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CN101368102B - Warm white LED and its bromide fluorescent powder - Google Patents

Warm white LED and its bromide fluorescent powder Download PDF

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Publication number
CN101368102B
CN101368102B CN2008101614927A CN200810161492A CN101368102B CN 101368102 B CN101368102 B CN 101368102B CN 2008101614927 A CN2008101614927 A CN 2008101614927A CN 200810161492 A CN200810161492 A CN 200810161492A CN 101368102 B CN101368102 B CN 101368102B
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bromide
fluorescent powder
warm white
emitting diode
led
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CN101368102A (en
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索辛纳姆
罗维鸿
蔡绮睿
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罗文渊
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The invention relates to bromide luminescent powder, which takes the rare earth oxidative garnet element as the foundation. The bromide luminescent powder is characterized in that bromide ion is added in garnet component, and the chemical equivalent composition formula of the bromide luminescent powder is (Sigma Ln)3Al2[Al(O1-xBr2x)4]3, wherein, Sigma Ln is equal to Gd and/or Y and/or Lu and/or Dy and/or Ce and/or pr, and the stoichiometric amount index X is equal to 0.0001 to 0.05; the cubical lattice parameter value a is equal to 12.1 to 12.6 A, the maximum radiation wavelength Lambada in the orange red emission zone of the optical spectrum is equal to 560 to 610 nm, the color coordinate x is equal to 0.46, and y is equal to 0.532. in addition, the invention also discloses a warm white light emitting diode adopting the bromide luminescent powder.

Description

Warm white light light-emitting diode (LED) and bromide fluorescent powder thereof
Technical field
The invention relates to a kind of electronic technology field, espespecially a kind of bromide fluorescent powder relevant with the lighting engineering that broadly is referred to as " solid state light emitter " (Solid state lighting) and use the warm white light light-emitting diode (LED) of this bromide fluorescent powder.
Background technology
Semiconductor light source take InGaN InGaN heterojunction (being the P-N junction) as the basis has replaced polytype lighting sources such as luminescent lamp, gas discharge lamp gradually, makes modern lighting engineering more perfect.
In this semiconductor lighting framework, contain a large amount of quantum well compositions, substantially in semicoductor radiating increased effective luminescent conversion, can increase effective electroluminescent switching process.Internal electrical turns optical efficiency 95~99%, and outside gets optical efficiency greater than 40%.
Second emphasis points out that efficient inner parameter not only depends on heterojunction semiconductor InGaN, the interaction of special luminescent spectrum and fluorescent material radiative material, and relevant portion has detailed description in the patent of www.espacenet.com.
At first, pointing out wherein nitride GaN semiconductor framework to be combined with stokes fluorescent material, is to repair one (please refer to S.N akanura Bluelaser Springer-Verlar Berlin 1997, be not described in detail at this) by village in the Japan to be proposed.The radioluminescence that adopts, maximum luminous radiation is distributed in the visible spectrum field, can produce the luminous of other tone.
Concrete about adopting the material Y that knows in the quality that is proposed in stokes fluorescent material 3Al 5O 12(please join S.G.Blasse Luminescent material.Amst.Berliu, 1997) is used on encapsulation architecture.The complementary color law that (please refer to the people's such as S.Schimizu U.S. US.20071149914 patent application case) in well-known day inferior (Nichia) house journal and utilize blue ray radiation and follow 17th century newton obtains effective white light.And early than before this piece Japanese Patent, the physics principle of luminosity of complementary color just once was utilized, and was used on the iconoscope of colour television set such as being combined by blue light and gold-tinted.
In the description of above-mentioned US20071149914 patent application case, it uses heterojunction InGaN is matrix.Although this technology is widely used, it still exists a series of shortcoming: 1. present sapphire luminous in instrument; 2. the high color temperature radiation that has T>6500K; 3. for the not high semicoductor radiating equipment of optical parametric; 4. the instable fluorescent material of suspension polymer has d 50=6~12 microns; And the scope of the optical technology parameter of 5. white light emitting diodes, in special fluorescent material building-up process, do not possess replicability etc.
These chief reasons appear in the WO2008/051486 A1 patent application case, and wherein about describing the yttrium aluminum garnet of nano-scale, its concrete formula is: (Y, A) 3(Al, B) 5(O, C) 12Wherein A=Tb, Gd, La, Sr, Ba, Ca, Mg, main for getting ion Y, B=Si, Ge, B, P, S replace ion A l etc.
Must be pointed out that this chemical formula abides by the content of former patent, for example the nitrogen ion N in the fluorescent material composition -3And sulfonium ion S -2Equally, mention in the patent before us in garnet fluorescent material composition and add F -1Ion and Si + 4Ion (please refer to Republic of China's patent of invention 2495678 of the people such as Sochchin N. ,/2006/02/07), however the shortcoming of this existence is solved its data and can adopting on this patent in WO2008/051486 A1 patent application case.
Yet it still exists shortcoming: under the exciting of blue light, have 6500K or higher colour temperature 1.; 2. the fluorescent material not high with respect to luminous efficiency is because do not add F in composition -1Ion and Cl -1Ion; 3. the garnet granule stability of nanometer is not high, combines the important blue light scattering on yellow particle fluorescent material of WO2008/051486 A1 patent application case.
Summary of the invention
For solving the shortcoming of above-mentioned known techniques, the present invention's main purpose provides a kind of bromide fluorescent powder, and it can eliminate the deficiency of the particle high color temperature of known materials.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides monobromide fluorescent material, and it can get rid of unstable and the work-ing life in instrument.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides a kind of bromide fluorescent powder, and it has rare earth element garnet matrix, can be used for the warm red luminescence phosphor of semiconductor diode.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides a kind of warm white light light-emitting diode (LED), and it creates the photodiode framework of becoming matrix with the InGaN heterogeneous semiconductor.
For reaching above-mentioned purpose, a kind of bromide fluorescent powder of the present invention is that it is characterized in that: this fluorescent material adds bromide anion in the garnet composition take rare-earth oxidation garnet element as the basis, and the chemical equivalent formula of its composition is (∑ Ln) 3Al 2[Al (O 1-xBr 2x) 4] 3, wherein ∑ Ln=Gd and/or Y and/or Lu and/or Dy and/or Ce and/or Pr.
For reaching above-mentioned purpose, a kind of warm white light light-emitting diode (LED) of the present invention, it is to become matrix with the InGaN heterogeneous semiconductor, and scribbles a luminescent conversion layer, it is characterized in that: this luminescent conversion layer has above-mentioned bromide fluorescent powder, and this fluorescent powder grain is to have diameter d 50=0.6~2.75 microns ellipse particle, it is distributed in the transparent polymkeric substance and combines with organic silica gel, its molecular mass M=15000~25000 carbosilane units.The weight ratio of this fluorescent powder grain in this luminescent conversion layer is 8~75%.This luminescent conversion layer has uniform thickness, and the thickness of its radiating surface and side is 80~160 microns.Described warm white light light-emitting diode (LED), wherein the form that is centrosymmetric of its main radiating surface distributes, and sees through a ball optic lens, and the specific refraction that produces is n 〉=1.45.Described warm white light light-emitting diode (LED), wherein for the radiation that is positioned at orange red spectrum zone, its chromaticity coordinates value x=0.46 ± 0.02, y=0.45 ± 0.03, I=100~500 candle lights during in 2 θ=60 °, the operating voltage of institute's employing instrument is 3.0~3.9V.Described warm white light light-emitting diode (LED) is 1 watt-hour in electric power wherein, its optical throughput 68~98 lumens.Described warm white light light-emitting diode (LED), when wherein the heating casing temperature reaches T=85 ℃, its colour temperature T=2500~4500K.Described warm white light light-emitting diode (LED), it is drilled colour system and counts R 〉=70.
Embodiment
At first, the present invention's the purpose shortcoming that is to eliminate above-mentioned fluorescent material and uses the warm white light light-emitting diode (LED) of this fluorescent material.In order to reach this target, the present invention's rare earth bromide fluorescent material, take rare-earth oxidation garnet element as the basis, it is characterized in that: this fluorescent material adds bromide anion in the garnet composition, and the chemical equivalent formula of its composition is (∑ Ln) 3Al 2[Al (O 1-xBr 2x) 4] 3, wherein ∑ Ln=Gd and/or Y and/or Lu and/or Dy and/or Ce and/or Pr.
Wherein, the atomic fraction of this fluorescent material composition mainly contains: 0.5≤Gd/ ∑ Ln≤0.95; 0.01<Y/ ∑ Ln≤0.5; 0.01≤Tb/ ∑ Ln≤0.11; 0.01<Ce/ ∑ Ln≤0.045; 0.0001<Pr/ ∑ Ln≤0.01; 0.001<Lu/ ∑ Ln≤0.03; 0.0001≤Dy/ ∑ Ln≤0.01.
Wherein, this stoichiometry index is x=0.0001~0.05; The cubic(al)grating parameter value is a=12.1~12.6A, and at the greatest irradiation wavelength X of the orange red light-emitting zone of spectrum=580~610nm, chromaticity coordinates x=0.46, y=0.532.
Wherein, the excitation spectrum of this fluorescent material is located at wavelength X on the sub-band=400~490nm.
Wherein, when the Br content in the increase synthetizing phosphor powder, its luminous radiation wavelength increases from λ=580~610nm.
Wherein, when reaching 85 ℃ of temperature, its luminosity also have under 25 ℃ of room temperatures 92%.
Wherein, when increasing in the furnace charge of introducing or reducing the Br composition, the particle of this fluorescent material has diameter d 50=0.6~2.75 microns, and be ellipse.
Wherein, further can be in conjunction with rare earth oxide element heat treatment, wherein this heat treatment is the 5%H at reducible gas 2+ 95%N 2In, it is Br that interpolation contains degree of oxidation -1The gaseous state of bromine, when the heat treatment temperature from T=800~1400 ℃, adopt Ce (BrO 3) 39H 2O is as activating composition.
At first, the present invention belongs to relevant gadolinium-aluminium garnet family element, the main Gd in the positively charged ion lattice + 3Ion, and and the unconventional garnet phosphor powder composition (please refer to above-mentioned known patent) of previously mainly knowing; The second, interpolation material proposed by the invention comprises large-sized Br -1Ion, the 3rd, material proposed by the invention belongs to the bilinearity garnet, not only has traditional oxonium ion, forms octahedra [AlO 4], but add Br in same second ligand -1, introduce [AlO 4-xBr 2x] form in.
The difference of fluorescent material proposed by the invention is to increase the parameter of lattice from a=12.1~12.16A.And for oxyfluoride (Y 1-xLn x) 3Al 2[Al (O 1-yF 2y) 4] 3, numerical value is a=11.95~11.98A.
Be arranged in and follow its feature of fluorescent material composition proposed by the invention: add at cationic lattice and introduce the rare earth additive, such a additive always has five, and this all additive is arranged in the spectrum of active, such as Tb + 3The interpolation of ion has guaranteed that the excitation of spectra expands fully, and radiation spectrum is on+10nm, gold-plating ion Lu + 3The interpolation excitation spectrum that guaranteed the displacement of fluorescent material shortwave Δ=-5nm.Then the rare earth additive is then as activator, at cerium ion Ce + 3At 5d 2Conversion in the composition has guaranteed that main luminous radiation is positioned at wavelength X=520~800nm place.For Pr + 3Ion is introduced 4f originally, special independently narrow wavestrip radiation areas are from λ=608~612nm, strengthen simultaneously activator Ce + 3Effect.
Emphasize at this, the best atomic fraction of every kind of material is for example and without limitation in the positively charged ion lattice: 0.5≤Gd/ ∑ Ln≤0.95; 0.01<Y/ ∑ Ln≤0.5; 0.01≤Tb/ ∑ Ln≤0.11; 0.01<Ce/ ∑ Ln≤0.045; 0.0001<Pr/ ∑ Ln≤0.01; 0.001<Lu/ ∑ Ln≤0.03; 0.0001≤Dy/ ∑ Ln≤0.01.
The speciality of such a fluorescent material is for the Y that knows 3Al 5O 12: the wavelength shift of Ce standards body sees through the Model Establishment Y of curing reaction 3Al 5O 12-Gd 3Al 5O 12, replaced by gadolinium for the part yttrium, when gadolinium ion concentration reached 40%, wavelength was displaced to λ=569nm from λ=540nm, displacement Δ=29nm.We point out, when adding Br -1During ion, have obvious displacement Δ=10nm, this displacement is presented at Br on the fluorescent material radiation wavelength -1Ion is very effective composition, in addition, also shows to enlarge the known wide λ of half-wave of tradition 0.5=120~128nm.In asymmetric spectral curve, Br -1The peak concentration value on the aluminum oxide tetrahedron equally also is positioned at not the Gauss's radiation curve figure to journey, in the redness of this part, orange luminescence partly has increase.
A uncommon speciality of fluorescent material proposed by the invention, namely in the matrix of fluorescent material with Pr + 3With Ce + 3And Dy + 3Its greatest irradiation spectrum that combines has lifting.
Fluorescent material proposed by the invention is characterized in that: the composition at fluorescent material wherein adds introducing Br -1Ion is that the material of matrix is from 0.0001~0.05 atomic fraction, Br -1Replacement replacement part centers on the oxygen aluminum ion arround the tetrahedron.
Br -1Ion enters in the complicated tetrahedron component, oxonium ion O -2o=1.38~1.40A) and Br -1Br=exist different sizes between 1.90A).
Its substantial advantage of fluorescent material proposed by the invention is characterized in that: add Br in the composition of fluorescent material -1But ion sensitization thing Ce + 3Ion can make activator Ce + 3Ionic concn is less.
Must be pointed out Br in the fluorescent material composition proposed by the invention -1An important characteristic, in chemical formula, change composition O -2← → Br -1An effective electronics filling has appearred.Replace O in the chemical formula medium value -2=2Br -1, in ionic radius, do not have different numerical value, because the proposed Ce that replaces that in stoichiometric equation, adds + 4Replace Gd + 3Ion is according to formula
Ce +4+Br -1→(CeGd)°+(Bro)`
Fluorescent material proposed by the invention also manifests an important characteristic, i.e. the thermostability of relevant fluorescent material.Generally the garnet luminescent phosphor for standard promotes temperature, its luminosity all can reduce, but fluorescent material of the present invention is when temperature increases to 75 ℃, and the brightness that produces has only reduced by 2~4%, when temperature increased to T=85 ℃, the brightness that produces had only reduced by 6~8%.Be similar to such brightness and descend few luminously, this material can be used on medium electric power and the high-power semiconductor instrument equipment.
Fluorescent material proposed by the invention adopts the composition dispersity d that disperses 50=4~8 microns, for adopting the required fluorescent material composition dispersity d of automated production equipment 50=1~2 microns.
It is similarly luminous that certainly such a minitype particle adopts, and the operation here sees through the particle form (formalness) that changes fluorescent material, and this has reduced its usefulness and its atomic arrangement is degenerated, and so can affect its thermostability.
(preparation of F>5001m), the heterojunction of employing absorb size greater than 1.5 * 1.5mm, and the fluorescent material that prepare in such luminescent conversion layer has correct form, and its composition of particle diameter of comparison fluorescent material is d to have individually large optical throughput 50=12~16 microns, in addition, fluorescent powder grain should have d 90〉=20 microns.
All light-emitting phosphor particle form have: miniature particle diameter, medium particle diameter and large particle diameter, and for the accurate fluorescent material combination mechanism of the need of production of complexity tissue.
For the synthetizing phosphor powder miniature and the moderate type discrete form that has proposed by the invention, this has determined medium-sized particle dispersion size and Br -1The dependence relation of amount of ions (concentration) synthetizing phosphor powder particle in air.If Br in the composition -1Concentration is less than 0.5% atomic fraction, so the neutrality line diameter d of particle 50=3~4 microns.If the aerial concentration of B r rises to 1%, and is perhaps higher, its fluorescent material neutrality line diameter can be decreased to 1.5~2.5 microns so.But suppose diameter and the Br of particle -1The concentration of composition synthetizing phosphor powder in air comprises; Br -1Ion in the fluorescent material synthetics solubility and the Br in the atmosphere -1Be directly proportional the Br in the fluorescent powder grain -1When ionic concn is too high, that is to say, work as Br -1Concentration rise always (during τ=1.90A), Br -1Ionic radius is excessive and cause in various degree breaking of scope of fluorescent material, and the minitype particle that occurs can see that in the fluorescent material test report such as Fig. 4 the particle shape of sample 1 is ellipse, and particle diameter reduces.
Realize such advantage at fluorescent material proposed by the invention, its material is created has disciform minitype particle, d 50=0.6~2.75 microns.
Diameter reduces, and increases independently Br -15 synthesis methods of material in stove prepare fluorescent material.
The fluorescent material with garnet framework that all are known generally adopts ceramic process method or gel synthesis method.In initial batching, mostly adopt oxide type Lu 2O 3, CeO 2, Al 2O 3Etc. necessary material, also can adopt oxyhydroxide, same such composition Lu (OH) 3, Ce (OH) 3, Al (OH) 3Deng.Synthesize at original material employing water and spirituous solution composition Y in employing gel technique technique 3(NO 3) 36H 2O Al (NO 3) 39H 2The material of O etc. and similar composition.
Novel synthetizing phosphor powder Technical Architecture proposed by the invention, the composition of employing rare-earth oxidation composition and aluminium in first reagent, for example: Ce (BrO 3) 39H 2O calcines in reducing gas afterwards.
By adding NBr 3And Br 2Bromine gas composition in the composition, stove and the ratio of nitrogen are Br 2: H 2: N 2=0.1: 4.9: 95~1: 4: 95, furnace temperature was T=800~1300 ℃, kept 6~16 hours, took out batching after the cooling, with dilution acid solution (HCl, HNO 3, H 3PO 4Deng) pickling.
The synthetic concrete special component of fluorescent material proposed by the invention is for example described in the table 1.
Table 1
The chemical composition of fluorescent material Greatest irradiation spectrum nm Predominant wavelength nm Relative luminous brightness The wide λ of half-wave 0.5 Colour temperature K
1 (Gd 0.7Y 0.215Tb 0.04Lu 0.01Ce 0.03Dy 0.005 ) 3Al 2[Al(O 3.99Br 0.02) 4] 3 571.9 581 24276 128 2858
2 (Gd 0.75Y 0.125Tb 0.08Lu 0.01Ce 0.03Dy 0.005 ) 3Al 2[Al(O 3.98Br 0.04) 4] 3 581.8 581 24703 129 2873
3 (Gd 0.7Y 0.21Tb 0.04Lu 0.01Ce 0.03Dy 0.005P r 0.005) 3Al 2[Al(O 3.99Br 0.02) 4] 3 609.4 582 23581 126 3116
Below, please in the lump with reference to Fig. 1~Fig. 5, in order to the influence of the composition of explaining fluorescent material proposed by the invention.Wherein, Fig. 1 is the spectrogram of sample 1 in the table 1; Fig. 2 is the spectrogram of sample 2 in the table 1; Fig. 3 is the spectrogram of sample 3 in the table 1; Fig. 4 is the particle shape figure of sample 1 in the table 1; The configuration diagram of Fig. 5 the present invention's photodiode.
As shown in Figure 5, it illustrates the configuration diagram of the made photodiode of fluorescent material according to the present invention.Wherein, this photodiode comprises two pins 2,3, one InGaN heterojunction semiconductor 4 (hereinafter referred to as heterojunction semiconductor), a taper luminous 5 and luminescent conversion layer 7, this luminescent conversion layer 7 is combined into by fluorescent powder grain 6 and polymkeric substance (not shown), and ball optic lens 8 further is equipped with on the top layer of this photodiode.Its interval of radiant output for exposure is between the transparent luminescent conversion layer 7 of ball optic lens 8 and polymkeric substance.
The photodiode that uses fluorescent material proposed by the invention begins to send the blue light that optical wavelength is λ=455nm when auxiliary voltage value U=3.0~3.9V.Its amount of luminescence is depending on permeability, and through the electric current of this heterojunction semiconductor 4, generally this parameter is I=20~350mA.
Blue light presents with fluorescent powder grain 6 and cooperatively interacts, be distributed on the polymer light-emitting conversion layer 7, at this moment fluorescent powder grain 6 sends the light of the orange-red λ of having=580nm, and having orange-yellow luminous combining through the first step blue light that this heterojunction semiconductor 4 is sent with this luminescent conversion layer 7, its result will present warm white hair light.Such luminescence distribution has the pyramid type of help luminescent conversion and sees through ball optic lens 8 at all faces.
Below with this luminescent conversion layer 7 of more detailed description.The surface that this a part of instrument is positioned at this heterojunction semiconductor 4 is comprised of 2 parts: polymkeric substance photic zone (not shown) and fluorescent powder grain 6 proposed by the invention distribute.The present invention checks with different tissues and combines in polymeric film layer: Resins, epoxy (epoxy), vinylformic acid ethene and organosilicon polymer.Point out that best polymkeric substance from silica gel, has molecular mass M=15000~25000 carbosilane units.
Same regulation, the weight ratio 8~75% of this fluorescent powder grain 6 in luminescent conversion layer 7.Have so strong luminescent conversion layer 7 again blue ray radiation guaranteed necessary warm white radiant light.
Be on the matrix at this heterojunction semiconductor 4, with luminescent conversion layer 7, it is characterized in that: the fluorescent material 6 in this luminescent conversion layer 7 is in the optical clear polymkeric substance that is distributed in take silica gel as matrix, have molecular mass M=15000~25000 carbosilane units, the weight ratio 8~75% of this fluorescent powder grain 6 in this luminescent conversion layer 7.
Contain the batching framework of specialty in these luminescent conversion layer 7 components on the top layer of heterojunction semiconductor 4.By selecting such sample in polymkeric substance and the fluorescent powder grain 6, all radiation faceted pebble and end face cover the uniform polymeric film layer of concentration.Ratio between polymkeric substance composition and the fluorescent powder grain 6 is 1 to 10 centipoise (cP).The optimum thickness of this luminescent conversion layer 7 is for example and without limitation to 80~160 microns, points out simultaneously, and this luminescent conversion layer 7 should have equal thickness.
This achievement that reaches in photodiode is characterized in that: realize having the same thickness form for photodiode, best top layer walled thickness is for example and without limitation to 80~160 microns.
The focus of this ball optic lens 8 should be direct, its lens centre and heterojunction semiconductor 4 main radiating surfaces are connected, 8 of the top layer of this heterojunction semiconductor 4 and semisphere optical lenses have been inserted optical clear polymkeric substance (not shown), its specific refraction that has is n 〉=1.45, and this has guaranteed the impact strength (weather resistance) of high machinery and photodiode.
It is characterized in that of above-mentioned white light emitting diode: its main radiating surface center is direct, combine the space of this ball optic lens 8 and be filled in the specific refraction that has n 〉=1.45 between the transparent polymer on luminescent conversion layer 7 top layers with ball optic lens 8.
Below point out, the present invention's white light emitting diode has at white and orange-yellow visible spectrum zone body, has the warm white radiation, its chromaticity coordinates x=0.46 ± 0.02, y=0.45 ± 0.03, blue ray radiation sees through electric current 100~500mA, operating voltage U=3.0~3.9V from I=100~500c d for 2 θ=60 ° lower photodiode.
Change optical throughput from the photodiode that the present invention proposed for the luminescence technology of specialty, it is 1 watt for exciting power, it is characterized in that: the power for photodiode is that its optical throughput of 1 watt-hour is F=68~98 lumens, the colour temperature T=2500 of luminescent spectrum~4500K.
Although the present invention discloses as above with preferred embodiment; so it is not to limit the present invention; anyly have the knack of this skill person; in the spirit that does not break away from the present invention and scope; when the change that can do a little and retouching, so the present invention's protection domain attached claim person of defining after looking is as the criterion.
Description of drawings
Brief description of drawingsfig:
Pin 2,4 tapers of 3 heterojunction semiconductors are sent out
Light 5 fluorescent powder grains 6 luminescent conversion layers 7
Ball optic lens 8
The primary clustering nomenclature:
Fig. 1 is a schematic diagram, and it illustrates the spectrum schematic diagram of sample 1 in the table 1.
Fig. 2 is a schematic diagram, and it illustrates the spectrogram of sample 2 in the table 1.
Fig. 3 is a schematic diagram, and it illustrates the spectrogram of sample 3 in the table 1.
Fig. 4 is a schematic diagram, and it illustrates the particle shape figure of sample 1 in the table 1.
Fig. 5 is a schematic diagram, and it illustrates the configuration diagram of the present invention's photodiode.

Claims (14)

1. bromide fluorescent powder, take rare-earth oxidation garnet element as the basis, it is characterized in that: this fluorescent material adds bromide anion in garnet ingredient, and the chemical equivalent formula of its composition is
(∑Ln) 3Al 2[Al(O 1-xBr 2x) 4] 3
∑ Ln=Gd and Y and Lu and Dy and Ce and Pr and Tb and x=0.0001~0.05 wherein,
Atomic fraction during wherein this fluorescent material forms mainly contains:
0.5≤Gd/∑Ln≤0.95;0.01<Y/∑Ln≤0.5;
0.01≤Tb/∑Ln≤0.11;0.01<Ce/∑Ln≤0.045;0.0001<Pr/∑Ln≤0.01;
0.001<Lu/∑Ln≤0.03;0.0001≤Dy/∑Ln≤0.01。
2. bromide fluorescent powder as claimed in claim 1, wherein this stoichiometry index is x=0.0001~0.05; The cubic(al)grating parameter value is a=12.1~12.6A, and at the greatest irradiation wavelength X of the orange red light-emitting zone of spectrum=580~610nm, chromaticity coordinates x=0.46, y=0.532.
3. bromide fluorescent powder as claimed in claim 1, its excitation spectrum are located at wavelength X on the sub-band=400~490nm.
4. bromide fluorescent powder as claimed in claim 1, wherein during the Br content in increasing synthetizing phosphor powder, its luminous radiation wavelength X rises to 610nm from 580.
5. bromide fluorescent powder as claimed in claim 1, wherein when reaching 85 ℃ of temperature, its luminosity also have under 25 ℃ of room temperatures 92%.
6. bromide fluorescent powder as claimed in claim 1, wherein when increasing in the furnace charge of introducing or reducing the Br composition, the particle of this fluorescent material has diameter d 50=0.6~2.75 microns, and be ellipse.
7. bromide fluorescent powder as claimed in claim 1, it further can be in conjunction with rare earth oxide element heat treatment, and wherein this heat treatment is the 5%H at reducible gas 2+ 95%N 2In, it is Br that interpolation contains degree of oxidation 1-Gaseous state, when the heat treatment temperature from T=800~1400 ℃, adopt Ce (BrO 3) 3.9H 2O is as activating composition.
8. warm white light light-emitting diode (LED), it is to become matrix with the InGaN heterogeneous semiconductor, and scribble a luminescent conversion layer, it is characterized in that: this luminescent conversion layer has as described in claim 6 bromide fluorescent powder, the size distribution of described ellipse is in the transparent polymer take organic silica gel as matrix, and its molecular mass M=15000~25000 carbosilane units and the weight ratio of this fluorescent powder grain in this luminescent conversion layer are 8~75%.
9. warm white light light-emitting diode (LED) as claimed in claim 8, wherein this luminescent conversion layer has uniform thickness, and the thickness of its radiating surface and side is 80~160 microns.
10. warm white light light-emitting diode (LED) as claimed in claim 8, wherein the form that is centrosymmetric of its main radiating surface distributes, and sees through a ball optic lens, and the specific refraction that produces is n 〉=1.45.
11. warm white light light-emitting diode (LED) as claimed in claim 8, wherein for the radiation that is positioned at orange red spectrum zone, its chromaticity coordinates value x=0.46 ± 0.02, y=0.45 ± 0.03, I=100~500 candle lights during in 2 θ=60 °, the operating voltage of institute's employing instrument is 3.0~3.9V.
12. warm white light light-emitting diode (LED) as claimed in claim 8 is 1 watt-hour in electric power wherein, its optical throughput 68~98 lumens.
13. warm white light light-emitting diode (LED) as claimed in claim 8, wherein the heating casing temperature reaches T=85 ℃, its colour temperature T=2500~4500K.
14. warm white light light-emitting diode (LED) as claimed in claim 8, it is drilled colour system and counts R 〉=70.
CN2008101614927A 2008-10-06 2008-10-06 Warm white LED and its bromide fluorescent powder Expired - Fee Related CN101368102B (en)

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