CN101724401A

CN101724401A - Red luminous silicon-oxygen nitride fluorescent material, preparation method and light emitting device using same

Info

Publication number: CN101724401A
Application number: CN200810228236A
Authority: CN
Inventors: 肖宇驰; 邓华; 夏威; 于晶杰; 温嘉琪; 桑石云; 徐晶; 肖志国
Original assignee: Dalian Luming Science and Technology Group Co Ltd
Current assignee: Dalian Luming Science and Technology Group Co Ltd
Priority date: 2008-10-21
Filing date: 2008-10-21
Publication date: 2010-06-09

Abstract

The invention relates to red luminous silicon-oxygen nitride fluorescent material, preparation method and light emitting device using same. The general formula of the fluorescent material is MIuMIIv(Sil-alphaAalpha)wO deltaN(2/3(u+v)+4/3w-2/3delta): Eux, Ry, Dz, wherein MI is a Ca or Sr element; MII is selected from at least one element of Sr or Ca, Ba and Zn; A is selected from at least one element of Ge, Al, Ca and In; R is selected from at least one element of Nd, Dy, Ho, Tm, Ce, Er, Pr, Bi, Sm, Yb, Lu, Gd, Tb and Mn; D is selected from at least one ion of F-, Cl-, Br- and I-; and u, v, w, alpha, delta, x, y and z are molar coefficients. The fluorescent material capable of being excited by ultraviolet-blue-green light and emitting red light is prepared by adopting a normal pressure self-reduction synthesis method and applied to manufacture LED devices.

Description

A kind of red luminous silicon-oxygen nitride fluorescent, preparation method and use its light-emitting device

Technical field

The present invention relates to a kind of silicon-oxygen nitride red fluorescence material, being particularly related to the white light system and the polychrome that comprise employing semiconductor light-emitting elements (LED) is the fluorescent material that light-emitting device is used, and this material can be applied to lighting engineering, demonstration and optoelectronic areas.

Background technology

The appearance of photodiode makes the LED (semiconductor light-emitting-diode, Light-Emitting Diode) be described as " illuminating following technology ", comes into our daily life just gradually.As the novel illumination technology, LED is just causing the revolution of a lighting field with plurality of advantages such as its energy-conservation and environmental protection, applying flexible, long lifetives.The appearance of white light LEDs is LED from Presentation Function to one step of substance that the general lighting function is stepped out.In the white light LEDs technology, warm white LED meets the euphorosia degree of human eye most near daylight, also more can better reflect the true colors of irradiating object, become the main direction that white light LEDs is popularized to the general lighting market development, application market will be very extensive.

In the prior art field, realize the mode of white light LEDs, at present to excite the fluorescent material conversion hysteria technology of yellow emission luminescent material by ultraviolet chip or blue chip.In patent US5998925, US6998771, ZL00801494.9, US6069440, TW38350, CN1268650, US6066861, EP0862794, JP2002317178, utilize blue chip to excite cerium activated rare earth garnet type aluminate fluorescent material (Y ₃Al ₅O ₁₂: Ce, (Y, Gd) ₃(Al, Ga) ₅O ₁₂: Ce, be called for short YAG; Or Tb ₃Al ₅O ₁₂: Ce, be called for short TAG), send by the blue chip excitation fluorescent material that the blue light of gold-tinted and part blue chip is compound to go out white light.In patent ZL98105078, US6093346, EP0927915, KR0477347, JP3948757, TW275629, US2004007961, WO03/080763, US2006/0027785, US20060028122, WO2006022792, WO2006022793, US2005200271, WO2004111156, utilize blue chip to excite europkium-activated alkaline earth metal silicate fluorescent material ((Sr, Ba, Ca) ₂SiO ₄: Eu), send by the blue chip excitation fluorescent material that the blue light of gold-tinted and part blue chip is compound to go out white light.

But in this technology, employed yellow emission aluminate and silicate fluorescent material have significant limitation in realization, performance and the application facet of warm white LED.The emmission spectrum maximum of these two kinds of yellow emitting phosphors can only arrive about 560nm, lack red composition, cause the colour rendering index of white light LEDs lower, colour temperature is too high, can only obtain photochromic colder positive white light and cold white light effect usually, can not show good presenting property of color.In addition, aluminate and silicate yellow fluorescent powder only have medium physical and chemical stability, the decay of luminous intensity can reach more than 50% under 150 ℃ of Working environments of LED, the limitations restrict of these yellow fluorescent powders the technical progress and the application popularization of warm white LED and power-type LED.

Based on above reason, proposed to utilize the excitated red emitted fluorescence material of blue chip to join in the yellow emitting phosphor in recent years in the world as the complementary color composition, in order to remedy the LED colour rendering index, reduce colour temperature, realize the scheme of warm white effect and raising fluorescent material temperature stability.In the excitated red emitted fluorescence material of few several blue chips, ((Ca, Sr) S:Eu) luminosity is low, chemical stability and ageing-resistant performance extreme difference, and corrosion chip for rare-earth ion activated alkaline earth sulfide fluorescent material.Rare-earth ion activated tungsten hydrochlorate fluorescent material (Ca (W, Mo) O ₄: Eu) be the emission of line peak, be unfavorable for that tone is saturated, chip adaptability is not good.

The existence of nitrogen ion in the luminescent material parent lattice has the effect that improves structure covalency degree and reduce the crystal field splitting energy, the possibility that obtains for the physical and chemical stability of rare-earth ion activated luminescent material and red emission is very favourable, makes nitrogenous material become the developing direction of LED with red illuminating material.

In patent DE102006008300A1, JP2006257385A, EP1413618, WO2004030109, CN1596478A and JP2004277547, a kind of rare-earth activated alkaline-earth metal silicon-oxygen nitride fluorescent material (Ba that can effectively excite in the UV-blue region is disclosed, Sr, Ca) Si ₂O ₂N ₂: Eu, the oxygen of equal amts and nitrogen ion occupy anion site separately in this material, there is the combination degree that has improved structure in the nitrogen ionic, but active ions only are the coordination relation with oxonium ion in the structure, the nitrogen ion can not be realized for the effect that reduces the crystal field splitting energy, therefore this material is only launched the green glow of wavelength at 520-540nm, can not realize red emission.In patent EP1264873A2, CN101035740A, JP2003336059A1, JP2005255885A, JP2006052337A, JP2006137902A, JP2007031201A, JP2007145919A, JP2007177075A, US2003168643A1, US2005116244A1 and JP2005036038A, a kind of rare-earth activated alkaline-earth metal silicon alumina nitride fluorescent material Me that can effectively excite in the UV-blue region is disclosed _xSi _12-(m+n)Al _M+nO _nN _16-n: Eu (Me=Ca, Li), oxonium ion and nitrogen ion also occupy the negatively charged ion case separately in this material, but the oxonium ion number obviously is less than the nitrogen ion populations, this feature has strengthened the intensity of structure on the one hand more, help the realization that crystal field splitting can reduce on the other hand, material emission wavelength generation red shift can realize the emission of 550～600nm.But the existence of fixed oxygen case has limited the effect that crystal field splitting can reduce in the structure, still can not realize the red emission that 600nm is above.In addition, the preparation of this material needs to carry out under the high-temperature and high-pressure conditions of 1800～2000 ℃ of temperature, pressure 0.1MPa～100MPa, has also limited the widespread use and the scale volume production of this material.

This shows that the existence of fixed oxygen case is unfavorable for the formation of red emission in the nitrogenous material structure.In patent EP1104799, US6649946, US6680569, EP1433831, WO03080764, WO2004039915, TW1258499, JP2007189254A, US20080089825A1, CN1522291A, JP2003336050A, JP2004161807A, JP2004182780A, JP2004182781A, JP2005060714A, US20060038477A1, a kind of nitride red fluorescent material (Ba of rare-earth activated alkaline-earth metal silicon that can effectively excite in the UV-blue region is disclosed, Sr, Ca) ₂Si ₅N ₈: Eu.The negatively charged ion case is the nitrogen ion in this material structure, only can there be the small portion of residual oxonium ion to be mingled on the nitrogen case, therefore material has strong covalency, active ions fully are the coordination relation with the nitrogen ion in the structure, so can realize the red emission of 600～650nm under the effect that crystal field splitting can obviously reduce.Yet, in above-mentioned disclosed patent, all adopting is the binary nitride with alkaline-earth metal and the nitrogenize of rare earth metal simple substance earlier, and then these binary nitride form the manufacture method of required silicon nitride material again under the high temperature reduction condition with silicon nitride or diimine silicon.Alkaline-earth metal simple substance, rare earth metal simple substance and binary nitride thereof and diimine silicon are air and the extremely responsive active material of extreme of humidity, therefore above-mentioned disclosed preparation method has the meticulous harshness of condition, complex steps, restive, limitation that cost is high, only be suitable for the laboratory and prepare on a small quantity, be unfavorable for the realization of industrially scalable volume production.In addition, feasible emission wavelength and the luminous intensity that is difficult to regulate and control as effective means such as composition adjustment, coactivator and fluorescence-enhancing agent introduction fluorescent material of the raw material of above-mentioned publication and the sensitivity of manufacturing process, harshness and restive feature by some, therefore fixedly the fluorescent material luminous intensity is lower to utilize the composition of above-mentioned publication preparation, far below the luminous intensity of yellow aluminate fluorescent powder, and the introducing of limited adjustment that only can be by self element and the crucible material trace elements emission wavelength and the luminous intensity of coming limited adjustment fluorescent material.The limitation of the red emission fluorescent material performance of above-mentioned patent disclosure makes that the matching of itself and yellow aluminate and silicate fluorescent powder is relatively poor, and the technical requirements of warm white LED can not be finely satisfied in bigger, the photochromic difficult adjusting of light efficiency decay.Patent CN1974713A has also proposed the patent requirement to the silicon nitride fluorescent material of the emitting red light of above-mentioned patent disclosure, even but its disclosed alkaline earth metal carbonate and silicon nitride under the constant-pressure and high-temperature reductive condition simple synthetic method may, also be difficult to remove fully oxygen in the alkaline earth metal oxide and synthetic oxygen-free single-phase silicon nitride fluorescent material fully.Bibliographical information is arranged, even (1600 ℃ of high pressure-temperatures, 0.5MPa) utilize alkaline earth metal carbonate and silicon nitride reaction also only can synthesize silicon nitride fluorescence under the condition to account for 60% multiphase mixture mutually, so there is big defective in the technical scheme of this patent disclosure.

Stable easily control, fluorescent material emission wavelength and luminous intensity of development raw material is good and be easy to regulate control, manufacturing process is simple, condition is eased up, be easy to realize that the novel red luminous nitrogenous fluorescent material of industrially scalable volume production is universal significant for the technical progress and the development of warm white LED.

Summary of the invention

An object of the present invention is to provide a kind of silicon-oxygen nitride fluorescent material of red emission, (300～550nm), transmitting boundary is wide, and (580～680nm), emission wavelength and luminous intensity are easy to control and regulate to have the wide ranges of exciting, the light conversion efficiency height, the characteristic of stable in properties; Another object of the present invention provides a kind of autoreduction synthetic method of above-mentioned red silicon-oxygen nitride fluorescent material, has the advantages that raw material is stablized easy control, simplified manufacturing process, is easy to the industrially scalable volume production; A further object of the present invention provides a kind of light-emitting device that contains red silicon-oxygen nitride fluorescent material of the present invention, particularly white light LEDs.

The chemical constitution general formula of silicon-oxygen nitride fluorescent material of the present invention can be expressed as with formula (1):

M ^I _uM ^II _v(Si _1-αA _α) _wO _δN _{(2/3(u+v)+4/3w-2/3δ)}:Eu _x，R _y，D _z????????????(1)

M wherein ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and Ba, the Zn ^IAnd M ^IICan not select identity element simultaneously for use, A is for being selected from least a element among Ge, Al, Ga, the In, and R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Bi, Sm, Yb, Lu, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-, Br ^-, I ^-In at least a ion; U, v, w, α, δ, x, y, z are mole coefficient, 0.3＜u≤1.2,0≤v＜2.0 and 0.5＜u+v＜3.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜1.0,0＜x≤1,0≤y≤0.5 and 1.0≤v+x+y＜2.0,0.001≤z≤0.05.This fluorescent material can be launched the ultraviolet-blue green light of spectrum spectrum spike length in 300～550nm scope and excite, be emitted at least 1 the luminescent spectrum that possesses in 580～680nm scope with upward peak, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.

Silica nitrogen fluorescent material according to a preferred embodiment of the present invention, in u, the v of chemical constitution expression (1), w, α, δ, x, y, the z mole coefficient, 0.3＜u≤1.2,0≤v＜1.2 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜1.0,0＜x≤1, y=0 and 1.0≤v+x≤1.4,0.001≤z≤0.05.

Silica nitrogen fluorescent material according to a preferred embodiment of the present invention, in u, the v of chemical constitution expression (1), w, α, δ, x, y, the z mole coefficient, 0.3＜u≤1.2,0≤v≤1.2 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜1.0,0＜x＜1.0,0＜y≤0.5 and 1.0≤v+x+y≤1.4,0.001≤z≤0.05.

Silica nitrogen fluorescent material according to a preferred embodiment of the present invention, in u, the v of chemical constitution expression (1), w, α, δ, x, y, the z mole coefficient, 0.34≤u≤0.48,0≤v＜2.0 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x≤1, y=0 and 1.6＜v+x＜2.0,0.001≤z≤0.05.

Silica nitrogen fluorescent material according to a preferred embodiment of the present invention, in u, the v of chemical constitution expression (1), w, α, δ, x, y, the z mole coefficient, 0.34≤u≤0.48,0≤v＜2.0 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x＜1.0,0＜y≤0.5 and 1.6＜v+x+y＜2.0,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-, Cl ^-In a kind of element ion or combination u, the v of two kinds of element ions, w, α, δ, x, y, z mole coefficient in, 0.4≤u＜1,1.2≤v+x≤1.4,4.5≤w≤5.5,0≤α≤1,0.2≤δ＜1.0,0＜x≤1, y=0,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 1.0≤u≤1.2,1.0≤v+x＜1.2,4.5≤w≤5.5,0≤α≤1,0.03≤δ＜0.7,0＜x≤1, y=0,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.4≤u＜1,1.2≤v+x+y≤1.4,4.5≤w≤5.5,0≤α≤1,0.2≤δ＜1.0,0＜x＜1.0,0＜y≤0.5,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 1.0≤u≤1.2,1.0≤v+x+y＜1.2,4.5≤w≤5.5,0≤α≤1,0.03≤δ＜0.7,0＜x＜1.0,0＜y≤0.5,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.34≤u≤0.48,0≤v＜2.0 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x≤1, y=0 and 1.6＜v+x＜2.0,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.34≤u≤0.48,0≤v＜2.0 and 0.5＜u+v＜2.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x＜1.0,0＜y≤0.5 and 1.6＜v+x+y＜2.0,0.001≤z≤0.05.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.4≤u＜1,1.2≤v+x≤1.4,0.2≤δ＜1.0,0.001≤z≤0.05, w=5.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 1.0≤u≤1.2,1.0≤v+x＜1.2,0.03≤δ＜0.7,0.001≤z≤0.05, w=5.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.4≤u＜1,1.2≤v+x+y≤1.4,0.2≤δ＜1.0,0.001≤z≤0.05, w=5.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 1.0≤u≤1.2,1.0≤v+x+y＜1.2,0.03≤δ＜0.7,0.001≤z≤0.05, w=5.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; In u, v, w, α, δ, x, y, the z mole coefficient, 0.34≤u≤0.48,1.6＜v+x＜2.0,0＜δ＜0.7,0.001≤z≤0.05, w=5.

According to the silica nitrogen fluorescent material of a preferred embodiment of the present invention, M in the chemical constitution expression (1) ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-In a kind of element ion or combination u, the v of two kinds of element ions, w, α, δ, x, y, z mole coefficient in, 0.34≤u≤0.48,1.6＜v+x+y＜2.0,0＜δ＜0.7,0.001≤z≤0.05, w=5.

Silica nitrogen fluorescent material according to a preferred embodiment of the present invention, wherein said silicon-oxygen nitride fluorescent material is by the optical excitation of the excitation light source with emission peak in UV-light-blue green light scope of 300～550nm, and the emission peak wavelength of fluorescent material is greater than the wavelength of the long wave side emission peak of excitation light source.This material can be by the optical excitation as the excitation light source with emission peak of emmission spectrum in UV-light-blue green light scope of 300～550nm of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 580～680nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.

In the present invention, adopt the stable M that is easy to get ^IThe organometallics of element is as reductibility raw material and part alkali earth metal source, the stable M that is easy to get ^IIThe carbonate of element and the oxide compound of active element are as main alkali earth metal and active ions source and being reduced property raw material, and the stable silicon nitride that is easy to get is as stay in place form.In building-up process, by M ^IThe organometallics of element decomposes the activated carbon that produces and oxide compound in the raw material is reduced to metal simple-substance and then enters the silicon nitride lattice, is the rare-earth ion activated fluorescent material of nitrogen ionic target thereby form the negatively charged ion case.This negatively charged ion case is that nitrogen ionic material has strong covalency and lower crystal field splitting energy, can realize the red emission that 600nm is above.In above-mentioned synthetic method, because M ^IThe organometallics of element is oxygen containing week reduction raw material, the oxonium ion of easy residual minute quantity in the nitrogen ion case of the final fluorescent material that forms, and the therefore final rare-earth ion activated fluorescent material that forms can be called silicon-oxygen nitride fluorescent material.But by meticulous adjustment M ^IElement and M ^IIThe ratio of element or select the different M of reductibility for use ^IThereby the organometallics of element can control the degree of autoreduction reaction can the final fluorescent material nitrogen of meticulous adjustment ion case in the content of oxonium ion, and then emission wavelength that can the described rare-earth ion activated silica nitrogen fluorescent material of finely regulating, this is a novelty of the present invention and distinctive feature, and this mode is not seen the report of domestic and international other pertinent literature and patent and disclosed.

Among the present invention, the silicon ion case in described fluorescent material crystalline structure has been introduced and has been comprised the A element that is selected from Ge, Al, Ga, In element.Compare with silicon ion, above-mentioned element has bigger ionic radius, its part substitutes the [Si of constituent material structure main frame, N (O)] coordination polyhedron will play the effect of structure compression, thereby making that the distance of zwitterion shortens relatively in the structure has adjusted the lattice environment of active ions and the interaction of active ions and crystal field, can further realize the red shift of material emission wavelength, be an important part of the present invention.Among the present invention, the purpose of introducing R is to utilize the transmission ofenergy between rare earth ion, promptly after luminescence center is excited, excitation energy can pass to another from certain of twinkler, or passes to another luminescence center from a luminescence center, thereby obtains to have the fluorescent material of high brightness.Radiationless efficiently transmission ofenergy can take place with the Eu interionic in R ion involved in the present invention such as Dy, Ho, Ce, Mn plasma, can improve the luminescent properties of fluorescent material of the present invention thus.

The stable raw material autoreduction synthetic method of uniqueness of the present invention makes introducing element D and R become possibility.The introducing of element D and R is another important discovery and the innovation among the present invention, and formed compound silica nitrogen fluorescent material is not seen relevant bibliographical information and patent disclosure at present.Introducing D has synthesis temperature, the diffusion of promotion particle that reduces matrix on the one hand and becomes effect mutually in the fluorescent material building-up process, it can make activator evenly enter matrix and form luminescence center and trap center, also can promote the crystallization degree and the crystal growth of substrate material; On the other hand, the univalent halide-ions has lower phonon energy, it enters the fluorescent material lattice and promptly can the balance Tricationic mixes and the valence state that forms is poor, also can further reduce anionic phonon vibration energy in the parent lattice, the effect that improves the fluorescent material luminous intensity is played in the radiationless relaxation or the loss of excitation energy and emitted energy in the minimizing lattice.

Silica nitrogen red fluorescence material of the present invention adopts the manufacturing of a kind of autoreduction synthetic method, and this is that the present invention's another on material manufacturing method has unique important discovery and innovation.Its principle is, under constant-pressure and high-temperature nitrogen or nitrogen/hydrogen weakly reducing atmosphere, contains M ^IThe reductibility activated carbon that the organic alkaline-earth compound thing of element decomposites will contain M ^IIReach the oxide compound and the M of Eu, R element ^ISelf degradation production autoreduction is a metal simple-substance, emits carbon monoxide and/or hydrogen and/or nitrogen and/or water, meanwhile, and M ^I, M ^IIAnd Eu, R metal simple-substance enter the silicon nitride lattice and form described rare-earth ion activated silica nitrogen fluorescent material under nitrogen atmosphere.By adjusting M ^I, M ^IIThe ratio of element or select the M of different reducing powers for use ^IThereby thereby organometallics can be controlled degree that autoreduction reaction carries out and regulates and control the emission wavelength that the oxygen level in the nitrogen ion case in the formed fluorescent material crystalline structure is adjusted material.Under the synthetic method stable at this raw material, that condition is gentle, introducing and the doping of elements A, D and R be can realize, thereby the emission wavelength of adjusting material and the effect that improves the material luminous intensity played.

When making silica nitrogen fluorescent material of the present invention, raw materials used is the compound of each element in the expression (1), and its element according to the mole proportioning of expression (1) is:

M ^I：0.5～1.5；

M ^II：0～1.5；

Si：0～5.5；

A：0～5.5；

Eu：0.001～1；

R：0～0.5；

D：0.001～0.05；

Wherein: M ^IRepresent the compound of Ca or Sr element;

M ^IIRepresent the compound of one or more elements among Sr or Ca and Ba, the Zn;

Si represents the compound of element silicon;

A represents the compound of one or more elements among Ge, Al, Ga, the In;

Eu represents the compound of europium element;

R represents the compound of one or more elements among Nd, Dy, Ho, Tm, Ce, Er, Pr, Bi, Sm, Yb, Lu, Gd, Tb, the Mn;

D represents F ^-, Cl ^-, Br ^-, I ^-In the compound of one or more elements;

M ^IThe compound of representative element adopts the organometallics of calcium, as calcium formiate (Ca (HCOO) ₂), lime acetate ((CH ₃COO) ₂CaxH ₂O), calcium propionate (Ca (C ₂H ₅COO) ₂), 2,4-diacetylmethane calcium (Ca (C ₅H ₇O ₂) xH ₂O), calcium ascorbate (C ₁₂H ₁₄CaO ₁₂2H ₂O), two (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) calcium (Ca (OCC (CH ₃) ₃CHCOC (CH ₃) ₃) ₂), cyclohexane butyric acid calcium ((C ₆H ₁₁(CH ₂) ₃CO ₂) ₂Ca), calcium iso-octoate ((CH ₃(CH ₂) ₃CH (C ₂H ₅) CO ₂) ₂Ca), calcium isopropoxide (Ca (OCH (CH ₃) ₂) ₂), hydration calcium lactate ((CH ₃CH (OH) COO) ₂CaxH ₂O), calcium methylate (Ca (OCH ₃) ₂), caoxalate (Cac ₂O ₄4H ₂O), calcium stearate ((C ₁₇H ₃₅COO) ₂Ca), citrate of lime (Ca ₃(C ₆H ₅O ₇) ₂4H ₂O), calglucon (C ₁₂H ₂₂CaO ₁₄H ₂O), calcium aminosuccinic acid ((C ₄H ₆NO ₄) ₂Ca3H ₂O), calcium citrate malate (C ₁₂H ₁₀O ₁₄Ca ₃4H ₂O), calcium malate (C ₄H ₄O ₅Ca3H ₂O); And the organometallics of strontium, as strontium formate (Sr (HCOO) ₂), strontium acetate ((CH ₃COO) ₂SrxH ₂O), propionic acid strontium (Sr (C ₂H ₅COO) ₂), strontium oxalate (SrC ₂O ₄4H ₂O), strontium citrate (Sr ₃(C ₆H ₅O ₇) ₂4H ₂O), gluconic acid strontium (C ₁₂H ₂₂SrO ₁₄H ₂O), hydration strontium lactate ((CH ₃CH (OH) COO) ₂SrxH ₂O), methyl ethyl diketone strontium ((CH ₃COCH=C (O-) CH ₃) ₂Sr), Virahol strontium (Sr (OCH (CH ₃) ₂) ₂) in at least aly originate as element.M ^IIThe compound of representative element adopts the form of carbonate and/or oxide compound to originate as element.The compound of Si representative element adopts the form of silicon nitride to originate as element.The compound of A representative element adopts the form of nitride to originate as element.The compound of Eu representative element adopts the form of europium sesquioxide to originate as element.The compound of R representative element adopts the form of oxide compound to originate as element.The compound of D representative element adopts the form of fluorochemical or muriate or bromide or iodide to originate as element.

Its manufacture method is for stablizing the normal pressure of raw material and the autoreduction synthetic method under the atmospheric condition, manufacturing process is a high-temperature solid phase reaction method, stabilizing reducing raw material, stable being reduced property body material and stay in place form raw material are taken by weighing by the mole proportioning, mix, insert in aluminum oxide or boron nitride or the molybdenum crucible, (in the presence of nitrogen, nitrogen and hydrogen or the carbon granules) under normal pressure inert atmosphere or the weakly reducing atmosphere in 1300-1700 ℃ carry out once or for several times, the time is 5 to 10 hours sintering, sintering is after pulverize, sieve, operations such as aftertreatment form.

By sieving the particle diameter materials at different levels that can obtain to satisfy different service requirementss, can improve luminescent quality and other physical chemistry application performance of fluorescent material by aftertreatment technologys such as pickling or coatings.

The invention still further relates to a kind of light-emitting device, have luminescence chip as excitation light source, and the fluorescent material that at least a portion light of excitation light source can be changed, wherein:

The emmission spectrum peak value of luminescence chip is in ultraviolet-blue green light regional extent of 300～550nm, fluorescent material can become to have at least more than one peak wavelength to be in 400～700nm wavelength region with the wavelength Conversion of first luminescent spectrum of at least a portion luminescence chip, and described fluorescent material has a kind of red silica nitrogen fluorescent material of the present invention that is at least.

According to a kind of light-emitting device of the present invention, the luminescent layer of luminescence chip is nitride-based semiconductor or has the nitride-based semiconductor that contains In.In ultraviolet-blue green light regional extent of 300～550nm, has glow peak wavelength more than 1 at least as the luminescence chip of excitation light source.Employed fluorescent material has a kind of red silica nitrogen fluorescent material of the present invention that is at least.

According to technique scheme, the light-emitting device of a preferred embodiment of the present invention, as the emmission spectrum peak value of the luminous element of excitation light source in UV-light-blue green light scope, employed fluorescent material is red silica nitrogen fluorescent material of the present invention or red silica nitrogen fluorescent material of the present invention and yellow second fluorescent material, and/or green the 3rd fluorescent material, and/or one or more combination of blue the 4th fluorescent material.At least a portion of other fluorescent material is luminous in that fluorescent material absorbs excitation light source and/or the combination, the wavelength Conversion of the luminescent spectrum of the described luminous element of at least a portion is become different have at least more than one peak wavelength to be in emmission spectrum in 400～700nm wavelength region to obtain mixed white light or gold-tinted or orange light or purple light or ruddiness.

Described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material are:

Rare earth doped activated nitric oxide fluorescent powder, and/or rare earth doped activated Nitride phosphor, and/or rare earth doped activated silicate fluorescent powder, and/or rare earth doped activated halogen silicate phosphor powder, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated aluminate fluorescent powder, and/or rare earth doped activated sulphide fluorescent material, and/or rare earth doped activated borate fluorescent powder, and/or rare earth doped activated phosphate phosphor, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated scandate fluorescent material, and/or rare earth doped activated thiogallate fluorescent material.

According to technique scheme, the light-emitting device of a preferred embodiment of the present invention is the luminescent conversion LED that a kind of fluorescent material directly or indirectly contacts with chip.

According to technique scheme, the light-emitting device of a preferred embodiment of the present invention, light-emitting device are to comprise the means of illumination that at least one uses the LED of described fluorescent material.

The excitation spectrum of fluorescent material and emmission spectrum adopt the test of F-4500 fluorescence spectrophotometer among the present invention.The chromaticity coordinate of LED and colour rendering index adopt the test of PMS-50 type ultraviolet-visible-near-infrared spectrum analytical system.Oxygen level in the fluorescent material is measured by IRO-I determination of oxygen content instrument.

The outstanding feature that the present invention has be fluorescent material of the present invention owing to halide-ions, coactivator ion and structural adjustment ion have been introduced in the use of novel method for synthesizing, played promote material grains growth, active ions uniform distribution, adjust the fluorescent material emission wavelength, the effect of raising fluorescent material luminous intensity.Compare with nitrogenizing reaction technological line synthetic pure silicon nitride fluorescent material under the existing severe condition, the red silica nitrogen fluorescent material that the present invention obtains has the better characteristics of luminescence by the introducing of above crystallization auxiliary, fluorescence-enhancing agent, luminous intensity can obviously strengthen, and has better luminous intensity matching with yellow YAG fluorescent material.Thereby utilize this novel method for synthesizing can also regulate the emission wavelength of the meticulous adjusting material of micro-oxygen content in the lattice by the degree of control autoreduction reaction, realization is adjustable continuously from 580～680nm's, have novelty and originality, also have better application and suitability.

Another outstanding feature that the present invention has is to have adopted the synthetic manufacture method of the autoreduction with novelty, become active binary nitride with existing active simple substance nitrification, active binary nitride is compared with the meticulous harsh synthetic method of silicon nitride or the synthetic red silicon nitride fluorescent material of active silicon imide reaction again, manufacture method involved in the present invention adopts the extremely stable organic alkaline-earth compound thing of character, alkaline earth metal carbonate and silicon nitride are as raw material, the organic alkaline-earth compound thing is reduced to metal simple-substance as reductive agent mutually with each oxide compound and also and then with silicon nitride reaction obtains red silicon-oxygen nitride fluorescent material of the present invention in constant-pressure and high-temperature atmosphere building-up process, has feedstock property and stablizes, composition principle is simple, the advantage that synthesis technique and synthesis condition simply are easy to control.

The 3rd outstanding feature that the present invention has is the above advantage and the distinctive feature of the synthetic manufacture method of the autoreduction invented;, synthesis technique loaded down with trivial details with link and synthesis condition existing red silicon nitride fluorescent material manufacture method meticulous and harsh, that need kinds of protect processing and synthesis device are compared; have more the advantage that is easy to the industrially scalable volume production, can better meet the growth requirement of warm white LED technical progress and application popularization.

Description of drawings

Fig. 1 excites and emmission spectrum for the silica nitrogen fluorescent material with the orange red emission of 591nm of embodiment 1;

Fig. 2 excites and emmission spectrum for the silica nitrogen fluorescent material with 632nm red emission of embodiment 28;

Fig. 3 excites and emmission spectrum for the silica nitrogen fluorescent material with 627nm red emission of embodiment 55;

Fig. 4 excites and emmission spectrum for the silica nitrogen fluorescent material with 621nm red emission of embodiment 63;

Fig. 5 excites and emmission spectrum for the silica nitrogen fluorescent material with 587nm orange emission of embodiment 86;

Fig. 6 excites and emmission spectrum for the silica nitrogen fluorescent material with 630nm red emission of embodiment 111;

Fig. 7 excites and emmission spectrum for the silica nitrogen fluorescent material with 628nm red emission of embodiment 23,24, goes up obviously as seen from scheming, and compares doped F with the primary sample of the halogen that undopes ^-And Cl ^-Ionic sample luminous intensity obviously improves, and mixes F ^-The luminous intensity of ion samples improves more.This phenomenon has proved aforesaid because halide-ions has the grain growing of promotion, the equally distributed effect of active ions on the one hand, can improve the luminescent properties of fluorescent material, has low phonon energy on the other hand, can reduce the radiationless loss of energy, also play the effect that improves luminous intensity.The introducing of halide-ions is obvious for the raising effect of material luminescent properties, becomes distinctive feature of the present invention and innovative point.

Fig. 8 is a kind of LED structural representation.1, semiconductor light emitting chip, 2, negative electrode, 3, positive electrode, 4, pin, 5, fluorescent material, 6, packaged material, 7, lead-in wire, 8, reflection cup

Fig. 8 a mode that to be fluorescent material directly contact with the semiconductor light emitting chip, fluorescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes.

Fig. 8 b is the mode of fluorescent material and the indirect contact of semiconductor light emitting chip, and fluorescent material is evenly distributed on epoxy skins.

Fig. 8 c is the mode of fluorescent material and the indirect contact of semiconductor light emitting chip, and fluorescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.

Embodiment

Narrate embodiments of the invention below.It is to be noted that the present invention is not subjected to the restriction of these embodiment.

Embodiment 1

Raw material	Purity
Raw material	Purity	??(CH ₃COO) ₂Ca·xH ₂O	??99.9％
??SrCO ₃	??99.9％	??(CH ₃COO) ₂Ca·xH ₂O	??99.9％
??SrCO ₃	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Si ₃N ₄	??99％

At first with above-mentioned each raw material with Ca: Sr: Eu: F: Si=0.85: 1.25: 0.04: 0.02: after 4.85 mole proportioning was carried out weighing, fully ground and mixed was even, and the boron nitride crucible of then packing into is put into accurate control heat treatment furnace, in high-purity N ₂In the atmosphere in 1300～1700 ℃ of sintering a few hours, M in this process ^IThe lime acetate of position is decomposed to form a certain amount of activated carbon, and activated carbon further is reduced to metal simple-substance mutually with various oxide compounds, meanwhile, obtains red loose target sintered compact thereby the oxide compound that is not reduced of each metal simple-substance and trace enters the silicon nitride lattice.Through pulverizing, grind and screening, obtain the orange red luminous silica nitrogen fluorescent material Ca that has among the present invention _0.85Sr _1.25Eu _0.04Si _4.85O _0.31F _0.02N _7.68The emission peak wavelength of this material under 460nm is blue-light excited is at 591nm.

Embodiment 2-62, preparation method and step are with embodiment 1.Adopt the lime acetate ((CH among the embodiment 1 ₃COO) ₂CaxH ₂O), partly replace M by Zn as the reductibility raw material ^IIPosition alkaline-earth metal, Ge partly replace Si, F ^-And/or Cl ^-Flux and fluorescence strengthens that ionic is introduced, other rare earth co-activation ionic is introduced and can be carried out meticulous adjusting to the emission peak wavelength and the luminous intensity of fluorescent material.The silica nitrogen fluorescent material fluorescent material that has prepared the embodiment 2-62 that emission peak wavelength changes according to preparation embodiment 1 Preparation of Fluorescent Material method and step in 580～680nm scope with orange red-red emission.

The coefficient value scope corresponding to expression formula (1), one-tenth that table 1 has provided each embodiment fluorescent material are grouped into and emission peak wavelength.

Table 1:

Embodiment 63

Raw material	Purity
Raw material	Purity	??Ca(C ₂H ₅COO) ₂	??99.9％
??SrCO ₃	??99.9％	??Ca(C ₂H ₅COO) ₂	??99.9％
??SrCO ₃	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Si ₃N ₄	??99％

At first with above-mentioned each raw material with Ca: Sr: Eu: F: Si=0.35: 1.75: 0.04: 0.02: after 5 mole proportioning was carried out weighing, fully ground and mixed was even, and the boron nitride crucible of then packing into is put into accurate control heat treatment furnace, in high-purity N ₂In the atmosphere in 1300～1700 ℃ of sintering a few hours, M in this process ^IThe calcium propionate of position is decomposed to form the activated carbon of volume, and activated carbon further is reduced to metal simple-substance mutually with various oxide compounds, meanwhile, obtains red loose target sintered compact thereby the oxide compound that is not reduced of each metal simple-substance and denier enters the silicon nitride lattice.Through pulverizing, grind and screening, obtain the orange red luminous silica nitrogen fluorescent material Ca that has among the present invention _0.35Sr _1.75Eu _0.04Si ₅O _0.11F _0.02N _8.01The emission peak wavelength of this material under 460nm is blue-light excited is at 621nm.

Embodiment 64-85, preparation method and step are with embodiment 63.Adopt the calcium propionate (Ca (C among the embodiment 63 ₂H ₅COO) ₂) as the reductibility raw material, partly replace M by Zn ^IIPosition alkaline-earth metal, Ge partly replace Si, F ^-And/or Cl ^-Flux and fluorescence strengthens that ionic is introduced, other rare earth co-activation ionic is introduced and can be carried out meticulous adjusting to the emission peak wavelength and the luminous intensity of fluorescent material.The silica nitrogen fluorescent material that has prepared the embodiment 64-85 that emission peak wavelength changes according to preparation embodiment 63 Preparation of Fluorescent Material methods and step in 600～630nm scope with orange red-red emission.

The coefficient value scope corresponding to expression formula (1), one-tenth that table 2 has provided each embodiment fluorescent material are grouped into and emission peak wavelength.

Table 2:

Embodiment 86

Raw material	Purity
Raw material	Purity	??(CH ₃COO) ₂Sr·xH ₂O	??99.9％
??CaCO ₃	??99.9％	??(CH ₃COO) ₂Sr·xH ₂O	??99.9％
??CaCO ₃	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Si ₃N ₄	??99％

At first with above-mentioned each raw material with Sr: Ca: Eu: F: Si=0.85: 1.35: 0.05: 0.02: after 4.85 mole proportioning was carried out weighing, fully ground and mixed was even, and the boron nitride crucible of then packing into is put into accurate control heat treatment furnace, in high-purity N ₂In the atmosphere in 1300～1700 ℃ of sintering a few hours, M in this process ^IThe strontium acetate of position decomposites a certain amount of activated carbon, and activated carbon further is reduced to metal simple-substance mutually with various oxide compounds, meanwhile, obtains red loose target sintered compact thereby the oxide compound that is not reduced of each metal simple-substance and trace enters the silicon nitride lattice.Through pulverizing, grind and the screening processing, obtain the orange red luminous silica nitrogen fluorescent material Sr that has among the present invention _0.85Ca _1.35Eu _0.05Si _4.85O _0.43F _0.02N _7.67The emission peak wavelength of this material under 460nm is blue-light excited is at 587nm.

Embodiment 87-147, preparation method and step are with embodiment 86.Adopt the strontium acetate ((CH among the embodiment 86 ₃COO) ₂SrxH ₂O), partly replace M by Zn as the reductibility raw material ^IIPosition alkaline-earth metal, Ge partly replace Si, F ^-And/or Cl ^-Flux and fluorescence strengthens that ionic is introduced, other rare earth co-activation ionic is introduced and can be carried out meticulous adjusting to the emission peak wavelength and the luminous intensity of fluorescent material.The silica nitrogen fluorescent material that has prepared the embodiment 87-147 that emission peak wavelength changes according to preparation embodiment 86 Preparation of Fluorescent Material methods and step in 600～630nm scope with orange red-red emission.

The coefficient value scope corresponding to expression formula (1), one-tenth that table 3 has provided each embodiment fluorescent material are grouped into and emission peak wavelength.

Table 3:

Embodiment 148

Raw material	Purity
Raw material	Purity	??Sr(C2H ₅COO) ₂	??99.9％
??CaCO ₃	??99.9％	??Sr(C2H ₅COO) ₂	??99.9％
??CaCO ₃	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Eu ₂O ₃	??99.9％
??NHF	??99.9％	??Si ₃N ₄	??99％

At first with above-mentioned each raw material with Sr: Ca: Eu: F: Si=0.35: 1.75: 0.06: 0.02: after 5 mole proportioning was carried out weighing, fully ground and mixed was even, and the boron nitride crucible of then packing into is put into accurate control heat treatment furnace, in high-purity N ₂In the atmosphere in 1300～1700 ℃ of sintering a few hours, M in this process ^IThe propionic acid strontium of position is decomposed to form the activated carbon of volume, and activated carbon further is reduced to metal simple-substance mutually with various oxide compounds, meanwhile, obtains red loose target sintered compact thereby the oxide compound that is not reduced of each metal simple-substance and denier enters the silicon nitride lattice.Through pulverizing, grind and screening, obtain the orange red luminous silica nitrogen fluorescent material Sr that has among the present invention _0.35Ca _1.75Eu _0.06Si ₅O _0.14F _0.02N _8.02The emission peak wavelength of this material under 460nm is blue-light excited is at 617nm.

Embodiment 149-170, preparation method and step are with embodiment 148.Adopt the propionic acid strontium (Sr (C among the embodiment 148 ₂H ₅COO) ₂) as the reductibility raw material, partly replace M by Zn ^IIPosition alkaline-earth metal, Ge partly replace Si, F ^-And/or Cl ^-Flux and fluorescence strengthens that ionic is introduced, other rare earth co-activation ionic is introduced and can be carried out meticulous adjusting to the emission peak wavelength and the luminous intensity of fluorescent material.The silica nitrogen fluorescent material that has prepared the embodiment 149-170 that emission peak wavelength changes according to preparation embodiment 148 Preparation of Fluorescent Material methods and step in 600～630nm scope with orange red-red emission.

The coefficient value scope corresponding to expression formula (1), one-tenth that table 4 has provided each embodiment fluorescent material are grouped into and emission peak wavelength.

Table 4:

The invention still further relates to the means of illumination that uses the fluorescent material among the present invention, particularly use is especially launched the LED of white light as the semiconductor LED of emission main peak in 350～550nm scope of the luminous element of excitation light source use.With the specific embodiment form claimed category of the present invention is illustrated below.

With reference to Fig. 8, LED of the present invention comprises semiconductor light emitting chip 1, negative electrode 2, positive electrode 3, pin 4, fluorescent material 5, packaged material 6, lead-in wire 7, reflection cup 8.The semiconductor light emitting chip is GaInN chip or GaN chip.At least comprise a kind of nitride red phosphor of the present invention in the fluorescent material.Packaged material is a transparent resin, can be transparent epoxy resin, transparent silica gel etc.

Fig. 8 a mode that to be fluorescent material directly contact with the semiconductor light emitting chip wherein, fluorescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes.Fig. 8 b is the mode of fluorescent material and the indirect contact of semiconductor light emitting chip, and fluorescent material is evenly distributed on epoxy skins.Fig. 8 c is the mode of fluorescent material and the indirect contact of semiconductor light emitting chip, and fluorescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.

Embodiment 171

Adopt the LED packaged type of Fig. 8 a among Fig. 8 to prepare warm white LED.Concrete packaging process is: choose the chip with the emission peak wavelength that is complementary according to effective excitation wavelength range of fluorescent material.In the present embodiment, the emission peak wavelength of semiconductor light emitting chip is 460nm, and fluorescent material selects the fluorescent material described in the embodiment of the invention 23 and a kind of 460nm to excite down the YAG fluorescent material non-of the present invention of emission 550nm gold-tinted.The chip of choosing is carried out solid crystalline substance, routing, oven dry.Take by weighing after above-mentioned two kinds of some grams of fluorescent material and transparent epoxy resin mix in accordance with the appropriate ratio according to 1: 19 ratio of weight ratio, evenly be coated in by (some glue) 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 warm white LED is X=0.3719, Y=0.3892, colour temperature 3700K, colour rendering index 85.Its emission spectrum is that the blue spectrum that the yellow that launched by the part blue chip to launch after blue-light excited by fluorescent material and emitting red light spectrum and rest parts blue chip are launched is composited.

Adopt LED packaged type can prepare LED as Fig. 8 a, Fig. 8 b, Fig. 8 c among Fig. 8.Its packaging process and embodiment 171 are similar.But fluorescent material and array mode can have multiple choices, and its principle is:

(1) the emission peak wavelength of the emission peak wavelength of effective excitation wavelength range of fluorescent material and semi-conductor chip and/or common other fluorescent material that use is complementary.

(2) under the prerequisite of the emission peak wavelength of determining semi-conductor chip, the glow color of LED product is as required selected fluorescent material.

(3) under the prerequisite of using nitride red phosphor of the present invention, the glow color of LED product is as required selected one or more yellow, green and blue fluorescent material simultaneously.

One or more yellow that can adopt, green and blue fluorescent material comprise: rare earth doped activated nitric oxide fluorescent powder, and/or rare earth doped activated Nitride phosphor, and/or rare earth doped activated silicate fluorescent powder, and/or rare earth doped activated halogen silicate phosphor powder, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated aluminate fluorescent powder, and/or rare earth doped activated sulphide fluorescent material, and/or rare earth doped activated borate fluorescent powder, and/or rare earth doped activated phosphate phosphor, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated scandate fluorescent material, and/or rare earth doped activated thiogallate fluorescent material.

The LED glow color of preparation is by the common decision of emmission spectrum, relative brightness and the array mode of the fluorescent material of the semi-conductor chip emmission spectrum that is adopted and relative brightness and use.

Be illustrated below by embodiment 172～185, concrete chip, fluorescent material and the selection of combination and the glow color of LED are shown in table 5.

Table 5:

Claims

1. red luminous silicon-oxygen nitride fluorescent is characterized by the chemical constitution expression formula and is:

M ^I _uM ^II _v(Si _1-αA _α) _wO _δN _{(2/3(u+v)+4/3w-2/3δ)}:Eu _x，R _y，D _z，

M wherein ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and Ba, the Zn ^IAnd M ^IICan not select identity element simultaneously for use, A is for being selected from least a element among Ge, Al, Ga, the In, and R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Bi, Sm, Yb, Lu, Gd, Tb, the Mn, and D is for being selected from F ^-, Cl ^-, Br ^-, I ^-In at least a ion; U, v, w, α, δ, x, y, z are mole coefficient, wherein: 0.3＜u≤1.2,0≤v＜2.0 and 0.5＜u+v＜3.5,4.5≤w≤5.5,0≤α≤1,0＜δ＜1.0,0＜x≤1,0≤y≤0.5 and 1.0≤v+x+y＜2.0,0.001≤z≤0.05;

After described fluorescent material is launched the ultraviolet-blue green light of peak wavelength in 300～550nm scope and excites, be emitted in the luminescent spectrum of one or more peak values in 580～680nm scope, can present the luminous of red color, perhaps mix with other one or more fluorescent material use realize white luminous.

2. a kind of red luminous silicon-oxygen nitride fluorescent according to claim 1 is characterized in that the mole coefficient y=0 in the chemical constitution expression.

3. a kind of red luminous silicon-oxygen nitride fluorescent according to claim 1 is characterized in that mole coefficient 0＜x＜1,0＜y≤0.5 in the chemical constitution expression.

4. a kind of red luminous silicon-oxygen nitride fluorescent according to claim 1 and 2 is characterized in that D is F in the chemical constitution expression ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.4≤u＜1,1.2≤v+x≤1.4,4.5≤w≤5.5,0≤α≤1,0.2≤δ＜1.0,0＜x≤1, y=0,0.001≤z≤0.05.

5. a kind of red luminous silicon-oxygen nitride fluorescent according to claim 1 and 2 is characterized in that D is F in the chemical constitution expression ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 1.0≤u≤1.2,1.0≤v+x＜1.2,4.5≤w≤5.5,0≤α≤1,0.03≤δ＜0.7,0＜x≤1, y=0,0.001≤z≤0.05.

6. according to claim 1 or 3 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that D is F in the chemical constitution expression ^-, Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.4≤u＜1,1.2≤v+x+y≤1.4,4.5≤w≤5.5,0≤α≤1,0.2≤δ＜1.0,0＜x＜1,0＜y≤0.5,0.001≤z≤0.05.

7. according to claim 1 or 3 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that D is F in the chemical constitution expression ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 1.0≤u≤1.2,1.0≤v+x+y＜1.2,4.5≤w≤5.5,0≤α≤1,0.03≤δ＜0.7,0＜x＜1,0＜y≤0.5,0.001≤z≤0.05.

8. a kind of red luminous silicon-oxygen nitride fluorescent according to claim 1 and 2 is characterized in that D is F in the chemical constitution expression ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.34≤u≤0.48,1.6＜v+x＜2.0,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x≤1, y=0,0.001≤z≤0.05.

9. according to claim 1 or 3 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that D is F in the chemical constitution expression ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.34≤u≤0.48,1.6＜v+x+y＜2.0,4.5≤w≤5.5,0≤α≤1,0＜δ＜0.7,0＜x＜1,0＜y≤0.5,0.001≤z≤0.05.

10. according to claim 1,2 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that M in the chemical constitution expression ¹Be Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.4≤u＜1,1.2≤v+x≤1.4,0.2≤δ＜1.0,0.001≤z≤0.05, w=5.

11., it is characterized in that M in the chemical constitution expression according to claim 1,2 described a kind of red luminous silicon-oxygen nitride fluorescent ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 1.0≤u≤1.2,1.0≤v+x＜1.2,0.03≤δ＜0.7,0.001≤z≤0.05, w=5.

12., it is characterized in that M in the chemical constitution expression according to claim 1,3 described a kind of red luminous silicon-oxygen nitride fluorescent ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.4≤u＜1,1.2≤v+x+y≤1.4,0.2≤δ＜1.0,0.001≤z≤0.05, w=5.

13., it is characterized in that M in the chemical constitution expression according to claim 1,3 described a kind of red luminous silicon-oxygen nitride fluorescent ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 1.0≤u≤1.2,1.0≤v+x+y＜1.2,0.03≤δ＜0.7,0.001≤z≤0.05, w=5.

14., it is characterized in that M in the chemical constitution expression according to claim 1,2 described a kind of red luminous silicon-oxygen nitride fluorescent ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; Mole coefficient 0.34≤u≤0.48,1.6＜v+x＜2.0,0＜δ＜0.7,0.001≤z≤0.05, w=5.

15., it is characterized in that M in the chemical constitution expression according to claim 1,3 described a kind of red luminous silicon-oxygen nitride fluorescent ^IBe Ca or Sr element, M ^IIFor being selected from least a element and M among Sr or Ca and the Zn ^IAnd M ^IICan not select identity element simultaneously for use, R is for being selected from least a element among Nd, Dy, Ho, Tm, Ce, Er, Pr, Gd, Tb, the Mn, and D is for being selected from F ^-Or Cl ^-In a kind of element ion or the combination of two kinds of element ions; 0.34≤u≤0.48,1.6＜v+x+y＜2.0,0＜δ＜0.7,0.001≤z≤0.05, w=5.

16. according to claim 1,2 or 3 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that, described silicon-oxygen nitride fluorescent material is sent the emmission spectrum of one or more peak values in 580～680nm scope by the optical excitation of the excitation light source with emission peak in UV-light-blue green light scope of 300～550nm.

17. according to claim 1,2 or 3 described a kind of red luminous silicon-oxygen nitride fluorescent, it is characterized in that, described silicon-oxygen nitride fluorescent material is by the optical excitation of the excitation light source with emission peak in UV-light-blue green light scope of 300～550nm, and the emission peak wavelength of fluorescent material is greater than the wavelength of the long wave side emission peak of excitation light source.

18. the preparation method of a red luminous silicon-oxygen nitride fluorescent is characterized in that, raw materials used is the compound of following each element, and its element is according to following expression M ^I _uM ^II _v(Si _1-αA _α) _wO _δN _{(2/3 (u+v)+4/3w-2/3 δ)}: Eu _x, R _y, D _zThe mole proportioning be:

M ^I：0.5～1.5；

M ^II：0～1.5；

Si：0～5.5；

A：0～5.5；

Eu：0.001～1；

R：0～0.5；

D：0.001～0.05；

Wherein: M ^IRepresent the compound of Ca or Sr element;

Si represents the compound of element silicon;

A represents the compound of one or more elements among Ge, Al, Ga, the In;

Eu represents the compound of europium element;

D represents F ^-, Cl ^-, Br ^-, I ^-In the compound of one or more elements;

M ^IThe compound of representative element adopts the organometallics of calcium, as calcium formiate (Ca (HCOO) ₂), lime acetate ((CH ₃COO) ₂CaxH ₂O), calcium propionate (Ca (C ₂H ₅COO) ₂), 2,4-diacetylmethane calcium (Ca (C ₅H ₇O ₂) xH ₂O), calcium ascorbate (C ₁₂H ₁₄CaO ₁₂2H ₂O), two (2,2,6,6-tetramethyl--3, the acid of 5-heptadione) calcium (Ca (OCC (CH ₃) ₃CHCOC (CH ₃) ₃) ₂), cyclohexane butyric acid calcium ((C ₆H ₁₁(CH ₂) ₃CO ₂) ₂Ca), calcium iso-octoate ((CH ₃(CH ₂) ₃CH (C ₂H ₅) CO ₂) ₂Ca), calcium isopropoxide (Ca (OCH (CH ₃) ₂) ₂), hydration calcium lactate ((CH ₃CH (OH) COO) ₂CaxH ₂O), calcium methylate (Ca (OCH ₃) ₂), caoxalate (CaC ₂O ₄4H ₂O), calcium stearate ((C ₁₇H ₃₅COO) ₂Ca), citrate of lime (Ca ₃(C ₆H ₅O ₇) ₂4H ₂O), calglucon (C ₁₂H ₂₂CaO ₁₄H ₂O), calcium aminosuccinic acid ((C ₄H ₆NO ₄) ₂Ca3H ₂O), calcium citrate malate (C ₁₂H ₁₀O ₁₄Ca ₃4H ₂O), calcium malate (C ₄H ₄O ₅Ca3H ₂O); And the organometallics of strontium, as strontium formate (Sr (HCOO) ₂), strontium acetate ((CH ₃COO) ₂SrxH ₂O), propionic acid strontium (Sr (C ₂H ₅COO) ₂), strontium oxalate (SrC ₂O ₄4H ₂O), strontium citrate (Sr ₃(C ₆H ₅O ₇) ₂4H ₂O), gluconic acid strontium (C ₁₂H ₂₂SrO ₁₄H ₂O), hydration strontium lactate ((CH ₃CH (OH) COO) ₂SrxH ₂O), methyl ethyl diketone strontium ((CH ₃COCH=C (O-) CH ₃) ₂Sr), Virahol strontium (Sr (OCH (CH ₃) ₂) ₂) in at least aly originate as element;

M ^IIThe compound of representative element adopts the form of carbonate and/or oxide compound to originate as element;

The compound of Si representative element adopts the form of silicon nitride to originate as element;

The compound of A representative element adopts the form of nitride to originate as element;

The compound of Eu representative element adopts the form of europium sesquioxide to originate as element;

The compound of R representative element adopts the form of oxide compound to originate as element;

The compound of D representative element adopts the form of fluorochemical or muriate or bromide or iodide to originate as element;

Its manufacture craft is the constant-pressure and high-temperature solid reaction process, and the raw material of each element is taken by weighing by the mole proportioning, mixes, 1300-1700 ℃ of sintering is 5 to 10 hours under normal pressure inert atmosphere or weakly reducing atmosphere, pulverize, sieve, then carry out aftertreatments such as pickling or coating and form.

19. the preparation method of the silicon-oxygen nitride fluorescent material described in claim 18 is characterized in that described inert atmosphere or weakly reducing atmosphere are that nitrogen, nitrogen and hydrogen or carbon granules exist down.

20. a light-emitting device, comprising luminescence chip as excitation light source, and the fluorescent material that at least a portion light of excitation light source can be changed, it is characterized in that:

In ultraviolet-blue green light regional extent of 300～550nm, employed fluorescent material has a kind of described red silicon-oxygen nitride fluorescent material of claim 1～17 that is at least as the emmission spectrum peak value of the luminescence chip of excitation light source; At least a portion of other fluorescent material is luminous in that fluorescent material absorbs excitation light source and/or the combination, the wavelength Conversion of the luminescent spectrum of the described luminous element of at least a portion is become different have at least more than one peak wavelength to be in emmission spectrum in 400～700nm wavelength region to obtain mixed white light or gold-tinted or orange light or purple light or ruddiness.

21. the light-emitting device described in claim 20 is characterized in that wherein said excitation light source is that luminescent layer is nitride-based semiconductor or has the nitride semiconductor light-emitting chip that contains In.

22. the light-emitting device described in claim 20, it is characterized in that, described fluorescent material, also contain yellow second fluorescent material that together uses with any one described more than one silicon-oxygen nitride fluorescent material in the claim 1～17, and/or green the 3rd fluorescent material, and/or blue the 4th fluorescent material;

Described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material are: rare earth doped activated nitric oxide fluorescent powder, and/or rare earth doped activated Nitride phosphor, and/or rare earth doped activated silicate fluorescent powder, and/or rare earth doped activated halogen silicate phosphor powder, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated sulphide fluorescent material, and/or rare earth doped activated aluminate fluorescent powder, and/or rare earth doped activated borate fluorescent powder, and/or rare earth doped activated phosphate phosphor, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated scandate fluorescent material, and/or rare earth doped activated thiogallate fluorescent material.

23. the light-emitting device described in claim 20 is characterized in that, described light-emitting device is the luminescent conversion LED that a kind of described fluorescent material directly or indirectly contacts with chip.

24. the light-emitting device described in claim 20 is characterized in that, described light-emitting device is to comprise the means of illumination that at least one uses the LED of described fluorescent material.