CN103184047B - One group of composite fluorescent material and preparation method thereof - Google Patents

One group of composite fluorescent material and preparation method thereof Download PDF

Info

Publication number
CN103184047B
CN103184047B CN201110444929.XA CN201110444929A CN103184047B CN 103184047 B CN103184047 B CN 103184047B CN 201110444929 A CN201110444929 A CN 201110444929A CN 103184047 B CN103184047 B CN 103184047B
Authority
CN
China
Prior art keywords
combination
elements
fluorescent material
composite fluorescent
simple substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201110444929.XA
Other languages
Chinese (zh)
Other versions
CN103184047A (en
Inventor
刘海军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deng Hua
Original Assignee
BEIJING HUAMEILIANG MATERIAL TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BEIJING HUAMEILIANG MATERIAL TECHNOLOGY Co Ltd filed Critical BEIJING HUAMEILIANG MATERIAL TECHNOLOGY Co Ltd
Priority to CN201110444929.XA priority Critical patent/CN103184047B/en
Publication of CN103184047A publication Critical patent/CN103184047A/en
Application granted granted Critical
Publication of CN103184047B publication Critical patent/CN103184047B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

One group of NEW TYPE OF COMPOSITE fluorescent material and preparation method thereof.Fluorescent complex by take nitrogen as anion binding, the second-phase of the nitrogen inert metal element simple substance such as fluorescence principal phase and Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn that take rare earth as active ions forms.The nitrogen 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 phase, heat resistanceheat resistant damping capacity improve.This composite fluorescent material adopts with the particulate of aforementioned nitrogen inert metal element simple substance as kind of a brilliant calcium cyanamide thermal reduction nitrogenizing reaction technique preparation, can be excited by UV-blue-green light and obtain the transmitting of red light or green-orange-colored light, be applied to the manufacture of efficient LED devices.

Description

One group of composite fluorescent material and preparation method thereof
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 ~ 550nm and excite, absorb the utilizing emitted light at least partially of excitation light source, launch wavelength within the scope of 500 ~ 700nm or red light or green light or sodium yellow or orange-colored 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, realize the mode of semiconductor lighting and display, mainly to be excited the fluorescent material conversion hysteria technology of the assorted fluorescent material launched by UV-blue-green light chip.Fluorescent material as utilized blue chip to excite yellow to launch can obtain the white light LEDs for throwing light on, and the fluorescent material of excitated red transmitting and the fluorescent material of green emitted can obtain the LED backlight for flat pannel display simultaneously to utilize blue chip.
In LED illumination technology, mainly utilize blue chip to excite the yellow fluorescent material launched to produce gold-tinted, and gold-tinted and remaining blue light can obtain white light.At present, yellow fluorescent powder mainly contains garnet structure material (Y, Gd) rare-earth ion activated disclosed in US Patent No. 5998925 3(Al, Ga) 5o 12: Ce, alkaline earth orthosilicate material (Sr, Ba, Ca) rare-earth ion activated disclosed in (being called for short YAG) and US Patent No. 7267787 2siO 4: Eu.
But, in the above-described techniques, the most efficient transmission of YAG material is 530 ~ 550nm, the most efficient transmission of orthosilicate material is 550nm, the red color components of longer wavelength is all lacked in its spectrum, make that the colour rendering index of the white light LEDs utilizing these two kinds of yellow material to be packaged into is lower, colour temperature is too high, usually can only obtain photochromic colder positive white light and cold quality white light, the warm white look illuminating effect of euphorosia can not be obtained.Therefore, in current technology, have employed to dose in these yellow material can be excited by chip simultaneously and the red emitting material of red-emitting as the scheme of complementary color component, be used for improving the colour rendering index of white light LEDs, reduce colour temperature, realize warm white illuminating effect.In addition, along with the development of flat pannel display, utilize blue chip to excite green emitted and red tranmitting phosphor powder and the technology manufacturing flat pannel display LED backlight has more advantage thus develops rapidly simultaneously.These demands all make to develop and can be excited by UV-blue-green light and the fluorescent material of launching more than 600nm ruddiness becomes and becomes more and more important, and propose very high requirement to the luminous efficiency of this red material and heat resistanceheat resistant damping capacity.
Be that the lattice of anion binding has very strong covalency, stable in properties with N, easily under the effect of activator, form larger crystal field engery level cracking and realize red transmitting, therefore becoming most possible red material matrix.Disclose in US Patent No. 6351069, US6649946, US7258816 and US7556744, Japanese Patent JP4221950, PCT patent application WO2009050171 and U.S. Patent application US2010163896 and a kind ofly can be excited by UV-blue-green light and launch the Eu of 600 ~ 650nm ruddiness 2+the alkaline-earth metal silicon nitride fluorescent material (Ba, Sr, Ca) activated 2si 5n 8.But the luminous efficiency of this material is lower, be only 13 4/10ths of YAG material, heat fade is also larger.
In addition; on above-mentioned patent or the material manufacturing method disclosed in patent application; all adopt the binary nitride first utilizing active alkaline-earth metal, rare earth metal simple substance Nitration synthesis active; the condition of reacting active binary nitride and silicon nitride or active silicon imide to synthesize fluorescent material is again harsh, need the complexity of protective atmosphere, loaded down with trivial details technology of preparing, cannot realize industrial volume production and cost is higher.A kind of carbothermal reduction-nitridation manufacture method for this material is disclosed in US Patent No. 7537710, PCT patent application WO2006073141, Chinese patent application CN101798510.Although The method avoids the use of active raw material, the simple and condition of technique is eased up, and the residual luminescent properties that greatly have impact on material of unavoidable external carbon, is difficult to the material obtaining excellent property.US Patent No. 7713443 discloses a kind of method utilizing under high pressure and stablize this material of Material synthesis, but this method can only obtain a kind of is the multiphase mixture of principal phase with this.
US Patent No. 7273568, US7476337, US7507354 and US7854859, PCT patent application WO2005052087, WO2006080535 and WO2006126567, U.S. Patent application US2009283721 and US2009121615 disclose another kind and can be excited by UV-blue-green light and launch the Eu of 600 ~ 700nm ruddiness 2+alkaline-earth nitride fluorescent material (Ca, the Sr) AlSiN activated 3.Although the luminescent properties of this material is better than (Ba, Sr, Ca) 2si 5n 8: Eu material, luminous efficiency improves about 15%, and heat fade is also less, but compared with the luminous efficiency of yellow material, gap is still larger.
In addition; above-mentioned patent or this material disclosed in patent application; remain by be first active binary nitride by the active simple substance nitrogenize of alkaline-earth metal and rare earth metal, harsh, the technique manufacture method that is loaded down with trivial details, that need protective atmosphere of the condition of active binary nitride and silicon nitride and aluminium nitride being reacted again synthesizes this material, is unfavorable for the industrial volume production of this material.Japanese patent application JP2007262122 discloses a kind of alloy for this material-nitrogenizing reaction manufacture method, and it still relates to the alloy processing of active metal, the higher and very difficult industrial production of complex process, cost.US Patent No. 7537710 and US7391060, Japanese patent application JP2009227714 disclose a kind of carbothermal reduction-nitridation synthesis manufacture method for this material.Utilize the carbonate of stable in properties, silicon nitride and aluminium nitride and carbon dust, by the reduction of carbon dust under high temperature and further nitrogenizing reaction obtains the synthesis of material.But this method still exists the insufficient and defect that makes external carbon residual of reaction, and being difficult to eliminate carbon impurity affects the deterioration of material emission performance, very difficult acquisition can the high performance material of practical application.
Except the red material of the above nitride obtained except being activated by Eu, the nitride fluorescent material that also obtain several redness or green-orange luminescence is activated, disclosed in US Patent No. 7537710 and US7262439, PCT patent application WO2007041402, WO2007041563 and WO2008078559 by Ce.These materials still also exist and activate the identical difficulty of red material and problem with aforementioned Eu in synthetic method and corresponding material property.
Develop luminous efficiency is better, better with the matching of yellow material, heat fade is less nitride red fluorescent material and other photochromic materials further, and the raw material developing this high application performance material is stablized, synthesis technique is simple, condition is eased up, be easy to the manufacture method of industrially scalable volume production for the technical progress of LED illumination and display and application popularization 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 simple substance microcrystalline domain of the low phonon energy of the nitrogen inert metal elements such as Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn in the crystalline domain structure of complex body fluorescence principal phase, make that the luminous intensity of material improves, heat fade reduces, be more conducive to the manufacture of efficient LED devices; More than one simple substance particulates stating nitrogen inert metal element that another object of the present invention is to provide above-mentioned composite fluorescence body are kind of a brilliant calcium cyanamide thermal reduction Nitration synthesis method, have raw material stablize be easy to get, manufacturing process is simple, material property improves and be 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):
aM1N αO β·bM2N 0.67·cCaN 0.67-0.33γX γ·uRN δ/vA(1)
Wherein M1 is for being selected from least one element in Si, Ge, B, Al, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W; M2 is for being selected from least one element in Be, Mg, Sr, Ba, 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 Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn.A, b, c, α, β, γ, δ, u, v are mole coefficient: 0.5 < a < 5.5,0≤b < 1.0,0.5≤c < 1.2, α is 1.17 or 1.33,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u≤1,0.001≤v < 0.8.The feature of this composite fluorescent material is, it is be anion binding with nitrogen and the complex body that forms of the simple substance of the host lattice material and Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn nitrogen inert metal element that there is rare earth activation ion; Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn nitrogen inert metal element simple substance is present in the domain in fluorescence principal phase crystalline domain structure or domain boundary with the form of the second-phase microcrystalline domain of tool orientation, 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 matrix material passes through with nitrogen inert metal element simple substance as kind of brilliant high-temperature solid phase reaction method obtains, it is launched after the UV-blue-green light of peak wavelength within the scope of 300 ~ 550nm excite, the luminescent spectrum of one or more peak values of peak wavelength within the scope of 500 ~ 700nm can be launched, the luminescence of redness or green-orange can be presented, be applied to the manufacture of efficient LED devices.
With take nitrogen as anion binding and form the content of Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn nitrogen inert metal element simple substance of complex body within the scope of 0.1 ~ 10wt.% containing the fluorescence major phase material of rare earth activation ion, it plays a part kind brilliant and is finally present in the form of the second-phase microcrystalline domain of tool orientation in the domain in principal phase crystalline domain structure or domain boundary in major phase material forming process.
The simple substance microcrystalline domain of nitrogen inert metal element has lower phonon energy, it is present in that covalency is extremely strong and phonon energy is higher, lattice thermal vibration is strong, in the crystalline domain structure of the fluorescence principal phase that take nitrogen as anion binding, significantly can weaken the lattice thermal vibration of principal phase, 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 principal phase and heat resistanceheat resistant damping capacity are improved significantly.
According to one group of composite fluorescent material of the present invention, mole coefficient in chemical constitution general formula (1): 0≤b < 1.0 and 2.0≤b+c+u < 2.2 and 2.2 < a/ (b+c+u) < 2.6, α=1.33,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u≤1,0.001≤v < 0.76.
According to one group of composite fluorescent material of the present invention, mole coefficient in chemical constitution general formula (1): 0.4 < b < 0.5 and 1.0≤b+c+u < 1.2 and 1.5 < a/ (b+c+u) < 2.2, α=1.17,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u < 0.1,0.001≤v < 0.33.
According to one group of composite fluorescent material of the present invention, mole coefficient in chemical constitution general formula (1): 0.35 < b < 0.5 and 1.0≤b+c+u < 1.2 and 0.7 < a/ (b+c+u) < 1.2, α=1.33,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u < 0.15,0.001≤v < 0.26.
According to a kind of composite fluorescent material of the present invention, it is characterized in that in chemical constitution general formula (1), M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 4.9≤a≤5.1,0≤b < 1.0,1.0≤c < 1.2, α=1.33,0≤β < 0.1,0≤γ≤0.5, δ=0.67,0 < u≤1,0.001≤v≤0.27.
According to a kind of composite fluorescent material of the present invention, it is characterized in that in chemical constitution general formula (1), M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 4.9≤a≤5.1,0.9≤b < 1.0,1.0≤c < 1.2, α=1.33,0≤β < 0.1,0≤γ≤0.5, δ=1.0,0 < u≤0.1,0.001≤v≤0.27.
According to a kind of composite fluorescent material of the present invention, it is characterized in that in chemical constitution general formula (1), M1 is the combination of at least one element in Si and Al or Si and Al and B, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 1.9≤a≤2.1,0.45≤b < 0.5,0.5≤c < 0.7, α=1.17,0≤β < 0.1,0≤γ≤0.25, δ=0.67,0 < u≤0.05,0.001≤v≤0.12.
According to a kind of composite fluorescent material of the present invention, it is characterized in that in chemical constitution general formula (1), M1 is the combination of at least one element in Si and Al or Si and Al and B, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 1.9≤a≤2.1,0.47≤b < 0.5,0.5≤c < 0.7, α=1.17,0≤β < 0.1,0≤γ≤0.25, δ=1.0,0 < u≤0.03,0.001≤v≤0.12.
According to a kind of composite fluorescent material 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 B, Al, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 0.9≤a≤1.1,0.4≤b < 0.5,0.5≤c < 0.7, α=1.33,0≤β < 0.1,0≤γ≤0.25, δ=0.67,0 < u≤0.1,0.001≤v≤0.09.
According to a kind of composite fluorescent material of the present invention, it is characterized in that in chemical constitution general formula (1), M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 0.9≤a≤1.1,0.45≤b < 0.5,0.5≤c < 0.7, α=1.33,0≤β < 0.1,0≤γ≤0.25, δ=1.0,0 < u≤0.05,0.001≤v≤0.09.
According to a kind of composite fluorescent material 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 the UV-light-blue green light of 300 ~ 550nm, be issued to rare one with the emmission spectrum of upward peak within the scope of 500 ~ 700nm, the green yellow or orange luminescence of redness 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 efficient LED devices.
In the present invention, providing a kind of is take nitrogen as the composite fluorescence body that the fluor of anion binding and the crystallite of nitrogen inert metal element simple substance are formed jointly by principal phase, in this species complex, the existence of nitrogen inert metal element simple substance crystallite can make that the luminous intensity of principal phase fluor significantly improves, heat resistanceheat resistant damping capacity strengthens, this is an important discovery of the present invention and innovation, and the associated viscera for related products does not see domestic and foreign literature and patent report.
In invention, the fluorescence principal phase in complex body is one group and has that silicon nitrogen tetrahedron (or silicon nitrogen tetrahedron and aluminium nitrogen tetrahedron) is tightly packed and the alkaline-earth metal of large radius and rare earth ion are filled in the lattice configuration in space.This is that the structure of anion binding has very strong covalency with nitrogen, easily realize the larger splitting of electronic level and realize red emission, and its extremely strong covalency also means that the phonon thermal vibration that is strong, lattice of the interaction of electrons of negative ions in structure is violent, make to excite rear transition of electron process to be subject to the impact of thermal vibration comparatively greatly, consequent stronger radiationless relaxation phenomena reduces luminous intensity and the heat resistanceheat resistant damping capacity of material.
Therefore, the present invention utilizes using the particulate of nitrogen inert metal element simple substance as kind of a brilliant calcium cyanamide thermal reduction nitriding method, the kind crystalline substance of nitrogen inert metal element simple substance synthesizes fluorescence principal phase, simultaneously by the former with in domain and boundary, the form of the second-phase microcrystalline domain of tool orientation is incorporated in the crystalline domain structure of fluorescence principal phase, thus obtains a kind of NEW TYPE OF COMPOSITE fluor.
Under the temperature and pressure that the simple substance of above-mentioned nitrogen inert metal element is formed in fluorescence principal phase on the one hand, atmospheric condition, there is stability, be both not easily also difficult to carburet with Nitrogen ion generation combination reaction, 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 the crystalline domain structure of principal phase, the 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 of the lattice phonon thermal vibration reducing fluorescence principal phase 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 obviously to alleviate on the yardstick of whole crystalline domain structure, and radiationless energy waste is suppressed, thus the luminous intensity of fluorescence principal phase and heat resistanceheat resistant damping capacity are significantly improved.The existence with the simple substance crystallite of the nitrogen inert metal element of orientation also can have good promoter action to the even diffusion of particle in principal phase forming process, crystallization and crystal growth.
In the present invention, adopt the elemental powders of nitrogen inert metal element and stable calcium cyanamide, other alkaline earth metal carbonates, rare earth oxide, silicon nitride and the aluminium nitride be easy to get as raw material.In building-up process, remain stable with the simple substance particulate of the Powdered nitrogen inert metal element directly added, and the sheet-like crystallite state formed with a kind of reason stressed due to batch mixing exists.In building-up process, calcium cyanamide thermolysis produces highly active reductibility carbon, is metal simple-substance by alkaline earth in raw material and rare earth ion Reduction of Oxide.Subsequently, these metal simple-substances enter silicon nitride or silicon nitride and aluminium nitride lattice and form the crystalline growth of principal phase.The crystallite being easy to the nitrogen inert metal element simple substance using having sheet orientation equally in the fluorescence principal phase crystallisation process that en plaque crystalline substance is practised is as the seed crystal of crystal growth to carry out the stacking of particle, the crystallite that finally can form nitrogen 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 species complex fluorescent material.
In complex body, the effective content of nitrogen inert metal element simple substance crystallite is roughly in 0.1 ~ 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 nitrogen inert metal element simple substance, the content of nitrogen inert metal element simple substance can obtain optimal luminescent intensity when about 1 ~ 1.5wt.%, the then continuation raising of nitrogen inert metal element simple substance content no longer includes benefit, and the luminous intensity of sample reduces gradually.The addition of nitrogen inert metal element simple substance, higher than being unfavorable for after 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.
In the present invention, have employed calcium cyanamide thermal reduction Nitration synthesis method, the activated carbon utilizing calcium cyanamide to be decomposed to form sloughs the oxygen element in M2 and R raw material, therefore can by the degree regulating the content ratio of Ca and M2 and R bit element to control deoxygenation, thus in precise controlling principal phase lattice, remain the content of oxygen or excess oxygen, thus the emission wavelength of meticulous adjustment fluorescence principal phase, this is a novelty of the present invention and distinctive feature, and this mode is also rare in domestic and international pertinent literature and patent report.
In the present invention, the R position in fluorescence principal phase lattice introduces other rare earth ions except primary activation ion Eu or Ce, the efficient radiationless transmission ofenergy between Eu or Ce and other rare earth ions can be utilized to improve the luminous intensity of fluorescent material.M1 position in fluorescence principal phase lattice introduces the element be selected from B, Al, Ge, Ga, In or B, Ge, Ga, In.The introducing of these elements can play the effect of adjustment lattice local coordination structure, thus the interaction of adjustment active ions and crystal field, can realize the adjustment of material emission wavelength further, be also an important part of the present invention.
Also can introduce halide-ions in the fluorescence principal phase of composite fluorescence body of the present invention, its effective content is between 0.001 ~ 0.5 mole.The existence of halide-ions in fluorescence phase lattice of low phonon energy, can alleviate the phonon thermal vibration in lattice further, the luminous intensity of composite fluorescence body is improved further, and this is also another important part of the present invention.
Composite fluorescent material of the present invention adopt a kind of with the particulate of nitrogen inert metal element simple substance for kind of brilliant calcium cyanamide thermal reduction Nitration synthesis method manufactures, this is that on material manufacturing method one of the present invention has unique important discovery and innovation.This is the synthetic method that easy control stablized by a kind of raw material, condition is eased up, its principle is, under normal pressure or mesolow power, high temperature and nitrogen hydrogen mixing weakly reducing atmosphere, keep stable with the particulate of the Powdered nitrogen inert metal element simple substance directly added and exist with sheet-like crystallite state, Reduction of Oxide containing M2 and R element is metal simple-substance by the reductibility activated carbon that calcium cyanamide decomposes goes out, release carbon monoxide and/or carbonic acid gas, subsequently, the metal simple-substance of M2, R and degradation production CaN 0.67enter silicon nitride and/or aluminium nitride lattice in a nitrogen atmosphere, and rely on the simple substance crystallite of the nitrogen inert metal element of sheet orientation to start the crystalline growth of fluorescence principal phase as seed crystal.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, there is orientation relationship in seed crystal wherein and principal phase domain, forms composite fluorescence body of the present invention thus.Deoxidation degree can be controlled by the ratio of adjustment Ca and M2, R element thus regulate in lattice the emission wavelength remaining oxygen or the next meticulous adjustment fluor of excess oxygen content.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.The luminescent properties of composite fluorescence body can be improved further by the introducing of halogen.
Thisly utilize self feed material degradation and the high-activity carbon formed carries out complete and sufficient thermal reduction and nitrogenize to form the method for multicomponent nitride, avoid the defect that the carbon caused because reacting incomplete that easily produces because of the introducing of external carbon in conventional carbon thermal reduction nitriding method is residual, avoid residual carbon to affect the deterioration of luminescent properties, fluorescent material of good performance can be obtained.
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:
M1:0.5~5.5;
M2:0~1.0;
Ca:0.5~1.2;
N:1.5~8;
X:0~1.0;
O:0~0.5;
R:0.001~1.0;
A:0.001~0.8;
Wherein: M1 represents one or more elements in Si, Ge, B, Al, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W;
M2 represents one or more elements in Be, Mg, Sr, Ba, Li, Na, K, Rb, Cs;
Ca represents Ca element;
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 Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn;
Element representated by M1 adopts the form of nitride as element source;
Element representated by M2 adopts carbonate and/or oxide compound and/or fluorochemical and/or muriatic form as element source;
Element representated by Ca adopts calcium cyanamide (CaCN 2) as element source;
Element representated by X adopts the form of fluorochemical, muriate, bromide, iodide as element source;
Element representated by R adopts oxide compound and/or nitrate and/or fluorochemical and/or muriatic form as element source;
Element representated by A adopts the form of metal simple-substance powder as element source.
Its manufacture method is for kind of a brilliant calcium cyanamide thermal reduction Nitration synthesis method with the particulate of nitrogen inert metal element simple substance.The raw material of calcium cyanamide and each element of M1, M2, R, X 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, insert in aluminum oxide or boron nitride or molybdenum crucible, under the weakly reducing atmosphere of 0 ~ 3 atmospheric nitrogen and hydrogen mixing in 1000 ~ 1800 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.
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, can directly carry out mating with the semiconductor luminous chip as excitation light source combining to encapsulate and manufacture ruddiness or other photochromic LED.Also can utilize one or more NEW TYPE OF COMPOSITE fluorescent materials provided by the present invention, from other yellow and or green and or orange fluorescent material carry out mating and combine to encapsulate various performance and photochromic LED to meet different requirements.The Emission Spectrum Peals of luminescence chip can in the UV-blue-green light regional extent of 300 ~ 550nm, 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 500 ~ 700nm 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.
Other fluorescent material above-mentioned comprises the materials such as rare-earth ion activated garnet structure compound, silicate, oxynitride, nitride, aluminate, halogen silicate, borate, phosphate phosphor, vanadate and scandate.
The composite fluorescent material of red emission of the present invention has the advantage that luminosity significantly improves, heat resistanceheat resistant damping capacity strengthens, therefore, the brightness matching of the various yellow fluorescent powders higher with brightness is better, is more conducive to carrying out the encapsulation of efficient warm white LED as complementary color component and not affecting its luminous efficiency.The advantage of this brightness and heat resistanceheat resistant decay also makes it more be conducive to mating with green emitting phosphor and encapsulate to manufacture for color developing and the higher display backlight source apparatus of thermal stability requirement.Obviously, this matrix material of the present invention be more conducive to efficiently, the manufacture of high stability LED.
In the present invention, the excitation and emission spectra of fluorescent material adopts the test of HITACHIF-4500 fluorescence spectrophotometer.Oxygen level in composite fluorescence body is measured by oxygen nitrogen elemental analyser.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 is that of obtaining a kind of by being anion binding with nitrogen and the NEW TYPE OF COMPOSITE fluor that jointly forms of the crystallite of the fluorescence principal phase and nitrogen inert metal element simple substance that there is rare earth activation ion.Compared with simple that be anion binding with nitrogen, rare-earth ion activated fluorescent material, there is in crystalline domain structure due to this composite fluorescence body the existence of the microcrystalline domain of the low phonon energy metallic element of orientation, the luminous intensity of composite fluorescence phase and heat resistanceheat resistant damping capacity are significantly improved, is thus more conducive to efficient, high-color rendering, high stability LED component manufacture.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.
Another outstanding feature that the present invention has have employed using the crystallite of nitrogen inert metal element simple substance as kind of a brilliant calcium cyanamide thermal reduction Nitration synthesis method, has originality.Compared with existing carbothermal reduction-nitridation method, calcium cyanamide thermal reduction nitriding method of the present invention avoids the existence of residual carbon, can acquired can better material.Compared with simple calcium cyanamide thermal reduction nitriding method, what novel method for synthesizing of the present invention was prepared is a kind of by taking nitrogen as the composite fluorescence body that the fluorescence principal phase of anion binding and the crystallite of metallic element simple substance are formed, and the existence of the metallic element simple substance crystallite due to the low phonon energy in principal phase crystalline domain structure with orientation, makes the luminous intensity of composite fluorescence body significantly improve further.
With traditional first by active alkaline earth, the binary nitride that rare earth metal simple substance Nitration synthesis is active, then active binary nitride reacts with silicon nitride or active silicon imide and synthesizes with nitrogen the meticulous of the accurate protective atmosphere of needs of the fluorescent material being anion binding, harsh synthetic method is compared, novel method for synthesizing of the present invention adopts the simple substance of the nitrogen inert metal element that character is extremely stable, calcium cyanamide and alkaline earth metal carbonate and silicon, the nitride of aluminium is as raw material, the activated carbon that in high-temperature atmosphere building-up process, calcium cyanamide is decomposed to form sloughs the oxygen in each raw material, each metal simple-substance and then rely on the inert metal element crystallite of orientation to carry out the crystalline growth of fluorescence principal phase with silicon nitride and aluminium nitride chemical combination, final acquisition composite fluorescent material of the present invention, there is feedstock property stablize, without the need to protective atmosphere, synthesis technique and synthesis condition are simply easy to control, the advantage that light-emitting phosphor brightness is better.
The 3rd outstanding feature that the present invention has to be invented with nitrogen the be fluorescent material of anion binding with nitrogen inert metal element simple substance crystallite for kind of a brilliant calcium cyanamide thermal reduction nitrogenize manufacture method, compared with existing various synthetic method, have that raw material is stable, the simple advantage of technique, be easier to industrially scalable volume production, the composite fluorescent material obtained has the advantage that brightness is better, heat fade is less, be more conducive to the actual use of this material in efficient LED manufactures, the growth requirement of LED technology progress and application popularization can be better met.
Accompanying drawing explanation
Fig. 1 is that the microcrystalline domain of nitrogen 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: 1,2,3,4 be respectively principal phase domain; 5 is domain circle; 6 is the second-phase microcrystalline domain in domain; 7 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 ~ 12 series of samples.In figure, 4,6,8 represent embodiment 4,6 and 8, c1 represents control sample respectively.
Fig. 4 is the transmitting collection of illustrative plates of several typical samples under 460nm is blue-light excited in embodiment 13 ~ 23 series of samples.In figure, 15,17,19 represent embodiment 15,17 and 19, c1 represents control sample respectively.
Fig. 5 is the excitation and emission spectra of embodiment 24 sample.
Fig. 6 is the excitation and emission spectra of embodiment 25 sample.
Fig. 7 is the transmitting collection of illustrative plates of embodiment 26 ~ 27 sample under 460nm is blue-light excited.In figure, 26,27 represent embodiment 26 and 27, c2 represents control sample respectively.
Fig. 8 is the excitation and emission spectra of embodiment 28 sample.
Fig. 9 is the excitation and emission spectra of embodiment 29 sample.
Figure 10 is embodiment 30 sample and the transmitting collection of illustrative plates of corresponding comparison sample under 540nm green glow excites not containing Pt.In figure, 30 represent embodiment 30, c3 and represent control sample.
Figure 11 is the luminous efficiency of the LED of embodiment 31 and the relation curve of working hour.In contrast, the response curve utilizing the LED packaged by fluorescent material not containing Au accordingly is also given.In figure, 31 represent embodiment 31 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: 5SiN 1.33o 0.060.99SrN 0.67caN 0.670.01EuN 0.67/ 0.035Au.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 415.19 gram, SrCO 39.49 grams, CaCN 25.20 grams, Eu 2o 30.11 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 ~ 1800 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is orange, orange red luminescence, emission peak wavelength 590nm.Sample excite and emission characteristic is shown in Fig. 2.
Embodiment 2 ~ 12:
Proportioning: 5SiN 1.33o 0.070.95SrN 0.67caN 0.670.05EuN 0.67/ xAu, 0.012≤x≤0.094.Taking proportioning is Si 3n 415.15 gram, SrCO 39.09 grams, CaCN 25.19 grams, Eu 2o 3the analytical pure of 0.57 gram or each ten portions of high pure raw material, take 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, 0.53 gram, 0.6 gram, 0.75 gram, 0.9 gram, 1.05 grams and 1.2 grams, the preparation method of variant Au content sample and step are with embodiment 1 subsequently.Sintered powder is orange red, red-emitting.The emission characteristic of each embodiment and the add-on of Au are in table 1.In contrast, the sample 5SiN not containing Au has also been prepared 1.33o 0.090.95SrN 0.67caN 0.670.05EuN 0.67(x=0 is labeled as c1).Fig. 3 is shown in by the transmitting collection of illustrative plates of several typical samples in embodiment 2 ~ 12 under 460nm is blue-light excited.
In Fig. 3, with not containing Au respective sample compared with, in series of samples of the present invention, along with the interpolation of Au, start to be formed the complex body of Au crystallite and fluorescence phase, fluorescence phase luminous intensity improves gradually.Au content is 0.035 mole time, and the luminous intensity of sample reaches maximum, and compared with not containing the sample of Au, the raising of luminous intensity reaches about 60%.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 ~ 12 and emission characteristic:
Embodiment 13 ~ 23:
Proportioning: 5SiN 1.33o 0.080.95SrN 0.67caN 0.670.05EuN 0.67/ xZn, 0.035≤x≤0.283.Taking proportioning is Si 3n 415.15 gram, SrCO 39.09 grams, CaCN 25.19 grams, Eu 2o 3the analytical pure of 0.57 gram or each ten portions of high pure raw material, take each 0.15 gram of high-purity Zn 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, 0.75 gram, 0.9 gram, 1.05 grams and 1.2 grams, the preparation method of variant Zn content sample and step are with embodiment 1 subsequently.Sintered powder is orange red, red-emitting.The emission characteristic of each embodiment and the add-on of Zn are in table 2.Also with the sample 5SiN not containing Zn 1.33o 0.090.95SrN 0.67caN 0.670.05EuN 0.67(c1) in contrast.Fig. 4 is shown in by the transmitting collection of illustrative plates of several typical samples in embodiment 13 ~ 23 under 460nm is blue-light excited.
In Fig. 4, compared with not containing the respective sample of Zn, in series of samples of the present invention, along with the interpolation of Zn, fluorescence phase luminous intensity also improves gradually.Zn content is that the luminous intensity of the sample of 0.106 mole reaches best, improves about 20%.
The Zn content of table 2. embodiment 13 ~ 23 and emission characteristic:
Embodiment 24:
Proportioning: 5SiN 1.33o 0.070.95Sr 0.95li 0.05n 0.67caN 0.670.05CeN/0.035Au.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 415.34 gram, SrCO 38.72 grams, CaCN 25.26 grams, CeO 20.56 gram, Li 2cO 30.12 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 ~ 1800 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is yellow-green colour, green emitting, emission peak wavelength 510nm.Fig. 5 is shown in exciting and launching collection of illustrative plates of sample.
Embodiment 25:
Proportioning: 2Si 0.5al 0.5n 1.17o 0.020.48SrN 0.670.6CaN 0.670.02EuN 0.67/ 0.019Ag.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 46.67 grams, AlN5.85 gram, SrCO 310.11 gram, CaCN 26.86 grams, Eu 2o 30.50 gram, fully mixed by above each raw material, grinding evenly, then takes 0.3 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 ~ 1800 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder takes on a red color, emitting red light, emission peak wavelength 635nm.Sample excite and emission characteristic is shown in Fig. 6.
Embodiment 26 ~ 27:
Proportioning: 2Si 0.5al 0.5n 1.17o 0.050.48SrN 0.670.5CaN 0.670.02EuN 0.67/ xAg, x are 0.009 or 0.019.Taking proportioning is Si 3n 46.94 grams, AlN6.08 gram, SrCO 310.51 gram, CaCN 25.94 grams, Eu 2o 3the analytical pure of 0.52 gram or each two parts of high pure raw material, take each 0.15 gram and 0.3 gram of the high-purity Ag powder that particle diameter is 10 ~ 1000nm, with the preparation method of latter two different Ag content sample and step with embodiment 25.Sintered powder takes on a red color, red-emitting.The emission characteristic of two embodiments and the add-on of Ag are in table 3.Also the sample 2Si not containing Ag has been prepared 0.5al 0.5n 1.17o 0.070.48SrN 0.670.5CaN 0.670.02EuN 0.67(x=0 is labeled as c2) in contrast.Fig. 7 is shown in by the transmitting collection of illustrative plates of embodiment 26 ~ 27 sample under 460nm is blue-light excited.
In Fig. 7, compared with not containing the respective sample of Ag, in series of samples of the present invention, along with the interpolation of Ag, the luminous intensity of fluorescence phase improves gradually.Ag content is that the luminous intensity of the sample of 0.019 mole reaches best, improves about 15%.
The Ag content of table 3. embodiment 26 ~ 27 and emission characteristic:
Embodiment 28:
Proportioning: 2Si 0.5al 0.5n 1.17o 0.070.49SrN 0.670.5CaN 0.670.01CeN/0.019Ag.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 46.95 grams, AlN6.09 gram, SrCO 310.75 gram, CaCN 25.95 grams, CeO 20.26 gram, fully mixed by above each raw material, grinding evenly, then takes 0.3 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 ~ 1800 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is orange-yellow, orange-yellow luminescence, emission peak wavelength 565nm.Fig. 8 is shown in exciting and launching collection of illustrative plates of sample.
Embodiment 29:
Proportioning: SiN 1.33o 0.020.485SrN 0.670.5CaN 0.670.015CeN/0.008Pt.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 48.71 grams, SrCO 313.34 gram, CaCN 27.46 grams, CeO 20.48 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 ~ 1800 DEG C under mixed atmosphere, 0 ~ 3 normal atmosphere.Sintered powder is orange red, emitting red light, emission peak wavelength 630nm.Sample excite and emission characteristic is shown in Fig. 9.
Embodiment 30:
Proportioning: SiN 1.33o 0.030.47SrN 0.670.5CaN 0.670.03CeN/0.008Pt.Taking purity by metering is analytical pure or high-purity various raw materials: Si 3n 48.69 grams, SrCO 312.9 grams, CaCN 27.45 grams, CeO 20.96 gram, take 0.3 gram, high-purity Pt powder that particle diameter is 10 ~ 1000nm, the preparation method of sample and step are with embodiment 29 subsequently.Sintered powder is orange red, emitting red light, emission peak wavelength 635nm.In contrast, the sample SiN not containing Pt has also been prepared 1.33o 0.060.47SrN 0.670.5CaN 0.670.03CeN (Pt=0 is labeled as c3).Figure 10 is shown in by the transmitting collection of illustrative plates of two samples under 540nm green glow excites.
Embodiment 31:
The NEW TYPE OF COMPOSITE fluorescent material described in the embodiment of the present invention 6 is adopted to carry out the encapsulation of red-light LED.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 600nm.Concrete packaging process is: the chip chosen is carried out die bond, routing, oven dry.Take some grams, above-mentioned fluorescent material according to suitable proportion, after mixing with transparent epoxy resin, 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 red-light LED is (0.6424,0.3244), colour temperature 1122K, colour rendering index 61.In contrast, the fluorescent material that do not contain Au corresponding to embodiment 6 is also utilized synchronously to encapsulate the LED (being labeled as c4) of comparison.Figure 11 gives the LED of embodiment 31 and the luminous efficiency of comparison LED and the relation curve of working hour.
In Figure 11, with not containing Au fluorescent material packaged by LED compared with, with the LED packaged by composite fluorescent material of the present invention in work after 150 hours, the amplitude lower (improving about 5%) that luminous efficiency declines, heat resistanceheat resistant damping capacity increases.

Claims (11)

1. one group of NEW TYPE OF COMPOSITE fluorescent material, its chemical constitution general formula is aM1N αo βbM2N 0.67cCaN 0.67-0.33 γx γuRN δ/ vA, wherein M1 is for being selected from least one element in Si, Ge, B, Al, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W; M2 is for being selected from least one element in Be, Mg, Sr, Ba, 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 Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn; A, b, c, α, β, γ, δ, u, v are mole coefficient: 0.5 < a < 5.5,0≤b < 1.0,0.5≤c < 1.2, α is 1.17 or 1.33,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u≤1,0.001≤v < 0.8; The feature of this composite fluorescent material is, it is be anion binding with nitrogen and the complex body that forms of the simple substance of the host lattice material and Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn nitrogen inert metal element that there is rare earth activation ion; Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn nitrogen inert metal element simple substance is present in the domain in fluorescence principal phase crystalline domain structure or domain boundary with the form of the second-phase microcrystalline domain of tool orientation, 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 matrix material passes through with nitrogen inert metal element simple substance as kind of brilliant high-temperature solid phase reaction method obtains, it is launched after the UV-blue-green light of peak wavelength within the scope of 300 ~ 550nm excite, the luminescent spectrum of one or more peak values of peak wavelength within the scope of 500 ~ 700nm can be launched, the luminescence of redness or green-orange can be presented, be applied to the manufacture of efficient LED devices.
2. one group of composite fluorescent material according to claim 1, it is characterized in that, mole coefficient in chemical constitution general formula: 0≤b < 1.0 and 2.0≤b+c+u < 2.2 and 2.2 < a/ (b+c+u) < 2.6, α=1.33,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u≤1,0.001≤v < 0.76.
3. one group of composite fluorescent material according to claim 1, it is characterized in that, mole coefficient in chemical constitution general formula: 0.4 < b < 0.5 and 1.0≤b+c+u < 1.2 and 1.5 < a/ (b+c+u) < 2.2, α=1.17,0≤β < 0.1,0≤γ < 1.0, δ is 0.67 or 1.0,0 < u < 0.1,0.001≤v < 0.33.
4. one group of composite fluorescent material according to claim 1, it is characterized in that, mole coefficient in chemical constitution general formula: 0.35 < b < 0.5 and 1.0≤b+c+u < 1.2 and 0.7 < a/ (b+c+u) < 1.2, α=1.33, 0≤β < 0.1, 0≤γ < 1.0, δ is 0.67 or 1.0, 0 < u < 0.15, 0.001≤v < 0.26.
5. a kind of composite fluorescent material according to claim 2, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 4.9≤a≤5.1,0≤b < 1.0,1.0≤c < 1.2, α=1.33,0≤β < 0.1,0≤γ≤0.5, δ=0.67,0 < u≤1,0.001≤v≤0.27.
6. a kind of composite fluorescent material according to claim 2, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 4.9≤a≤5.1,0.9≤b < 1.0,1.0≤c < 1.2, α=1.33,0≤β < 0.1,0≤γ≤0.5, δ=1.0,0 < u≤0.1,0.001≤v≤0.27.
7. a kind of composite fluorescent material according to claim 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si and Al or Si and Al and B, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 1.9≤a≤2.1,0.45≤b < 0.5,0.5≤c < 0.7, α=1.17,0≤β < 0.1,0≤γ≤0.25, δ=0.67,0 < u≤0.05,0.001≤v≤0.12.
8. a kind of composite fluorescent material according to claim 3, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si and Al or Si and Al and B, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 1.9≤a≤2.1,0.47≤b < 0.5,0.5≤c < 0.7, α=1.17,0≤β < 0.1,0≤γ≤0.25, δ=1.0,0 < u≤0.03,0.001≤v≤0.12.
9. a kind of composite fluorescent material according to claim 4, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Eu or Eu and Ce, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 0.9≤a≤1.1,0.4≤b < 0.5,0.5≤c < 0.7, α=1.33,0≤β < 0.1,0≤γ≤0.25, δ=0.67,0 < u≤0.1,0.001≤v≤0.09.
10. a kind of composite fluorescent material according to claim 4, is characterized in that in chemical constitution general formula, M1 is the combination of at least one element in Si or Si and B, Al, Ge, Ga, In; M2 is the combination of one or more elements in one or more elements and Li, Na, K in one or more elements or Mg, Sr, Ba in Mg, Sr, Ba; X is the combination of one or more elements in F, Cl; R is the combination of at least one element in Ce or Ce and Eu, Pr, Sm, Dy, Ho, Er, Yb, Mn; A is at least one element in Au, Ag, Pt, Pd, Zn; Mole coefficient 0.9≤a≤1.1,0.45≤b < 0.5,0.5≤c < 0.7, α=1.33,0≤β < 0.1,0≤γ≤0.25, δ=1.0,0 < u≤0.05,0.001≤v≤0.09.
The preparation method of 11. NEW TYPE OF COMPOSITE fluorescent materials, is characterized in that, raw materials used is compound or the simple substance of following each element, and its element is according to following expression aM1N αo βbM2N 0.67-0.33 γx γcCaN 0.67uRN δthe mol ratio scope of/vA is:
M1:0.5~5.5;
M2:0~1.0;
Ca:0.5~1.2;
N:1.5~8;
X:0~1.0;
O:0~0.5;
R:0.001~1.0;
A:0.001~0.8;
Wherein:
M1 represents one or more elements in Si, Ge, B, Al, Ga, In, Sc, Ti, V, Nb, Zr, Mo, W;
M2 represents one or more elements in Be, Mg, Sr, Ba, Li, Na, K, Rb, Cs;
Ca represents Ca element;
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 Co, Rh, Ir, Cu, Au, Ag, Ni, Pd, Pt, Ru, Os, Zn;
Element representated by M1 adopts the form of nitride as element source;
Element representated by M2 adopts carbonate and/or oxide compound and/or fluorochemical and/or muriatic form as element source;
Element representated by Ca adopts calcium cyanamide (CaCN 2) as element source;
Element representated by X adopts the form of fluorochemical, muriate, bromide, iodide as element source;
Element representated by R adopts oxide compound and/or nitrate and/or fluorochemical and/or muriatic form 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 calcium cyanamide high-temperature hot reduction nitridation reaction method with the particulate of element A simple substance, the raw material of calcium cyanamide and each element of M1, M2, R, X 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 ~ 1800 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.
CN201110444929.XA 2011-12-28 2011-12-28 One group of composite fluorescent material and preparation method thereof Expired - Fee Related CN103184047B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110444929.XA CN103184047B (en) 2011-12-28 2011-12-28 One group of composite fluorescent material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110444929.XA CN103184047B (en) 2011-12-28 2011-12-28 One group of composite fluorescent material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103184047A CN103184047A (en) 2013-07-03
CN103184047B true CN103184047B (en) 2016-03-16

Family

ID=48675498

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110444929.XA Expired - Fee Related CN103184047B (en) 2011-12-28 2011-12-28 One group of composite fluorescent material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103184047B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087290B (en) * 2014-07-15 2016-08-17 江苏罗化新材料有限公司 A kind of preparation method of nitride red fluorescent powder
CN114933902B (en) * 2022-06-30 2023-07-14 烟台布莱特光电材料有限公司 Preparation method and composition of fluorescent compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011126971A1 (en) * 2010-04-05 2011-10-13 Central City Concern Bedbug infestation-resistant bed

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4009828B2 (en) * 2002-03-22 2007-11-21 日亜化学工業株式会社 Nitride phosphor and method of manufacturing the same
SG173925A1 (en) * 2002-03-22 2011-09-29 Nichia Corp Nitride phosphor and production process thereof, and light emitting device
US7518160B2 (en) * 2005-10-31 2009-04-14 Kyocera Corporation Wavelength converter, lighting system, and lighting system assembly
CN101255338B (en) * 2008-04-15 2013-02-13 罗维鸿 Warm-white semiconductor and yellow-orange luminescent silicate fluorescent powder thereof
CN101571235B (en) * 2008-04-30 2012-10-03 大连路明发光科技股份有限公司 Optical conversion luminous film and preparation method thereof
CN101775291B (en) * 2010-01-25 2013-06-19 华东理工大学 Preparation method of nitride and oxynitride fluorescent powder containing alkaline-earth metal elements
CN101812299B (en) * 2010-04-23 2013-03-13 同济大学 Nanocrystal reinforced rare earth doped tellurate luminous film material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011126971A1 (en) * 2010-04-05 2011-10-13 Central City Concern Bedbug infestation-resistant bed

Also Published As

Publication number Publication date
CN103184047A (en) 2013-07-03

Similar Documents

Publication Publication Date Title
CN102348778B (en) Phosphor, method for producing same, light-emitting device, and image display apparatus
CN101273109B (en) Fluorescent substance, process for producing the same, and light emitting device using said fluorescent substance
Guo et al. White-light emission from a single-emitting-component Ca 9 Gd (PO 4) 7: Eu 2+, Mn2+ phosphor with tunable luminescent properties for near-UV light-emitting diodes
CN102206491B (en) Phosphor and light emission appliance using phosphor
CN101688116B (en) Temperature-stable oxynitride phosphor and light source comprising a corresponding phosphor material
JP2012046766A (en) Phosphor and utilization thereof
CN106047341B (en) A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device
CN105018080B (en) A kind of preparation method of specular removal fluorescent material
JP6323177B2 (en) Semiconductor light emitting device
CN103314074A (en) Sialon phosphor, method for producing same, and light-emitting device package using same
JP2014503605A (en) Nitrogen compound luminescent material, method for preparing the same, and illumination light source manufactured thereby
CN104962282A (en) High-luminous decay resistance nitride and nitrogen oxide fluorescent materials and preparation method thereof
CN111808608B (en) Phosphor compound, preparation method and composition thereof
CN103184048B (en) Composite fluorescent material and preparation method thereof
CN103184047B (en) One group of composite fluorescent material and preparation method thereof
CN104962286A (en) Garnet-structure multiphase fluorescent material and preparation method thereof
CN105985772A (en) Fluorescent material for solid light source, manufacturing method of fluorescent material and composition containing fluorescent material
CN1946829B (en) Phosphor
CN102492420A (en) Cesium aluminosilicate phosphor and preparation method thereof
CN101735809A (en) Fluorescent material for converting blue light or purple light into red light and preparation method thereof
CN108148591A (en) A kind of nitride red fluorophor, preparation method and white light-emitting diodes lighting source
CN101144015B (en) Method for preparing fluorescent material
CN105820817A (en) Scandate green phosphor and preparation method thereof
CN102399554A (en) Nitride red luminescence material, and luminescent part and luminescent device containing the same
CN101613601B (en) Sr-Al-O-N series phosphor powder used in white light LED

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
DD01 Delivery of document by public notice

Addressee: Beijing Huameiliang Material Technology Co.,Ltd.

Document name: Notification that Application Deemed not to be Proposed

TR01 Transfer of patent right

Effective date of registration: 20190625

Address after: 264006 Jincheng District, Fulaishan Street, Yantai Development Zone, Shandong Province 39-4-401

Patentee after: Deng Hua

Address before: Room 601, 6th floor, No. 4 Building, No. 1 Hospital, Shangdi Tenth Street, Haidian District, Beijing 100085

Patentee before: Beijing Huameiliang Material Technology Co.,Ltd.

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160316

CF01 Termination of patent right due to non-payment of annual fee