CN103184048B - Composite fluorescent material and preparation method thereof - Google Patents
Composite fluorescent material and preparation method thereof Download PDFInfo
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- CN103184048B CN103184048B CN201110444952.9A CN201110444952A CN103184048B CN 103184048 B CN103184048 B CN 103184048B CN 201110444952 A CN201110444952 A CN 201110444952A CN 103184048 B CN103184048 B CN 103184048B
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- 239000000126 substance Substances 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 nitrogen ion Chemical class 0.000 claims abstract description 35
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- 239000001301 oxygen Substances 0.000 claims abstract description 35
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- Luminescent Compositions (AREA)
Abstract
One group of NEW TYPE OF COMPOSITE fluorescent material and preparation method thereof.Fluorescent complex is by being main anion binding with oxygen, being that the second-phase of the inert metal element simple substance such as fluorescence principal phase and Au, Ag, Pd, Pt, Rh, Ir, Ru, Os of active ions is formed with rare earth.The inert metal element simple substance of low phonon energy, with in the principal phase domain of the formal distribution of second-phase microcrystalline domain in fluorescence principal phase crystalline domain structure or on domain boundary, makes the luminous intensity of fluorescence principal phase and heat resistanceheat resistant damping capacity improve.Part oxygen in complex body fluorescence principal phase lattice jointly can be substituted by trivalent nitrogen ion and monovalence halide-ions and adjust microcrystal field environment in lattice and the intense adjustment realizing emission wavelength.This composite fluorescent material adopts with the particulate of aforementioned inert metal element simple substance for kind of a brilliant solid phase reaction process preparation, and it can be excited by UV-blue-green light and obtain the transmitting from blueness to orange-red light, is applied to the manufacture of efficient LED devices.
Description
Technical field
The present invention relates to one group of NEW TYPE OF COMPOSITE fluorescent material for semiconductor light-emitting apparatus, it can be launched the UV-blue-green light chip of wavelength within the scope of 300 ~ 500nm and excite, absorb the utilizing emitted light at least partially of excitation light source, launch wavelength within the scope of 450 ~ 600nm or blue light or green light or sodium yellow or orange-red light, belong to lighting engineering, display and optoelectronic areas.
Background technology
Utilize photodiode and the semiconductor lighting that realizes and technique of display, have that current consumption is minimum, the plurality of advantages such as environmental friendliness, life-span long and applying flexible, just day by day obtain various countries and pay attention to and the application popularization that obtains social life each side.At present, the mode of semiconductor lighting and display is realized, mainly based on the fluorescent material conversion hysteria technology utilizing UV-light, purple light or blue green light chip to excite assorted emission luminescent material.As utilized blue chip to excite the yellow fluorescent material launched to obtain white light LEDs, the fluorescent material of excitated red transmitting and the fluorescent material of green emitted can obtain display LED backlight simultaneously to utilize blue chip.
Realize in the assorted fluorescent material launched being excited by UV-blue-green light chip, the yellow material launched is a kind of main material, in LED illumination technology, occupy critical role.At present, main yellow material is Ce
3+the yttrium aluminum garnet material (Y, Gd) activated
3(Al, Ga)
5o
12(being called for short YAG).The material of this garnet structure, at the blue-light excited lower gold-tinted can launching 530 ~ 550nm, has that luminous efficiency is high, the advantage of stable chemical nature, becomes the LED yellow fluorescent material be applicable to the most.But, the use of this material in LED technology has worldwide been carried out patent limitation and covering by Japanese Ya company, as multinomial in US Patent No. 5998925, European Union patent EP0936682, PCT patent WO9805078, Japanese Patent JP3503139 and Chinese patent CN1893133 etc.
In order to evade the patent limitation of YAG material, the company of countries in the world or research institution carry out the development of other yellow fluorescent materials launched always.US Patent No. 7267787, US7311858, Chinese patent CN100590172, Japanese patent application JP2007009141 and U.S. Patent application US2007158614 disclose and a kind ofly can be excited by UV-blue-green light wide range and launch the Eu of the green-yellow light of 500 ~ 560nm
2+the alkaline earth orthosilicate material (Sr, Ba, Ca) activated
2siO
4, the doping that yellow is wherein emitted through halogens can make its luminosity close to real requirement, and the one becoming YAG material may substitute.In addition, US Patent No. 7648650, PCT patent application WO2007035026, WO2007018260 and Chinese patent application CN101186818 disclose another kind and can be excited by UV-blue-green light and launch the Eu of the orange-colored light of 567 ~ 575nm
2+the alkaline earth metal silicate material (Sr, Ba) activated
3siO
5: Eu.
But above-mentioned rare-earth ion activated alkaline earth metal silicate material, particularly the yellow material launched, has some significantly not enough.These materials only do not have medium physical and chemical stability, acidproof and soluble in water, and thermostability is not good.Especially, this silicate material is because structural symmetry is lower, the more high factor of complicacy, and luminous luminous efficiency is lower slightly.The yellow silicate material that 550nm launches, even adulterated by halide-ions and make luminous intensity be optimized, its luminous efficiency still has the gap of more than 5% with YAG material, and heat fade is also more remarkable.These deficiencies constrain it for the well substituting of YAG material and the practical application in high-power situation.
In addition, the white light that the fluorescent material of yellow transmitting and blue chip combination package obtain lacks red color components, the colour rendering index of LED is lower, colour temperature is too high, the photochromic colder cold quality white light of positive bletilla can only be obtained, the warm white illuminating effect of euphorosia cannot be obtained, thus usually need the material adding red emission in yellow material to increase red color components in actual applications.The deficiency that the nitride red material ubiquity lumen brightness of launching due to more than 600nm the is too low and matched well of the yellow material higher with brightness cannot be realized, thus current most producer adopt about 570nm to launch aforementioned silicate orange material as red complementary color component, disclosed in US Patent No. 7601276.But as previously mentioned, the silicate material of orange emission still also exists luminosity gap and the too high deficiency of heat fade to some extent.
In addition, the technology utilizing blue chip and green emitting phosphor and red fluorescence powder to combine to manufacture various flat pannel display LED backlight day by day comes into one's own and obtains and develops rapidly, and the importance of the fluorescent material of green emitted is given prominence to gradually.Although the orthosilicate material of aforementioned patent or the green emitted disclosed in patent application can meet the requirement of LED backlight technology in purity of color, but its heat fade is too high, at 150 DEG C, the decay of luminous intensity can reach 30%, and the working temperature of display LED backlight is often at about 150 DEG C, therefore this material is not the ideal chose of display backlight.
US Patent No. 7837898 and US7794624, PCT patent application WO2007096333 and Chinese patent application CN101045860 disclose a kind of alkaline-earth metal oxymtride material (Ba, Sr, Ca) Si of green emitted
2o
2n
2: Eu, but the purity of color of this material does not meet the requirement of LED backlight.PCT patent application WO2009016096 discloses the green emissive material Ba of another kind of oxynitride
2.5si
6o
11.5n
2: Eu.The over-all properties of this material is better, but the uncertainty of its metering proportion makes the fluctuation of the luminosity of material and chromaticity coordinate larger comparatively greatly.
Develop the fluorescent material of the simple and yellow that luminous intensity is better, heat resistanceheat resistant damping capacity is more stable of manufacturing process, orange and green emitted further, the application progress and developing for LED illumination and technique of display is popularized significant.
Summary of the invention
An object of the present invention is to provide one group of NEW TYPE OF COMPOSITE fluorescent material being applied to LED component and manufacturing, due to the introducing of the low phonon energy microcrystalline domain of the inert metal element simple substances such as Au, Ag, Pd, Pt, Rh, Ir, Ru, Os in complex body fluorescence principal phase crystalline domain structure, make that the luminous intensity of material improves, heat fade reduces, more be conducive to manufacture that is efficient, high stability LED component, and the part oxygen in fluorescence principal phase lattice is substituted the flexible adjustment that can realize material emission wavelength jointly by trivalent nitrogen ion and monovalence halide-ions; More than one particulates stating inert metal element simple substance that another object of the present invention is to provide above-mentioned composite fluorescence body are kind of a brilliant high temperature solid state reaction synthetic method, have that manufacturing process is simple, material property improves and are easy to the feature of industrially scalable volume production.
The chemical constitution general formula of one group of NEW TYPE OF COMPOSITE fluorescent material of the present invention can be expressed as with formula (1):
aM1O
αN
β+γ1·bM2O
1-0.5γ2X
γ2·uRO/vA(1)
Wherein M1 is for being selected from least one element in Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W; M2 is for being selected from least one element in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, Cs; X is for being selected from least one element in F, Cl, Br, I; R is for being selected from least one element in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is for being selected from least one element in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os.A, b, α, β, γ 1, γ 2, u, v are mole coefficient: 0.5 < a < 4,0.5≤b < 3,0.3 < α≤2,0≤β < 1.5,0≤γ 1 < 0.67,0≤γ 2 < 2.0,0 < u≤0.5,0.001≤v < 0.55.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, also can realize white or multicolor luminous with other one or more fluorescent material is used in combination, be applied to the manufacture of efficient LED devices.
It is the complex body formed with the simple substance of oxygen for main anion binding and containing inert metal elements such as the fluorescence major phase material of rare earth activation ion and Au, Ag, Pd, Pt, Rh, Ir, Ru, Os.The content of inert metal element simple substance is within the scope of 0.1 ~ 10wt.%, and it plays a part kind brilliant and finally with in the domain of the formal distribution of second-phase microcrystalline domain in principal phase crystalline domain structure or domain boundary in major phase material forming process.Part oxygen in fluorescence principal phase lattice is substituted by halide-ions, forms one group of NEW TYPE OF COMPOSITE fluor, and halide-ions substitutes amount in 0.001 ~ 1.0 molar range.Part oxygen in fluorescence principal phase lattice is substituted jointly by trivalent nitrogen ion and monovalence halide-ions, and form another group NEW TYPE OF COMPOSITE fluor, the alternative total amount of non-oxygen anion is in 0.002 ~ 1.5 molar range.
The microcrystalline domain of inert metal element simple substance has lower phonon energy, it is present in that lattice thermal vibration is comparatively strong, the heat fade of luminous intensity is comparatively significant with in the crystalline domain structure of the oxygen fluorescence principal phase that is main anion binding, the lattice thermal vibration of principal phase can be alleviated further, make to be subject to during excitation electron transition lattice thermal vibration impact and the radiationless relaxation phenomena that produces alleviates, thus the luminous intensity of fluorescence major phase material and heat resistanceheat resistant damping capacity are further enhanced.In fluorescence principal phase, introduce part trivalent nitrogen ion by jointly substituting the mode of oxygen with monovalence halide-ions and maintain Stability Analysis of Structures, realize the adjustment of the features such as micro-symmetry in lattice, negatively charged ion occupy-place/defect, electrons state and microcrystal field environment thus and make the transmitting red shift of fluorescence phase, can the emission wavelength of intense adjustment composite fluorescence body.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that mole coefficient 1 < α≤2 in chemical constitution general formula, β=0.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that mole coefficient 0.3 < α < 2, the 0.1 < β < 1.5 in chemical constitution general formula.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is for being selected from least one element in Si, B, Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn, Li, Na, K; X is for being selected from least one element in F, Cl; R is for being selected from least one element in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is for being selected from least one element in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os; Mole coefficient: 1.5≤b < 2 and 2.0≤b+u < 2.2 and 0.4 < a/ (b+u) < 0.6,1 < α≤2, β=0,0≤γ 1 < 0.67 and α=2-1.5 γ 1,0≤γ 2 < 0.67,0 < u≤0.5,0.001≤v < 0.37.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is for being selected from least one element in Si, B, Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn, Li, Na, K; X is for being selected from least one element in F, Cl; R is for being selected from least one element in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is for being selected from least one element in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os; Mole coefficient: 2.5≤b < 3 and 3.0≤b+u < 3.2 and 0.2 < a/ (b+u) < 0.4,1.5 < α≤2, β=0,0≤γ 1 < 0.33 and α=2-1.5 γ 1,0≤γ 2 < 0.4,0 < u≤0.5,0.001≤v < 0.52.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is for being selected from least one element in Si, B, Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn, Li, Na, K; X is for being selected from least one element in F, Cl; R is for being selected from least one element in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is for being selected from least one element in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os; Mole coefficient: 0.5≤b < 1 and 1.0≤b+u < 1.2 and 0.5 < a/ (b+u) < 4,0.3 < α < 2,0.1 < β < 1.5, γ 1=0,0≤γ 2 < 2.0,0 < u≤0.5,0.001≤v < 0.38.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,1.5≤b < 2,1.16≤α≤2, β=0,0≤γ 1≤0.56,0≤γ 2≤0.53,0 < u≤0.5,0.001≤v≤0.11.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,1.5≤b < 2,1.16≤α≤2, β=0,0≤γ 1≤0.56,0≤γ 2≤0.53,0 < u≤0.5,0.001≤v≤0.11.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,2.5≤b < 3,1.67≤α≤2, β=0,0≤γ 1≤0.22,0≤γ 2≤0.32,0 < u≤0.5,0.001≤v≤0.15.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,2.5≤b < 3,1.67≤α≤2, β=0,0≤γ 1≤0.22,0≤γ 2≤0.32,0 < u≤0.5,0.001≤v≤0.15.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤3.8,0.5≤b < 1,0.33≤α≤1.75,0.15≤β≤1.35, γ 1=0,0≤γ 2≤1.6,0 < u≤0.5,0.001≤v≤0.15.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤3.8,0.5≤b < 1,0.33≤α≤1.75,0.15≤β≤1.35, γ 1=0,0≤γ 2≤1.6,0 < u≤0.5,0.001≤v≤0.15.
According to the composite fluorescent material of a preferred embodiment of the present invention, wherein said composite fluorescent material is by the optical excitation with the excitation light source of emission peak within the scope of UV-light one blue green light of 300 ~ 500nm, be issued to rare one with the emmission spectrum of upward peak within the scope of 450 ~ 600nm, the luminescence from blueness to orange red color can be presented, also can with other one or more fluorescent material used in combination realize white or polychrome system luminous and be applied to the manufacture of LED component.
In the present invention, providing a kind of is the composite fluorescence body jointly formed with the crystallite of the oxygen fluor that is main anion binding and inert metal element simple substance by principal phase.The existence of the inert metal element simple substance crystallite in this species complex, can make that the luminous intensity of principal phase fluor improves, heat resistanceheat resistant damping capacity strengthens.This is an important discovery of the present invention and innovation, and associated viscera does not see domestic and foreign literature and patent report.
Trivalent nitrogen ion is introduced by trivalent and the common Substitute For Partial oxygen of univalent anion in complex body fluorescence principal phase, on the one hand the micro-symmetry in fluorescence phase structure and electrons state are changed, on the other hand, the key that N and positively charged ion are formed has stronger covalency, the change of crystal field microenvironment in lattice can be caused, the splitting of electronic level increases, and easily realizes the red shift of emission wavelength, and makes the emission wavelength of described fluorescence principal phase obtain obvious red shift.Thisly utilize the negatively charged ion of non-equivalence, different radii jointly to substitute oxygen and adjust the method for the meticulous emission characteristic of described fluorescent material flexibly, be also another important discovery and innovation of the present invention, associated viscera does not also see domestic and foreign literature and patent report.
In invention, the fluorescence principal phase in complex body is one group of lattice types having that silica (with silicon nitrogen) tetrahedron tightly packed and the alkaline-earth metal of large radius and rare earth ion are filled in space.This lattice can obtain moderate electronic level splitting and realize from green to orange luminescence down exciting.But, this material make its radiationless relaxation in excitation electron transition stronger compared with low symmetry and more complicated constitutional features, luminous intensity is not ideal, heat fade is larger, even by the best halogens doping of about 0.2 mole, after optimizing, its luminous intensity still has gap with YAG material.
Therefore, the present invention utilizes using the particulate of inert metal element simple substance as kind of a brilliant high-temperature solid phase reaction method, the basis of inert metal element simple substance kind crystalline substance synthesizes the fluorescence principal phase with halide-ions Substitute For Partial oxygen, simultaneously by the former with in domain and the form of the second-phase microcrystalline domain of boundary be incorporated in the crystalline domain structure of fluorescence principal phase, and obtain a kind of novel composite fluorescence body.Also jointly replaced by trivalent nitrogen and monovalence halogen by the part oxygen in fluorescence principal phase lattice, and correspondingly obtain another kind of novel composite fluorescence body.
Under the temperature and pressure that above-mentioned inert metal element simple substance is formed in fluorescence principal phase on the one hand, atmospheric condition, there is stability, a kind of seed crystal condition can be provided and not affect the formation of fluorescent host.These metal simple-substances are good conductor of heat on the other hand, there is very low phonon energy, its with the formal distribution of second-phase crystallite in principal phase crystalline domain structure, the comparatively strong lattice phonon of principal phase can be made to vibrate in the process transmitted between each principal phase domain weaken to some extent, serve the effect reducing the thermal vibration of fluorescence principal phase lattice phonon on the whole, the impact of the lattice dot matrix thermal vibration be subject to during transition of electron under excited state can be made to alleviate further on whole crystalline domain structure yardstick, thus inhibit radiationless energy waste, the luminous intensity of fluorescence principal phase and heat resistanceheat resistant damping capacity are improved further.The existence with the inert metal element simple substance crystallite of orientation also can have good promoter action to the even diffusion of particle in principal phase forming process, crystallization and crystal growth.
On this basis, the method for the oxonium ion that the present invention also utilizes the larger Nitrogen ion of trivalent, radius and monovalence, halide-ions that radius is less substitutes divalence jointly, radius is moderate obtains the NEW TYPE OF COMPOSITE fluor that there is multiple anion binding in one group of fluorescence principal phase.In this species complex, because the electricity price of the negatively charged ion of co-doped and the whole matching of radius and principal phase lattice improve, the trivalent nitrogen ion that usually directly can not substitute oxonium ion in described fluorescence principal phase structure is introduced in lattice, and can makes lattice in larger anion doped weight range, keep stable.The introducing of Nitrogen ion obviously can change the microcrystal field environmental characteristic of lattice, easily make the splitting of crystal field middle orbit electronic level increase and realize the red shift of emission wavelength, and common the substituting of equivalent or inequality non-equivalence negatively charged ion also makes to occur the micro-symmetry in local, the change of negatively charged ion occupy-place and the change of local electronic/hole feature in structure, make the emission wavelength of fluor occur the maximum obvious red shift reaching about 4nm, thus provide the novel method of the described fluor emission wavelength of a kind of meticulous adjustment.In lattice, effective existence of coordinating nitrogen ion also can be helpful for the raising of the physical and chemical stability of material.
In the present invention, adopt the elemental powders of inert metal element or compound and alkaline earth metal carbonate, rare earth oxide, silicon-dioxide and silicon nitride as raw material.In building-up process, with Powdered that directly add or remain stable with the simple substance particulate of inert metal element that compound thermolysis form obtains, and the sheet-like crystallite state formed with a kind of reason stressed due to batch mixing exists.These crystallites can as kind of a crystalline substance, carry out silicon ion, alkaline-earth metal ions and oxonium ion, Nitrogen ion and halide-ions particle stacking and formed with oxygen for main anion binding and can containing one or both Doped anions, rare-earth ion activated fluorescence principal phases, the crystallite that finally can form inert metal element simple substance is wrapped in principal phase domain or is positioned at two kinds of microcosmic crystalline domain structure features (see Fig. 1) of principal phase domain boundary, thus forms a kind of novel complex body fluorescent material.
In complex body, the effective content of inert metal element simple substance crystallite is roughly in 0.1wt.% ~ 3 or 4wt.%, can obtain simple composite fluorescence body within the scope of this.The luminous intensity of fluorescence principal phase improves gradually along with the content increase of inert metal element simple substance, inert metal element simple substance content can obtain optimal luminescent intensity when about 1 ~ 1.5wt.%, the then continuation raising of inert metal element simple substance content no longer includes benefit, and the luminous intensity of sample reduces gradually.The addition of inert metal element simple substance, higher than being unfavorable for behind 3 or 4wt.% that the crystallization of fluorescence principal phase is formed, occurs in sample that a large amount of luminescence phenomenon worsens rapidly or buries in oblivion without luminous dephasign, can not obtain the single-phase or aforementioned simple complex body of fluorescence principal phase.
Have in the composite fluorescence body of the fluorescence principal phase of halide-ions Substitute For Partial oxygen, halide-ions substitutes the significant quantity of oxygen at about 0.001 ~ 0.8 mole.The luminous intensity of fluor substitutes amount increase with halogen and improves gradually, and being about 0.2 ~ 0.25 mole at content of halide ions can obtain optimal luminescent intensity, and the increase of content of halogen subsequently makes the luminous intensity of sample decline gradually.
Have in the composite fluorescence body of the fluorescence principal phase of Nitrogen ion and the common Substitute For Partial oxygen of halide-ions, because nitrogen and the common of halogen substitute, the matching of its electricity price on the whole and radial features and fluorescence principal phase lattice is significantly improved, makes lattice can keep stable in a larger negatively charged ion alternate range.In this species complex, the amount that effectively substitutes of nitrogen is at about 0.001 ~ 0.2 or 0.5 mole, and the total amount of non-oxygen anion is 0.002 ~ 1.2 mole.The sample that nitrogen name content is 0.5 mole, chlorine name content is 0.5 mole, be rendered as homogeneous pale green sintered compact, its emission wavelength is 519nm, and the emission wavelength of unazotized corresponding congruent sample is 515nm, there is the red shift of 4nm in the former emission wavelength, most Nitrogen ion that can prove in nominal proportioning enter lattice and define the composite fluorescence body that the part oxygen in principal phase substituted jointly by nitrogen and halide-ions.Trivalent and univalent anion doping total amount are higher than after 1.2 moles, there is melting and phase-splitting state in sample, in spectrum test emission wavelength not red shift or red shift limited, illustrate and can not form the fluorescence principal phase that Nitrogen ion enters lattice, be only the fluorescence phase of halide-ions Substitute For Partial oxygen and the mixed phase of other phase.
In the present invention, the R position in fluorescence principal phase lattice introduces except primary activation ion Eu other rare earth ions to improve the luminous intensity of fluorescent material.M1 position in fluorescence principal phase lattice introduces the interaction that the unit be selected from B, Al, Ge, Ga, In usually adjusts active ions and crystal field, can realize the adjustment of material emission wavelength further, is also an important part of the present invention.
Composite fluorescent material of the present invention adopt a kind of with the simple substance particulate of inert metal element for kind of brilliant solid state reaction kinetics method manufactures, this is that on material manufacturing method one of the present invention has unique important discovery and innovation.Its principle is, normal pressure or mesolow power, under high temperature and nitrogen hydrogen mixing weakly reducing atmosphere, keep stable with the particulate of Powdered inert metal element simple substance that is that directly add or that obtain with compound thermolysis form and exist with sheet-like crystallite state, meanwhile, M1, the positively charged ions such as M2 and R and nitrogen, oxygen and halide anion rely on the crystallite with the inert metal element simple substance of orientation to carry out particle stacking as seed crystal to carry out crystalline growth, the concentration of crystallization particle and the difference of stacking speed finally can form two kinds of microcosmic crystalline domain structure features that seed crystal is positioned at principal phase domain inside or principal phase domain boundary, form composite fluorescence body of the present invention thus.Jointly substituting oxygen by trivalent and univalent anion can regulate the micro-coordination environment of lattice and electrons state to carry out meticulous adjustment fluor emission wavelength.Emission wavelength and the luminous intensity of fluor can be regulated further by the element substitution of M1 position and the introducing of R position co-activation ion.
When manufacturing composite fluorescent material of the present invention, raw materials used is compound or the simple substance of each element in expression (1), and its element according to the mol ratio of expression (1) is:
M1：0.5～4；
M2：0.5～3.0；
O：1.0～8.0；
N：0～4.0；
X：0～1.0；
R：0.001～0.5；
A：0.001～0.55；
Wherein: M1 represents the compound of one or more elements in Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W;
M2 represents the compound of one or more elements in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, Cs;
X represents the compound of one or more elements in F, Cl, Br, I;
R represents the compound of one or more elements in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn;
A represents simple substance or the compound of one or more elements in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os;
The compound of element representated by M1 adopts the form of oxide compound and/or nitride as element source;
The compound of element representated by M2 adopts the form of carbonate and/or oxide compound as element source;
The compound of element representated by X adopts the form of fluorochemical or muriate or bromide or iodide as element source;
The compound of element representated by R adopts the form of oxide compound and/or nitrate as element source;
The simple substance of element representated by A or compound adopt the form of metal simple-substance powder or oxide compound or carbonate or nitrate as element source.
Its manufacture method is for kind of a brilliant solid state reaction kinetics method with the particulate of inert metal element simple substance.The raw material of each to M1, M2, X, R element is taken by mol ratio, Homogeneous phase mixing, then fully mix at the elemental powders of the element A of 10 to 1000 nanometer range or compound with appropriate, particle diameter again, insert in aluminum oxide or boron nitride crucible, under the weakly reducing atmosphere of 0 ~ 3 atmospheric 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 the subsequent disposal such as fragmentation, screening, aftertreatment and form.
The size particle materials at different levels of satisfied different service requirements can be obtained by screening, luminescent quality and other physical chemistry application performance of fluorescent material can be improved by aftertreatment technology further.
Utilize one or more NEW TYPE OF COMPOSITE fluorescent materials provided by the present invention, that can carry out various ways with the semiconductor luminous chip as excitation light source mates the light-emitting device combining to encapsulate and produce various photochromic, various uses.The Emission Spectrum Peals of luminescence chip can in the UV-blue-green light regional extent of 300 ~ 500nm, the emission wavelength of luminescence chip at least partially can convert to by fluorescent material to be had at least more than one peak wavelength to be in the emmission spectrum in 450 ~ 600nm wavelength region and mixes the LED obtaining various photochromic effect, comprises white light or blue light or green glow or gold-tinted or orange light or purple light or ruddiness.
Composite fluorescent material of the present invention has the advantage that luminosity improves, heat resistanceheat resistant damping capacity strengthens, therefore, compared with the LED utilized packaged by other fluorescent material, utilize the LED packaged by composite fluorescent material of the present invention be more conducive to the raising of brightness, coupling and serviceability stable, lasting, be thus more conducive to manufacture that is efficient, high stability LED.
Also can utilize one or more composite fluorescent materials of the present invention and other yellow and or green and or the fluorescent material of redness carry out mating and combine to encapsulate various performance and photochromic LED to meet different requirement.These other fluorescent material comprises the materials such as rare-earth ion activated garnet structure compound, silicate, oxynitride, nitride, aluminate, halogen silicate, borate, phosphoric acid salt, vanadate and scandate.
In the present invention, the excitation and emission spectra of fluorescent material adopts the test of HITACHIF-4500 fluorescence spectrophotometer.The chromaticity coordinate of LED and colour rendering index adopt the test of EVERFINEPMS-80 type spectroscopic analysis system.
The outstanding feature that the present invention has be that of obtaining a kind of by with oxygen for main anion binding and the NEW TYPE OF COMPOSITE fluor that jointly formed of the crystallite of the fluorescence principal phase and inert metal element simple substance that there is rare earth activation ion.The microcrystalline domain of inert metal element simple substance is introduced in complex body fluorescence principal phase crystalline domain structure.Obtain one group of composite fluorescence body by halide-ions Substitute For Partial oxygen in complex body fluorescence principal phase, obtain another by Nitrogen ion and the common Substitute For Partial oxygen of halide-ions in fluorescence principal phase and organize composite fluorescence body.
Replace compared with the fluorescent material of part oxygen with simple with halide-ions, the existence of the inert metal element simple substance microcrystalline domain of the low phonon energy in the crystalline domain structure of composite fluorescence body of the present invention, the luminous intensity of fluorescence phase and heat resistanceheat resistant damping capacity are improved, is thus more conducive to manufacture that is efficient, high stability LED component.In complex body fluorescence principal phase, non-equivalence negatively charged ion substitutes for the common of part oxygen, serves the effect of adjustment lattice microcrystal field environment and electrons state, can make the obvious red shift of its emission wavelength, realize the meticulous adjustment of fluorescence phase emission wavelength.This composite fluorescence body and have significantly unique and novelty to the raising effect of luminous intensity and heat resistanceheat resistant damping capacity, does not see document both domestic and external and patent report.The method utilizing non-equivalence negatively charged ion jointly to substitute oxygen meticulous adjustment fluor emission wavelength in invention also has significantly unique and novelty, does not see document both domestic and external and patent report.
Another outstanding feature that the present invention has have employed using the crystallite of inert metal element simple substance as kind of a brilliant novel method for synthesizing, has originality.Compared with traditional solid state reaction kinetics method, what novel method for synthesizing of the present invention was prepared is a kind of composite fluorescence body be made up of the crystallite of fluorescence principal phase and inert metal element simple substance, the introducing of the inert metal element simple substance crystallite of the low phonon energy in fluorescence principal phase crystalline domain structure, makes the luminescent properties of material and heat resistanceheat resistant damping capacity improve.The advantage that this novel method has synthesis technique and synthesis condition is simple, material property improves further, is more conducive to the actual use of this material in LED manufactures.
Accompanying drawing explanation
Fig. 1 is that the microcrystalline domain of inert metal element simple substance in the crystalline domain structure of composite fluorescence body and the position relationship of fluorescence principal phase domain are illustrated.In figure: 1,2,3 be respectively principal phase domain; 4 is domain circle; 5 is the second-phase microcrystalline domain in domain; 6 is the second-phase microcrystalline domain of domain circle.Different decorative patterns in each domain illustrate the difference of crystallization property.It is pointed out that the physical location of the actual crystalline domain structure of composite fluorescence body and principal phase domain and second-phase microcrystalline domain, form and relation with contents by the restriction of this schematic diagram.
Fig. 2 is the excitation and emission spectra of embodiment 1 sample.
Fig. 3 is the transmitting collection of illustrative plates of several typical samples under 460nm is blue-light excited in embodiment 2 ~ 9 series of samples.In figure, 3,6,7 represent embodiment 3,6 and 7, c1 represents control sample respectively.
Fig. 4 is the excitation and emission spectra of embodiment 10 sample.
Fig. 5 is the emmission spectrum of embodiment 11 ~ 14 series of samples under 450nm is blue-light excited.In figure, 13,14 represent embodiment 13 and 14 respectively.
Fig. 6 is the excitation and emission spectra of embodiment 15 sample.
Fig. 7 is the transmitting collection of illustrative plates of several typical samples under 465nm is blue-light excited in embodiment 16 ~ 22 series of samples.In figure, 16,18,20 represent embodiment 16,18 and 20, c2 represents control sample respectively.
Fig. 8 is the emmission spectrum of embodiment 24 ~ 28 series of samples under 460nm is blue-light excited.In figure, 27,28 represent embodiment 27 and 28 respectively.
Fig. 9 is the excitation and emission spectra of embodiment 29 sample.
Figure 10 is the transmitting collection of illustrative plates of several typical samples under 460nm is blue-light excited in embodiment 30 ~ 40 series of samples.In figure, 32,34,36 represent embodiment 32,34 and 36, c3 represents control sample respectively.
Figure 11 is the luminous efficiency of LED sample and the relation curve of working hour of embodiment 41.In contrast, the response curve utilizing the corresponding LED sample do not encapsulated containing the fluorescent material of Au is also given.In figure, 41 represent embodiment 41 sample, and c4 represents control sample.
Embodiment
Be below embodiments of the invention.It is pointed out that the present invention not by the restriction of these embodiments.
Embodiment 1:
Proportioning: SiO
21.95Sr
0.487ba
0.513o
0.949f
0.1030.05EuO/0.031Au.Taking purity by metering is analytically pure various raw material: SiO
24.35 grams, SrCO
310.17 gram, BaCO
314.30 gram, NH
4f0.54 gram, Eu
2o
30.64 gram, fully mixed by above each raw material, grinding evenly, then takes 0.45 gram, high-purity Au powder that particle diameter is 10 ~ 1000nm, inserts in compound, fully mixes and grinds evenly, loading alumina crucible subsequently, put into air pressure heat treatment furnace, in high-purity N
2and H
24 ~ 8 hours are sintered in 1000 ~ 1600 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is light green, green emitting, emission peak wavelength 520nm.Sample excite and emission characteristic is shown in Fig. 2.
Embodiment 2 ~ 9:
Proportioning: SiO
21.95Sr
0.795ba
0.205o
0.949f
0.1030.05EuO/xAu, 0.01≤x≤0.059.Taking proportioning is SiO
24.69 grams, SrCO
317.87 gram, BaCO
36.17 grams, NH
4f0.58 gram, Eu
2o
30.69 gram, purity is each eight parts of analytically pure raw material, takes each 0.15 gram of high-purity Au powder that particle diameter is 10 ~ 1000nm, 0.23 gram, 0.3 gram, 0.38 gram, 0.45 gram, 0.6 gram, 0.75 gram and 0.9 gram, the preparation method of variant Au content sample and step are with embodiment 1 subsequently.Sintered powder, in yellow, launches gold-tinted.The emission characteristic of each embodiment and Au add-on thereof are in table 1.In contrast, the sample SiO not containing Au has also been prepared
21.95Sr
0.795ba
0.205o
0.949f
0.1030.05EuO (x=0 is labeled as c1).In embodiment 2 ~ 9, Fig. 3 is shown in by the transmitting collection of illustrative plates of several typical sample under 460nm is blue-light excited.
In Fig. 3, with not containing Au control sample compared with, along with Au adds, start to be formed the complex body of Au crystallite and fluorescence phase.Due to the existence of the Au crystallite of the low phonon energy in crystalline domain structure, fluorescence phase luminous intensity is improved.Au content is 0.029 mole time, and the luminous intensity of sample reaches maximum, and compared with not containing the sample of Au, luminous intensity about has the raising of 15%.Thereafter the luminous intensity of sample reduces gradually with the raising of Au content, and the volume of Au exists the luminescence feature being unprofitable to fluorescence phase.
The Au content of table 1. embodiment 2 ~ 9 and emission characteristic:
Embodiment 10:
Proportioning: SiO
1.55n
0.31.95Sr
0.487ba
0.513o
0.923f
0.1540.05EuO/0.032Au.Taking purity by metering is analytically pure each raw material: SiO
23.37 grams, Si
3n
40.76 gram, SrCO
310.15 gram, BaCO
314.28 gram, NH
4f0.80 gram, Eu
2o
30.64 gram, fully mixed by above each raw material, grinding evenly, then takes 0.45 gram, high-purity Au powder that particle diameter is 10 ~ 1000nm, inserts in compound, fully mixes and grinds evenly, loading alumina crucible subsequently, put into air pressure heat treatment furnace, in high-purity N
2and H
24 ~ 8 hours are sintered in 1000 ~ 1600 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is light green, green emitting, emission peak wavelength 523nm.Sample excite and emission characteristic is shown in Fig. 4.
Embodiment 11 ~ 13:
Proportioning: SiO
2-1.5yn
y1.95Sr
0.179ba
0.821o
1-0.257ycl
0.513y0.05EuO/0.034Au, 0.1≤y≤0.5.N and Cl equivalent is added, and addition is respectively respectively 0.1 mole, 0.3 mole and 0.5 mole.The raw material dosage of the sample of variant codoped anion-content, in table 2, is raw materials usedly analytical pure or high-purity, and the size range of Au powder used is 10 ~ 1000nm.The preparation method of each sample and step are with embodiment 10 subsequently.In contrast, SiO has also been prepared
21.95Sr
0.179ba
0.821o
0.795cl
0.410.05EuO/0.036Au sample (embodiment 14).Sintered powder is light green, transmitting green light.The emission wavelength of embodiment 11 ~ 14 sample under 450nm is blue-light excited and emmission spectrum are in table 2 and Fig. 5.
In Fig. 5, the co-doped of N and Cl can make trivalent nitrogen ion enter the lattice of fluorescence phase, and this lattice can not replace oxygen by direct N usually.When N content is increased to 0.5 mole, there are micro-grayish green form and aspect in sample, has reached maximum interpolation scope.Compared with comparative sample, the emission wavelength of sample increases with N content and increases, and N content is that the emission wavelength of 0.5 mole of sample rises to 519nm from 515nm, occurs the red shift of 4nm, provides a kind of new tool of meticulous adjustment electromagnetic radiation wavelength.
Raw material dosage and the transmitting of table 2. embodiment 11 ~ 14 are special:
Embodiment 15:
Proportioning: SiO
22.95SrO
0.966f
0.0680.05EuO/0.026Pt.Taking purity by metering is analytically pure each raw material: SiO
23.52 grams, SrCO
325.53 gram, NH
4f0.43 gram, Eu
2o
30.52 gram, fully mixed by above each raw material, grinding evenly, then takes 0.3 gram, high-purity Pt powder that particle diameter is 10 ~ 1000nm, inserts in compound, fully mixes and grinds evenly, loading alumina crucible subsequently, put into air pressure heat treatment furnace, in high-purity N
2and H
24 ~ 8 hours are sintered in 1000 ~ 1600 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is orange-yellow, orange-yellow luminescence, emission peak wavelength 567nm.Sample excite and emission characteristic is shown in Fig. 6.
Embodiment 16 ~ 22:
Proportioning: SiO
22.95Sr
0.949ba
0.051o
0.966f
0.0680.05EuO/xPt, 0.013≤x≤0.053.Taking proportioning is SiO
23.47 grams, SrCO
323.88 gram, BaCO
31.71 grams, NH
4f0.43 gram, Eu
2o
3each seven parts of the analytical pure raw material of 0.51 gram, takes each 0.15 gram of high-purity Pt powder that particle diameter is 10 ~ 1000nm, 0.23 gram, 0.3 gram, 0.38 gram, 0.45 gram, 0.53 gram and 0.6 gram, and the preparation method of the sample of variant Pt content and step are with embodiment 15 subsequently.Sintered powder is orange, launches orange-colored light.The emission characteristic of each embodiment and Pt add-on thereof are in table 3.In contrast, the sample SiO not containing Pt has also been prepared
22.95Sr
0.949ba
0.051o
0.966f
0.0680.05EuO (x=0 is labeled as c2).In embodiment 16 ~ 22, Fig. 7 is shown in by the transmitting collection of illustrative plates of several typical sample under 465nm is blue-light excited.
In Fig. 7, compared with not containing the respective sample of Pt, along with the interpolation of Pt, the luminous intensity of fluorescence phase improves gradually.Pt content is 0.027 mole time, and the luminous intensity of sample reaches maximum, and compared with not containing the sample of Pt, luminous intensity about has the raising of 10%.
The Pt content of table 3. embodiment 16 ~ 22 and emission characteristic:
Embodiment 23:
Proportioning: SiO
1.85n
0.12.95Sr
0.949ba
0.051o
0.983cl
0.0340.05EuO/0.027Pt.Taking purity by metering is analytically pure each raw material: SiO
23.23 grams, Si
3n
40.20 gram, SrCO
324.02 gram, BaCO
31.72 grams, NH
4cl0.31 gram, Eu
2o
30.51 gram, fully mixed by above each raw material, grinding evenly, then takes 0.3 gram, high-purity Pt powder that particle diameter is 10 ~ 1000nm, inserts in compound, fully mixes and grinds evenly, loading alumina crucible subsequently, put into air pressure heat treatment furnace, in high-purity N
2and H
24 ~ 8 hours are sintered in 1000 ~ 1600 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is orange, orange luminescence, emission peak wavelength 570nm.
Embodiment 24 ~ 27:
Proportioning: SiO
2-1.5yn
y2.95SrO
1-0.17yf
0.339y0.05EuO/0.026Pt, 0.05≤y≤0.2.N and F equivalent is added, and addition is respectively respectively 0.05 mole, 0.1 mole, 0.15 mole and 0.2 mole.The analytical pure of the sample of variant codoped anion-content or the consumption of high pure raw material are in table 4, and the size range of Pt powder used is 10 ~ 1000nm.The preparation method of each sample and step are with embodiment 23 subsequently.In contrast, SiO has also been prepared
22.95SrO
0.924f
0.1530.05EuO/0.026Pt sample (embodiment 28).Sintered powder is orange ~ orange, launches orange ~ orange-colored light.The emission wavelength of embodiment 24 ~ 28 sample under 460nm is blue-light excited and emmission spectrum are in table 4 and Fig. 8.
In Fig. 8, the co-doped of N and F can make a small amount of trivalent nitrogen ion enter lattice.When N content is increased to 0.2 mole, there are a small amount of grey form and aspect in sample, has reached maximum interpolation scope.Compared with fluorescence phase (b=2) lattice of embodiment 10 ~ 14, the solid solubility of its N is less, and this feature having more stiff stability with the lattice of this phase (b=3) is consistent.Compared with comparative sample, the emission wavelength of sample increases with N content and slightly increases, and N content is that the emission wavelength of 0.2 mole of sample rises to 569nm from 567nm, occurs the red shift of 2nm.
The raw material dosage of table 4. embodiment 24 ~ 28 and emission characteristic:
Embodiment 29:
Proportioning: 2SiO
0.5n0.95BaO
0.79f
0.4210.05EuO/0.043Ag.Taking purity by metering is analytically pure each raw material: SiO
22.90 grams, Si
3n
46.76 grams, BaCO
318.07 gram, NH
4f1.43 gram, Eu
2o
30.85 gram, fully mixed by above each raw material, grinding evenly, then takes 0.45 gram, the high-purity Ag powder that particle diameter is 10 ~ 1000nm, inserts in compound, fully mixes and grinds evenly, loading alumina crucible subsequently, put into air pressure heat treatment furnace, in high-purity N
2and H
24 ~ 8 hours are sintered in 1000 ~ 1600 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is light green, and blue-greenish colour is luminous, emission peak wavelength 495nm.Sample excite and emission characteristic is shown in Fig. 9.
Embodiment 30 ~ 40:
Proportioning: 2SiO
0.5n0.95BaO
0.895f
0.2110.05EuO/xAg, 0.014≤x≤0.085.Taking proportioning is SiO
22.97 grams, Si
3n
46.92 grams, BaCO
318.51 gram, NH
4f0.73 gram, Eu2O
3the analytical pure raw material each ten of 0.87 gram is a, take each 0.15 gram of the high-purity Ag powder that particle diameter is 10 ~ 1000nm, 0.23 gram, 0.3 gram, 0.38 gram, 0.45 gram, 0.53 gram, 0.6 gram, 0.68 gram, 0.75 gram, 0.83 gram and 0.9 gram, the preparation method of the sample of variant Ag content and step are with embodiment 29 subsequently.Sintered powder is light green, launches blue green light.The emission characteristic of each embodiment and Ag add-on thereof are in table 5.In contrast, the sample 2SiO not containing Ag has also been prepared
0.5n0.95BaO
0.895f
0.2110.05EuO (x=0 is labeled as c3).In embodiment 30 ~ 40, Figure 10 is shown in by the transmitting collection of illustrative plates of several typical sample under 460nm is blue-light excited.
In Figure 10, compared with not containing the respective sample of Ag, along with the interpolation of Ag, the luminous intensity of fluorescence phase improves gradually.Ag content is 0.042 mole time, and the luminous intensity of sample reaches maximum, and compared with not containing the sample of Ag, luminous intensity about has the raising of 20%.
The Ag content of table 5. embodiment 30 ~ 40 and emission characteristic:
Embodiment 41:
The NEW TYPE OF COMPOSITE fluorescent material described in the embodiment of the present invention 6 is adopted to carry out the encapsulation of white light LEDs.The chip with the transmitting peak wavelength matched is have chosen according to effective excitation wavelength range of fluorescent material.Semiconductor luminous chip is GaInN chip, and it launches peak wavelength is 460nm, and the emission wavelength of fluorescent material is 550nm.Concrete packaging process is: the chip chosen is carried out die bond, routing, oven dry.Take some grams, described fluorescent material according to suitable proportion, mix with transparent epoxy resin, then in a glue mode, it is evenly applied on a semiconductor die.To put the lead-in wire cup of glue, after putting into vacuum drying oven solidification, inserting to fill with has in the mould of epoxy resin, then through vacuum drying oven solidification, finally demould.The chromaticity coordinate of this white light LEDs is (0.3012,0.3087), colour temperature 7368K, colour rendering index 83.In contrast, the fluorescent material that do not contain Au corresponding to embodiment 6 is also utilized synchronously to encapsulate comparison LED (being labeled as c4).Figure 11 gives the LED sample of embodiment 41 and the luminous efficiency of comparison LED sample and the relation curve of working hour.
In Figure 11, compared with the LED sample encapsulated with the fluorescent material not containing Au, with the LED sample packaged by composite fluorescent material of the present invention in work after 150 hours, the amplitude less (improving about 5%) that luminous efficiency declines, heat resistanceheat resistant damping capacity increases.
Claims (10)
1. one group of NEW TYPE OF COMPOSITE fluorescent material, its chemical constitution general formula is: aM1O
αn
β+γ 1bM2O
1-0.5 γ 2x
γ 2uRO/vA, wherein M1 is for being selected from least one element in Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W; M2 is for being selected from least one element in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, Cs; X is for being selected from least one element in F, Cl, Br, I; R is for being selected from least one element in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is for being selected from least one element in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os; A, b, α, β, γ 1, γ 2, u, v are mole coefficient and meet following relation: (1) is as 1.5≤b < 2,1 < α≤2, during β=0,2.0≤b+u < 2.2 and 0.4 < a/ (b+u) < 0.6,0≤γ 1 < 0.67 and α=2-1.5 γ 1,0≤γ 2 < 0.67,0 < u≤0.5,0.002≤v < 0.37; (2) as 2.5≤b < 3,1.5 < α≤2, during β=0,3.0≤b+u < 3.2 and 0.2 < a/ (b+u) < 0.4,0≤γ 1 < 0.33 and α=2-1.5 γ 1,0≤γ 2 < 0.4,0 < u≤0.5,0.002≤v < 0.52; (3) as 0.5≤b < 1,0.3 < α < 2, during 0.1 < β < 1.5,1.0≤b+u < 1.2 and 0.5 < a/ (b+u) < 4, γ 1=0,0≤γ 2 < 2.0,0 < u≤0.5,0.002≤v < 0.38; The feature of this composite fluorescent material is, it is for main anion binding and the complex body that formed of the simple substance that part halide-ions can be had to replace the host lattice material and Au, Ag, Pd, Pt, Rh, Ir, Ru, Os inert metal element that oxygen or part halide-ions and Nitrogen ion jointly replace oxygen and there is rare earth activation ion with oxygen; The simple substance of Au, Ag, Pd, Pt, Rh, Ir, Ru, Os inert metal element is present in the principal phase domain in fluorescence principal phase crystalline domain structure or domain boundary with the form of second-phase microcrystalline domain, the thermal vibration of fluorescence principal phase lattice can be alleviated, radiationless relaxation phenomena in transition of electron is weakened, and the luminous intensity of composite fluorescence body and heat resistanceheat resistant damping capacity are improved; This composite fluorescent material passes through with inert metal element simple substance as kind of brilliant high-temperature solid phase reaction method obtains, it is launched after ultraviolet one 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.
2. one group of composite fluorescent material according to claim 1, is characterized in that, the part oxygen in complex body fluorescence principal phase crystalline network is substituted by halide-ions, and the alternative amount of halide-ions is between 0.001 ~ 1.0 mole.
3. one group of composite fluorescent material according to claim 1, it is characterized in that, part oxygen in complex body fluorescence principal phase crystalline network is substituted jointly by trivalent nitrogen ion and monovalence halide-ions, microcrystal field environment and electrons state in structure are changed, and make the emission wavelength red shift of fluorescence phase, realize the meticulous adjustment of emission wavelength, the alternate range of non-oxygen anion is between 0.002 ~ 1.5 mole.
4. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,1.5≤b < 2,1.16≤α≤2, β=0,0≤γ 1≤0.56,0≤γ 2≤0.53,0 < u≤0.5,0.002≤v≤0.11.
5. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,1.5≤b < 2,1.16≤α≤2, β=0,0≤γ 1≤0.56,0≤γ 2≤0.53,0 < u≤0.5,0.002≤v≤0.11.
6. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,2.5≤b < 3,1.67≤α≤2, β=0,0≤γ 1≤0.22,0≤γ 2≤0.32,0 < u≤0.5,0.002≤v≤0.15.
7. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤1.1,2.5≤b < 3,1.67≤α≤2, β=0,0≤γ 1≤0.22,0≤γ 2≤0.32,0 < u≤0.5,0.002≤v≤0.15.
8. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is Eu; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤3.8,0.5≤b < 1,0.33≤α≤1.75,0.15≤β≤1.35, γ 1=0,0≤γ 2≤1.6,0 < u≤0.5,0.002≤v≤0.15.
9. a kind of composite fluorescent material according to Claims 2 or 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and Al, Ge, Ga, In; M2 is for being selected from least one element in Mg, Ca, Sr, Ba, Zn; X is at least one element in F, Cl; R is the combination of at least one element in Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, Mn; A is at least one element in Au, Ag, Pd, Pt; Mole coefficient: 0.9≤a≤3.8,0.5≤b < 1,0.33≤α≤1.75,0.15≤β≤1.35, γ 1=0,0≤γ 2≤1.6,0 < u≤0.5,0.002≤v≤0.15.
10. the preparation method of NEW TYPE OF COMPOSITE fluorescent material, 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 aM1O
αn
β+γ 1bM2O
1-0.5 γ 2x
γ 2the mol ratio scope of uRO/vA is:
M1：0.5～4；
M2：0.5～3.0；
O：1.0～8.0；
N：0～4.0；
X：0～1.0；
R：0.001～0.5；
A：0.001～0.55；
Wherein: M1 represents one or more elements in Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W;
M2 represents one or more elements in Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, Cs;
X represents one or more elements in F, Cl, Br, I;
R represents one or more elements in Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Mn;
A represents one or more elements in Au, Ag, Pd, Pt, Rh, Ir, Ru, Os;
Element representated by M1 adopts the form of oxide compound and/or nitride as element source;
Element representated by M2 adopts the form of carbonate and/or oxide compound as element source;
Element representated by X adopts the form of fluorochemical or muriate or bromide or iodide as element source;
Element representated by R adopts the form of oxide compound and/or nitrate as element source;
Element representated by A adopts the form of metal simple-substance powder as element source;
Its preparation technology is for kind of a brilliant high-temperature solid phase reaction method with the particulate of element A simple substance, the raw material of each to M1, M2, X, R element is taken by mol ratio, Homogeneous phase mixing, then again with take according to proportioning, particle diameter mixes the elemental powders of the element A of 10 to 1000 nanometer range is full and uniform, under the weakly reducing atmosphere of 0 ~ 3 atmospheric 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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102155338A (en) * | 2011-04-11 | 2011-08-17 | 李贵阳 | Air inlet system of automobile engine with electronic control device |
| CN102337120A (en) * | 2010-07-15 | 2012-02-01 | 海洋王照明科技股份有限公司 | Fluorescent material and preparation method thereof |
| CN102373058A (en) * | 2010-08-13 | 2012-03-14 | 海洋王照明科技股份有限公司 | Silicate fluorescent material and preparation method thereof |
| CN102477293A (en) * | 2010-11-23 | 2012-05-30 | 海洋王照明科技股份有限公司 | Electroluminescent material and preparation method thereof |
| CN103168087A (en) * | 2010-12-14 | 2013-06-19 | 海洋王照明科技股份有限公司 | Halo-borate fluorescent materials and preparation methods thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102337120A (en) * | 2010-07-15 | 2012-02-01 | 海洋王照明科技股份有限公司 | Fluorescent material and preparation method thereof |
| CN102373058A (en) * | 2010-08-13 | 2012-03-14 | 海洋王照明科技股份有限公司 | Silicate fluorescent material and preparation method thereof |
| CN102477293A (en) * | 2010-11-23 | 2012-05-30 | 海洋王照明科技股份有限公司 | Electroluminescent material and preparation method thereof |
| CN103168087A (en) * | 2010-12-14 | 2013-06-19 | 海洋王照明科技股份有限公司 | Halo-borate fluorescent materials and preparation methods thereof |
| CN102155338A (en) * | 2011-04-11 | 2011-08-17 | 李贵阳 | Air inlet system of automobile engine with electronic control device |
Non-Patent Citations (1)
| Title |
|---|
| Intensification of the Photosynthetic Action Spectrum of Ba3MgSi2O8:Eu2+, Mn2+ Phosphor with Metal-Enhanced Fluorescence;Yi Cai等;《Electrochemical and Solid-State Letters》;20111214;第15卷(第2期);P1-P5 * |
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