CN104962286A - Garnet-structure multiphase fluorescent material and preparation method thereof - Google Patents
Garnet-structure multiphase fluorescent material and preparation method thereof Download PDFInfo
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- CN104962286A CN104962286A CN201510296298.XA CN201510296298A CN104962286A CN 104962286 A CN104962286 A CN 104962286A CN 201510296298 A CN201510296298 A CN 201510296298A CN 104962286 A CN104962286 A CN 104962286A
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Abstract
The invention discloses a novel garnet-structure multiphase fluorescent material and a preparation method thereof. The novel garnet-structure multiphase fluorescent material has a chemical formula of AaM1bM2cM3dO12-delta N delta: xRe, yR. zT. The novel garnet-structure multiphase fluorescent material has a multiphase structure comprising a rare earth ion-activated garnet structure fluorescent solid solution phase and inert metal particles such as one or more of Au, Ag, Pt and Pd, and the fluorescent phase contains nitrogen replacing a part of oxygen and halogen ions replacing a part of oxygen Through low-phonon energy inert metal particles in the multiphase structure, luminescence performances of the garnet-structure fluorescent solid solution phase are obviously improved. The multiphase fluorescent material can produce a luminescence spectrum with one or more peaks after UV-blue and green light excitation, can emit lights from blue lights to orange red lights and can be used in LED device manufacture.
Description
Technical field
The present invention relates to the garnet structure complex phase fluor used in the lighting units such as display unit and photodiode (LED), luminescent lamp such as cathode tube (CRT), plasma display panel (PDP), field effect transistor (FED), electroluminescent (EL), fluorescent display tube, particularly be suitable for having the LED of UV-light, blue light, bluish-green light activated visible ray or white light, light source and lighting unit fluorescent material, this at least one launched orange-yellow, sodium yellow, yellow-green colour, green fluorescent material is used for partly converting primary ray to.
Background technology
Yttrium aluminum garnet (YAG:Ce) fluorescent material of the white light LEDs developed in the last few years primarily of blue-light excited Yellow light-emitting low temperature, synthesizes white light.Japanese Patent JP 10 056 208, JP 10 065 221, JP 11 243 232, international PCT patent WO 9 812 757, WO 9 805 078, US Patent No. 6 630 691, US 6 069 440, US 6 614 179, US 6 669 866, US 6 576 930 etc. all propose the light source activation of the short wavelength with visible blue spectral range and the garnet structure A of Yellow light-emitting low temperature
3b
5o
12: the luminophore of Ce aluminate-base.On 460nm, launch blue Ga (In) N-LED by combination and launch yellow garnet fluorescent materials, generate the luminescent conversion LED exporting white light, these two main ripples blue, yellow are only contained in luminescent spectrum due to them, lack corresponding red component, thus there is colour temperature higher, the problem of color developing difference, use that can only be limited, does not meet generalized lighting requirements.
Although defect to some extent, but the yellow fluorescent powder of above-mentioned garnet structure is with the luminous efficiency of clear superiority, quantum yield and be easy to the main flow that production becomes industrial application all the time, although block and restriction for the patent of yttrium aluminium garnet fluorescent powder in the world to break through in recent years, international application WO 2,007 109978, WO 2,007 035 026, CN 101 113 330, CN 101 292 009, US 2,008 0 031797, US 2,008 0 116 786, CN 101 496 136 discloses the silicate fluorescent material (Sr of the higher yellow of luminous efficiency and orange-yellow transmitting, Ba)
2siO
4: Eu and (Sr, Ba)
3siO
5: Eu, the fluorescent material mentioned in the baric orthosilicate structure that the pyrosilicate system related in CN 98,105 078, US 2,006 00 277 871 and US 2,006 0 027 785 relate to and US 6 255 670, US 6 504 179 is also the fluorescent material of silicate sturcture system, excitation spectrum is at 280 ~ 470nm, and emmission spectrum is within the scope of 460 ~ 590nm.Although above-mentioned silicate fluorescent powder starts widespread use in recent years, but comparatively the chemical stability of cakes with moulded designs and thermostability seriously constrain the application of this material, its luminous intensity is also poor, and the granularity of the fluorescent material of silicate systems is large, poor with the matching of existing fluorescent material, within the scope of the blue area 420 ~ 470nm of visible ray, the transformation efficiency of the light of fluorescent material is low, can not get the luminescence of very strong brightness, have significant limitation in actual applications, YAG garnet structure fluorescent material has irreplaceable advantage all the time in some.
Based on above situation, the technical development for garnet structure fluorescent material remains the main flow direction of association area.Chinese patent application CN 103 351 861 discloses a kind of fluor Lu of garnet structure
3ga
5o
12: Eu, Taiwan Patent application TW 2,013 39 280 discloses Ca
3sc
2si
3o
12: Ce fluorescent material, Taiwan Patent application TW 2,014 16 414, TW 2,014 32 026 disclose a kind of fluor (Lu, Yb) of garnet structure
3al
5o
12: Ce.At Y
3al
5o
12: on Ce yellow fluorescent powder basis, replaced the fluorescent material Y of the yellow-green colour transmitting that Al is formed in recent years by part Ga
3(Al, Ga)
5o
12: Ce also more and more becomes and CaAlSiN
3: Eu red fluorescence powder jointly encapsulates and realizes the comparatively good material of the ideal encapsulation of high aobvious illumination and display and develop rapidly, and obviously, the fluorescent material of garnet structure still has important researching value and development meaning.
Summary of the invention
The object of this invention is to provide one group and under ultraviolet ~ blue green light (particularly 400nm ~ 470nm) excites, complex phase fluorescent material of the garnet structure of the novelty of green, yellow-green colour and yellow light and preparation method thereof can be launched.This complex phase fluorescent material by garnet structure fluorescence solid solution phase be present in its crystalline phase or the inert metal particulate of crystal boundary is formed.With aforementioned Y
3al
5o
12: Ce or Lu
3al
5o
12: Ce fluor is compared, in matrix material, the fluorescence of garnet structure exists that nitrogen and halide-ions are broken down into divalent alkaline-earth metal ion position to the replacement of oxygen, single Al position, three distinct crystalline degrees of Al position and tetravalence Si position are put mutually, and four kinds of cation positions also exist the element substitution feature mutually different from above-mentioned 3512 garnets.And the fluorescence phase of garnet structure and inert metal particulate forming composite structure are also that to have essence mutually with above-mentioned 3512 garnets different.In complex body, the existence of inert metal particulate obviously can reduce the phonon thermal vibration of fluorescence phase and significantly improve the luminescent properties of fluorescence phase.
The complex phase fluorescent material of a kind of garnet structure of the present invention, particularly comprises the fluorescent material of the light-emitting device of LED, and chemical constitution expression is: A
am1
bm2
cm3
do
12-δn
δ: xRe, yRzT; Wherein A is selected from the combination of one or more elements in Y, Gd, Lu, Tb, La; M1 is selected from the combination of one or more elements in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Ti, Zr, Hf; M2 is selected from the combination of one or more elements in C, Si, Ge, Sn, Pb, K, Na, Li, Rb, Cs; M3 is selected from the combination of element in B, Al, Ga, In, Tl, Sc, Ti, V, Nb, Mo, W or multiple element; Re is selected from the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn; R is selected from F
-, Cl
-, Br
-, I
-, S
2-in the combination of one or more element ions; T is selected from the combination of one or more elements in Au, Ag, Pt, Pd; A, b, c, d, x, y, z, δ are mole coefficient: 0.5 < a < 3.5,0≤b < 2,0≤c < 2 and 0≤b+c < 3.5,2.5 < d < 5.5,0 < δ≤0.5,0 < x≤0.5 and 1 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25; Described complex phase fluorescent material is the multiphase structure that rare-earth ion activated garnet structure fluorescence solid solution phase and inert metal particulate form, fluorescence mutually in there is nitrogen element and replace part oxygen, halide-ions also partly can replace oxygen; In multiphase structure, the existence of inert metal particulate obviously can improve the luminescent properties of fluorescence solid solution phase; This composite fluorescent material is launched after the UV-blue-green light of peak wavelength within the scope of 300 ~ 500nm excite, the luminescent spectrum of one or more peak values of peak wavelength within the scope of 450 ~ 600nm can be launched, can present from blueness to orange-red luminescence, be applied to the manufacture of efficient LED devices.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, without M1 and M2, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5, b=0, c=0,4.5 < d < 5.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5,0.5 < b < 1.5,0.5 < c < 1.5 and 1.5 < b+c < 2.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 0.5 < a < 1.5,1 < b < 2,1 < c < 2 and 2.5 < b+c < 3.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 1 < a+x < 2,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5,0.5 < b < 1.5,0.5 < c < 1.5 and 1.5 < b+c < 2.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or both elements in Y, Gd, is the combination of one or both elements in Al, Ga without M1 and M2, M3, and Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2, b=0, c=0,4.8≤d≤5.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or both elements in Lu, Gd, is the combination of one or both elements in Al, Ga without M1 and M2, M3, and Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2, b=0, c=0,4.8≤d≤5.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or both elements in Lu, Gd, M1 is the combination of one or more elements in Mg, Sr, Ba, M2 is the combination of one or both elements in Si, Ge, M3 is the combination of one or both elements in Al, Ga, and Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2,0.8≤b≤1.2,0.8≤c≤1.2 and 1.6≤b+c≤2.4,2.8≤d≤3.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
Further, the complex phase fluorescent material of garnet structure of the present invention, in fluorescence solid solution phase, A is the combination of one or both elements in Y, Gd, M1 is the combination of one or more elements in Ca, Sr, Ba, M2 is the combination of one or both elements in Si, Ge, M3 is the combination of one or both elements in Al, Ga, and Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 0.8≤a < 1.7,1.3≤b≤1.7,1.3≤c≤1.7 and 2.8≤b+c≤3.2,3.3≤d≤3.7,0 < δ≤0.5,0 < x≤0.5 and 1.3≤a+x≤1.7,0≤y≤0.5,0.005≤z≤0.25.
Present invention also offers a kind of preparation method of garnet structure complex phase fluor as above, raw materials used is compound or the simple substance of following each element, and its element is according to chemical constitution expression A
am1
bm2
cm3
do
12-δn
δ: the mol ratio scope of xRe, yRzT is:
A：0.5～3.5；
M1：0～2.0；
M2：0～2.0；
M3：2.5～5.5；
O：11.5～12；
N：0～0.5；
Re：0～0.5；
R：0～0.5；
T：0.005～0.25；
Wherein: A represents the compound of one or more elements in Y, Gd, Lu, Tb, La;
M1 represents the compound of one or more elements in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Ti, Zr, Hf;
M2 represents the compound of one or more elements in C, Si, Ge, Sn, Pb, K, Na, Li, Rb, Cs;
M3 represents the compound of one or more elements in B, Al, Ga, In, Tl, Sc, Ti, V, Nb, Mo, W;
Re represents the compound of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn;
R represents the compound of one or more elements in F, Cl, Br, I, S;
T represents simple substance or the compound of one or more elements in Au, Ag, Pt, Pd;
The compound of element representated by A adopts the form of oxide compound and/or nitride and/or nitrate as element source;
The compound of element representated by M1 adopts the form of oxide compound and/or carbonate as element source;
The compound of element representated by M2 adopts the form of oxide compound and/or nitride as element source;
The compound of element representated by M3 adopts the form of oxide compound and/or nitride and/or nitrate as element source;
The compound of element representated by Re adopts oxide compound and/or nitrate and/or fluorochemical or muriatic form as element source;
The compound of element representated by R adopts the form of fluorochemical or muriate or bromide or iodide or sulfide as element source;
The simple substance of element representated by T or compound adopt the form of metal simple-substance powder or oxide compound or nitride or nitrate as element source;
Its preparation technology is combined high temperature solid reaction process, the raw material of each to A, M1, M2, M3, Re, R element is taken by mol ratio, Homogeneous phase mixing, then again with take according to proportioning, the elemental powders of T element that particle diameter is in 1000 nanometer range or compound is full and uniform mixes, under the weakly reducing atmosphere of 0 ~ 3 atmospheric oxygen or nitrogen and hydrogen mixing in 1000 ~ 1600 DEG C carry out once or for several times, the sintering of 4 to 8 hours, then carry out fragmentation, screening, rear subsequent disposal form.
The excitation and emission spectra of the fluorescent material described in the present invention adopts the test of F-4500 fluorescence spectrophotometer.
In the present invention, enter the technical scheme of inert metal particle by compound in one group of fluorescent material of garnet structure, define the fluorescent material that a group has compound structure, its by the fluorescence principal phase of garnet structure of luminous function (as Y
3al
5o
12: Ce, Lu
3al
5o
12: Ce, Y
3(Al, Ga)
5o
12: Ce, Lu
3mgAL
3siO
12: Ce and Y
1.5ca
1.5al
3.5si
1.5o
12: Ce) formed with the inert metal particle be present in outside fluorescence principal phase structure with second-phase.The technical scheme of this structure and former garnet structure fluor, the fluor as above-mentioned simple garnet structure is compared, and has the difference of essence.The inert metal particle introduced in the present invention is the metallic element with low phonon energy, its compound in fluorescence phase structure can play the effect that the lattice thermal vibration that alleviates fluorescence structure and thermal vibration are transmitted between domain, thus can radiationless relaxation phenomena in lightening material excitation-emission process, the luminescent properties of material is significantly improved, and this is an obviously progress in the fluorescent material technical field of garnet structure.In addition, in the fluorescence principal phase of garnet structure of the present invention, also there is nitrogen and halide-ions replacement part oxygen, Si and Mg or Sr or Ca replacement Al, Sr, Ca replace Mg, Mg or Sr or Ca replaces the opinions such as Y, with technology before, as simple YAG, LuAG, Lu
3mgSiAl
3o
12and Y
1.5ca
1.5al
3.5si
1.5o
12fluorescent material is obviously different.By more than, fluorescent material of the present invention constructively, all there is essence with prior art in composition and distinguish, and this introducing with the technical scheme of the difference of essence significantly improves the luminescent properties of fluorescent material, increasing amount can reach more than 10%, and this is an obviously progress of the fluorescent material technical field of garnet type structure.
Accompanying drawing explanation
Fig. 1 is the emmission spectrum of the embodiment of the present invention 1 and comparative example 1 fluorescent material, and in figure, 1 represents embodiment 1 sample, and 0 represents comparative example 1 sample;
Fig. 2 is the excitation spectrum of the embodiment of the present invention 3 fluorescent material;
Fig. 3 is the emmission spectrum of the embodiment of the present invention 3 fluorescent material;
Fig. 4 is the excitation spectrum of the embodiment of the present invention 4 fluorescent material;
Fig. 5 is the emmission spectrum of the embodiment of the present invention 4 fluorescent material;
Fig. 6 is the emmission spectrum of the embodiment of the present invention 4 and comparative example 2 fluorescent material, and in figure, 4 represent embodiment 4 sample, and 0 represents comparative example 2 sample;
Fig. 7 is the excitation and emission spectra of the embodiment of the present invention 5 fluorescent material.
Embodiment
Below by embodiment, content of the present invention is described in further detail.It is to be noted the present invention not by the restriction of these embodiments.
Embodiment 1:Y
2.95al
5.2o
11.4n
0.6: 0.05Ce, 0.025F0.15Ag
Y is taken according to molar ratio
2o
3333.07g, CeO
28.61g, Al
2o
3234.51g, AlN24.59g, BaF
22.19g, mixed grinding, Ag powder 16.19g is taken according to molar ratio, both are mixed again, by the first 1400-1500 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1500 DEG C, pulverizes after sintered compact cooling, grinds, the complex phase fluor of the garnet structure described in acquisition.The transmitting collection of illustrative plates of the complex phase fluor that Fig. 1 obtains for embodiment 1, its emission wavelength at 550nm, with following identical component but not containing the simple fluor of Ag particulate comparative example 1 compared with, the luminous intensity of complex phase fluor improves about 5%.
Comparative example 1:Y
2.95al
5.2o
11.4n
0.6: 0.05Ce, 0.025F
Y is taken according to molar ratio
2o
3333.07g, CeO
28.61g, Al
2o
3234.51g, AlN24.59g, BaF
22.19g, mixed grinding, by the first 1400-1500 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1500 DEG C, pulverize after sintered compact cooling, grind, obtain the simple fluor identical with fluorescence phase composition in embodiment 1.
Embodiment 2:Y
2.95al
4.7ga
0.5o
11.4n
0.6: 0.05Ce, 0.025F0.15Ag
Y is taken according to molar ratio
2o
3333.07g, CeO
28.61g, Al
2o
3209.02g, AlN24.59g, Ga
2o
346.86g, BaF
22.19g, mixed grinding, Ag powder 16.19g is taken according to molar ratio, both are mixed again, by the first 1400-1500 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1400-1500 DEG C, pulverizes after sintered compact cooling, grinds, the complex phase fluor of the garnet structure described in acquisition.
Embodiment 3:Lu
2.95al
5.2o
11.4n
0.6: 0.05Ce, 0.025F0.15Ag
Lu is taken according to molar ratio
2o
3587.05g, CeO
28.61g, Al
2o
3234.51g, AlN24.59g, BaF
22.19g, mixed grinding, Ag powder 16.19g is taken according to molar ratio, both are mixed again, by the first 1400-1500 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1400-1500 DEG C, pulverizes after sintered compact cooling, grinds, the complex phase fluor of the garnet structure described in acquisition.The complex phase fluor that Fig. 2 obtains for embodiment 3 excite collection of illustrative plates, the transmitting collection of illustrative plates of the complex phase fluor that Fig. 3 obtains for embodiment 3, its emission wavelength is at 527nm.
Embodiment 4:Lu
2.95mg
1.05si
1.05al
3o
11.5n
0.5: 0.05Ce, 0.025F0.15Ag
Lu is taken according to molar ratio
2o
3587.05g, CeO
28.61g, MgO 42.32, SiO
263.08g, Al
2o
3127.45g, AlN 20.5g, BaF
22.19g, mixed grinding, Ag powder 16.19g is taken according to molar ratio, both are mixed again, by the first 1450-1550 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1450-1550 DEG C, pulverizes after sintered compact cooling, grinds, the complex phase fluor of the garnet structure described in acquisition.Figure 4 and 5 are respectively exciting and launching collection of illustrative plates of the complex phase fluor that embodiment 4 obtains, and its emission wavelength is at 560nm.The complex phase fluor that Fig. 6 obtains for embodiment 4 and following identical component but contrast containing the transmitting collection of illustrative plates of the comparative example 2 of the simple fluor of Ag particulate, the luminous intensity raising about 10% of complex phase fluor.
Comparative example 2:Lu
2.95mg
1.05si
1.05al
3o
11.5n
0.5: 0.05Ce, 0.025F
Lu is taken according to molar ratio
2o
3587.05g, CeO
28.61g, MgO 42.32, SiO
263.08g, Al
2o
3127.45g, AlN 20.5g, BaF
22.19g, mixed grinding, by the first 1450-1550 DEG C of pre-burning after 6 hours in air atmosphere of the raw material that mixes, heat preservation sintering 5 hours under the weakly reducing atmosphere of 1450-1550 DEG C, pulverize after sintered compact cooling, grind, obtain the simple fluor identical with fluorescence phase composition in embodiment 4.
Embodiment 5:Y
1.45ca
1.5si
1.5al
3.5o
11.5n
0.5: 0.05Ce, 0.025F0.15Ag
Y is taken according to molar ratio
2o
3163.71g, CeO
28.61g, CaCO
3150.14, SiO
290.12g, Al
2o
3152.94g, AlN 20.5g, BaF
22.19g, mixed grinding, takes Ag powder 16.19g according to molar ratio, both are mixed again, by the raw material that mixes first 1000-1200 DEG C of sintering 6 hours in air atmosphere, to pulverize after sintered compact cooling, grinding, the complex phase fluor of the garnet structure described in acquisition.The exciting and launch collection of illustrative plates of the complex phase fluor that Fig. 7 obtains for embodiment 5, its emission wavelength is at 534nm.
Claims (10)
1. a complex phase fluorescent material for garnet structure, for comprising the light-emitting device of LED, is characterized in that: the chemical constitution expression of described complex phase fluorescent material is: A
am1
bm2
cm3
do
12-δn
δ: xRe, yRzT; Wherein A is the combination of one or more elements be selected from Y, Gd, Lu, Tb, La; M1 is the combination of one or more elements be selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Ti, Zr, Hf; M2 is the combination of one or more elements be selected from C, Si, Ge, Sn, Pb, K, Na, Li, Rb, Cs; M3 is the combination being selected from element in B, Al, Ga, In, Tl, Sc, Ti, V, Nb, Mo, W or multiple element; Re is the combination of one or more elements be selected from Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn; R is for being selected from F
-, Cl
-, Br
-, I
-, S
2-in the combination of one or more element ions; T is the combination of one or more elements be selected from Au, Ag, Pt, Pd; A, b, c, d, x, y, z, δ are mole coefficient: 0.5 < a < 3.5,0≤b < 2,0≤c < 2 and 0≤b+c < 3.5,2.5 < d < 5.5,0 < δ≤0.5,0 < x≤0.5 and 1 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25; Described complex phase fluorescent material is the multiphase structure that rare-earth ion activated garnet structure fluorescence solid solution phase and inert metal particulate form, fluorescence mutually in there is nitrogen element and replace part oxygen, halide-ions part replaces oxygen; Described complex phase fluorescent material is launched after the UV-blue-green light of peak wavelength within the scope of 300 ~ 500nm excite, launch the luminescent spectrum of one or more peak values of peak wavelength within the scope of 450 ~ 600nm, present from blueness to orange-red luminescence.
2. the complex phase fluorescent material of garnet structure according to claim 1, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, without M1 and M2, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5, b=0, c=0,4.5 < d < 5.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
3. the complex phase fluorescent material of garnet structure according to claim 1, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5,0.5 < b < 1.5,0.5 < c < 1.5 and 1.5 < b+c < 2.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
4. the complex phase fluorescent material of garnet structure according to claim 1, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 0.5 < a < 1.5,1 < b < 2,1 < c < 2 and 2.5 < b+c < 3.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 1 < a+x < 2,0≤y≤0.5,0.005≤z≤0.25.
5. the complex phase fluorescent material of garnet structure according to claim 1, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or more elements in Y, Gd, Lu, Tb, La, M1 is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn, M2 is the combination of one or more elements in Si, Ge, Rb, Cs, M3 is the combination of one or both elements in Al, Ga, Re is the combination of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn, and R is F
-, Cl
-, Br
-, I
-in the combination of one or more element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2 < a < 3.5,0.5 < b < 1.5,0.5 < c < 1.5 and 1.5 < b+c < 2.5,2.5 < d < 3.5,0 < δ≤0.5,0 < x≤0.5 and 2.5 < a+x < 3.5,0≤y≤0.5,0.005≤z≤0.25.
6. the complex phase fluorescent material of garnet structure according to claim 2, is characterized in that: in fluorescence solid solution phase, A is the combination of one or both elements in Y, Gd, and be the combination of one or both elements in Al, Ga without M1 and M2, M3, Re is Ce; R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2, b=0, c=0,4.8≤d≤5.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
7. the complex phase fluorescent material of garnet structure according to claim 2, is characterized in that: in fluorescence solid solution phase, A is the combination of one or both elements in Lu, Gd, and be the combination of one or both elements in Al, Ga without M1 and M2, M3, Re is Ce; R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2, b=0, c=0,4.8≤d≤5.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
8. the complex phase fluorescent material of garnet structure according to claim 3, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or both elements in Lu, Gd, M1 is the combination of one or more elements in Mg, Sr, Ba, M2 is the combination of one or both elements in Si, Ge, M3 is the combination of one or both elements in Al, Ga, Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 2.3≤a < 3.2,0.8≤b≤1.2,0.8≤c≤1.2 and 1.6≤b+c≤2.4,2.8≤d≤3.2,0 < δ≤0.5,0 < x≤0.5 and 2.8≤a+x≤3.2,0≤y≤0.5,0.005≤z≤0.25.
9. the complex phase fluorescent material of garnet structure according to claim 4, it is characterized in that: in fluorescence solid solution phase, A is the combination of one or both elements in Y, Gd, M1 is the combination of one or more elements in Ca, Sr, Ba, M2 is the combination of one or both elements in Si, Ge, M3 is the combination of one or both elements in Al, Ga, Re is Ce, R is F
-, Cl
-in the combination of one or both element ions, T is the combination of one or more elements in Au, Ag, Pt, Pd; 0.8≤a < 1.7,1.3≤b≤1.7,1.3≤c≤1.7 and 2.8≤b+c≤3.2,3.3≤d≤3.7,0 < δ≤0.5,0 < x≤0.5 and 1.3≤a+x≤1.7,0≤y≤0.5,0.005≤z≤0.25.
10. a preparation method for garnet structure complex phase fluor, is characterized in that, raw materials used is compound or the simple substance of following each element, and its element is according to chemical constitution expression A
am1
bm2
cm3
do
12-δn
δ: the mol ratio scope of xRe, yRzT is:
A：0.5～3.5；
M1：0～2.0；
M2：0～2.0；
M3：2.5～5.5；
O：11.5～12；
N：0～0.5；
Re：0～0.5；
R：0～0.5；
T：0.005～0.25；
Wherein: A represents the compound of one or more elements in Y, Gd, Lu, Tb, La;
M1 represents the compound of one or more elements in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Ti, Zr, Hf;
M2 represents the compound of one or more elements in C, Si, Ge, Sn, Pb, K, Na, Li, Rb, Cs;
M3 represents the compound of one or more elements in B, Al, Ga, In, Tl, Sc, Ti, V, Nb, Mo, W;
Re represents the compound of one or more elements in Ce, Eu, Nd, Dy, Ho, Tm, Er, Pr, Bi, Sm, Sn, Sb, Mn;
R represents the compound of one or more elements in F, Cl, Br, I, S;
T represents simple substance or the compound of one or more elements in Au, Ag, Pt, Pd;
The compound of element representated by A adopts the form of oxide compound and/or nitride and/or nitrate as element source;
The compound of element representated by M1 adopts the form of oxide compound and/or carbonate as element source;
The compound of element representated by M2 adopts the form of oxide compound and/or nitride as element source;
The compound of element representated by M3 adopts the form of oxide compound and/or nitride and/or nitrate as element source;
The compound of element representated by Re adopts oxide compound and/or nitrate and/or fluorochemical or muriatic form as element source;
The compound of element representated by R adopts the form of fluorochemical or muriate or bromide or iodide or sulfide as element source;
The simple substance of element representated by T or compound adopt the form of metal simple-substance powder or oxide compound or nitride or nitrate as element source;
Its preparation technology is combined high temperature solid reaction process, the raw material of each to A, M1, M2, M3, Re, R element is taken by mol ratio, Homogeneous phase mixing, then again with take according to proportioning, the elemental powders of T element that particle diameter is in 1000 nanometer range or compound is full and uniform mixes, under the weakly reducing atmosphere of 0 ~ 3 atmospheric oxygen or nitrogen and hydrogen mixing in 1000 ~ 1600 DEG C carry out once or for several times, the sintering of 4 to 8 hours, then carry out fragmentation, screening, aftertreatment subsequent disposal form.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018001370A1 (en) * | 2016-06-30 | 2018-01-04 | 有研稀土新材料股份有限公司 | Lutetium nitride-based phosphor and light emitting device comprising same |
| CN109987932A (en) * | 2018-01-02 | 2019-07-09 | 上海航空电器有限公司 | Complex phase fluorescence ceramics, preparation method and light supply apparatus for white-light illuminating |
| CN110386822A (en) * | 2018-04-19 | 2019-10-29 | 深圳光峰科技股份有限公司 | A kind of complex phase fluorescence ceramics and preparation method thereof |
| CN112159209A (en) * | 2020-09-29 | 2021-01-01 | 湖州市汉新科技有限公司 | High-color rendering index high-thermal conductivity fluorescent ceramic, preparation method and application in laser display |
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2015
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| XIAOJUN WANG，ET AL.: "Luminescent properties of yellowish orange Y3Al5-xSixO12-xNx:Ce phosphors and their applications in warm white light-emitting diodes", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018001370A1 (en) * | 2016-06-30 | 2018-01-04 | 有研稀土新材料股份有限公司 | Lutetium nitride-based phosphor and light emitting device comprising same |
| US11066600B2 (en) | 2016-06-30 | 2021-07-20 | Grirem Advanced Materials Co., Ltd. | Lutetium nitride-based phosphor and light emitting device comprising same |
| CN109987932A (en) * | 2018-01-02 | 2019-07-09 | 上海航空电器有限公司 | Complex phase fluorescence ceramics, preparation method and light supply apparatus for white-light illuminating |
| CN109987932B (en) * | 2018-01-02 | 2022-08-09 | 上海航空电器有限公司 | Complex phase fluorescent ceramic for white light illumination, preparation method and light source device |
| CN110386822A (en) * | 2018-04-19 | 2019-10-29 | 深圳光峰科技股份有限公司 | A kind of complex phase fluorescence ceramics and preparation method thereof |
| CN110386822B (en) * | 2018-04-19 | 2021-02-26 | 深圳光峰科技股份有限公司 | Complex phase fluorescent ceramic and preparation method thereof |
| CN112159209A (en) * | 2020-09-29 | 2021-01-01 | 湖州市汉新科技有限公司 | High-color rendering index high-thermal conductivity fluorescent ceramic, preparation method and application in laser display |
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Application publication date: 20151007 |