CN101134895B - Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same - Google Patents

Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same Download PDF

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CN101134895B
CN101134895B CN2007101467618A CN200710146761A CN101134895B CN 101134895 B CN101134895 B CN 101134895B CN 2007101467618 A CN2007101467618 A CN 2007101467618A CN 200710146761 A CN200710146761 A CN 200710146761A CN 101134895 B CN101134895 B CN 101134895B
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fluorescent material
light
rare earth
earth doped
light source
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CN101134895A (en
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夏威
于晶杰
肖志国
边福强
朝克夫
桑石云
邓华
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Dalian Luming Science and Technology Group Co Ltd
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Dalian Luming Science and Technology Group Co Ltd
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Abstract

The present invention is one kind of fluorescent material capable of being excited with light from ultraviolet ray to green light and especially for use in LED and its synthesis process. The fluorescent material has the general formula of aMO.bA2O3.cSiO2.dR: xEu.yLn.zLv.wLm, where, M is one or several selected from Sr, Ca, Ba and Mg; A is one or several selected from Y, Al and Gd; R is B2O3 and/or P2O5; Ln is one or several selected from Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn and Pb; Lv is one or several selected from halogen ions; Lm is one or several selected from Li<+>, Na<+>, K<+> and Ag<+>; a, b, c, d, x, y, z, w are molar coefficients.

Description

A kind of wide-spectrum excitation fluorescent material and synthetic method thereof and the light-emitting device that uses it
Technical field
The present invention relates to a kind of fluorescent material, be particularly related to and comprise that the white light system and the polychrome that adopt semiconductor light-emitting elements (LED) are the fluorescent material that light-emitting device is used, relate to cathode ray tube (CRT) simultaneously, plasma display panel (PDP), field effect transistor (FED), electroluminescent (EL), the fluorescent material that uses in the lighting units such as display unit such as fluorescent display tube and luminescent lamp, it can be used as the ultraviolet of the emmission spectrum of excitation light source at 240～530nm---and the luminous element in green glow zone excites, absorb at least a portion emission light of excitation light source, send in 420～700nm scope, have at least～individual, belong to photoelectron and lighting technical field with the emmission spectrum of upward peak in 430～680nm scope.
Background technology
Show and the development of lighting engineering brings huge change for the mankind's life that the especially appearance of white light LEDs is LED from identification function to one step of substance that illumination functions is stepped out.White light LEDs more can better reflect the true colors of irradiating object near daylight.Because it also has pollution-free, long lifetime, vibration resistance and shock proof distinguishing feature, from technical standpoint, white light LEDs is undoubtedly the most advanced technology of LED, will become the light source of new generation of 21 century---the 4th generation electric light source, the application market of white light LEDs will be very extensive.
At present in the prior art field, realize illumination and the mode that shows, based on by the method for ultraviolet chip or blue chip excitation fluorescent material or the method for the ultraviolet ray excited fluorescent material of low-pressure mercury discharge generation.But owing to be subjected to the restriction of fluorescent material, all there is certain limitation in these methods.
In patent US5998925, US6998771, ZL00801494.9, all be utilize blue chip excite cerium activated rare-earth garnet fluorescent material (as Y3Al5O12:Ce, (and Y, Gd) 3 (Al, Ga) 5O12:Ce are called for short YAG; Or the Tb-garnet, 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 this method, employed fluorescent material has significant limitation at the application and the aspect of performance of white light LEDs.At first, this fluorescent material excite scope in the scope of 420～490nm, the most effective exciting in the scope of 370～470nm do not excite for the short wavelength side zone and the green glow zone of UV-light zone and visible light; Secondly, the emmission spectrum maximum of the fluorescent material of this rare-earth garnet structure can only arrive about 540nm, lacks red composition, causes the colour rendering index of white light LEDs lower.
In patent US6649946, USPA20040135504, CN1522291A, CN1705732A, CN1596292A, CN1596478A, US6680569, related is rare-earth activated nitride or the nitrogen oxide fluorescent material that the UV-blue region can effectively excite.Effective excitation wavelength range of the fluorescent material of this method increases to some extent, transmitting boundary also can be from the green glow to ruddiness, but the luminosity of this fluorescent material is lower, and manufacturing cost is higher, uses as the LED fluorescent material of practicability to also have significant limitation.
As related among the patent USPA6351069 be sulfide red fluorescent material, this fluorescent material can be used as the complementary color composition and joins in the white light LEDs, in order to remedy colour rendering index, reduces colour temperature.But the luminosity of all-sulphide phosphor is low, though improve colour rendering index, reduces the luminous efficiency of LED; And, its chemical stability and loss of properties on aging, and corrode chip, shortened the work-ing life of LED.
In fact, existing other authorized or all kinds of fluorescent materials that the patent of applying for is set forth in, the excitation spectrum of aluminate class fluorescent material is difficult to be implemented in effectively exciting of visible region; Silicates or halogen silicate class fluorescent material then aspect thermally-stabilised performance poor slightly.
Summary of the invention
An object of the present invention is to provide a kind of fluorescent material, have the wide ranges of exciting (240～530nm), transmitting boundary wide (430～680nm), light conversion efficiency height, the fluorescent material of ageing-resistant performance excellence; Another object of the present invention provides a kind of manufacture method of fluorescent material; Another object of the present invention provides a kind of light-emitting device that contains fluorescent material of the present invention, particularly white light LEDs.
The main chemical constitution of fluorescent material of the present invention can be used formula (1) expression:
aMO·bA 2O 3·cSiO 2·dR:xEu·yLn·zLv·δLm (1)
Wherein M is selected from one or more element combinations of Sr, Ca, Ba, Mg; A is selected from one or more element combinations among Y, Al, the Gd; R is selected from B 2O 3, P 2O 5In one or both compositions; Ln is one or more element combinations among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn, the Pb; Lv is selected from Cl -, F -, Br -, I -In the combination of one or more element ions; Lm is selected from Li +, Na +, K +, Ag +In the combination of one or more element ions; A, b, c, d, x, y, z, δ are mole coefficient, 0.5≤a≤4.0; 0.5≤b≤2.0; 1.0≤c≤6; 0≤d≤0.5; 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2; This material can by as the emmission spectrum of excitation light source 240～530nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission light of excitation light source, send in 420～700nm scope, have one at least with the emmission spectrum of upward peak in 430～680nm scope, and can compoundly send white luminous.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: MA 2Si 2O 8: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: M 3A 2Si 6O 18: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: MA 2Si 6O 16: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: M 2A 4Si 5O 18: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: M 3A 2SiO 8: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: M 4A 2Si 2O 11: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
According to the fluorescent material of a preferred embodiment of the present invention, the main chemical constitution expression of wherein said fluorescent material is: M 3A 2Si 2O 10: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0≤δ＜0.2.
Fluorescent material according to a preferred embodiment of the present invention, wherein said fluorescent material is by the UV-light at 240～530nm---the optical excitation of the excitation light source in the green range with emission peak, be issued to rare one with the emmission spectrum of upward peak in 430～680nm scope, and the emission peak wavelength of fluorescent material is greater than the wavelength of the long wave side emission peak of excitation light source.
In the present invention, realize the wide excitation peak of fluorescent material and the wavelength of emission peak by the alkaline-earth metal M of meticulous adjustment fluorescent material and/or the content of A with combination.Rare earth ion transition between energy level feature and crystalline structure have obvious dependence, form the luminous of different colours by absorption or the emission wavelength that uses this relation to regulate rare earth ion.Among the present invention, employed Eu, Ln ion, residing crystal field environment is very obvious to the influence of its 5d energy state and 4f-5d transition in crystal, obvious variation takes place along with the variation of parent lattice environment in the maximum absorption of transition and the position of launching centre, emission wavelength can be from ultraviolet to the ruddiness zone in meticulous adjusting change.And content and the combination of alkaline-earth metal M and/or A by meticulous adjustment fluorescent material make in some homeomorphism series compound, and the launching centre position can clocklike be moved to long wave or shortwave direction with the variation of matrix chemical constitution.In the present invention, utilize charge migration (CTS) transition, be electronics when the molecular orbital(MO) that is full of of part (oxygen and Lv etc.) is moved to the partially filled 4f shell of rare earth ion inside, in spectrum, produce the charge migration of broad, the position of bands of a spectrum is changed along with the variation of environment.
In addition, the change in concentration of the europium ion radiative peak position that influences the fluorescent material among the present invention moves.By adjusting the radiative peak position of the adjusting fluorescent material that Eu, Ln ionic concentration ratio also can be meticulous.
The purpose of introducing Ln among the present invention is, utilize the transmission ofenergy between rare earth ion, promptly after luminescence center was excited, excitation energy can pass to another from certain of twinkler, or pass to another luminescence center, thereby obtain to have the fluorescent material of high brightness from a luminescence center.Radiationless efficiently transmission ofenergy can take place with the Eu interionic in related Ln ion such as Mn, Ce, Bi plasma among the present invention.
Introducing R, Lv, Lm are important discovery and innovation among the present invention.Introducing R has synthesis temperature, the diffusion of promotion particle and the effect that becomes phase that reduces matrix in the fluorescent material building-up process, it can make activator enter matrix easily and form luminescence center and trap center, promotes that matrix forms small crystal; Introduce the excitation spectrum scope that Lv can obviously widen fluorescent material, that improves fluorescent material excites wave band adaptability, especially can impel fluorescent material Eu 2+Intensity at red partially emission band obviously improves; The introducing of Lm is to utilize the ionic radius of alkali metal to be far smaller than the characteristic of the ionic radius of alkaline-earth metal, causes Eu 2+In different matrix, produce than big-difference in the residing lattice environment, work as Eu 2+Replacing alkalimetal ion enters behind the lattice and O 2-Distance than Eu in the alkaline-earth metal matrix 2+With O 2-Distance reduce, make Eu 2+The 5d energy raise i.e. Eu 2+5d energy level lower limit and its ground state energy difference become big, improve the luminous intensity of fluorescent material.
When making fluorescent material of the present invention, raw materials used is the compound of each element in the expression (1), generally selects for use in the raw material, and M represents the compound of one or more element among Sr, Ca, Ba, the Mg; A represents the compound of one or both elements among Y, Al, the Gd; R is the compound of boron, phosphorus; Si represents the compound of Si; Eu represents the compound of Eu; Ln represents the compound of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn, the Pb; Lv represents the compound of one or more elements among Cl, F, Br, the I; Lm represents the compound of one or more elements among Li, Na, K, the Ag; Element mole proportioning is in raw materials used:
M： 0.5～4.0；
A： 1.0～4.0；
Si：?1.0～6.0；
R： 0～0.5；
Eu：?0.001～0.2；
Ln：?0～0.5；
Lv：?0～0.5；
Lm：?0～0.2；
Wherein M represents the compound of one or more element among Sr, Ca, Ba, the Mg; A represents the compound of one or both elements among Y, Al, the Gd; R represents the compound of one or both elements among B, the P; Si represents the compound of Si; Eu represents the compound of Eu; Ln represents the compound of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn, the Pb; Lv represents the compound of one or more elements among Cl, F, Br, the I; Lm represents the compound of one or more elements among Li, Na, K, the Ag.
Manufacture craft is a high-temperature solid phase reaction method, and the raw material of each element is taken by weighing by the mole proportioning, mixes, and 1000-1300 ℃ of sintering 2～16 hours under reducing atmosphere after the cooling, pulverized again, and sieving forms.
In order to improve the quality of material, can in mixing raw material, add the NH that accounts for raw material weight 0～30% 4Cl, NH 4F, (NH 4) 2HPO 4, glucose, urea element, BaF 2, CaF 2, ZnF 2, ZnS, SrS, CaS, SrSO 4, SrHPO 4Or CaHPO 4, Li 2CO 3, KNO 3, Na 2CO 3Participate in solid state reaction.
The invention still further relates to a kind of light-emitting device, have luminous element 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 luminous element is in the ultraviolet of 240～530nm---in the green glow regional extent, and the wavelength Conversion of first luminescent spectrum of the described luminous element of at least a portion become to have at least more than one peak wavelength to be in the light-emitting device of the fluorescent material of second emmission spectrum in 430～680nm wavelength region, it is any fluorescent material of the present invention that fluorescent material wherein has more than one at least.
According to the light-emitting device of a preferred embodiment of the present invention, absorb the ultraviolet of 240～530nm of luminous element at fluorescent material as the luminous element of excitation light source---have the glow peak wavelength more than 1 in the green glow regional extent at least.
According to the light-emitting device of a preferred embodiment of the present invention, the luminescent layer of luminous element is nitride-based semiconductor or has the nitride-based semiconductor that contains In.
According to the light-emitting device of a preferred embodiment of the present invention, employed fluorescent material is any fluorescent material of the present invention.
According to the light-emitting device of a preferred embodiment of the present invention, in ultraviolet light range, employed fluorescent material is one or more combination of fluorescent material of the present invention as the emmission spectrum peak value of the luminous element 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 at least a portion luminous element is become different have at least more than one peak wavelength to be in emmission spectrum in 430～680nm wavelength region to obtain mixed white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness.
According to 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 at blue light in the scope of green glow, employed fluorescent material is one or more combination of fluorescent material of the present invention; At least a portion of other fluorescent materials is luminous in that fluorescent material absorbs excitation light source and/or the combination, the wavelength Conversion of the luminescent spectrum of at least a portion luminous element is become different have at least more than one peak wavelength to be in emmission spectrum in 430～680nm wavelength region to obtain mixed white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness.
According to the light-emitting device of a preferred embodiment of the present invention, employed fluorescent material also contains second fluorescent material that together uses with more than one fluorescent material of the present invention, and/or the 3rd fluorescent material, and/or the 4th fluorescent material; This second fluorescent material, and/or the 3rd fluorescent material, and/or the part of the light of the 4th fluorescent material self-excitation in the future light source, and/or from least a portion wavelength Conversion of the light of fluorescent material of the present invention, and has the luminescent spectrum that has at least one emission peak wavelength at blue light in the visible region of ruddiness.
Light-emitting device according to a preferred embodiment of the present invention, as the emmission spectrum peak value of the luminous element of excitation light source in the scope of UV-light, from least a portion light of fluorescent material of the present invention, mix to obtain white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness from the above light of at least two bundles of the light of second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material.
Light-emitting device according to a preferred embodiment of the present invention, as the emmission spectrum peak value of the luminous element of excitation light source at blue light in the scope of green glow, from least a portion light of excitation light source, from least a portion light of fluorescent material of the present invention, mix to obtain white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness from the above light of at least two bundles of the light of second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material.
According to the light-emitting device of a preferred embodiment of the present invention, second fluorescent material wherein and/or the 3rd fluorescent material and/or the 4th fluorescent material are: rare earth doped activated nitrogen oxide fluorescent material, and/or rare earth doped activated nitride fluorescent material, and/or rare earth doped activated halogen silicate fluorescent material, and/or rare earth doped activated silicate fluorescent material, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated all-sulphide phosphor, and/or rare earth doped activated oxide fluorescent material, and/or rare earth doped activated oxysulfide fluorescent material, and/or rare earth doped activated aluminate fluorescent material, and/or the sour magnesium fluorescent material of doped with Mn activated fluorine arsenic (germanium), and/or rare earth doped activated borate fluorescent material, and/or rare earth doped activated phosphate fluorescent, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated titanate fluorescent material, and/or rare earth doped activated thiogallate fluorescent material.
Light-emitting device according to a preferred embodiment of the present invention, the part of the light of second fluorescent material wherein and/or the 3rd fluorescent material and/or the 4th fluorescent material self-excitation in the future light source, and/or from least a portion wavelength Conversion of the light of fluorescent material of the present invention, and has the luminescent spectrum that has at least one emission peak at blue light in the visible region of ruddiness.
According to the light-emitting device of a preferred embodiment of the present invention, light-emitting device is the luminescent conversion LED that a kind of fluorescent material directly or indirectly contacts with chip.
According to the light-emitting device of a preferred embodiment of the present invention, light-emitting device is to comprise the means of illumination that at least one uses the LED of fluorescent material.
The excitation spectrum of fluorescent material and emmission spectrum adopt the test of F-4500 fluorescence spectrophotometer among the present invention.
The relative spectral power of LED distributes and chromaticity coordinate adopts the test of PMS-50 type ultraviolet-visible-near-infrared spectrum analytical system.
Description of drawings
Fig. 1 excites and emmission spectrum for embodiment 1 fluorescent material.
Fig. 2 excites and emmission spectrum for embodiment 6 fluorescent materials.
Fig. 3 excites and emmission spectrum for embodiment 9 fluorescent materials.
Fig. 4 excites and emmission spectrum for embodiment 13 fluorescent materials.
Fig. 5 excites and emmission spectrum for embodiment 23 fluorescent materials.
Fig. 6 excites and emmission spectrum for embodiment 24 fluorescent materials.
Fig. 7 is for using the LED structural representation of fluorescent material.
The a mode that to be luminescent material directly contact with the semiconductor light emitting chip, luminescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes;
B is the mode of luminescent material and the indirect contact of semiconductor light emitting chip, and luminescent material is evenly distributed on epoxy skins;
C is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.
D is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material mixes the back film forming form of preparation and is covered on the semiconductor light emitting chip again with transparent medium;
Wherein 1, the 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, 9, pad pasting.
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:Sr 0.5Ba 0.5Al 2Si 2O 8: Eu 0.1, Ce 0.05
With SrCO 3, BaCO 3, Al 2O 3, SiO 2, Eu 2O 3, Ce (NO 3) 3Take by weighing according to molar ratio, mixed raw materials, is cooled off after 15 hours in 1000 ℃ of pre-burnings under the air atmosphere earlier, add fusing assistant 5% (wt) BaF 2With 2% (wt) H 3BO 3Grind the back in 1500 ℃ of heat preservation sinterings 16 hours.Sintered compact cooling back is pulverized, is ground.The gained powder is scattered in the ethanol, carries out classification, guarantee the fluorescent material even particle size distribution, obtain the fluorescent material that medium particle diameter is 15 μ m after the drying by adopting the continuous fluid sedimentation-separation technology.
Embodiment 2-5, preparation method and step are with embodiment 1.
The embodiment title Fluorescent material is formed Glow color
Embodiment
2 Sr 0.5Ba 0.5Al 2Si 2O 8:Eu 0.1，Ce 0.05:F - Green (em:529nm)
Embodiment 3 Sr 0.6Ba 0.4Al 2Si 2O 8:Eu 0.1，Ce 0.05 Yellow-green colour (em:532nm)
Embodiment 4 Sr 0.6Ba 0.4Al 2Si 2O 8:Eu 0.1，Ce 0.05:Cl - Yellow-green colour (em:531nm)
Embodiment 5 Ba 0.5Mg 0.5Al 2Si 2O 8:Eu 0.05 Green (em:527nm)
Embodiment 6:SrBaCaAl 2Si 6O 18: Eu 0.1, Ce 0.05, Mn 0.02
With SrCO 3, BaCO 3, CaCO 3, Al 2O 3, SiO 2, Eu 2O 3, Ce (NO 3) 3, MnO 2Take by weighing according to molar ratio, with mixed raw materials 1100 ℃ of pre-burnings 15 hours under air atmosphere earlier, cooling adds fusing assistant 7% (wt) NH 4Cl, 1% (wt) H 3BO 3And 0.8% (wt) Li 2CO 3Grinding the back burnt till 12 hours in 1450 ℃ of high temperature, fluorescent material is pulverized the back, is scattered in the dispersion medium ethanol, by adopting the continuous fluid sedimentation-separation technology to carry out classification, guarantee the fluorescent material even particle size distribution, obtain the fluorescent material that medium particle diameter is 12 μ m after the drying.
Embodiment 7-8, preparation method and step are with embodiment 6.
The embodiment title Fluorescent material is formed Glow color
Embodiment
7 SrBaCaAl 2Si 6O 18:Eu 0.1，Ce 0.05，Mn 0.02，Li + Yellow-green colour (em:531nm)
Embodiment 8 SrBaCaAl 2Si 6O 18:Eu 0.1，Ce 0.05，Mn 0.02，K + Yellow-green colour (em:532nm)
Embodiment 9:Ba 0.5Sr 1.5Y 1Al 1Si 6O 16: Eu 00.05, Dy 0.015, K 0.02
With SrCO 3, BaCO 3, KCl, Al 2O 3, Y 2O 3, SiO 2, Eu 2O 3, Dy 2O 3Molar ratio takes by weighing, and with mixed raw materials 950 ℃ of pre-burnings 12 hours under air atmosphere earlier, cooling adds fusing assistant 3% (wt) MgF 2, 2% (wt) H 3BO 3And 0.8% (wt) SrSO 4Grinding the back burns till in 1200 ℃ of high temperature, time is 20 hours, and fluorescent material is pulverized the back, is scattered in the dispersion medium ethanol, carries out classification by adopting the continuous fluid sedimentation-separation technology, guarantee the fluorescent material even particle size distribution, obtain the fluorescent material that medium particle diameter is 9 μ m after the drying.
Embodiment 10-12, preparation method and step are with embodiment 9.
The embodiment title Fluorescent material is formed Glow color
Embodiment
10 Ba 0.25Sr 0.75YAlSi 6O 16:Eu 0.1，Dy 0.03，Li 0.02，F 0.05 Yellow (em:563nm)
Embodiment 11 Ba 0.15Sr 0.85YAl 0.5Gd 0.5Si 6O 16:Eu 0.1，Dy 0.03，Na 0.02， K 0.02 Yellow (em:560nm)
Embodiment 12 Ba 0.05Sr 0.95YAlSi 6O 16:Eu 0.1，Dy 0.03，Na 0.02 Yellow (em:558nm)
Embodiment 13 Ba 0.25Sr 0.55Mg 0.2GdAlSi 6O 16:Eu 0.1，Dy 0.03，Sn 0.03， K 0.02 Yellow (em:565nm)
Embodiment 14 BaAl 2Si 6O 16:Eu 0.1，Dy 0.03，K 0.02 Orange-yellow (em:570nm)
Embodiment 15 (Mg 0.86Ca 0.14) 2Al 4Si 5O 18: Eu 0.08
With MgCO 3, CaCO 3, Al 2O 3, SiO 2, Eu 2O 3Example takes by weighing in molar ratio, and with mixed raw materials 800 ℃ of pre-burnings 15 hours under air atmosphere earlier, cooling adds fusing assistant 5% (wt) NH 4F, 3% (wt) H 3BO 3And 1% (wt) SrSO 4Grinding the back burns till in 1100 ℃ of high temperature, time is 20 hours, and fluorescent material is pulverized the back, is scattered in the dispersion medium ethanol, carries out classification by adopting the continuous fluid sedimentation-separation technology, guarantee the fluorescent material even particle size distribution, obtain the fluorescent material that medium particle diameter is 5 μ m after the drying.
Embodiment 16-20, preparation method and step are with embodiment 15.
The embodiment title Fluorescent material is formed Glow color
Embodiment 16 (Mg 0.86Ca 0.1) 2Al 4Si 5O 18:Eu 0.08:Na + Blue (em:444nm)
Embodiment 17 (Mg 0.86Sr 0.1) 2Al 4Si 5O 18:Eu 0.08 Blue (em:448nm)
Embodiment 18 (Mg 0.85Sr 0.1) 2Al 4Si 5O 18:Eu 0.08，Mn 0.02 Blue (em:452nm)
Embodiment 19 (Mg 0.86Ba 0.1) 2Al 4Si 5O 18:Eu 0.08 Blue (em:454nm)
Embodiment 20 (Mg 0.85Ba 0.1) 2Al 4Si 5O 18:Eu 0.08，Mn 0.02 Blue (em:458nm)
Embodiment 21:(Ca 0.95Sr 0.05) (Al 0.95B 0.05) 2Si 2O 8: Eu 0.01
Raw material Consumption
SrCO 3 0.738g
CaCO 3 9.5g
Al 2O 3 9.69g
H 3BO 3 0.61g
SiO 2 12g
Eu 2O 3 0.176g
CaF 2 0.1g
(NH 4) 2HPO 4 0.1g
Above-mentioned each raw material is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 800 ℃ of pre-burnings are 6 hours under oxygen atmosphere, and cooling is ground back 1000 ℃ of high temperature in reducing atmosphere and burnt till, and the time is 12 hours.After the pulverizing fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the luminescent material (Ca among the present invention after the drying 0.95Sr 0.05) (Al 0.95B 0.05) 2Si 2O 8: Eu 0.01The medium particle diameter of material is the material of 5.6 μ m, and emission wavelength is 462nm.
Embodiment 22:0.48CaO0.12SrO0.855Al 2O 30.03B 2O 32SiO 2: Eu 0.01
Raw material Consumption
SrCO 3 1.77g
CaCO 3 1.8g
Al 2O 3 8.72g
H 3BO 3 0.55g
SiO 2 12g
Eu 2O 3 0.176g
NH 4F 0.12g
H 3BO 3 0.1g
Above-mentioned each raw material is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 750 ℃ of pre-burnings are 5 hours under oxygen atmosphere, and cooling is ground back 1100 ℃ of high temperature in reducing atmosphere and burnt till, and the time is 10 hours.After the pulverizing fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the luminescent material 0.48CaO0.12SrO0.855Al among the present invention after the drying 2O 30.03B 2O 32SiO 2: Eu 0.01, the medium particle diameter of material is the material of 4.8 μ m.
Embodiment 23
Raw material Weight (g)
SrCO 3 442.89
Al 2O 3 101.96
SiO 2 60.08
Eu 2O 3 1.76
NH 4F 0.19
Li 2CO 3 0.18
The abundant ball milling of each raw material of above-mentioned composition is mixed, behind the crucible of packing into, put it into sintering in the stove of mixed gas of the hydrogen that is connected with 95% nitrogen and 5% after the cooling again, and 1200 ℃ of following heat preservation sinterings 6 hours.After the sintered compact cooling, pulverize, grind with ball mill, utilize the sieve of 325 order specifications to sieve again, the chemical constitution that obtains among the present invention is 3.0SrOAl 2O 31.0SiO 2: 0.01Eu0.02F -0.07Li +Or Sr 3Al 2SiO 8: 0.01Eu0.02F -0.07Li +Fluorescent material.The excitation spectrum of this material is in 240～500nm scope; Emmission spectrum is in 500～700nm scope, and its emission peak wavelength lays respectively at 558nm.
Embodiment 24
Raw material Weight (g)
CaCO 3 300.24
Al 2O 3 101.96
SiO 2 60.08
Eu 2O 3 1.76
The abundant ball milling of each raw material of above-mentioned composition is mixed, behind the crucible of packing into, put it into sintering in the stove that is connected with nitrogen hydrogen mixeding gas, and 1410 ℃ of following heat preservation sinterings 2 hours.After the sintered compact cooling, pulverize, grind with ball mill, utilize the sieve of 325 order specifications to sieve again, the chemical constitution that obtains among the present invention is 3.0CaOAl 2O 31.0SiO 2: 0.01Eu or Ca 3Al 2SiO 8: the fluorescent material of 0.01Eu.The excitation spectrum of this material is in 280～400nm scope; Emmission spectrum is in 400～500nm scope, and its emission peak wavelength lays respectively at 441nm.
The invention still further relates to the means of illumination that uses any above 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 240～530nm 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. 7, 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, pad pasting 9.The semiconductor light emitting chip is GaInN chip or GaN chip.Comprise at least a above fluorescent material of the present invention in the fluorescent material.Packaged material is a transparent resin, can be transparent epoxy resin, transparent silica gel etc.
Wherein scheme a and be the mode that fluorescent material and semiconductor light emitting chip directly contact, fluorescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes.Figure 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.Figure c is the mode of fluorescent material semiconductor light emitting chip indirect contact, and fluorescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.Figure d is the mode of fluorescent material semiconductor light emitting chip indirect contact, and fluorescent material mixes the back film forming form of preparation and is covered on the semiconductor light emitting chip again with transparent medium.
Embodiment 25
Adopt the LED packaged type of figure a among Fig. 7 to prepare white light LEDs.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 450nm, and fluorescent material is selected embodiment 23 described fluorescent materials.The chip of choosing is carried out solid crystalline substance, routing, oven dry.Take by weighing after some grams of fluorescent material and transparent epoxy resin mix in accordance with the appropriate 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.Its chromaticity coordinate is X=0.3471, Y=0.3513, colour temperature 5127K.The yellow emmission spectrum that fluorescent material is launched by chip to launch after the royal purple optical excitation and the royal purple photorecombination of chip form white light.
Embodiment 26
Adopt the LED packaged type of figure b among Fig. 7 to prepare emitting red light LED.In the present embodiment, packaging process and embodiment 25 are similar, are evenly distributed on epoxy skins but have red emission spectrographic fluorescent material.
Embodiment 27
Adopt the LED packaged type of figure c among Fig. 7 to prepare green light LED.In the present embodiment, packaging process and embodiment 25 are similar, are evenly distributed among the Resins, epoxy but have green emitted spectrographic fluorescent material, on the semiconductor light emitting chip.
Adopt LED packaged type can prepare LED as scheming a, figure b, figure c, figure d among Fig. 7.Packaging process and embodiment 25,26,27 are similar.But the array mode of fluorescent material 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 materials 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 at least a above fluorescent material of the present invention, the glow color of while LED product is as required selected non-second fluorescent material of the present invention and/or the 3rd fluorescent material and/or the 4th fluorescent material.
The fluorescent material kind that can be used as the use of second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material comprises: rare earth doped activated nitrogen oxide fluorescent material, rare earth doped activated nitride fluorescent material, rare earth doped activated halogen silicate fluorescent material, rare earth doped activated silicate fluorescent material, the fluorescent material of rare earth doped activated garnet structure, rare earth doped activated all-sulphide phosphor, rare earth doped activated oxide fluorescent material, rare earth doped activated oxysulfide fluorescent material, rare earth doped activated aluminate fluorescent material, the sour magnesium fluorescent material of doped with Mn activated fluorine arsenic (germanium), rare earth doped activated borate fluorescent material, rare earth doped activated phosphate fluorescent, rare earth doped activated halogen-phosphate fluorescent material, rare earth doped activated titanate fluorescent material, rare earth doped activated thiogallate fluorescent material.
The LED glow color of preparation is determined jointly by the emmission spectrum of the fluorescent material of the semi-conductor chip emmission spectrum that is adopted and relative brightness and use and fluorescent material and relative brightness.
Compared with prior art, the outstanding feature that fluorescent material of the present invention has is: have wider excitation spectrum, can be at the ultraviolet light of 240～530nm---effectively excite under the light-emitting component shooting condition in green glow zone, and anti-aging property and excellent heat stability. Has significant novelty and creativeness.

Claims (18)

1. fluorescent material, its chemical constitution expression is: aMObA 2O 3CSiO 2DR:xEuyLnzLv δ Lm, wherein M is selected from one or more element combinations of Sr, Ca, Ba, Mg; A is selected from one or more element combinations among Y, Al, the Gd; R is selected from B 2O 3, P 2O 5In one or both compositions; Ln is a kind of among Dy, Ce, the Mn; Lv is selected from Cl -, F -In a kind of element ion; Lm is selected from Li +, Na +, K +, Ag +In the combination of one or more element ions; A, b, c, d, x, y, z, δ are mole coefficient, 0.5≤a≤4.0; 0.5≤b≤2.0; 1.0≤c≤6; 0≤d≤0.5; 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2; This material can by as the emmission spectrum of excitation light source 240～530nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission light of excitation light source, send in 420～700nm scope, have one at least with the emmission spectrum of upward peak in 430～680nm scope, and can compoundly send white luminous.
2. fluorescent material as claimed in claim 1 is characterized in that the chemical constitution expression is: M 3A 2Si 6O 18: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2.
3. fluorescent material as claimed in claim 1 is characterized in that the chemical constitution expression is: MA 2Si 6O 16: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2.
4. fluorescent material as claimed in claim 1 is characterized in that the chemical constitution expression is: M 2A 4Si 5O 18: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2.
5. fluorescent material as claimed in claim 1 is characterized in that the chemical constitution expression is: M 3A 2SiO 8: xEuyLnzLv δ Lm, wherein 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2.
6. a light-emitting device has as the luminous element of 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:
The emmission spectrum peak value of luminous element is in the ultraviolet of 240～530nm---in the green glow regional extent, and the wavelength Conversion of first luminescent spectrum of the described luminous element of at least a portion become to have at least more than one peak wavelength to be in the light-emitting device of the fluorescent material of second emmission spectrum in 430～680nm wavelength region, described fluorescent material has at least more than one for the chemical constitution expression to be: aMObA 2O 3CSiO 2The fluorescent material of dR:xEuyLnzLv δ Lm, wherein M is selected from one or more element combinations of Sr, Ca, Ba, Mg; A is selected from one or more element combinations among Y, Al, the Gd; R is selected from B 2O 3, P 2O 5In one or both compositions; Ln is a kind of among Dy, Ce, the Mn; Lv is selected from Cl -, F -In a kind of element ion; Lm is selected from Li +, Na +, K +, Ag +In the combination of one or more element ions; A, b, c, d, x, y, z, δ are mole coefficient, 0.5≤a≤4.0; 0.5≤b≤2.0; 1.0≤c≤6; 0≤d≤0.5; 0.001≤x≤0.2; 0≤y≤0.5; 0≤z＜0.5; 0＜δ＜0.2.
7. light-emitting device as claimed in claim 6 is characterized in that described luminous element as excitation light source absorbs the ultraviolet of 240～530nm of luminous element at fluorescent material---have the glow peak wavelength more than 1 in the green glow regional extent at least.
8. as claim 6 or 7 described light-emitting devices, the luminescent layer that it is characterized in that described luminous element is nitride-based semiconductor or has the nitride-based semiconductor that contains In.
9. as claim 6 or 7 described light-emitting devices, it is characterized in that employed fluorescent material is any one described fluorescent material in the claim 1～5.
10. light-emitting device as claimed in claim 6, it is characterized in that emmission spectrum peak value as the luminous element of excitation light source in ultraviolet light range, employed fluorescent material is one or more combination of any one described fluorescent material in the claim 1～5; At least a portion of other fluorescent materials 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 430～680nm wavelength region to obtain mixed white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness.
11. light-emitting device as claimed in claim 6, it is characterized in that emmission spectrum peak value as the luminous element of excitation light source at blue light in the scope of green glow, employed fluorescent material is one or more combination of any one described fluorescent material in the claim 1～5; At least a portion of other fluorescent materials 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 430～680nm wavelength region to obtain mixed white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness.
12. as claim 6,7,10 or 11 described light-emitting devices, described fluorescent material, also contain second fluorescent material that together uses with any one described more than one fluorescent material in the claim 1～5, and/or the 3rd fluorescent material, and/or the 4th fluorescent material; This second fluorescent material, and/or the 3rd fluorescent material, and/or the 4th fluorescent material will be from the part of the light of described excitation light source, and/or from least a portion wavelength Conversion of the light of any one described fluorescent material in the described claim 1～5, and has the luminescent spectrum that has at least one emission peak wavelength at blue light in the visible region of ruddiness.
13. as claim 6,7,10 or 11 described light-emitting devices, it is characterized in that, as the emmission spectrum peak value of the luminous element of excitation light source in the scope of UV-light, from least a portion light of described fluorescent material, mix to obtain white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness from the above light of at least two bundles of the light of described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material.
14. as claim 6,7,10 or 11 described light-emitting devices, it is characterized in that, as the emmission spectrum peak value of the luminous element of excitation light source at blue light in the scope of green glow, from least a portion light of described excitation light source, from least a portion light of described fluorescent material, mix to obtain white light or blue light or blue green light or green glow or yellow green light or gold-tinted or yellow ruddiness or ruddiness from the above light of at least two bundles of the light of described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material.
15. as claim 6,7,10 or 11 described light-emitting devices, it is characterized in that described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material are: rare earth doped activated nitrogen oxide fluorescent material, and/or rare earth doped activated nitride fluorescent material, and/or rare earth doped activated halogen silicate fluorescent material, and/or rare earth doped activated silicate fluorescent material, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated all-sulphide phosphor, and/or rare earth doped activated oxide fluorescent material, and/or rare earth doped activated oxysulfide fluorescent material, and/or rare earth doped activated aluminate fluorescent material, and/or the sour magnesium fluorescent material of doped with Mn activated fluorine arsenic (germanium), and/or rare earth doped activated borate fluorescent material, and/or rare earth doped activated phosphate fluorescent, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated titanate fluorescent material, and/or rare earth doped activated thiogallate fluorescent material.
16. as claim 6,7,10 or 11 described light-emitting devices, it is characterized in that, described second fluorescent material and/or the 3rd fluorescent material and/or the 4th fluorescent material will be from the parts of the light of described excitation light source, and/or from least a portion wavelength Conversion of the light of any one described fluorescent material in the described claim 1～8, and has the luminescent spectrum that has at least one emission peak at blue light in the visible region of ruddiness.
17., it 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 as claim 6,7,10 or 11 described light-emitting devices.
18., it 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 as claim 6,7,10 or 11 described light-emitting devices.
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