CN101262038B - Warm white semiconductor and fluorescent powder with red garnet structure - Google Patents
Warm white semiconductor and fluorescent powder with red garnet structure Download PDFInfo
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- CN101262038B CN101262038B CN2008100890065A CN200810089006A CN101262038B CN 101262038 B CN101262038 B CN 101262038B CN 2008100890065 A CN2008100890065 A CN 2008100890065A CN 200810089006 A CN200810089006 A CN 200810089006A CN 101262038 B CN101262038 B CN 101262038B
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Abstract
The invention provides a warm white light semiconductor and a phosphor with the structure of red spectrum garnet; the warm white light semiconductor is at least provided with a semiconducting heterojunction and a light emitting conversion layer; the semiconducting heterojunction contacts the light emitting conversion layer; the warm white light semiconductor is characterized in that a warm white light emitting system consists of three spectrums that is associated with catalysts Ce and Pr in inorganic phosphor of the light emitting conversion layer and the radiation of Dy; the chemical quantitative formulae of the phosphor is (Y2-x-y-z-pGdxCeyPrzDypO3)1.5 plus or minus alpha(Al2O3)2.5plus or minus beta, wherein, x is more than or equal to 0.001 and less than or equal to 0.4, y is more thanor equal to 0.01 and less than or equal to 0.2, z is more than or equal to 0.0001 and less than or equal to 0.1, p is more than or equal to 0.0001 and less than or equal to 0.1, alpha is more than orequal to 0.01 and less than or equal to 0.1 and beta is more than or equal to 0.01 and less than or equal to 0.1. In the invention, the color coordinates of the warm white semiconductor are x being more than or equal to 0.405 and less than or equal to 0.515, y being more than or equal to 0.355 and less than or equal to 0.550, correction color temperature is T being less than or equal to 4000K, color rendering index R being more than or equal to 80 and major wave length lambda being more than or equal to 565nm.
Description
[technical field that the present invention belongs to]
The present invention system is about a kind of materialogy field, and the fluorescent material of being touched upon is applied in the production of warm-white semiconductor (warm white illumination light-emitting diode).Used luminescent conversion layer in this light-emitting diode, the warm-white light-emitting of this light-emitting diode is made up of three bands, is respectively λ
I Max=450 ± 25nm, λ
II Max=560 ± 20nm and λ
III Max=610 ± 3nm, wherein the brightest red zone and the catalyst P r in the fluorescent material
+ 3Relevant.
[prior art]
Though global semiconductor electronics has developed more than 60 year, solid state light emitter only realized 10 years; Although the works of relevant light-emitting diode (LED) just begins known from eighties of last century the sixties, but the appearance that about the research of solid state light emitter is the works [" Blue laser " Springer Verlag, 1997] with S.Nakamura is sign (please refer to S.Nakamuura and.Blue laser.Springer Verl.Berlin1997).
Initial light-emitting diode is as signal and Warning Mark, this develop in " light-emitting diode " book (please refer to V.Abramov et.USSR 1977).The establishment of first developing stage of light-emitting diode is the little radiator of area to have occurred, and at this moment the optical tech parameter of light-emitting diode is not high, it is characterized by: 1. for half-value angle 2 θ=30 °, axial light intensity is little, is 100-500mcd (milli candela); 2. luminous flux is not high, is 0.1-0.2lm; 3. average life span is 10
4Hour etc.
Created owing to have the assembly of quantum size member, so the parameter of light-emitting diode has obtained substantive raising.Its feature is increased to: 1. for 2 θ=30 °, axial light intensity is 100cd; 2. chip area is 100 * 200m
2, luminous intensity is brought up to 5-10lm, when chip area is 1 * 1.5mm
2The time be 200-300lm; 3. the life-span extends to 10
5Hour; 4. luminous efficiency is 80-1001m/W.
Although substantial growth has appearred in the technical parameter of semiconductor lighting assembly, still there are some problems, these problems need us to scrutinize and conscientiously discuss.The first,, determine by color rendering index (Ra=95) about high-quality light.In the place of retention of the showroom of press, textile industry and jewelry production and museum, gallery and paint, this problem is extremely important.The second, the lighting environment of being accustomed to during evolution with human eye is relevant, makes it reproduce high temperature white heat object at work: such as burn red tungsten filament in the carbon in the candle wick, bonfire, Edison's light source.The luminance temperature of all these objects is T≤4000K.
If the solution of first relevant look transmission problem has the light-emitting diode of GaInN basis heterojunction (P-N connects face) by application, light-emitting diode emission near UV light wherein, and use three primary colors RGB fluorescent material to be achieved simultaneously; The solution of second problem then depends on the support of many patents so.One of these problems are that the light emitting diode construction of the luminous composition of binary that proposes of S.Schimisu (please refer to the United States Patent (USP) US 5 that authorizes to people such as S.Schimisu, 988, No. 925 7.12.1999), wherein heterojunction is launched the blue light of 450-475nm and is excited (Y
1-x-yGd
xCe
y)
3Al
5O
12The strong sodium yellow photoluminescence of forming of inorganic fluorescent powder.The mixing of blue (coming from heterojunction) and yellow (coming from fluorescent material) two kinds of bright bands accords with newton's complementary colours principle, and obtains white light.
These initial led configurations (please refer to 5,988, No. 925 7.12.1999 of United States Patent (USP) US that authorize to people such as S.Schimisu) have guaranteed so-called " cold white light ", and its colour temperature is T＞10000K.This case is adopted these known tip assemblies as reference object, they still have some substantial defectives, and its main cause comprises: (Y
1-x-yGd
xCe
y)
3Al
5O
12Lack red during the radiation of standard fluorescence powder is formed fully.By a large amount of experiments, the redness that has increased in the fluorescent material radiation is formed, and in the United States Patent (USP) that the inventor the proposed US2005/0088077 of this case A1 patent application case (please refer to the United States Patent (USP) US 2005/0088077 A1 patent application cases that the people proposed such as N. Soschin), develop, this patent application case has proposed the novel dual catalyst prescription about garnet phosphor powder, has comprised and traditional catalyst Ce
+ 3Arranged side by side second kind is added catalyst P r
+ 3, main in addition cation lattice elements-yttrium and gadolinium have accurate ratio.The high-quality fluorescent material of being discussed in this patent application case can reduce colour temperature to T≤5500K, and makes the light-emitting diode color coordinate reach 0.32≤x≤0.36,0.32≤y≤0.37.Because these light-emitting diodes have stable production technology and high optical tech parameter, thereby they have obtained to use widely.
Although known light-emitting diode has the advantage of having discussed, they still have some defectives.The first, in light-emitting diode under high colour temperature T 〉=5500K, eyes are easy to generate fatigue, and visual sensitivity is delayed etc.The second, with everyday objects such as flower, fruits and vegetables in the color transmission situation under compare, traditional incandescent source colourity distorts easily.These substantial defectives require us to solve as early as possible, however the prescription that in addressing these problems process, is adopted provisional often and of low quality.For example, with (Ca, Sr) the bi-component compound of the S:Eu fluorescent material replacement (Y that are filled with red radiation
1-x-yGd
xCe
y)
3Al
5O
12Single-component fluorescent powder.This compound durability is not high, can only make light-emitting diode obtain necessary warm white hair light in non-stop run in several thousand hours.Always have some not very successful performances such or that proposed like that in the light-emitting diode with warm white hair light current industrial producing, even can overcome fully without any a world-class optical tech company.
Just as is known, when come from the blue of heterojunction and come from light-emitting diode yellow or orange-yellow between balance when changing, luminous efficiency reaches minimum value sometimes, this value just in time is positioned at
The Tc zone.If now for
Known luminescence efficient is η=90-150lm/W, must create the light-emitting diode of luminous efficiency η＞80-85lm/W so for the warm white hair light of standard.
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention is the fluorescent material that a kind of warm white semiconductor is provided and has the red spectrum garnet structure, this warm-white semiconductor is the warm white radiation light-emitting diode with optical tech meaning, and its colour temperature is T≤4000K.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of warm white semiconductor and has the fluorescent material of red spectrum garnet structure, the radiation of this warm-white semiconductor has orange clearly-red tone, can show suitable radiation color coordinate.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of warm white semiconductor and has the fluorescent material of red spectrum garnet structure, and this warm-white semiconductor has sufficiently high luminous efficiency.
For achieving the above object, the invention provides a kind of warm white semiconductor, it has a semiconductor heterojunction and a luminescent conversion layer, this heterojunction semiconductor contacts with this luminescent conversion layer, it is characterized in that: this warm-white light-emitting system is made up of three kinds of bands, it is relevant with catalyst Ce, Pr and the radiation of Dy in the inorganic fluorescent powder of this luminescent conversion layer, and the chemometric equation of this fluorescent material is (Y
2-x-y-z-pGd
xCe
yPr
zDy
pO
3)
1.5 ± α(Al
2O
3)
2.5 ± β, 0.001≤x≤0.4,0.01≤y≤0.2,0.0001≤z≤0.1,0.0001≤p≤0.1,0.01≤α≤0.1 and 0.01≤β≤0.1 wherein.
For achieving the above object, the invention provides a kind of fluorescent material with red spectrum garnet structure, it is used for the warm white semiconductor, and its chemometric equation is (Y
2-x-y-z-pGd
xCe
yPr
zDy
pO
3)
1.5 ± α(Al
2O
3)
2.5 ± β, 0.001≤x≤0.4,0.01≤y≤0.2,0.0001≤z≤0.1,0.0001≤p≤0.1,0.01≤α≤0.1 and 0.01≤β≤0.1 wherein.
[accompanying drawing summary]
Fig. 1 is the structural representation with warm-white semiconductor (light-emitting diode) of red spectrum mark of the present invention, and wherein 1 is heterojunction semiconductor; 2,3 is lead; 4 is heat-conducting base; 5 is conical reflector; 6 is luminescent conversion layer; 7 is inorganic fluorescent powder; 8 are the optical frames lid; 9 is the light transmission medium conversion layer; 10 is the light-emitting diodes pipe electrode.
Fig. 2-the 4th, the optical color parameter analytical test report of fluorescent material of the present invention.
[execution mode]
At first, the objective of the invention is to eliminate the shortcoming of above-mentioned fluorescent material and warm-white light-emitting diode.Please refer to Fig. 1, it has illustrated the structural representation with warm-white semiconductor (light-emitting diode) of red spectrum mark of the present invention.As shown in the figure, the warm-white semiconductor (light-emitting diode) with red spectrum mark of the present invention comprising: semiconductor heterojunction 1; Lead 2,3; One heat-conducting base 4; One conical reflector 5 and a luminescent conversion layer 6.Wherein, this heterojunction semiconductor 1 is placed on this heat-conducting base 4; This heat-conducting base 4 is for example and without limitation to and comes from Al
2O
3Sapphire heat-conducting base, and 4 of this bases are positioned on this conical reflector 5.
Wherein, this heterojunction semiconductor 1 contacts with this luminescent conversion layer 6, it is characterized in that: this warm-white light-emitting system is made up of three kinds of bands, and it is relevant with catalyst Ce, Pr and the radiation of Dy in the inorganic fluorescent powder 7 of this luminescent conversion layer 6, and the chemometric equation of this fluorescent material is (Y
2-x-y-z-pGd
xCe
yPr
zDy
pO
3)
1.5 ± α(Al
2O
3)
2.5 ± β, wherein
0.001≤x≤0.4，0.01≤y≤0.2，0.0001≤z≤0.1，
0.0001≤p≤0.1,0.01≤α≤0.1 and 0.01≤β≤0.1.
Wherein, these three kinds of bands are respectively λ
I Max=450 ± 25nm, λ
II Max=560 ± 20nm and λ
III Max=610 ± 3nm.
Wherein, this inorganic fluorescent powder 7 has chemometric equation Y
2.66Gd
0.32Ce
0.03Pr
0.005Dy
0.005Al
5.02O
12.06, and in this inorganic fluorescent powder 7 atomic fraction than Ce/ (Ce+Pr+Dy) 〉=0.75, Pr
+ 3Form the third emission band, and be suitable for ' D2-' C4 internal transitions.
Wherein, the main active ions Ce of this inorganic fluorescent powder 7
+ 3Spectrum red-label and Pr on the long wave direction of radiation
+ 3In ' radiation of D2-' C4 internal transitions is relevant, Pr
+ 3Concentration is Ce
+ 33-25%.
Wherein, the color coordinate of this warm-white semiconductor (light-emitting diode) is 0.405≤x≤0.515,0.355≤y≤0.550, colour temperature T≤4000K, color rendering index R 〉=80, dominant wavelength λ 〉=565nm.
Warm-white light-emitting diode electrode of the present invention provides voltage U=3.2-3.4V, and when electric current I=20mA, In-Ga-N heterojunction 1 produces bright electroluminescence.The optical tech parameter of this phenomenon provides in Fig. 2.All data are in that " Sensing " obtains on the spectroradiometer simultaneously.Obtain the spectrum picture of experiment apparatus by scanning in the zone of 380-800nm.Image is made up of two groups of spectral bands, and one of them has spectrum maximum λ=465nm and interrelates with 1 radiation of In-Ga-N heterojunction, and another is a broadband, and is relevant with the luminescent conversion layer radiation of heterojunction surface and contacts side surfaces.
The necessary synthesis condition that in the invention narration of back, argumentation is used for the high-quality fluorescent material 7 of warm-white semiconductor (light-emitting diode).The first, the present invention has pointed out to be used for known current seven kinds of basic chemiluminescence powder families of warm-white semiconductor on the structure: the A of 1.ZnS-ZnSeCu type
IIB
VICompound; 2.CaGa
2S
4: the A of Eu type
II(Me
III)
2(B
VI)
4Compound; 3. synthetic garnet (∑ Ln)
3Al
5O
124. has Me
3Al
2(SiO
4)
3The fluorescent material of nature mineral stone garnet chemometric equation; (5.Me ∑ Ln) Al
7O
16The poly-aluminate class of type; 6. metal silicate; 7.N
-3Or N
-3 4Polyanionic polymer.
For some silicate, sulfide and garnet, they have very high radiation lumen-equivalent value, are embodied in, and minimum efficiency is showed by three kinds of above-mentioned fluorescent material families in the light-emitting diode, and the centre position is by N
-3Or N
-3 4Polymeric material on the basis occupies, and at this moment big Stokes shift can reduce the gross efficiency value.Consider that sulphide fluorescent material does not always have high-durability in real assembly, therefore a large amount of employings have the fluorescent material of garnet structure and the change type of various silicate and polysilicate in industry, the quantum efficiency of these fluorescent material families has substantive distinguishing features, for silicate, be characterized as η=70-75%, for garnet phosphor powder, be η=95%.
In the present invention, as main inorganic fluorescent powder 7, synthetic garnet (∑ Ln) has been proposed
3Al
5O
12Host material, wherein ∑ Ln=Y, Gd, Ce, Pr and Dy, this material also develop in [Luminescent material] book (please refer to G Blasse etand.Luminescent material.Springer Verlag.Berlin 1994) that G.Blasse proposed and as the very effective radiant body that is used for the electron ray instrument.The main advantage of this instrument comprises very large information area processing speed (burgundy is applied to satellite photo) 50MHz.Y in the natural radiation body
3Al
5O
12: Ce fluorescent material can guarantee this high speed information processing speed, and its spectrum maximum is λ=538nm, and be τ persistence
e≤ 120ns.For the saturated interpolation Gd that needs of color that increases fluorescent material 7
+ 3, its emission spectrum is to yellow spectrum zone displacement, Lu
+ 3And/or Tb
+ 3Emission spectrum is to shortwave blueness-green spectral zone displacement.In industry, good known research material had just appearred before Japanese light-emitting diode researcher Mr. S.Schimisu, thus unique priority of being emphasized of these white light-emitting diodes producer and simultaneously synthetic garnet " discovery " it seems and definitely can't restrain basis.
Point out at the same time,, can adopt the garnet of two kinds of different chemical metering formula: 1. first kind of compound (∑ Ln) proposed by the invention for fluorescent material 7
3Al
5O
12And 2. natural mineral stone garnet formula Me
II 3Me
III 2Si
4O
12The present invention will point out the difference of these two kinds of compound properties, quote these data simultaneously in table 1.
Table 1
| Parameter | (∑Ln) 3Al 5O 12 | Me II 3Me III 2Si 4O 12 |
| Atomic quantity in the formula | 20 | 20 |
| |
5 | 5 |
| The cationic oxidation degree | +3 | +2，+3 |
| Anion oxidation degree | +3 | +4 |
| Lattice types | Cube | Cube |
| Spatial group | Ia3d | Ia3d |
| Lattice parameter | a≤12A | a≥12A |
| Catalyst: Ce, Eu ion isomorphous volume | Be lower than 10
20 |
10 21Atom |
| Form | Six sides-dodecahedron | Six sides-dodecahedron |
As pointing out relatively that by above-mentioned the garnet crystal chemistry characteristics of two kinds of same structure different formulas are very similar.Here the cation characteristics are, for the formula, can add IIA family element such as Mg, Ca, Sr for " nature " in molecule, at this moment only add the element of oxidizability+3 for synthetic molecules.Similarly anion lattice is also different, in lattice for natural formula S i
+ 4More preponderate, for composite formula Al
+ 3(Ga
+ 3More rare) more important.For natural garnet, lattice parameter characteristics isomorphous volume reduce and with active ions (Ce normally
+ 3Or Eu
+ 2) concentration proportional.This defective can embody in radiation to some extent, because usually along with the reduction of catalyst concn, fluorescent material 7 radiation intensity also decrease.
Based on above reason for warm white semiconductor proposed by the invention, such as but not limited to warm white radiation light-emitting diode (to call light-emitting diode in the following text), the preferential fluorescent material 7 that comes from synthetic medium that uses when selecting material, these fluorescent material 7 can be put into multi-catalyst yttrium-gadolinium-aluminium garnet family.Used in the present inventionly when synthetic graphicly be: from small to large or from the nanometer to the micron.
Below will explain these graphic and traditional adopt graphic, the reagent that comes from micron-scale in these are graphic is synthetic by tens kinds of micro materials powder, and is crushed to micron-scale.With regard to of the present invention synthetic graphic with regard to, initial reagent uses the nano-scale form
By professional medium they are machined to d=1-2 μ m size in the heat treatment process subsequently.Nanometer proposed by the invention → micron transforms graphic substantial advantage and is to lack in the past graphic middle necessary pulverizing process.Its advantage not only shows this respect.Just as pointed out in the present invention, fluorescent material 7 powder have obtained solid shape, mainly are six sides-dodecahedrons.In addition, fluorescent material 7 powder of the present invention are monocrystalline, i.e. the crystallite oriented structure.Because fluorescent material 7 powder of the present invention have little monocrystalline, thereby have high optical lens photosensitiveness, in Fig. 3, can see, quoted the photo that fluorescent material proposed by the invention 7 powder come from 600 times of the amplifications of display screen therein.Because high optical lens photosensitiveness heterojunction semiconductor 1 navy blue exciting light enters fluorescent material 7 powder, therefore in powder, take place actively to interact and cause the luminescence generated by light that they are strong with luminescence center.The high optical lens photosensitiveness of powder has determined high photon efficient, is η=0.95.
The present invention also points out the characteristic that its employed fluorescent material 7 is formed, in fact this fluorescent material can be used for hard-core concentration part (calculating by quality is 5-45%) in luminescent conversion layer 6, for most of known product in the world, think that concentration is 12-16%.The comminuted powder concentration of fluorescent material 7 can not obtain white light when big, and the gold-tinted deepening that radiation obtained, and tarnishes.This is important process characteristics of forming the fluorescent material proposed by the invention of light-emitting diode conversion layer 6, and it is characterized in that: above-mentioned fluorescent material 7 exists with solid shape printing opacity form of powder, has six sides-dodecahedral shape, and average-size is 1.5≤d
Cp≤ 2.5 μ m, specific surface are S
Yd〉=3610
3Cm
2/ cm
3, when so guaranteeing in light-emitting diode proposed by the invention to produce warm white radiation in this luminescent conversion layer 6 mass concentration of fluorescent material 7 be 5-65%.Thereby, the characteristics that showing in warm white source proposed by the invention not only are the characteristics of light emitting diode construction-parameter, the solid shape that also comprises fluorescent material 7 powder, they have very big optical transmittance, the concentration of polymerization-fluorescent material 7 compounds has wide scope simultaneously, they form the matrix of luminescent conversion layer 6, and interact with InGaN shortwave radiation heterojunction 1.
Below will discuss the composition of the fluorescent material 7 in the light-emitting diode that adds the present invention's proposition in detail.As above pointed, this fluorescent material 7 is that the oxygen garnet compound that contains with rare earth element and aluminium is matrix (a known fluoride garnet not use), comprises " gently " Ce of family, Pr simultaneously in employed rare earth element is formed; Also have " weight " Gd of family, Y, Dy.The essential distinction sign of garnet phosphor powder 7 used in the present invention is that this fluorescent material 7 has controllable stoichiometry degree when synthesizing, and that is to say the ratio of divided oxide quantum count, promptly forms ∑ (Lu
2O
3) cation lattice and the Al that forms anion lattice
2O
3The ratio of molecular amounts.If for traditional garnet ratio ∑ Lu
2O
3/ ∑ Al
2O
3Be 3: 5, be suitable for compound proposed by the invention so, first, this value do not have integer value; The second, can change, divide the rate augment direction, also have Al equally as cation oxide
2O
3Anion oxidation thing divides the rate augment direction, also comprises " control stoichiometry " of the present invention.
On the other hand, in order to increase the quantum efficiency of fluorescent material proposed by the invention 7, anion oxidation thing divides rate should surpass 5.0 units.The present invention points out, stoichiometry batching ∑ Lu
2O
3/ ∑ Al
2O
3=3: during 5=0.6, the quantum efficiency of prepared fluorescent material 7 is no more than η≤0.89 usually.Cause the reason of this phenomenon a lot, the present invention does not prepare to enumerate one by one.If stoichiometry index β is increased 0.01 fen rate, the photon efficient of fluorescent material 7 increases 1% so, when keeping constant value, and stoichiometry exponential quantity α=0.On the other hand, the present invention points out that stoichiometry index α reduces to show the wide value of spectrum half-wave of fluorescent material 7 radiation.If stoichiometric composition has the wide λ of half-wave
0.5=118nm, so along with the cation mole fraction reduces α=0.005, the little 0.5-0.8nm of radiation spectrum half-wave reductions.In the present invention about the wide smallest reduction of emission band half-wave to λ
0.5=115nm.Yet at this moment observing fluorescent material proposed by the invention 7 luminosity part losses is Δ L=2-4%.Thereby as preferred plan, the present invention adopts stable stoichiometry exponential quantity α, is α 〉=0.01.This result who determines can accurately calculate second index β value, and its increase is no more than 0.03 mole fraction.The garnet phosphor powder 7 quantity formula that drawn in the concrete chemometric equation for fluorescent material proposed by the invention 7 are Y
2.66Gd
0.32Ce
0.03Pr
0.005Dy
0.005Al
5.02O
12.06Pure (Y, Ce)
3Al
5O
12Compound has spectrum maximum wavelength X=538nm.The present invention points out that adding gadolinium ion in composition can be moved to λ=558nm with the spectrum maximum.Concentration value [Ce]=0.03 atomic fraction can be with spectrum maximum displacement 2nm to λ=560nm.Increased the absorption of fluorescent material 7 powder that be activated simultaneously for heterojunction semiconductor 1 radiation first order energy.Point out in the cation lattice superfluous Al as the present invention
2O
3Can improve luminosity and broadening Ce to a certain degree
+ 3The radiation half-wave is wide.
Must be pointed out Dy that the present invention adds
+ 3Effect, it can broadening Ce
+ 3Emission spectrum and to a certain degree increase its brightness (+2-4%).Yet, pointed as the present invention, Dy
+ 3Main effect not only comprises for Ce
+ 3Sensibilization, and increase second kind of catalyst ion Pr being added
+ 3Radiation efficiency.The present invention points out in front, adds Ce in the composition
+ 3And Pr
+ 3Produce good effect, and become solution of the present invention.Yet Pr
+ 3Radiation does not increase in known combination can band strength, this and Pr
+ 3In internal transitions ' D2-C4 is relevant.(Y, Gd, Ce)
3Al
5O
12In the garnet at Ce
+ 3Can observe Pr on the emission spectrum long wave wing
+ 3Correlation peak is little.The present invention points out Pr first
+ 3Radiation intensity can increase to has maximum signal amplitude degree.Produced thundering result for this reason, comprised that the fluorescent material 7 spectrum maximums that yttrium-gadolinium proposed by the invention-aluminium is formed are positioned at λ=609.7nm wavelength.This spectrogram is also had no talent and is observed (please refer to Fig. 4) before the present invention.Because Pr
+ 3Luminous intensity, substantive " center of gravity " displacement has taken place in fluorescent material 7 emission spectrum of λ=575nm.This before high " dominance " value same nobody in the garnet radiation observe.Pr
+ 3At Ce
+ 3And Dy
+ 3The red radiation branch rate that is increased in the combination and the result of acquisition thereof make the correction color temperature value of pointing out in the present invention be decreased to T≤4000K.
These superiority are achieved in the fluorescent material 7 with garnet crystalline texture among the present invention, it is characterized in that, above-mentioned material is suitable for chemometric equation Y
2.66Gd
0.32Ce
0.03Pr
0.005Dy
0.005Al
5.02O
12.06, the atomic fraction of main catalyst is than being Ce/ (Ce+Pr+Dy) 〉=0.75, Pr simultaneously
+ 3Strong the 3rd band that is suitable for its internal electron transition that radiation forms.Just as pointed out in the present invention, the viewed spectrogram of the present invention is unusual and never discussed in above-mentioned patent and scientific and technical literature.Pr
+ 3The spectrum maximum is improved, as pointing out for example have superfluous Al in the series of factors results of interaction
2O
3The stoichiometry of fluorescent material 7 lattices that anion is formed is added Dy
+ 3And sensitization Ce
+ 3And Pr
+ 3, the main emission spectrum of fluorescent material 7 narrows down simultaneously.In the interactional process of all of these factors taken together of fluorescent material proposed by the invention 7, obtained bright spectrum red-label, these materials are distinguished (please refer to Fig. 4) easily by Optical Analysis Method simultaneously.
Fluorescent material proposed by the invention 7 with garnet structure has these remarkable advantages, it is characterized in that: bright spectrum is marked at main Ce
+ 3On the long-wave radiation direction with Pr
+ 3In internal transitions ' the inner tracks electron radiation of D2-' C4 interrelates, Pr wherein
+ 3Concentration is Ce
+ 3The 3-25% of concentration.Like this, because the light-emitting diode proposed by the invention and the advantage of luminescent conversion layer 6 thereof, important science-technical problem is solved, and can create stable on technology and warm-white light-emitting diode efficiently, and its optical tech parameter is that brightness and luminous flux are all very high.
In sum, warm-white light-emitting diode with fluorescent material of red spectrum garnet structure of the present invention has the optical tech meaning, its colour temperature is that T≤4000K, its radiation have orange clearly-red tone, can show suitable radiation color coordinate and have advantages such as sufficiently high luminous efficiency, therefore, really can improve the shortcoming of known warm white diode.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to limit the present invention; anyly have the knack of this skill person, without departing from the spirit and scope of the invention when change and the retouching that can do a little, so protection scope of the present invention is when looking being as the criterion that accompanying Claim defines.
Claims (9)
1. warm white semiconductor, it has a semiconductor heterojunction and a luminescent conversion layer at least, this heterojunction semiconductor contacts with this luminescent conversion layer, it is characterized in that: this warm-white light-emitting system is made up of three kinds of bands, it is relevant with catalyst Ce, Pr and the radiation of Dy in the inorganic fluorescent powder of this luminescent conversion layer, and the chemometric equation of this fluorescent material is
(Y
2-x-y-z-pGd
xCe
yPr
zDy
pO
3)
1.5 ± α(Al
2O
3)
2.5 ± β, wherein
0.001≤x≤0.4，0.01≤y≤0.2，0.0001≤z≤0.1，
0.0001≤p≤0.1,0.01≤α≤0.1 and 0.01≤β≤0.1.
2. warm white semiconductor as claimed in claim 1, wherein this fluorescent material is the fluorescent material with red spectrum garnet structure.
3. warm white semiconductor as claimed in claim 1, wherein these three kinds of bands are divided into first kind of emission band λ
I Max=450 ± 25nm, second kind of emission band λ
II Max=560 ± 20nm and the third emission band λ
III Max=610 ± 3nm.
4. warm white semiconductor as claimed in claim 3, wherein this inorganic fluorescent powder has chemometric equation Y
2.66Gd
0.32Ce
0.03Pr
0.005Dy
0.005Al
5.02O
12.06, and in this inorganic fluorescent powder atomic fraction than Ce/ (Ce+Pr+Dy) 〉=0.75, Pr
+ 3Form the third emission band, and be suitable for ' D2-' C4 internal transitions.
5. warm white semiconductor as claimed in claim 1, the wherein main active ions Ce of this inorganic fluorescent powder
+ 3Spectrum red-label and Pr on the long wave direction of radiation
+ 3In ' radiation of D2-' C4 internal transitions is relevant, Pr
+ 3Concentration is Ce
+ 33-25%.
6. warm white semiconductor as claimed in claim 1, wherein the color coordinate of this warm-white semiconductor is 0.405≤x≤0.515,0.355≤y≤0.550, colour temperature T≤4000K, color rendering index R 〉=80, dominant wavelength λ 〉=565nm.
7. fluorescent material with red spectrum garnet structure, it is used for the warm white semiconductor, and its chemometric equation is
(Y
2-x-y-z-pGd
xCe
yPr
zDy
pO
3)
1.5 ± α(Al
2O
3)
2.5 ± β, wherein
0.001≤x≤0.4，0.01≤y≤0.2，0.0001≤z≤0.1，
0.0001≤p≤0.1,0.01≤α≤0.1 and 0.01≤β≤0.1.
8. fluorescent material as claimed in claim 7, wherein this inorganic fluorescent powder has chemometric equation Y
2.66Gd
0.32Ce
0.03Pr
0.005Dy
0.005Al
5.02O
12.06, and in this fluorescent material atomic fraction than Ce/ (Ce+Pr+Dy) 〉=0.75, Pr
+ 3Form the third emission band, and be suitable for ' D2-' C4 internal transitions.
9. fluorescent material as claimed in claim 7, the wherein main active ions Ce of this fluorescent material
+ 3Spectrum red-label and Pr on the long wave direction of radiation
+ 3In ' radiation of D2-' C4 internal transitions is relevant, Pr
+ 3Concentration is Ce
+ 3325%.
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|---|---|---|---|
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|---|---|---|---|---|
| CN1729267A (en) * | 2002-12-20 | 2006-02-01 | 丰田合成株式会社 | Luminous bodies and optical devices using them |
| CN1922741A (en) * | 2004-02-18 | 2007-02-28 | 独立行政法人物质·材料研究机构 | Light emitting device and lighting fixture |
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|---|---|---|---|---|
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| CN1922741A (en) * | 2004-02-18 | 2007-02-28 | 独立行政法人物质·材料研究机构 | Light emitting device and lighting fixture |
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