuncle type aluminosilicate fluorescent powder.
To achieve the above object, on the one hand, the invention provides a kind of carbuncle type aluminosilicate fluorescent powder, its chemical formula
For (Lu1-x-yLnxCey)aMgbAlcSidOe, wherein, 1.8≤a≤2.2,1.8≤b≤2.1,1.8≤c≤2.2,1.8≤d≤
One or more kinds of combinations according to arbitrary proportion in 2.1,11.8≤e≤12.2, Ln Sc, Y, Gd, La, 0≤x≤
0.15,0<y≤0.08.
According to carbuncle type aluminosilicate fluorescent powder of the present invention, wherein, the fluorescent material belongs to cubic system,
Ia-3d space groups, and be A with formula3B2(XO4)3, wherein, A, B, X occupy eight-coordinate, hexa-coordinate, four-coordination case respectively,
And it is correspondingly formed dodecahedron, octahedron, tetradecahedral crystal structure with adjacent O atom respectively.In fluorescent material of the present invention,
Lu, Ln, Ce and part Mg elements occupy eight-coordinate (A positions) case of lattice, and part Mg and part Al elements occupy hexa-coordinate (B
Position) case, part Al and Si element occupies four-coordination (X positions) case.By in eight-coordinate (A positions) case and hexa-coordinate (B positions)
Case introducing ionic valence condition is relatively low, the less Mg of electronegativity2+, strengthen the covalency between Ce-O, reduce Ce3+5d energy level weights
Heart position, and introduce the small Si of ionic radius in four-coordination (X positions) case4+Crystal field strength can be strengthened, these two aspects is all
Energy difference between 5d1-4f is advantageously reduced, effectively facilitates spectral red shift.Therefore, fluorescent material of the present invention is successfully realized relatively
Commercial YAG:Ce3+Red shift of wavelength, red color light component is added, matched with blue chip and advantageously reduce colour temperature.
It is Lu, Mg, Al, Si and O that the matrix of fluorescent material of the present invention, which includes essential element, with the institute of non-patent literature 4
It is identical comprising element to state the matrix of fluorescent material, still, the ratio of the two contained identical element is different, naturally, every kind of case
Occupied element species and content are also had any different.In fluorescent material matrix described in non-patent literature 4, eight-coordinate (A positions) is occupied
The element of case is all Lu elements, and in this patent, eight-coordinate (A positions) case of lattice is mainly occupied by Lu and Mg elements;
In fluorescent material matrix described in non-patent literature 4, Al/Si ratios are 2:1, and its ratio is 1 in this patent:2.In addition, with it is non-
The difference of patent document 3, patent document 2 and patent document 3 is that contained rare earth is first in the matrix of fluorescent material described in this patent
Element is mainly Lu rather than Y element, and the purpose of this design is:Among garnet structure, adjacent dodecahedron has rib altogether
The characteristics of, so the ionic radius for occupying eight-coordinate (A positions) is closer more to advantageously form garnet pure phase, in addition to Sc
In trivalent rare earth ionses, Lu radius is minimum, closest with the Mg ionic radius that occupy eight-coordinate, and occupies eight-coordinate (A
Position) average ionic radius it is too small be also difficult to synthesize garnet structure pure phase in atmospheric conditions, therefore ion can not be selected
The too small Sc elements of radius are as the main rare-earth elements for occupying eight-coordinate (A positions).Two aspects are for ionic radius based on more than
The consideration of size, Lu elements are selected to be advantageous to Stability Analysis of Structures, compound stone as the main rare-earth elements for occupying eight-coordinate (A positions)
Garnet pure phase structure, ensures preferable luminescent properties.In addition, in lanthanide series rare-earth elements, Lu atomic mass is maximum, is advantageous to
Enhancing structure rigidity, therefore the heat endurance of phosphor material powder can be improved.
Preferably, b:D=0.95~1.05.
According to carbuncle type aluminosilicate fluorescent powder of the present invention, wherein, b:D=0.95~1.05.Fluorescent material
Matrix can be regarded as on the basis of LuAG, substituted in pairs by Mg-Si Lu-Al and Mg-Si substitute in pairs Al-Al develop and
Come, Mg and Si atom number approach, and are advantageous to maintain the valence state of whole crystal to balance, and reduce hole and produce, ensure fluorescent material
Luminous efficiency it is higher.
According to carbuncle type aluminosilicate fluorescent powder of the present invention, wherein, 3.9≤a+b≤4.1.The present invention's
In fluorescent material, rare earth ion and part Mg ions occupy eight-coordinate (A positions) case of lattice jointly, and sum of the two is too small, can make
Into the appearance for crossing multi-hole;Sum of the two is too big, and rare earth ion and Mg ions squeeze mutually, cause and dephasign occur, both feelings
Condition, it can cause the decline of material emission performance, therefore, sum of the two should be maintained in a suitable scope, i.e., 3.9≤
a+b≤4.1。
According to carbuncle type aluminosilicate fluorescent powder of the present invention, wherein, it is a kind of or more in Ln Sc, Y, Gd
Plant the combination according to arbitrary proportion, it is preferable that Ln is selected from one or both of Y, Gd, 0≤x≤0.1.In eight-coordinate (A positions)
Some rare earth ions bigger than Lu radius are appropriately introduced into, Ce-O bond distance can be compressed, strengthen crystal field strength, further such that
Spectral red shift, improve aobvious refer to.For other rare earth ions, relatively, solid solution enters the radius of Y and Gd radius and Lu
Distortion of lattice is smaller caused by case, it is possible to reduce dephasign occurs, therefore Ln is preferably Y, Gd one kind;But Y and Gd are a large amount of
It if doping, can cause dephasign occur, reduce light efficiency, be preferably 0≤x≤0.10 by doping therefore.
Inventor has found that Ce concentration is subject to certain restrictions, on the one hand, when Ce concentration is too low, the centre of luminescence very little, then
The brightness of fluorescent material is low;On the other hand, excessive Ce can not generate dephasign completely into case, and enter the activator of lattice
Meeting generation concentration is quenched and causes brightness to decline between Ce.Therefore, Ce concentration is controlled in appropriate scope:0.01≤y≤
0.08;Preferably, 0.01≤y≤0.06.
On the other hand, it is described present invention also offers a kind of preparation method of above-mentioned carbuncle type aluminosilicate fluorescent powder
Fluorescent material is synthesized using high temperature solid-state method, and key step is as follows:
1) raw material of weight corresponding to fluorescent material is stoichiometrically weighed, it is finely ground, it is well mixed;
2) raw material is placed in high-temperature roasting in 1300 DEG C -1450 DEG C of sintering furnace, sinters 2-10h under reducing atmosphere;
3) product of roasting obtained by step 2) is post-processed, that is, the fluorescent material is made.
Step 1) the corresponding raw material includes oxide, carbonate, hydroxide;
Step 2) the high temperature sintering can one or many calcinations, each calcination temperature is 1300 DEG C -1450 DEG C, during calcination
Between be 2-10h;
Step 2) the reducing atmosphere is selected from carbon monoxide and nitrogen and hydrogen mixture;
Step 3) the post processing includes that hand-crushed, ball milling be finely ground, grain size grading process.
Another aspect, the present invention also provide a kind of luminescent device for including above-mentioned carbuncle type aluminosilicate fluorescent powder.Should
Luminescent device includes radiation source and fluorescent material, wherein, at least one fluorescent material is selected from above-mentioned fluorescent material or according to above-mentioned system
Fluorescent material prepared by Preparation Method.
According to luminescent device of the present invention, wherein, the radiation source includes ultraviolet or purple light or blue emission source.
Compared with prior art, the beneficial effects of the invention are as follows:Fluorescent material of the present invention is purple light-blue light by wavelength
LED chip excite strongly and can emission peak be 560nm it is glimmering to adjustable yellow-orange color visible ray between 590nm, relatively commercial yellow
Light powder YAG:Ce3+(540nm) has obvious red shift, while the fluorescent material has higher quantum efficiency and excellent thermal quenching
Performance, it can effectively improve colour rendering index for white light LEDs, reduce colour temperature.And the fluorescent material is easily prepared, does not need harshness
Condition, it is easy to accomplish industrialized production.
Brief description of the drawings
Fig. 1 is the (Lu of the embodiment of the present invention 10.98Ce0.02)2Mg2Al2Si2O12The X-ray diffraction spectrogram of fluorescent material.
Fig. 2 is the (Lu of the embodiment of the present invention 10.98Ce0.02)2Mg2Al2Si2O12(437nm swashs the launching light spectrogram of fluorescent material
Hair).
Fig. 3 is the (Lu of the embodiment of the present invention 10.98Ce0.02)2Mg2Al2Si2O12(569nm is supervised the exciting light spectrogram of fluorescent material
Survey).
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after present disclosure has been read, those skilled in the art
The present invention can be made various changes or modifications, these equivalent form of values equally fall within what the application appended claims were limited
Scope.
It will be helpful to understand the present invention by following embodiments, but the scope of the present invention can not be limited.
Comparative example:Y1.94Ce0.06Mg2Al2Si2O12The preparation of fluorescent material
Stoichiometrically weigh raw material Y2O36.1748g、MgO2.2721g、Al2O32.8742g、SiO23.3878g、
CeO20.2911g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, in N2/H2Roasted under reducing atmosphere
Burn, sintering temperature is 1380 DEG C and is incubated 6 hours.After natural cooling, it is through post processings such as broken, ball milling, sieving, washing, drying
The fluorescent material accordingly formed.The emission peak wavelength and relative luminous intensity of the fluorescent material are as shown in table 1.
Embodiment 1:(Lu0.98Ce0.02)2Mg2Al2Si2O12The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O38.3602g、MgO1.7285g、Al2O32.1865g、SiO22.5772g、
CeO20.1476g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, be calcined under CO reducing atmospheres,
Sintering temperature is 1450 DEG C and is incubated 2 hours.After natural cooling, obtained through post processings such as broken, ball milling, sieving, washing, drying
The fluorescent material accordingly formed.Its excitation spectrum wavelength cover is 310-520nm, and emission spectrum wavelength cover is 480-
750nm, emission peak wavelength 569nm.
Embodiment 2:(Lu0.81Gd0.15Ce0.04)2Mg2Al1.9Si2.1O12.05The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O36.9643g、Gd2O31.1749g、MgO1.7421g、Al2O32.0936g、
SiO22.7274g、CeO20.2976g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, in N2/H2
It is calcined under reducing atmosphere, sintering temperature is 1350 DEG C and is incubated 8 hours.After natural cooling, through broken, ball milling, sieving, washing, baking
It is dry wait post processing be obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-520nm, emission spectrum ripple
Long coverage is 480-750nm, emission peak wavelength 585nm.
Embodiment 3:(Lu0.91La0.08Ce0.01)1.8Mg2.1Al2.2Si2O12.1The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O37.3020g、La2O30.5246g、MgO1.8968g、Al2O32.5137g、
SiO22.6935g、CeO20.0694g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, reduced in CO
It is calcined, is calcined twice under atmosphere, for the first time in the case where temperature is 1400 DEG C of insulations 2 hours;It is laggard through crushing grinding after natural cooling
Second of roasting of row, 7 hours are incubated at 1350 DEG C.After natural cooling, locate after broken, ball milling, sieving, washing, drying etc.
Reason i.e. obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-520nm, and emission spectrum wavelength covers model
It is 573nm to enclose for 480-750nm, transmitting main peak.
Embodiment 4:(Lu0.92Sc0.05Ce0.03)2.1Mg1.9Al2.1Si1.9O12The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O38.2326g、Sc2O30.1551g、MgO1.6404g、Al2O32.2936g、
SiO22.4660g、CeO20.2322g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, in N2/H2
It is calcined under reducing atmosphere, sintering temperature is 1300 DEG C and is incubated 10 hours.After natural cooling, through broken, ball milling, sieving, washing, baking
It is dry wait post processing be obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-520nm, emission spectrum ripple
Long coverage is 480-750nm, and transmitting main peak is 568nm.
Embodiment 5:(Lu0.84La0.05Sc0.05Ce0.06)2Mg1.8Al2Si2O11.8The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O37.4517g、La2O30.3625g、Sc2O30.1538g、MgO1.6177g、
Al2O32.2737g、SiO22.6801g、CeO20.4605g, above-mentioned raw materials are fully ground with agate mortar it is even after, load aluminum oxide
Crucible, it is calcined under CO reducing atmospheres, three times, first time sintering temperature is 1400 DEG C and is incubated 2 hours for roasting;Passed through after natural cooling
Carry out being calcined for second after crushing grinding, 6 hours are incubated at 1350 DEG C;Carried out after natural cooling after crushing grinding second
Roasting, 5 hours are incubated at 1300 DEG C.After natural cooling, obtained through post processings such as broken, ball milling, sieving, washing, drying
The fluorescent material accordingly formed.Its excitation spectrum wavelength cover is 310-520nm, and emission spectrum wave-length coverage is 480-
750nm, transmitting main peak are 578nm.
Embodiment 6:(Lu0.86Y0.1Ce0.04)2.1Mg2Al1.8Si2O11.85The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O37.8098g、Y2O30.5155g、MgO1.7524g、Al2O31.9951g、
SiO22.6129g、CeO20.3143g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, in N2/H2
It is calcined under reducing atmosphere, sintering temperature is 1380 DEG C and is incubated 5 hours.After natural cooling, through broken, ball milling, sieving, washing, baking
It is dry wait post processing be obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-520nm, emission spectrum ripple
Long coverage is 480-750nm, and transmitting main peak is 579nm.
Embodiment 7:(Lu0.89Gd0.075Ce0.035)2Mg1.8Al2Si2.1O12The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O37.6527g、Gd2O30.5875g、MgO1.5680g、Al2O32.2039g、
SiO22.7276g、CeO20.2604g, above-mentioned raw materials are fully ground with agate mortar it is even after, load alumina crucible, reduced in CO
It is calcined under atmosphere, sintering temperature is 1370 DEG C and is incubated 5 hours.After natural cooling, through broken, ball milling, sieving, washing, drying etc.
Post processing i.e. obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-520nm, and emission spectrum wavelength covers
Lid scope is 480-750nm, and transmitting main peak is 581nm.
Embodiment 8:(Lu0.77Y0.1Gd0.05Ce0.08)2.2Mg2.1Al2Si1.8O12The preparation of fluorescent material
Stoichiometrically weigh raw material Lu2O37.1511g、Y2O30.5272g、Gd2O30.4230g、MgO1.7962g、
Al2O32.1640g、SiO22.2956g、CeO20.6429g, above-mentioned raw materials are fully ground with agate mortar it is even after, load aluminum oxide
Crucible, it is calcined under N2/H2 reducing atmospheres, sintering temperature is 1380 DEG C and is incubated 5 hours.After natural cooling, through broken, ball milling,
Sieving, washing, drying etc. post processing be obtain respective sets into fluorescent material.Its excitation spectrum wavelength cover is 310-
520nm, emission spectrum wavelength cover are 480-750nm, and transmitting main peak is 590nm.
Embodiment 9:The fluorescent material that embodiment 1 obtains is dispersed in resin, the InGaN coated in 455nm is blue after sizing mixing
In light LED chip, solidification, and circuit is welded, with resin sealed knot, you can the light-emitting device to be emitted white light, its chromaticity coordinates are
(0.3465,0.3196), colour rendering index 83.7, correlated colour temperature 4759K.
Embodiment 10:The fluorescent material that embodiment 7 obtains is dispersed in resin, the InGaN coated in 455nm is blue after sizing mixing
In light LED chip, solidification, and circuit is welded, with resin sealed knot, you can the light-emitting device to be emitted white light, its chromaticity coordinates are
(0.3627,0.3317), colour rendering index 85.9, correlated colour temperature 4493K.
The chemical composition of the embodiment 1-8 of table 1 and comparative example, 450nm excite under transmitting peak position and relative luminous it is strong
Degree (chooses 450nm and excites down (Lu0.98Ce0.02)2Mg2Al2Si2O12Luminous intensity for 100%)
1-8 of embodiment of the present invention fluorescent material by wavelength be purple light-blue-light LED chip excite strongly and can emission peak be
560nm is to 590nm, although there is certain blue shift relative to comparative example, but relative to commercial yellow fluorescent powder YAG:Ce3+
(540nm) but has obvious red shift, can effectively improve colour rendering index for white light LEDs, reduce colour temperature.Significantly, phase
For comparative example, the embodiment of the present invention has higher quantum efficiency and more excellent thermal quenching performance, therefore, has more preferable
Application value.And the fluorescent material is easily prepared, does not need exacting terms, it is easy to accomplish industrialized production.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., be all contained within protection scope of the present invention.
Claims (11)
- A kind of 1. aluminosilicate carbuncle type fluorescent material, it is characterised in that:Its chemical formula is (Lu1-x-yLnxCey)aMgbAlcSidOe, wherein, 1.8≤a≤2.2,1.8≤b≤2.1,1.8≤c≤2.2,1.8≤d≤2.1,11.8≤e≤ One or more kinds of combinations according to arbitrary proportion in 12.2, Ln Sc, Y, Gd, La, 0≤x≤0.15,0<y≤0.08.
- 2. fluorescent material according to claim 1, wherein, b:D=0.95~1.05.
- 3. fluorescent material according to claim 1, wherein, 3.9≤a+b≤4.1.
- 4. according to the fluorescent material described in claim 1-3, wherein, Ln is selected from one or both of Y, Gd, 0≤x≤0.1.
- 5. according to the fluorescent material described in claim 1-3, wherein, 0.01≤y≤0.06.
- A kind of 6. method for preparing the fluorescent material according to claim 1-5, it is characterised in that:The fluorescent material is consolidated using high temperature Phase method synthesizes, and key step is as follows:1) raw material of weight corresponding to fluorescent material is stoichiometrically weighed, it is finely ground, it is well mixed;2) raw material is placed in high-temperature roasting in 1300 DEG C -1450 DEG C of sintering furnace, sinters 2-10h under reducing atmosphere;3) product of roasting obtained by step 2) is post-processed, that is, the fluorescent material is made.
- 7. the preparation method of fluorescent material according to claim 6, wherein, the raw material of step 1) includes corresponding aoxidize Thing, carbonate, hydroxide.
- 8. the preparation method of fluorescent material according to claim 6, wherein, the high-temperature roasting of step 2) can carry out once or Repeatedly roasting, sintering temperature are 1300 DEG C -1450 DEG C, roasting time 2-10h.
- 9. preparation method according to claim 6, wherein, the reducing atmosphere of step 2) is selected from carbon monoxide and nitrogen Hydrogen gaseous mixture.
- 10. a kind of luminescent device, includes radiation source and fluorescent material, it is characterised in that:At least one fluorescent material is selected from according to right It is required that the fluorescent material described in any one of 1-5 or the fluorescence prepared by the preparation method according to claim any one of 6-9 Powder.
- 11. luminescent device according to claim 10, the radiation source includes ultraviolet or purple light or blue emission source.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109628093A (en) * | 2019-01-02 | 2019-04-16 | 吉林大学 | A kind of Eu2+Ion doping alumino-silicate blue colour fluorescent powder and preparation method thereof |
CN115305088A (en) * | 2022-08-22 | 2022-11-08 | 杭州爱视芙健康科技有限公司 | Garnet structure-derived fluorescent powder material and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104212455A (en) * | 2014-08-11 | 2014-12-17 | 浙江工业大学 | Ce<3+> activated fluorescent powder with garnet structure and preparation method thereof |
CN105038787A (en) * | 2015-07-01 | 2015-11-11 | 上海应用技术学院 | Ce, Tb and Mn-coactivated single-matrix phosphate white phosphor powder and preparation method thereof |
-
2016
- 2016-09-29 CN CN201610868043.0A patent/CN107880885B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104212455A (en) * | 2014-08-11 | 2014-12-17 | 浙江工业大学 | Ce<3+> activated fluorescent powder with garnet structure and preparation method thereof |
CN105038787A (en) * | 2015-07-01 | 2015-11-11 | 上海应用技术学院 | Ce, Tb and Mn-coactivated single-matrix phosphate white phosphor powder and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
ZAIFA PAN等: "Combination cation substitution tuning of yellow orange emitting phosphor Mg2Y2Al2Si2O12:Ce3+", 《RSC ADV》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109628093A (en) * | 2019-01-02 | 2019-04-16 | 吉林大学 | A kind of Eu2+Ion doping alumino-silicate blue colour fluorescent powder and preparation method thereof |
CN115305088A (en) * | 2022-08-22 | 2022-11-08 | 杭州爱视芙健康科技有限公司 | Garnet structure-derived fluorescent powder material and preparation method and application thereof |
CN115305088B (en) * | 2022-08-22 | 2024-05-14 | 杭州爱视芙健康科技有限公司 | Garnet structure-based derived fluorescent powder material and preparation method and application thereof |
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