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.