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 PDF

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CN107880885A
CN107880885A CN201610868043.0A CN201610868043A CN107880885A CN 107880885 A CN107880885 A CN 107880885A CN 201610868043 A CN201610868043 A CN 201610868043A CN 107880885 A CN107880885 A CN 107880885A
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fluorescent material
preparation
roasting
luminescent device
fluorescent
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CN107880885B (en
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庄卫东
周宇楠
刘荣辉
刘元红
李彦峰
胡运生
徐会兵
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Grirem Advanced Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774Aluminates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier 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
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008Processes
    • H01L2933/0033Processes relating to semiconductor body packages
    • H01L2933/0041Processes relating to semiconductor body packages relating to wavelength conversion elements

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

Carbuncle type aluminosilicate fluorescent powder and preparation method thereof and the luminescent device for including it
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)

  1. 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. 2. fluorescent material according to claim 1, wherein, b:D=0.95~1.05.
  3. 3. fluorescent material according to claim 1, wherein, 3.9≤a+b≤4.1.
  4. 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. 5. according to the fluorescent material described in claim 1-3, wherein, 0.01≤y≤0.06.
  6. 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. 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. 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. 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. 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. 11. luminescent device according to claim 10, the radiation source includes ultraviolet or purple light or blue emission source.
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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

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