CN103184048A - Composite fluorescent material and preparation method thereof - Google Patents
Composite fluorescent material and preparation method thereof Download PDFInfo
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- CN103184048A CN103184048A CN2011104449529A CN201110444952A CN103184048A CN 103184048 A CN103184048 A CN 103184048A CN 2011104449529 A CN2011104449529 A CN 2011104449529A CN 201110444952 A CN201110444952 A CN 201110444952A CN 103184048 A CN103184048 A CN 103184048A
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Abstract
The invention provides a group of composite fluorescent materials and a preparation method thereof. A fluorescent complex is composed of a fluorescence main phase and a second phase, wherein the fluorescence main phase takes oxygen as a main anionic ligand and rare earth as activated ions, and the second phase is inert elemental metal including Au, Ag, Pd, Pt, Rh, Ir, Ru, Os and the like. Low phonon energy inert elemental metals are distributed in main phase domain or on domain boundary of the fluorescence main phase domain structure in the form of a second phase micro-domain, so that the light intensity and the anti-heat damping capacity of the fluorescence main phase is improved. Part of oxygen in the complex fluorescent main phase lattice can be replaced by trivalent nitrogen ions and monovalent halogen ions together to adjust the micro crystal field environment in the lattice to achieve fine adjustment of the emission wavelength. The composite fluorescent material is prepared by a solid phase reaction process using the microparticles of the inert elemental metals as a seed crystal, can be excited by UV-blue-green light to obtain emission from blue to orange light, and can be applied to manufacturing efficient LED devices.
Description
Technical field
The present invention relates to one group of NEW TYPE OF COMPOSITE fluorescent material that is used for semiconductor light-emitting apparatus, it can be launched the ultraviolet-blue green light chip of wavelength in 300～500nm scope and excite, absorb at least a portion emission light of excitation light source, launch wavelength in 450～600nm scope or blue light or green light or sodium yellow or orange-red light, belong to lighting engineering, demonstration and optoelectronic areas.
Background technology
The semiconductor lighting that utilizes photodiode and realize and technique of display have that current consumption is minimum, environmental friendliness, the life-span is long and plurality of advantages such as applying flexible, obtain just day by day that various countries pay attention to and the application popularization that obtains the social life each side.At present, realize the mode of semiconductor lighting and demonstration, main to utilize UV-light, purple light or blue green light chip to excite the fluorescent material conversion hysteria technology of emission luminescent material of all kinds.As utilize blue chip to excite the fluorescent material of yellow emission can obtain white light LEDs, utilize the fluorescent material of blue chip excitated red emission simultaneously and the fluorescent material of green emitted can obtain to show the LED-backlit source of using.
Can excited by ultraviolet-blue green light chip and realize in the fluorescent material of emission of all kinds that the material of yellow emission is a kind of main material, occupies critical role in the LED lighting engineering.At present, main yellow material is Ce
3+The yttrium aluminum garnet material that activates (Y, Gd)
3(Al, Ga)
5O
12(being called for short YAG).The material of this garnet structure is at the blue-light excited gold-tinted that can launch down 530～550nm, has luminous efficiency height, advantage that chemical property is stable, becomes the LED yellow fluorescent material that is fit to the most.Yet, the use of this material in the LED technology worldwide carried out patent limitation and covering by Japanese Ri Ya company, and be multinomial as US Patent No. 5 998 925, the patent EP of European Union 0 936 682, PCT patent WO 9 805 078, Japanese Patent JP 3 503 139 and Chinese patent CN 1 893 133 etc.
In order to evade the patent limitation of YAG material, the company of countries in the world or research institution are carrying out the development of the fluorescent material of other yellow emissions always.US Patent No. 7 267 787, US 7 311 858, Chinese patent CN 1 0,059 0172, Japanese patent application JP 2,007 009 141 and U.S. Patent application US 2,007 158 614 disclose a kind of can being excited by ultraviolet-blue green light wide range and have launched the Eu of green-sodium yellow of 500～560nm
2+The alkaline-earth metal orthosilicate material that activates (Sr, Ba, Ca)
2SiO
4, yellow emission wherein can make its luminosity near practical requirement by the doping of halogens, may substitute and become a kind of of YAG material.In addition, US Patent No. 7 648 650, PCT patent application WO 2,007 035 026, WO 2,007 018 260 and Chinese patent application CN 101 186 818 disclose another kind of can being excited by ultraviolet-blue green light and have launched the Eu of the orange-colored light of 567～575nm
2+The alkaline earth metal silicate material that activates (Sr, Ba)
3SiO
5: Eu.
Yet above-mentioned rare-earth ion activated alkaline earth metal silicate material, the particularly material of yellow emission have some significantly not enough.These materials only have medium physical and chemical stability, and are not acidproof and soluble in water, and thermostability is not good.Especially, this silicate material is owing to lower, the more high factor of complicacy of structural symmetry, and luminous luminous efficiency is lower slightly.The yellow silicate material of 550nm emission is optimized luminous intensity even mix by halide-ions, and its luminous efficiency still has gap more than 5% with the YAG material, and heat fade is also more remarkable.These deficiencies have restricted it for the good substituting of YAG material and the practical application under high-power situation.
In addition, the white light that the fluorescent material of yellow emission and blue chip combination package obtain lacks red composition, the colour rendering index of LED is lower, colour temperature is too high, can only obtain the cold white light effect of photochromic colder positive bletilla, can't obtain the warm white illuminating effect of euphorosia, thereby the material that need add red emission in actual applications usually in yellow material increases red composition.Because the nitride red low excessively deficiency of material ubiquity lumen brightness of the above emission of 600nm and can't realize matched well with the higher yellow material of brightness, thereby the orange material of launching about present most employing 570nm of producer of aforementioned silicate is disclosed as US Patent No. 7 601 276 as red complementary color composition.Yet as previously mentioned, the silicate material of orange emission still exists luminosity gap and the too high deficiency of heat fade to some extent.
In addition, utilize blue chip and green emitting phosphor and red fluorescence powder to make up to make various flat pannel display and come into one's own day by day and obtain with the technology in LED-backlit source and develop rapidly, make that the importance of fluorescent material of green emitted is outstanding gradually.Though the orthosilicate material of aforementioned patent or the disclosed green emitted of patent application can satisfy the requirement of LED-backlit source technology on purity of color, but its heat fade is too high, the decay of 150 ℃ of following luminous intensities can reach 30%, and show with the working temperature in LED-backlit source that often about 150 ℃ therefore this material is not that the ideal of display backlight is selected.
US Patent No. 7 837 898 and US 7 794 624, PCT patent application WO 2,007 096 333 and Chinese patent application CN 101045860 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 in LED-backlit source.PCT patent application WO 2,009 016 096 discloses the green emitted material B a of another kind of oxynitride
2.5Si
6O
11.5N
2: Eu.The over-all properties of this material is better, makes that but the uncertainty of its metering proportion is big the fluctuation of the luminosity of material and chromaticity coordinate is bigger.
Further develop the fluorescent material of manufacturing process is simple and luminous intensity is better, the heat resistanceheat resistant damping capacity is more stable yellow, orange and green emitted, popularize significant for LED illumination and application progress and the development of technique of display.
Summary of the invention
An object of the present invention is to provide one group and be applied to the NEW TYPE OF COMPOSITE fluorescent material that the LED device is made, because the introducing of the low phonon energy microcrystalline domain of Au, Ag, Pd, Pt, Rh, Ir, inert metal element simple substances such as Ru, Os in the complex body fluorescence principal phase domain structure, make luminous intensity raising, the heat fade of material reduce, more be conducive to manufacturing efficient, high stability LED device, and the partial oxygen in the fluorescence principal phase lattice is substituted the flexible adjustment that can realize the material emission wavelength jointly by trivalent nitrogen ion and monovalence halide-ions; More than one particulates of stating the inert metal element simple substance that another object of the present invention provides above-mentioned composite fluorescence body are kind of a brilliant high temperature solid state reaction synthetic method, have the advantages that manufacturing process is simple, material property improves and be easy to the 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 a element among Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, the W; M2 is for being selected from least a element among Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, the Cs; X is for being selected from least a element among F, Cl, Br, the I; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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, and 0≤γ 2＜2.0,0＜u≤0.5,0.001≤v＜0.55.After this composite fluorescent material is launched the ultraviolet-blue green light of peak wavelength in 300～500nm scope and excites, can launch the luminescent spectrum of one or more peak values of peak wavelength in 450～600nm scope, can present from blueness to orange-red luminous, also can mix to use with other one or more fluorescent material and realize white or multicolor luminous, be applied to the manufacturing of efficient LED device.
It is for oxygen being the complex body of the simple substance formation of main anion binding and the fluorescence principal phase material that contains rare earth activation ion and Au, Ag, Pd, Pt, Rh, Ir, inert metal elements such as Ru, Os.The content of inert metal element simple substance is in 0.1～10wt.% scope, and it plays a part kind of crystalline substance and finally is distributed in the domain in the principal phase domain structure or the domain border with the form of the second phase microcrystalline domain in principal phase material forming process.Partial oxygen in the 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.Partial oxygen in the fluorescence principal phase lattice is substituted jointly by trivalent nitrogen ion and monovalence halide-ions, forms another group NEW TYPE OF COMPOSITE fluor, and 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 the lattice thermal vibration is strong, the heat fade of luminous intensity is in the domain structure of fluorescence principal phase of main anion binding with oxygen comparatively significantly, can further alleviate the lattice thermal vibration of principal phase, the radiationless relaxation phenomena that is subject to lattice thermal vibration influence when making the excitation electron transition and produces alleviates, thereby the luminous intensity of fluorescence principal phase material and heat resistanceheat resistant damping capacity are further enhanced.In the fluorescence principal phase, keep Stability Analysis of Structures by having introduced part trivalent nitrogen ion with the mode of the common replace oxygen of monovalence halide-ions, realize the adjustment of features such as little symmetry in the lattice, negatively charged ion occupy-place/defective, electrons/state and microcrystal field environment thus and make the emission red shift of fluorescence phase, emission wavelength that can meticulous 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 the 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＜2,0.1＜β＜1.5 in the chemical constitution general formula.
According to the composite fluorescent material of a preferred embodiment of the present invention, it is characterized in that M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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 M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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 M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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 M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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.
Composite fluorescent material according to a preferred embodiment of the present invention, wherein said composite fluorescent material is by the optical excitation of the excitation light source with emission peak in the UV-light one blue green light scope of 300～500nm, be issued to rare one with the emmission spectrum of upward peak in 450～600nm scope, can present luminous from blueness to orange red color, also can mix with other one or more fluorescent material to use and realize that white or polychrome are luminous and be applied to the manufacturing of LED device.
Among the present invention, provide a kind of by principal phase for oxygen being the composite fluorescence body that the crystallite of the fluor of main anion binding and inert metal element simple substance constitutes jointly.The existence of the inert metal element simple substance crystallite in this species complex can make luminous intensity raising, the heat resistanceheat resistant damping capacity of principal phase fluor strengthen.This is an important discovery of the present invention and innovation, and associated viscera does not see domestic and foreign literature and patent report.
Substitute partial oxygen jointly by trivalent and univalent anion in the complex body fluorescence principal phase and introduced the trivalent nitrogen ion, on the one hand little symmetry and electrons/state in the fluorescence phase structure are changed, on the other hand, the key that N and positively charged ion form has stronger covalency, can cause the change of crystal field microenvironment in the lattice, the splitting of electronic level increases, and realizes the red shift of emission wavelength easily, and makes the emission wavelength of described fluorescence principal phase obtain obvious red shift.Thisly utilizing the common replace oxygen of negatively charged ion of non-equivalence, different radii and adjust the method for the meticulous emission characteristic of described fluorescent material flexibly, also is another important discovery and innovation of the present invention, and associated viscera does not also see domestic and foreign literature and patent report.
In invention, the fluorescence principal phase in the complex body is that one group of alkaline-earth metal with the tightly packed and long radius of silica (with silicon nitrogen) tetrahedron and rare earth ion filling are in the lattice types in space.This lattice down can obtain moderate electronic level splitting and realizes from green to orange luminous exciting.Yet, low crystal symmetry and the complicated constitutional features of this material make its radiationless relaxation in the excitation electron transition stronger, luminous intensity is not ideal, heat fade is bigger, even by about 0.2 mole best halogens mix optimize after, its luminous intensity still has gap with the YAG material.
Therefore, the present invention utilizes with the particulate of the inert metal element simple substance high-temperature solid phase reaction method as kind of crystalline substance, synthesize the fluorescence principal phase with the alternative partial oxygen of halide-ions on the basis of inert metal element simple substance kind crystalline substance, simultaneously the former is incorporated in the domain structure of fluorescence principal phase with the form that reaches the second phase microcrystalline domain of boundary in the domain, and has obtained a kind of novel composite fluorescence body.Also replaced jointly by trivalent nitrogen and monovalence halogen by the partial oxygen in the fluorescence principal phase lattice, and correspondingly obtained another kind of novel composite fluorescence body.
Above-mentioned inert metal element simple substance has stability on the one hand under temperature and pressure that the fluorescence principal phase forms, atmospheric condition, a kind of seed crystal condition can be provided and not influence the formation of fluorescence main body.These metal simple-substances are good conductor of heat on the other hand, has very low phonon energy, its form with the second phase crystallite is distributed in the principal phase domain structure, weaken to some extent in the process that the comparatively strong lattice phonon vibration of principal phase is transmitted between each principal phase domain, played the effect that reduces the thermal vibration of fluorescence principal phase lattice phonon on the whole, the influence of the lattice dot matrix thermal vibration that is subjected in the time of can making transition of electron under the excited state further alleviates on whole domain structure dimension, thereby suppressed radiationless energy waste, the luminous intensity of fluorescence principal phase and heat resistanceheat resistant damping capacity are further improved.Existence with inert metal element simple substance crystallite of orientation also can have good promoter action to even diffusion, crystallization and the crystal growth of particle in the principal phase forming process.
On this basis, the present invention method of also utilizing the bigger nitrogen ion of trivalent, radius and monovalence, the less halide-ions of radius to substitute the moderate oxonium ion of divalence, radius has jointly obtained to exist in one group of fluorescence principal phase the NEW TYPE OF COMPOSITE fluor of multiple anion binding.In this species complex, because the electricity price of the common negatively charged ion that mixes and the whole matching raising of radius and principal phase lattice, the trivalent nitrogen ion that can not directly substitute oxonium ion in the described fluorescence principal phase structure usually can be introduced in the lattice, and can make lattice in bigger anion doped weight range, keep stable.The introducing of nitrogen ion can obviously change the microcrystal field environmental characteristic of lattice, the splitting of crystal field middle orbit electronic level is increased and the red shift of realization emission wavelength, and equivalent or inequality non-equivalence negatively charged ion common substitutes and also makes and local little symmetry, the variation of negatively charged ion occupy-place and the variation of local electronic/hole feature occur in the structure, make the emission wavelength of fluor obvious red shift about up 4nm occur, thereby the novel method of the described fluor emission wavelength of a kind of meticulous adjusting is provided.Effective existence of coordination nitrogen ion also can be helpful for the raising of the physical and chemical stability of material in the lattice.
In the present invention, the simple substance powder of employing inert metal element or compound and alkaline earth metal carbonate, rare earth oxide, silicon-dioxide and silicon nitride are as raw material.In building-up process, remain stablely with the simple substance particulate of inert metal element Powdered direct adding or that obtain with compound thermolysis form, and exist with a kind of because sheet-like crystallite state former thereby that form that batch mixing is stressed.These crystallites can be used as kind of a crystalline substance, carrying out the particle stacking of silicon ion, alkaline-earth metal ions and oxonium ion, nitrogen ion and halide-ions and forming with oxygen is that main anion binding also can contain fluorescence principal phase one or both doping negatively charged ion, rare-earth ion activated, the crystallite that finally can form the inert metal element simple substance is wrapped in the principal phase domain or is positioned at two kinds of microcosmic domain constitutional features (see figure 1)s on principal phase domain border, thereby forms a kind of novel complex body fluorescent material.
The effective content of inert metal element simple substance crystallite roughly in 0.1wt.%～3 or 4wt.%, can obtain simple composite fluorescence body in the complex body in this scope.The luminous intensity of fluorescence principal phase is along with the content of inert metal element simple substance increases and improves gradually, inert metal element simple substance content can obtain optimal luminescent intensity when 1～1.5wt.% left and right sides, the raising of the continuation of inert metal element simple substance content has then no longer included benefit, and the luminous intensity of sample reduces gradually.The addition of inert metal element simple substance be higher than 3 or 4wt.% after be unfavorable for that the crystallization of fluorescence principal phase forms, a large amount of no luminous dephasigns appear in the sample, luminescence phenomenon worsens rapidly or buries in oblivion, and 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 that halide-ions substitutes partial oxygen, the significant quantity of halide-ions replace oxygen is about 0.001～0.8 mole.The luminous intensity of fluor substitutes amount with halogen to be increased and improves gradually, is to obtain optimal luminescent intensity about 0.2～0.25 mole at content of halide ions, and the increase of content of halogen subsequently descends the luminous intensity of sample gradually.
Have in the composite fluorescence body of the fluorescence principal phase that nitrogen ion and halide-ions substitute partial oxygen jointly, because the common of nitrogen and halogen substitutes, make its on the whole electricity price and the matching of radial features and fluorescence principal phase lattice obviously improve, make lattice can in a bigger negatively charged ion alternate range, keep stable.In this species complex, the amount that effectively substitutes of nitrogen is about 0.001～0.2 or 0.5 mole, and the total amount of non-oxygen anion is 0.002～1.2 mole.Nitrogen name content is that 0.5 mole, chlorine name content are 0.5 mole sample, be rendered as even light green sintered compact, its emission wavelength is 519nm, and the emission wavelength of unazotized corresponding congruent sample is 515nm, the red shift of 4nm appears in the former emission wavelength, can prove that the most nitrogen ions in the nominal proportioning enter lattice and formed the partial oxygen in the principal phase by nitrogen and the common composite fluorescence body that substitutes of halide-ions.After trivalent and univalent anion doping total amount are higher than 1.2 moles, fusion and phase-splitting state appear in sample, not red shift of emission wavelength or red shift are limited in the spectrum test, illustrate to form the fluorescence principal phase that the nitrogen ion enters lattice, only substitute the fluorescence of partial oxygen and the mixed phase of other phase for halide-ions.
Among the present invention, except main active ions Eu, introduced the luminous intensity that other rare earth ions improve fluorescent material on the R position in fluorescence principal phase lattice.The interaction that the unit that is selected among B, Al, Ge, Ga, the In usually adjusts active ions and crystal field has been introduced in M1 position in fluorescence principal phase lattice, can further realize the adjusting of material emission wavelength, also is an important part of the present invention.
The solid state reaction synthetic method manufacturing that it is kind of crystalline substance that composite fluorescent material of the present invention adopts a kind of simple substance particulate with the inert metal element, this is important discovery and the innovation with uniqueness of the present invention on material manufacturing method.Its principle is, normal pressure or mesolow power, under high temperature and the nitrogen hydrogen mixing weakly reducing atmosphere, keep stable and exist with the sheet-like crystallite state with the particulate of inert metal element simple substance Powdered direct adding or that obtain with compound thermolysis form, meanwhile, M1, positively charged ion such as M2 and R and nitrogen, oxygen and halide anion rely on the crystallite of the inert metal element simple substance with orientation to carry out the particle stacking as seed crystal to come crystalline growth, the difference of the concentration of crystallization particle and stacking speed finally can form two kinds of microcosmic domain constitutional featuress that seed crystal is positioned at principal phase domain inside or principal phase domain border, forms composite fluorescence body of the present invention thus.Can regulate the little coordination environment of lattice and the next meticulous adjusting fluor emission wavelength of electrons/state by trivalent and the common replace oxygen of univalent anion.Emission wavelength and luminous intensity that fluor can be further regulated in element substitution by the M1 position and the introducing of R position co-activation ion.
When making composite fluorescent material of the present invention, raw materials used is compound or the simple substance of each element in the expression (1), and its element according to the mole proportioning 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 among Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, the W;
M2 represents the compound of one or more elements among Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, the Cs;
X represents the compound of one or more elements among F, Cl, Br, the I;
R represents the compound of one or more elements among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn;
A represents simple substance or the compound of one or more elements among Au, Ag, Pd, Pt, Rh, Ir, Ru, the Os;
The compound of M1 representative element adopts the form of oxide compound and/or nitride to originate as element;
The compound of M2 representative element adopts the form of carbonate and/or oxide compound to originate as element;
The compound of X representative element adopts the form of fluorochemical or muriate or bromide or iodide to originate as element;
The compound of R representative element adopts the form of oxide compound and/or nitrate to originate as element;
The simple substance of A representative element or compound adopt the form of metal simple-substance powder or oxide compound or carbonate or nitrate to originate as element.
Its manufacture method is the solid state reaction synthetic method of kind of crystalline substance for the particulate with the inert metal element simple substance.The raw material of M1, M2, X, each element of R is taken by weighing by the mole proportioning, evenly mix, then fully mix at simple substance powder or the compound of the A element of 10 to 1000 nanometer range with an amount of, particle diameter again, insert in aluminum oxide or the boron nitride crucible, under the weakly reducing atmosphere that 0～3 atmospheric nitrogen and hydrogen mix, carry out once or sintering for several times, 4 to 8 hours in 1000～1600 ℃, then carry out subsequent disposal such as fragmentation, screening, aftertreatment and form.
By sieving the particle diameter materials at different levels that can obtain to satisfy different service requirementss, can further improve luminescent quality and other physical chemistry application performance of fluorescent material by aftertreatment technology.
Utilize one or more NEW TYPE OF COMPOSITE fluorescent materials provided by the present invention, the coupling that can carry out various ways with the semiconductor light emitting chip as excitation light source makes up to encapsulate the light-emitting device that produces various photochromic, various uses.The emmission spectrum peak value of luminescence chip can be in ultraviolet-blue green light regional extent of 300～500nm, fluorescent material can convert the emission wavelength of at least a portion luminescence chip 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 that obtains various photochromic effects, 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, the heat resistanceheat resistant damping capacity strengthens, therefore, the LED packaged with the fluorescent material that utilizes other compares, utilize the packaged LED of composite fluorescent material of the present invention more to be conducive to raising, coupling and serviceability stable, lasting of brightness, thereby more be conducive to manufacturing efficient, high stability LED.
Also can utilize one or more composite fluorescent materials of the present invention with other yellow and or green and or red fluorescent material mate combination and encapsulate various performances and photochromic LED to satisfy different requirements.These other fluorescent material comprises rare-earth ion activated materials such as garnet structure compound, silicate, oxynitride, nitride, aluminate, halogen silicate, borate, phosphoric acid salt, vanadate and scandate.
Exciting with emmission spectrum of fluorescent material adopted the test of HITACHI F-4500 fluorescence spectrophotometer among the present invention.The chromaticity coordinate of LED and colour rendering index adopt the test of EVERFINE PMS-80 type spectroscopic analysis system.
The outstanding feature that the present invention has is to have obtained a kind of NEW TYPE OF COMPOSITE fluor that is made of jointly the crystallite that is main anion binding and the fluorescence principal phase that has rare earth activation ion and inert metal element simple substance with oxygen.Introduced the microcrystalline domain of inert metal element simple substance in the complex body fluorescence principal phase domain structure.Substitute partial oxygen and obtain one group of composite fluorescence body by halide-ions in the complex body fluorescence principal phase, substitute partial oxygen jointly and obtain another group composite fluorescence body by nitrogen ion and halide-ions in the fluorescence principal phase.
Compare with the simple fluorescent material with halide-ions replacement partial oxygen, the existence of the inert metal element simple substance microcrystalline domain of the low phonon energy in the domain structure of composite fluorescence body of the present invention, luminous intensity and the heat resistanceheat resistant damping capacity of fluorescence phase are improved, thereby more be conducive to manufacturing efficient, high stability LED device.The non-equivalence negatively charged ion substitutes for the common of partial oxygen in the complex body fluorescence principal phase, has played the effect of adjusting lattice microcrystal field environment and electrons/state, can make the obvious red shift of its emission wavelength, realizes the meticulous adjusting of fluorescence phase emission wavelength.This composite fluorescence body and the raising effect of luminous intensity and heat resistanceheat resistant damping capacity had tangible uniqueness and novelty does not see document both domestic and external and patent report.Utilize the common replace oxygen of non-equivalence negatively charged ion to come the method for meticulous adjusting fluor emission wavelength also to have tangible uniqueness and novelty in the invention, do not see document both domestic and external and patent report.
Another outstanding feature that the present invention has is to have adopted with the crystallite of the inert metal element simple substance novel method for synthesizing as kind of crystalline substance, has originality.Compare with traditional solid state reaction synthetic method, what novel method for synthesizing of the present invention was prepared is a kind of composite fluorescence body that is made 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 the fluorescence principal phase domain structure improves the luminescent properties of material and heat resistanceheat resistant damping capacity.The advantage that this novel method has synthesis technique and synthesis condition is simple, material property further improves more is conducive to the actual use of this material in LED makes.
Description of drawings
Fig. 1 is the microcrystalline domain of inert metal element simple substance in the domain structure of composite fluorescence body and the position relation signal of fluorescence principal phase domain.Among the figure: 1,2,3 be respectively the principal phase domain; 4 is domain circle; 5 is the second phase microcrystalline domain in the domain; 6 is the second phase microcrystalline domain of domain circle.Different decorative patterns in each domain have been illustrated the difference of crystallization property.It is pointed out that the actual domain structure of composite fluorescence body and principal phase domain and physical location, form and the relation with contents of the second phase microcrystalline domain are not subjected to the restriction of this synoptic diagram.
Fig. 2 excites and emmission spectrum for embodiment 1 sample.
Fig. 3 is the emission collection of illustrative plates of several typical samples under 460nm is blue-light excited in embodiment 2～9 series of samples.Among the figure 3,6,7 represent respectively embodiment 3,6 and 7, c1 represent control sample.
Fig. 4 excites and emmission spectrum for embodiment 10 samples.
Fig. 5 is the emmission spectrum of embodiment 11～14 series of samples under 450nm is blue-light excited.13,14 represent embodiment 13 and 14 respectively among the figure.
Fig. 6 excites and emmission spectrum for embodiment 15 samples.
Fig. 7 is the emission collection of illustrative plates of several typical samples under 465nm is blue-light excited in embodiment 16～22 series of samples.Among the figure 16,18,20 represent respectively embodiment 16,18 and 20, c2 represent control sample.
Fig. 8 is the emmission spectrum of embodiment 24～28 series of samples under 460nm is blue-light excited.27,28 represent embodiment 27 and 28 respectively among the figure.
Fig. 9 excites and emmission spectrum for embodiment 29 samples.
Figure 10 is the emission collection of illustrative plates of several typical samples under 460nm is blue-light excited in embodiment 30～40 series of samples.Among the figure 32,34,36 represent respectively embodiment 32,34 and 36, c3 represent control sample.
Figure 11 is the luminous efficiency of LED sample of embodiment 41 and the relation curve of working hour.In contrast, also provided the corresponding response curve that does not contain the fluorescent material encapsulated LED sample of Au of utilization.41 represent embodiment 41 samples among the figure, and c4 represents control sample.
Embodiment
Below be embodiments of the invention.It is pointed out that the present invention is not subjected to the restriction of these embodiment.
Embodiment 1:
Proportioning: SiO
21.95Sr
0.487Ba
0.513O
0.949F
0.1030.05EuO/0.031Au.Taking by weighing purity by metering is analytically pure various raw material: SiO
24.35 gram, SrCO
310.17 gram, BaCO
314.30 gram, NH
4F 0.54 gram, Eu
2O
30.64 gram fully mixes above each raw material, grinds evenly, then taking by weighing particle diameter is high-purity Au powder 0.45 gram of 10～1000nm, inserts in the compound, fully mixes and grinds evenly, and the alumina crucible of packing into is subsequently put into the air pressure heat treatment furnace, in high-purity N
2And H
2Under mixed atmosphere, 0～3 normal atmosphere in 1000～1600 ℃ of sintering 4～8 hours.Sintered powder is light green, green emitting, emission peak wavelength 520nm.Sample excite and emission characteristic is seen Fig. 2.
Proportioning: SiO
21.95Sr
0.795Ba
0.205O
0.949F
0.1030.05EuO/xAu, 0.01≤x≤0.059.Taking by weighing proportioning is SiO
24.69 gram, SrCO
317.87 gram, BaCO
36.17 gram, NH
4F 0.58 gram, Eu
2O
30.69 gram, purity is each eight parts of analytically pure raw materials, takes by weighing particle diameter and be each 0.15 gram of high-purity Au powder of 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.It is yellow that sintered powder is, the emission gold-tinted.The emission characteristic of each embodiment and Au add-on thereof see Table 1.In contrast, also prepared the sample SiO that does not contain Au
21.95Sr
0.795Ba
0.205O
0.949F
0.103(0.05EuO x=0 is labeled as c1).The emission collection of illustrative plates of several typical samples under 460nm is blue-light excited seen Fig. 3 among the embodiment 2～9.
Among Fig. 3, compare with the control sample that does not contain Au, along with Au adds, begin to form the complex body of Au crystallite and fluorescence phase.Because the existence of the Au crystallite of the low phonon energy in the domain structure improves fluorescence phase luminous intensity.Au content is in the time of 0.029 mole, and it is maximum that the luminous intensity of sample reaches, and compares with the sample that does not contain Au, and luminous intensity has 15% raising approximately.Thereafter the luminous intensity of sample reduces gradually with the raising of Au content, and there is the luminescence feature that has been unprofitable to the fluorescence phase in the volume of Au.
Au content and the emission characteristic of table 1. embodiment 2～9:
Embodiment 10:
Proportioning: SiO
1.55N
0.31.95Sr
0.487Ba
0.513O
0.923F
0.1540.05EuO/0.032Au.Taking by weighing purity by metering is analytically pure each raw material: SiO
23.37 gram, Si
3N
40.76 gram, SrCO
310.15 gram, BaCO
314.28 gram, NH
4F 0.80 gram, Eu
2O
30.64 gram fully mixes above each raw material, grinds evenly, then taking by weighing particle diameter is high-purity Au powder 0.45 gram of 10～1000nm, inserts in the compound, fully mixes and grinds evenly, and the alumina crucible of packing into is subsequently put into the air pressure heat treatment furnace, in high-purity N
2And H
2Under mixed atmosphere, 0～3 normal atmosphere in 1000～1600 ℃ of sintering 4～8 hours.Sintered powder is light green, green emitting, emission peak wavelength 523nm.Sample excite and emission characteristic is seen 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 are added, and addition respectively is respectively 0.1 mole, 0.3 mole and 0.5 mole.The raw material consumption of the sample of variant codoped anion-content sees Table 2, the raw materials used analytical pure or high-purity that is, and the size range of used Au powder is 10～1000nm.The preparation method of each sample and step are with embodiment 10 subsequently.In contrast, also prepared SiO
21.95Sr
0.179Ba
0.821O
0.795Cl
0.410.05EuO/0.036Au sample (embodiment 14).Sintered powder is light green, transmitting green light.Emission wavelength and the emmission spectrum of embodiment 11～14 samples under 450nm is blue-light excited sees Table 2 and Fig. 5.
Among Fig. 5, the common doping of N and Cl can make the trivalent nitrogen ion enter fluorescence lattice mutually, and this lattice can not directly replace oxygen with N usually.When N content was increased to 0.5 mole, micro-grayish green form and aspect appearred in sample, had reached maximum interpolation scope.Compare with comparative sample, the emission wavelength of sample increases with N content, and N content is that the emission wavelength of 0.5 mole of sample rises to 519nm from 515nm, the red shift of 4nm occurs, and a kind of new tool of meticulous adjusting sample emission wavelength is provided.
The raw material consumption of table 2. embodiment 11～14 and emission are special:
Embodiment 15:
Proportioning: SiO
22.95SrO
0.966F
0.0680.05EuO/0.026Pt.Taking by weighing purity by metering is analytically pure each raw material: SiO
23.52 gram, SrCO
325.53 gram, NH
4F 0.43 gram, Eu
2O
30.52 gram fully mixes above each raw material, grinds evenly, then taking by weighing particle diameter is high-purity Pt powder 0.3 gram of 10～1000nm, inserts in the compound, fully mixes and grinds evenly, and the alumina crucible of packing into is subsequently put into the air pressure heat treatment furnace, in high-purity N
2And H
2Under mixed atmosphere, 0～3 normal atmosphere in 1000～1600 ℃ of sintering 4～8 hours.It is orange-yellow that sintered powder is, orange-yellow luminous, emission peak wavelength 567nm.Sample excite and emission characteristic is seen 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 by weighing proportioning is SiO
23.47 gram, SrCO
323.88 gram, BaCO
31.71 gram, NH
4F 0.43 gram, Eu
2O
30.51 each seven parts of the analytical pure raw materials of gram, taking by weighing particle diameter is each 0.15 gram of high-purity Pt powder of 10～1000nm, 0.23 gram, and 0.3 gram, 0.38 gram, 0.45 gram, 0.53 gram and 0.6 gram, the preparation method of the sample of variant Pt content and step are with embodiment 15 subsequently.It is orange that sintered powder is, the emission orange-colored light.The emission characteristic of each embodiment and Pt add-on thereof see Table 3.In contrast, also prepared the sample SiO that does not contain Pt
22.95Sr
0.949Ba
0.051O
0.966F
0.068(0.05EuO x=0 is labeled as c2).The emission collection of illustrative plates of several typical samples under 465nm is blue-light excited seen Fig. 7 among the embodiment 16～22.
Among Fig. 7, compare with the respective sample that does not contain Pt, along with the interpolation of Pt, the luminous intensity of fluorescence phase improves gradually.Pt content is in the time of 0.027 mole, and it is maximum that the luminous intensity of sample reaches, and compares with the sample that does not contain Pt, and luminous intensity has 10% raising approximately.
Pt content and the emission characteristic of table 3. embodiment 16～22:
Embodiment 23:
Proportioning: SiO
1.85N
0.12.95Sr
0.949Ba
0.051O
0.983Cl
0.0340.05EuO/0.027Pt.Taking by weighing purity by metering is analytically pure each raw material: SiO
23.23 gram, Si
3N
40.20 gram, SrCO
324.02 gram, BaCO
31.72 gram, NH
4Cl 0.31 gram, Eu
2O
30.51 gram fully mixes above each raw material, grinds evenly, then taking by weighing particle diameter is high-purity Pt powder 0.3 gram of 10～1000nm, inserts in the compound, fully mixes and grinds evenly, and the alumina crucible of packing into is subsequently put into the air pressure heat treatment furnace, in high-purity N
2And H
2Under mixed atmosphere, 0～3 normal atmosphere in 1000～1600 ℃ of sintering 4～8 hours.It is orange that sintered powder is, 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 are added, and addition respectively is respectively 0.05 mole, and 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 see Table 4, and the size range of used Pt powder is 10～1000nm.The preparation method of each sample and step are with embodiment 23 subsequently.In contrast, also prepared SiO
22.95SrO
0.924F
0.1530.05EuO/0.026Pt sample (embodiment 28).That sintered powder is is orange～and orange, launch orange～orange-colored light.Emission wavelength and the emmission spectrum of embodiment 24～28 samples under 460nm is blue-light excited sees Table 4 and Fig. 8.
Among Fig. 8, the common doping of N and F can make a small amount of trivalent nitrogen ion enter lattice.When N content was increased to 0.2 mole, a small amount of grey form and aspect appearred in sample, had reached maximum interpolation scope.Compare with fluorescence phase (b=2) lattice of embodiment 10～14, the solid solubility of its N is littler, and the characteristics that this lattice with this phase (b=3) has more stiff stability are consistent.Compare with comparative sample, the emission wavelength of sample increases and slightly increases with N content, and N content is that the emission wavelength of 0.2 mole of sample rises to 569nm from 567nm, the red shift of 2nm occurs.
Raw material consumption and the emission characteristic of table 4. embodiment 24～28:
Embodiment 29:
Proportioning: 2SiO
0.5N0.95BaO
0.79F
0.4210.05EuO/0.043Ag.Taking by weighing purity by metering is analytically pure each raw material: SiO
22.90 gram, Si
3N
46.76 gram, BaCO
318.07 gram, NH
4F 1.43 grams, Eu
2O
30.85 gram fully mixes above each raw material, grinds evenly, then taking by weighing particle diameter is high-purity Ag powder 0.45 gram of 10～1000nm, inserts in the compound, fully mixes and grinds evenly, and the alumina crucible of packing into is subsequently put into the air pressure heat treatment furnace, in high-purity N
2And H
2Under mixed atmosphere, 0～3 normal atmosphere in 1000～1600 ℃ of sintering 4～8 hours.Sintered powder is light green, and blue-greenish colour is luminous, emission peak wavelength 495nm.Sample excite and emission characteristic is seen Fig. 9.
Embodiment 30～40:
Proportioning: 2SiO
0.5N0.95BaO
0.895F
0.2110.05EuO/xAg, 0.014≤x≤0.085.Taking by weighing proportioning is SiO
22.97 gram, Si
3N
46.92 gram, BaCO
318.51 gram, NH
4F 0.73 gram, Eu2O
30.87 each ten portion of the analytical pure raw material of gram, taking by weighing particle diameter is each 0.15 gram of high-purity Ag powder of 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, the emission blue green light.The emission characteristic of each embodiment and Ag add-on thereof see Table 5.In contrast, also prepared the sample 2SiO that does not contain Ag
0.5N0.95BaO
0.895F
0.211(0.05EuO x=0 is labeled as c3).The emission collection of illustrative plates of several typical samples under 460nm is blue-light excited seen Figure 10 among the embodiment 30～40.
Among Figure 10, compare with the respective sample that does not contain Ag, along with the interpolation of Ag, the luminous intensity of fluorescence phase improves gradually.Ag content is in the time of 0.042 mole, and it is maximum that the luminous intensity of sample reaches, and compares with the sample that does not contain Ag, and luminous intensity has 20% raising approximately.
Ag content and the emission characteristic of table 5. embodiment 30～40:
Embodiment 41:
Adopt the embodiment of the invention 6 described NEW TYPE OF COMPOSITE fluorescent materials to carry out the encapsulation of white light LEDs.Chosen the chip with the emission peak wavelength that is complementary according to effective excitation wavelength range of fluorescent material.The semiconductor light emitting chip is the GaInN chip, and its emission peak wavelength is 460nm, and the emission wavelength of fluorescent material is 550nm.Concrete packaging process is: the chip of choosing is carried out solid crystalline substance, routing, oven dry.Take by weighing the some grams of described fluorescent material according to suitable proportion, mix with transparent epoxy resin, then in a glue mode it evenly is coated on the semi-conductor chip.To put the lead-in wire cup of glue, after putting into vacuum drying oven and solidifying, inserting to irritate has in the mould of Resins, epoxy, solidifies finally demould again through vacuum drying oven.The chromaticity coordinate of this white light LEDs is (0.3012,0.3087), colour temperature 7368K, colour rendering index 83.In contrast, also utilize the fluorescent material that does not contain Au accordingly with embodiment 6 to encapsulate comparison LED (being labeled as c4) synchronously.Figure 11 has provided LED sample and the luminous efficiency of comparison LED sample and the relation curve of working hour of embodiment 41.
Among Figure 11, and compare with the fluorescent material encapsulated LED sample that does not contain Au, with the packaged LED sample of composite fluorescent material of the present invention after working 150 hours, luminous efficiency decline scope less (having improved about 5%), the heat resistanceheat resistant damping capacity increases.
Claims (17)
1. one group of NEW TYPE OF COMPOSITE fluorescent material and preparation method thereof, 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 a element among Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, the W; M2 is for being selected from least a element among Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, the Cs; X is for being selected from least a element among F, Cl, Br, the I; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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, and 0≤γ 2＜2.0,0＜u≤0.5,0.001≤v＜0.55; After this composite fluorescent material is launched the ultraviolet-blue green light of peak wavelength in 300～500nm scope and excites, can launch the luminescent spectrum of one or more peak values of peak wavelength in 450～600nm scope, can present from blueness to orange-red luminous, be applied to the manufacturing of efficient LED device.
2. a kind of composite fluorescent material according to claim 1, it is characterized in that, it is for being the complex body of the simple substance formation of main anion binding and the host lattice material that has rare earth activation ion and Au, Ag, Pd, Pt, Rh, Ir, inert metal elements such as Ru, Os with oxygen, and the content of inert metal element simple substance is between 0.1～10wt.%.
3. the simple substance of Au, the Ag in the composite fluorescence body according to claim 1 and 2, Pd, Pt, Rh, Ir, inert metal elements such as Ru, Os, it is characterized in that, its form with the second phase microcrystalline domain is present in the principal phase domain in the fluorescence principal phase domain structure or the domain border, can alleviate the thermal vibration of fluorescence principal phase lattice, radiationless relaxation phenomena in the transition of electron is weakened, and the luminous intensity of composite fluorescence body and heat resistanceheat resistant damping capacity are improved.
4. according to claim 1 or 2 or 3 described one group of composite fluorescent material, it is characterized in that the partial oxygen in the complex body fluorescence principal phase crystalline network is substituted by halide-ions, the alternative amount of halide-ions is between 0.001～1.0 mole.
5. according to claim 1 or 2 or 3 described one group of composite fluorescent material, it is characterized in that, partial oxygen in the complex body fluorescence principal phase crystalline network is substituted jointly by trivalent nitrogen ion and monovalence halide-ions, make that microcrystal field environment and electrons/state change in the structure, and make the emission wavelength red shift of fluorescence phase, realize the meticulous adjusting of emission wavelength, the alternate range of non-oxygen anion is between 0.002～1.5 mole.
6. according to claim 1 or 2 or 3 or 4 or 5 described one group of composite fluorescent material, it is characterized in that mole coefficient 1＜α≤2 in the chemical constitution general formula, β=0.
7. according to claim 1 or 2 or 3 or 4 or 5 described one group of composite fluorescent material, it is characterized in that mole coefficient 0.3＜α＜2,0.1＜β＜1.5 in the chemical constitution general formula.
8. according to claim 1 or 2 or 3 or 4 or 5 or 6 described a kind of preferred composite fluorescent materials, it is characterized in that M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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.
9. according to claim 1 or 2 or 3 or 4 or 5 or 6 described a kind of preferred composite fluorescent materials, it is characterized in that M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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.
10. according to claim 1 or 2 or 3 or 4 or 5 or 7 described a kind of preferred composite fluorescent materials, it is characterized in that M1 is for being selected from least a element among Si, B, Al, Ge, Ga, the In in the chemical constitution general formula; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, Zn, Li, Na, the K; X is for being selected from least a element among F, the Cl; R is for being selected from least a element among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is for being selected from least a element among Au, Ag, Pd, Pt, Rh, Ir, Ru, the 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.
11. according to claim 1,2,3,4,5,6,8 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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.
12. according to claim 1,2,3,4,5,6,8 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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.
13. according to claim 1,2,3,4,5,6,9 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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.
14. according to claim 1,2,3,4,5,6,9 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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.
15. according to claim 1,2,3,4,5,7,10 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is Eu; A is at least a element among Au, Ag, Pd, the 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.
16. according to claim 1,2,3,4,5,7,10 described a kind of preferred composite fluorescent materials, it is characterized in that M1 in the chemical constitution general formula is the combination of at least a element among Si or Si and Al, Ge, Ga, the In; M2 is for being selected from least a element among Mg, Ca, Sr, Ba, the Zn; X is at least a element among F, the Cl; R is the combination of at least a element among Eu and Ce, Pr, Pm, Sm, Tb, Dy, Ho, Er, Tm, Yb, the Mn; A is at least a element among Au, Ag, Pd, the 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.
17. NEW TYPE OF COMPOSITE Preparation of Fluorescent Material method 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 mole ratio range 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 the compound of one or more elements among Si, B, Al, Ge, Ga, In, Sc, Ti, V, Nb, Zr, Mo, the W;
M2 represents the compound of one or more elements among Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Li, Na, K, Rb, the Cs;
X represents the compound of one or more elements among F, Cl, Br, the I;
R represents the compound of one or more elements among Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Mn;
A represents simple substance or the compound of one or more elements among Au, Ag, Pd, Pt, Rh, Ir, Ru, the Os;
The compound of M1 representative element adopts the form of oxide compound and/or nitride to originate as element;
The compound of M2 representative element adopts the form of carbonate and/or oxide compound to originate as element;
The compound of X representative element adopts the form of fluorochemical or muriate or bromide or iodide to originate as element;
The compound of R representative element adopts the form of oxide compound and/or nitrate to originate as element;
The simple substance of A representative element or compound adopt the form of metal simple-substance powder or oxide compound or carbonate or nitrate to originate as element;
Its preparation technology is the high-temperature solid phase reaction method of kind of crystalline substance for the particulate with the A element simple substance, the raw material of M1, M2, X, each element of R is taken by weighing by the mole proportioning, evenly mix, then again with take by weighing according to proportioning, particle diameter is at the simple substance powder of the A element of 10 to 1000 nanometer range or compound is full and uniform mixes, under the weakly reducing atmosphere that 0～3 atmospheric nitrogen and hydrogen mix, carry out once or sintering for several times, 4 to 8 hours in 1000～1600 ℃, then carry out subsequent disposal such as fragmentation, screening, aftertreatment and form.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520120A (en) * | 2016-11-08 | 2017-03-22 | 河北利福光电技术有限公司 | LED nitride red fluorescent powder and preparation method thereof |
| CN106544027A (en) * | 2016-11-08 | 2017-03-29 | 河北利福光电技术有限公司 | A kind of red fluorescence powder based on nitride and preparation method thereof |
| CN107359230A (en) * | 2017-07-10 | 2017-11-17 | 深圳诺好技术有限公司 | The new material and its production technology of a kind of optical package |
| CN114933902A (en) * | 2022-06-30 | 2022-08-23 | 烟台布莱特光电材料有限公司 | Preparation method and composition of phosphor compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070096128A1 (en) * | 2005-10-31 | 2007-05-03 | Kyocera Corporation | Wavelength Converter, Lighting System, and Lighting System Assembly |
| CN102155338A (en) * | 2011-04-11 | 2011-08-17 | 李贵阳 | Air inlet system of automobile engine with electronic control device |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| 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 |
-
2011
- 2011-12-28 CN CN201110444952.9A patent/CN103184048B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070096128A1 (en) * | 2005-10-31 | 2007-05-03 | Kyocera Corporation | Wavelength Converter, Lighting System, and Lighting System Assembly |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
| 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 (2)
| Title |
|---|
| YI CAI等: "Intensification of the Photosynthetic Action Spectrum of Ba3MgSi2O8:Eu2+, Mn2+ Phosphor with Metal-Enhanced Fluorescence", 《ELECTROCHEMICAL AND SOLID-STATE LETTERS》 * |
| 洪广言: "《稀土发光材料-基础与应用》", 30 April 2011, 科学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520120A (en) * | 2016-11-08 | 2017-03-22 | 河北利福光电技术有限公司 | LED nitride red fluorescent powder and preparation method thereof |
| CN106544027A (en) * | 2016-11-08 | 2017-03-29 | 河北利福光电技术有限公司 | A kind of red fluorescence powder based on nitride and preparation method thereof |
| CN106544027B (en) * | 2016-11-08 | 2018-10-23 | 河北利福光电技术有限公司 | A kind of red fluorescence powder and preparation method thereof based on nitride |
| CN107359230A (en) * | 2017-07-10 | 2017-11-17 | 深圳诺好技术有限公司 | The new material and its production technology of a kind of optical package |
| CN114933902A (en) * | 2022-06-30 | 2022-08-23 | 烟台布莱特光电材料有限公司 | Preparation method and composition of phosphor compound |
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|---|---|
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