CN101325238A - White light LED and lighting conversion layer thereof - Google Patents
White light LED and lighting conversion layer thereof Download PDFInfo
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- CN101325238A CN101325238A CNA2008101473971A CN200810147397A CN101325238A CN 101325238 A CN101325238 A CN 101325238A CN A2008101473971 A CNA2008101473971 A CN A2008101473971A CN 200810147397 A CN200810147397 A CN 200810147397A CN 101325238 A CN101325238 A CN 101325238A
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Abstract
The invention relates to a white light emitting diode (LED), which is based on an In-Ga-N nitride heterojunction. The white LED is characterized in that the LED can radiate a primary blue light with a specific wavelength and has an emitted light conversion layer for converting the blue light to white light. The invention also discloses an emitted light conversion layer and oxyfluoride garnet phosphor powders used by the emitted light conversion layer.
Description
[technical field that the present invention belongs to]
The present invention system is about a kind of electronic technology field, refers to a kind of fluorine oxygen garnet phosphor powder relevant with the lighting technology that broadly is referred to as ' solid state light emitter ' (Solid state lighting) especially and uses the white light emitting diode of this fluorine oxygen garnet phosphor powder.
[prior art]
On this technical foundation, produce lighting apparatus daily and that view is used, even also had the industrial high lighting apparatus.The colour temperature of these lighting apparatus is lower, and T≤3500K belongs to ' the warm white illumination '.If colour temperature T＞4600K, so this semiconductor equipment just belongs to ' cold white light '.
For most lighting apparatus now, general volume is excessive.With respect to this defective, have small size, the semiconductor lighting equipment of high power output has very large market prospects.
The eliminating of this defective depends on the high-power component that has special single assembling in the semiconductor light sources.This technical prospect development was less than 20 years, Japan engineer S.Nakanura has proposed with indium nitride (In-N), gallium nitride (Ga-N) is the novel framework light source of matrix, wherein contain a large amount of ' quantum well " InGaN (In-Ga-N) heterojunction framework (also can be described as P-N and connect face) (please refer to the disquisition that S.Nakanura delivered in 97 years ' The bule laser diode Sp.1997 ', be not described in detail at this).
And this result's appearance is based on before 30 years, the device on the heterojunction basis that Soviet Union engineer proposes, the Stokes inorganic fluorescent powder conversion layer that comes from the gallium nitride semiconductor framework covers, and conversion layer covering source is used for the anti-Stokes fluorescence powder of light-emitting diode.
The engineer (S.Nakanura) of Japan in 1998 ' Ri Ya chemical company ' has proposed to process on the basis that semiconductor first order blue light is created in the light-emitting diode, has proposed the combination white light emitting diode.Newton's complementary colours (blue, yellow) principle is followed in semiconductor In-Ga-N heterojunction blue ray radiation and a large amount of gold-tinted radiation that fluorescent material produced in the light-emitting diode, and two kinds of light mixing with complementation obtain the uniform white light radiation.This radiation is since the crt screen production and radar instruments that are widely used in black and white television set the 17th century～20 century.
The Japan engineer utilizes their patented technology and experience, has guaranteed their whole white light radiation of heterojunction semiconductor luminescent conversion layer.Draw at complementary colours Optical devices, taper reflection, interior tapered instrument, optical lens and light in the instrument and equipment such as equipment, the position of luminescent conversion layer is very important, yet technology still exists deficiency in this respect.In the time of on the sapphire single crystal substrate that heterojunction is placed in, as performance number W during greater than 100 milliwatts, can produce heat during heterojunction energising work, this point and all combining before, because of sapphire thermal conductivity coefficient low (about 45W/MK), the heat that is produced can not well remove from the chip of light-emitting diode.In order to improve this respect, people have adopted different solutions, replace sapphire substrate with similar material, as the type of dielectric SiC of heat conduction, because of its thermal conductivity coefficient than before the sapphire height more than 3 times, guaranteed more high-power exciting.Such device theory is by U.S. Cree company initiative, but their installation cost is very high.
The thermal stability problems that has fundamentally solved on light-emitting diode is ' Semileds ', they propose heterojunction semiconductor directly is built in the copper substrate.' engineers of Semileds ' directly is placed in the copper substrate for the heterojunction semiconductor of component with InGaN (In-Ga-N).This point is to utilize very special barrier layer, has hindered the diffusion process between heterojunction and copper base plate.
But they also exist substantial defective, though the encapsulation of High Power LED (LED) has the characteristic of low thermal resistance, but still can be to the particle heating of the fluorescent material in the luminescent conversion layer, so the output of the luminescent quantum of fluorescent material will reduce, aluminium-yttrogarnet (Y that ' Ri Ya chemical company ' proposes as famous, Gd, Ce)
3Al
5O
12, when T=373K, parameter reduces by 25% usually.For the fluorescent material of this particular series, it is more to descend when the Gd atom is added to [Gd]=0.5 atomic fraction, and when T=350K, parameter reduces by 50% especially
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention is that a white light emitting diode and employed fluorine oxygen garnet phosphor powder thereof are provided, and it can eliminate above-mentioned shortcoming.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a white light emitting diode and employed fluorine oxygen garnet phosphor powder thereof, and it can create brighter white light emitting diode, at voltage 〉=3.1V, and electric current
Luminous efficiency surpasses every watt 100 lumen.
For solving the shortcoming of above-mentioned known technology, another object of the present invention system provides a kind of white light emitting diode and employed fluorine oxygen garnet phosphor powder thereof, and it does not check power to descend after going through first operating time of 5～10 minutes.
For achieving the above object, the invention provides a kind of white light emitting diode, it is that the nitride heterojunction of being made up of In-Ga-N is the basis, be formed directly in the copper substrate, it is characterized in that: the first blue ray radiation and the luminescent conversion layer that have specific wavelength on this light-emitting diode, produce white light thus, wherein this specific wavelength is λ=450 ± 2nm.
For achieving the above object, the invention provides a kind of luminescent conversion layer, it can be used in the white light emitting diode, convert white light in order to blue light with In-Ga-N heterojunction institute radiation, it is characterized in that: these luminescent conversion series of strata are matrix with fluorescent material, the organosilicon polymer that also comprises molecular mass M=15000～25000 carbosilane units is between 15～55% at the polymer quality ratio of this inorganic fluorescent powder, and makes its curing in a following a period of time of specified temp.
[accompanying drawing summary]
Fig. 1 is the schematic diagram of white light emitting diode of the present invention, and wherein the instrument electrode input end 1, polymer shell 2, and negative pole end 3, R1-R4 are thermal resistance.
Fig. 2-the 8th, the parameter of fluorescent material of the present invention is analyzed schematic diagram.
[execution mode]
At first, the shortcoming that the objective of the invention is to eliminate above-mentioned fluorescent material and use the white light emitting diode of this fluorescent material.In order to reach this target, white light emitting diode of the present invention is that the nitride heterojunction of being made up of In-Ga-N is the basis, it is formed directly in the copper substrate, it is characterized in that: have the first blue ray radiation and a luminescent conversion layer of specific wavelength on this light-emitting diode, produce white light thus.
Wherein, this specific wavelength is λ=450 ± 2nm.
The colour temperature of this white light is 5500～6600K, and the luminous flux that gross power equals 1 watt-hour is F＞100 lumens.
When the gross area of this nitride heterojunction is 1.0～1.2 square millimeters, this luminescent conversion layer forms light at radiating surface, chromaticity coordinate value in the radiation of integrated form white light is: under 0.31＜x≤0.34,0.316≤y≤0.354 situation, light flux values F/y surpasses 310 lumens.
Wherein, be enclosed in the profile that radiating surface around this luminescent conversion layer and faceted pebble have same thickness, the symmetrical centre of profile conforms to the diagonal crosspoint on head-on radiation surface, and the optical thickness on this each limit of luminescent conversion layer is 80～120 microns.
Wherein, be under the situation of 2 θ=60 ° in the half-power angle, its luminous intensity 1 〉=102cd.
Wherein, the luminous efficiency η of this white light emitting diode 〉=106 lumens/watt, after the continual work through 1000 hours, the variation of numerical value Δ η is no more than 1～2%.
Wherein, the colour index of drilling of this white light emitting diode is Ra 〉=82.
Wherein, these luminescent conversion series of strata are matrix with the fluorescent material that is activated by cerium, the organosilicon polymer that also comprises molecular mass M=15000～25000 carbosilane units, quality ratio at this inorganic fluorescent powder polymer is between 15～55%, and under ℃ temperature of T 〉=110, make it solidify more than 1 hour, in addition, further can add the oxygen atom of fluorine ion replacement in lattice during it is formed, this fluorescent material is had
The cubic lattice parameter value, the chemometric equation that forms this fluorescent material is: (∑ Ln)
3Al
5O
12-xF
2x, wherein ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr, 0.001≤x≤1.5.These luminescent conversion series of strata are matrix with fluorescent material.Wherein, the optium concentration of this fluorine ion is 0.015～0.04 atomic fraction, at this moment, and τ persistence of this fluorescent material
e＜8 * 10
-8Second.
Wherein, this fluorescent material is the ellipse grains shape, and the neutrality line diameter is 1.2≤d
50≤ 2.8 μ m, each particle are independently, the natural crystalline form of dodecahedron, and this fluorescent material has
Density.
Wherein, in the aluminium cations coordination valence, have two different anions element O
-2And F
-1Guaranteed the very narrow spectral radiance of this fluorescent material, its spectrum maximum is λ
Max=538～556nm is distributed on the sub-band, and half-wave is wide only λ
0.5=112nm.
Below explain the physical-chemical essence of white light emitting diode of the present invention.In light-emitting diode framework proposed by the invention, directly be based upon the suprabasil nitride radiation of metal (copper) matter framework layer, it is characterized in that: this light-emitting diode has closely knit luminescent conversion under the first order blue ray radiation of wavelength X=450 ± 2nm.Under thickness δ=30 micron, the absorption of light has 1/e doubly, and wherein parameter e is a natural constant 2.71.The thickness that light fully absorbs is 100 microns.The density of transducer radiation is not absorbed partially mixed with the blue radiation of the heterojunction first order, formed strong white light.Colour temperature T=4500～6600K, gross power is that 1 watt luminous flux F value is greater than 100 lumens.
According to our understanding, in glow color, the blue light of first order radiation dominant wavelength 450 ± 2nm, and photoconverter part have the gold-tinted of dominant wavelength 545～550nm.The amount of radiation of the second level gold-tinted that this luminescent conversion layer is excited is bigger than first order blue ray radiation amount, and two kinds of radiation are combined into one group of light beam, and near white color, this radiant light colour temperature is T=5500～6600K, definitely is best to vision.
The phenomenon that has kind of energy to disappear is called ' Stokes ' the energy disappearance.The difference of energy is between first order blue ray radiation wavelength X=450nm and second level gold-tinted radiation wavelength λ=545nm.The conversion efficiency of gold-tinted is
Yet first order blue radiation light is lower for people's visual sensitivity, and second level yellow radiation light is higher than 6～8 times of blue radiation light for people's visual sensitivity.Therefore ' Stokes ' phenomenon that energy disappears, though the white light that is produced has, total brightness still promotes to some extent.
White light emitting diode of the present invention is characterized in that: at heterojunction gross area S=1～1.2mm
2The light flux values F/y=300 lumen that the convert light of upper surface radiation causes.White light radiation chromaticity coordinates is: 0.31≤x≤0.34,0.316≤y≤0.354.Particularly point out the physical characteristic of this white light emitting diode.At first, the numerical value of high light flux depends on its height ratio chromaticness amount, and this parameter has determined that the big or small F (lumen) of branch light flux values exists ' radiation on the y ' coordinate figure, when its chromaticity coordinates is about
The time, the light flux values F/y of the concrete numerical value of instrument is greater than 340 lumens.The normal light amount of flux adopts the comparative parameter of semiconductor instrument, the white light of different tones.For this warm white situation, chromaticity coordinates is 0.44≤x≤0.46,0.43≤y≤0.45.Luminous flux imports parameter L/y≤120 lumens.
By shown in Figure 1, numeral 1 is represented the instrument electrode input end among the figure, and 3 of instrument assembling is a negative pole end, and its element together is encapsulated in the transparent polymer shell 2.Adopt elargol that chip is fixed on the support, and connect both positive and negative polarity with gold thread.Top layer at chip exists luminescent conversion layer, produces thermal resistance between single element framework, and the form of the thermal resistance that is proposed is R
1, R
2, R
3And R
4
Has area S=1mm
2The instrument internal chip thermal resistance of chip may reach R
1+ R
2+ R
3Such numerical value, the coefficient of heat conduction of Ga-N are K
GaN=170W/MK, thickness are δ=5 micron, and its thermal resistance is: R
1=0.029 ℃/W.If it is in the framework of substrate that the nitride heterojunction layer is installed in copper, the thermal resistance of copper substrate is R
2=0.38 ℃/W.The thermal resistance of elargol layer is R
3=4.0 ℃/W, the thermal resistance of copper stent is about R
4=2.0 ℃/W, therefore whole thermal resistance is R=6.4 ℃/W.Exist the thermal resistance that is positioned at luminescent conversion layer owing to having used polymer adhesive (silicones), cause R with conductivity R=0.02W/cmK
uThe thermal resistance of=1000 ℃/W.
What particularly point out is that luminescent conversion layer architecture proposed by the invention has: 1. Bao critical limit; 2. the greatest limit scope is loaded fluorescent powder grain; And 3. high radiation efficiency and high heat radiation parameter.
Conclude the description of this part, that can affirm says, what propose in the present invention is that the light-emitting diode of matrix is characterized in that with indium nitride-gallium heterojunction (In-Ga-N): this heterojunction semiconductor has R=6.4 ℃/W thermal resistance, and the thermal resistance of this luminescent conversion layer is R
u〉=1000 ℃/W, this shows that the heat that this heterojunction semiconductor produced can't be transmitted to the fluorescent powder grain of this luminescent conversion layer in a large number, and has ensured that the working temperature of fluorescent powder grain is unlikely to too high.
Must consider that all are arranged in the fluorescent powder grain quantitative proportion of this luminescent conversion layer, because amounts of particles should equate in the distribution of particles concentration and the size of this luminescent conversion laminar surface.Concentration evenly is necessary condition.Whole luminescent conversion layer should possess this essential condition, the distribution that is centrosymmetric of this spectrum transducer, thickness is even, and the thickness on the radiating surface can not be greater than 80～120 microns, and thickness evenly can well solve solving the mixing bicomponent material of luminescent conversion layer.
For being matrix with similar material silicon ketone polymer; it has chemical framework and organizes O-Si-O-C (silicate coupling); particularly the similar polymerization thing is in high viscosity; the condition of second necessity is; can utilize polymer to be positioned at the limit-92～94% of its transparency; the 3rd condition is to be arranged in to solidify attitude, guarantees the activity between the mix ingredients.Three conditions of all this all allow first radiation of this luminescent conversion layer outside to have high output radiance, are 40～50%, have high efficiency to guarantee light-emitting diode proposed by the invention.
The thickness that obtains in experimentation of the present invention is 80～120 microns, and one-level blue ray radiation 20% penetrates this luminescent conversion layer, with a large amount of fluorescent material regeneration yellow radiation, has formed white-light emitting with first order blue ray radiation again.Above-mentioned this semiconductor instrument has exclusive advantage, it is characterized in that: when in the power bracket of W=1 watt, its brightness exceeds value L=3.410
7Cd/m
2
Equally, determine to utilize under professional optical lens the high light radiation light-emitting diode to combine with tool housing, these lens have been realized the casting in professional pressing mold.On the made of lens, utilize the Merlon casting.Proposition obtains the result as table one:
Table one
| Half- |
Light intensity radiation (cd) |
| 6 | 12300+10％ |
| 12 | 3080+10％ |
| 24 | 772+10％ |
| 30 | 500+10％ |
| 60 | 125+10％ |
| 120 | 35+10％ |
Must be pointed out, light-emitting diode proposed by the invention lens in high light (2 θ=6 °) have very strong focusing, 100 such light-emitting diodes are almost arranged in one group of fitting structure, and the axial light intensity of then whole group led lamp is 1.23 * 10
6Cd is enough to provide the lighting demand that is similar to the Marine Navigating Light utilization and satisfies the airport.
The same light-emitting diode with optical technology parameter is measured through accurate physical parameter production equipment, helps the pass photosphere to be full of luminous flux.Basically it should be noted that to concentrate in the luminous flux test that exciting power is the W=1 watt-hour that abideing by average voltage is 3.0～3.4V, current average I=320mA.Suitable luminous flux is F=102 ± 4% lumen.Maximum luminous flux F
Max=106 lumens, in for 1 watt of powerful instrument and equipment, luminous efficiency is ζ=106 lumens/watt.
This very high numerical value has been drawn its effective parameter and luminous efficiency, and in present stage, for incandescent lamp, its luminous efficiency has only ζ=14～16 lumens/watt.For electricity-saving lamp, utilizing at the mercury discharge with wavelength X=254nm and mixed radiation at RGB ' three primary colors ' to reach the light efficiency value be ζ=45～50 lumens/watt to fluorescent material.Point out that the standard for the luminous efficiency of 20/40 watt fluorescent lamp is ζ=82～85 lumens/watt.In the advertisement of ' Oslan ', declare that they can reach light efficiency and have 100 lumens/watt in renowned company now.
It must be noted that, in measuring condition, analyze that light source is not able to do in time to heat during the course, therefore cause luminous efficiency different with light-emitting diode index proposed by the invention.
On light-emitting diode proposed by the invention, we record the durability parameter, and we measure after continual work in 1000 hours in experiment, and its light efficiency does not change in essence, even luminous efficiency has increased by 2～6% on original basis.But this only is the utilization for power W=1 watt.Originally, the light efficiency of light-emitting diode=106 lumens/watt.Analyze this data, must indicate, the attached property of the light efficiency of light-emitting diode comes from power and excites characteristic of nonlinear.So, in the time of the W=1 watt, luminous efficiency=106 lumens/watt, in a half-power, luminous efficiency is 112 lumens/watt,, normal power reduction 10 times, excite to guarantee to have obtained luminous flux and in the light-emitting diode that is proposed, be the F=12.4 lumen.Such state reaches light efficiency numerical value ζ
0.1=124 lumens/watt.Excite electrical power less than the W=100 milliwatt.
The light-emitting diode that it may be noted that senior staff officer's numerical value luminous efficiency is positioned at priority, and the special light efficiency of the light-emitting diode that is proposed is ζ=106 lumens/watt, and electrical power excites the W=1 watt and guarantees semiconductor instrument non-stop run in 1000 hours.
In Fig. 2～8, show the spectral radiance map of light-emitting diode proposed by the invention respectively, this spectrum has utilized ' instrument of Sensing ' company measures.
Luminescent spectrum in this light-emitting diode has two peak values, and first is the blue light of λ=450～460nm, and second is the sodium yellow of λ=549～560nm.It is luminous to be similar to senior staff officer's numerical technique, and its standard is included in to be had the farm labourer in the special light-emitting diode that is proposed and make time response.Table two is the luminescence technology parameter of the light-emitting diode of made of the present invention:
Table two:
| Sample | Voltage V) | Maximum crest (nm) | Main crest (nm) | x | y | CCT(K) |
| 1 | 3.362 | 451.260 | 505.876 | 0.325 | 0.343 | 5792.843 |
| 2 | 3.220 | 448.340 | 559.812 | 0.337 | 0.356 | 5276.976 |
| 3 | 3.472 | 450.890 | 496.160 | 0.322 | 0.338 | 5911.246 |
| 4 | 3.482 | 450.890 | 562.170 | 0.342 | 0.373 | 5111.566 |
| 5 | 3.455 | 450.890 | 545.167 | 0.330 | 0.354 | 5543.467 |
| 6 | 3.133 | 452.350 | 561.181 | 0.341 | 0.372 | 5148.611 |
Point out that in manufacture process of the present invention ratio between most polymers and the fluorescent powder grain is positioned at 15～65% scope, optimum value is between 35～55%.The fluorescent powder grain suspended substance has goodish adhesion under similar concentration value, this peel off and situation that viscosity changes in bad symptom does not take place, for the organic polymer that the preparation suspended substance utilizes, it has following molecular structure:
Molecular weight to the M=25000 carbosilane unit, utilizes the data survey of the specialty of radiation cohort from the M=15000 carbosilane unit, in organosilicon polymer, and H
2-C=CH has the unsaturated response that two groups connect.For accelerating the curing process, with its temperature increase to 105～120 ℃ 1～2 hour.High concentration fluorescent material enters and has guaranteed stability in the suspended substance.
' Ri Ya chemical company ' utilize the luminescent material that contains the garnet composition of development to make white light emitting diode, its chemical formula is: Y
3Al
5O
12: Ce; Propose to add Gd after this again
+ 3, Lu
+ 3, Tb
+ 3Ionic constituent is partly or completely replaced the Y among the YAGCe
+ 3Ion, and extensively apply to CRT cathodoluminescence fluorescent material (Y, Gd)
3(Al, Ga)
5O
12: among the Ce, the famous researcher of Holland obtained the patent of this material in 1967, described in detail in the disquisition of inferior chemistry of day in 1994 afterwards.
For crystal chemistry type ' garnet ', possible sintetics component is analyzed and is prepared in all these expectations.Select best chemical constituent to guarantee the high luminescence technology parameter of the polymer of the light-emitting diode light that proposed.Wherein comprise: high numerical value luminous flux F (lumen), the chromaticity coordinates value of standard (x, y) and colour temperature (CK).Obviously, all polymer can both be at higher calorific power instrument W=100W/cm
2Middle work.Instrument should have high thermal stability.
For addressing this problem, we begin to address the material that more meets the device that is proposed.(∑ Ln)
3Al
5O
12-xF
2x, wherein ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr, 0.001≤x≤1.5.The variable of analysis and research fluorescent material, luminous from garnet tissue and activator Ce
+ 3Atom combines: 1. the chemical equivalent garnet in the overall formula: (∑ Ln)
3Al
5O
122. the garnet of equivalent non-chemically in overall formula: ((∑ Ln)
2O
3)
1.5 ± α(Al
2O
3)
2.5 ± β(α β ≠ 0); 3. have two mixing garnets of forming part: ((∑ Ln)
2O
3)
1.5 ± α(Al
2O
3)
2.5 ± βMeOAl
2O
34. garnet comprises to remove and is had from cation sublattice Y ion and Gd ion: (La, Ce) Sc
2Al
5O
12And polymer lattice
5. the garnet overall composition of silicate: Ca
3Lu
2Si
3O
12: Ce; 6. garnet has replacement partial oxygen ion in the anion sublattice.
Many garnet compositions have oxonium ion to be arranged, and forms the coordination matrix around lanthanum and aluminium ion.Protrude halide ion such as F
-1Ion, Cl
-1Ion, Br
-1Ion.Research of the present invention comprises that LED luminous flux may reach F＞100 lumens, colour temperature T 〉=3500K.
Selection is seven set types of matrix with the framework that combines with garnet, as the following sample of seeing:
Table three
| The garnet phosphor powder numbering | 1 watt of luminous flux | Colour temperature CK | Radiation wavelength | Average grain diameter size μ |
| 1 | 80 | 6500 | λ＝560 | 6～8 |
| 2 | 90～94 | 5500～6500 | 545≤λ ≤570 | 3～8 |
| 3 | 88～94 | 5500～6500 | 550＜570 | 4～6 |
| 4 | 78～86 | 7500 | ＜560 | 2～6 |
| 5 | 74～82 | 3000 | ＜570 | 8～10 |
| 6 | 100 | 4000 | ＜560 | 6～10 |
| 7 | ＞105 | 3500～4500 | 550～565 | 2～6 |
Labor for the histioid data of the garnet of high thermal stability white light emitting diode.Aim of the present invention is the multiple proposal that solves based on luminescent conversion layer.Rare earth element with oxide and garnet framework proposed by the invention is integrated as the inorganic fluorescent powder of matrix, with cerium as activator, it is characterized in that: imported the partial cation in the fluorine ion replacement lattice in its fluorescent material composition, its ratio is to arrive at 0.5: 11.5: 9, set up the chemical equivalent formula, in formula: (∑ Ln)
3Al
5O
12-xF
2x, wherein ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr, 0.001≤x≤1.5.
Below describe the characteristic of new phosphors in detail.Point out that before this this fluorescent material is relevant with double-deck crystallo-luminescence material, in this case, we understand have two types ion to have oxonium ion O in anion fluorescent powder sublattice
-2, and fluorine ion F
-1, this ion forms polyhedron ion coordination ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr adaptably in the anion sublattice, have the coordination valence of K=8, and the present invention will import the garnet crystal framework, the lattice parameter value
This synthetic has redness and olive drab(O superficial layer, and its excitation spectrum can be with λ=445～475nm.
The fluorescent material radioluminescence of made is positioned at the visible range of yellow green district and yellow region according to the present invention.It is excited by short wavelength's spectrum, and the displacement of 4～8nm takes place its luminous maximum spectral value.All parameters such as table four show.
Table four:
| Numbering | The component of fluorescent material | λ max，nm | λ 1/2，nm | Chromaticity coordinates | Colour temperature CK | The unit luminosity |
| 1 | Y 2.94Lu 0.03Ce 0.03Al 5O 11.75F 0.5 | 541 | 114 | .3692.4710 | 4716 | 35098 |
| 2 | Y 2.8Lu 0.07Tb 0.1Ce 0.03Al 5O 11.5F 1 | 542.2 | 112.5 | .3741.4731 | 4623 | 35140 |
| 3 | Y 2.87Tb 0.06Lu 0.04Ce 0.03 Al 5O 11.5F 1 | 544.6 | 112.3 | .3819.4814 | 4495 | 35057 |
| 4 | Y 2.89Lu 0.07Ce 0.04Al 5O 11.5F 1 | 545.8 | 111.2 | .3870.4870 | 4418 | 35889 |
| 5 | Y 2.85Tb 0.12Ce 0.03Al 5O 11.6F 0.8 | 547.7 | 112.9 | .3854.4772 | 4413 | 35098.2 |
| 6 | Y 2.87Gd 0.1Ce 0.03Al 5O 11.7F 0.6 | 547.5 | 113 | .3972.4918 | 4251 | 34472.7 |
| 7 | Y 2.85Gd 0.1Tb 0.02Ce 0.03 Al 5O 11.5F 1 | 548 | 111.9 | 3999.4920 | 4205 | 32299.0 |
Analytical table four is that matrix is arranged in the anion sublattice and needs careful analysis to the fluorine ion that comprises exact magnitude.Because at the total weight composition, the present invention at first quotes chemical formula calculating and is used for the furnace charge composition.Must be noted that fluorine ion approximately occupies two positions to greatest extent in the cards in the anion sublattice in the time of conversion: 1. replacing oxonium ion, may be to be effective filling of anion at form D o; 2. at Al
+ 3Between a special notion is arranged, identical loading O
-2=Fo
-1+ F
i -1, or abide by geometrical concept and form.For the sintering range of product at 1420～1520 ℃, 19 hours reaction time; 3. product heat treatment process is afterwards washed in 1N nitric acid (T=50 ℃), at the surface attachment thin film ZnO.SiO of fluorescent powder grain
2, descended air-dry 2 hours at T=130 ℃ at last.All fluorescent material has high radiance numerical value L=32298～35889 units.This high optical parameter has ensured the inorganic fluorescent powder that is proposed, and its optimum material formula is Y
2.87Lu
0.1Ce
0.03Al
5O
11.95F
0.1, for the blue-light excited wavelength X of heterojunction=450 ± 5nm, it is λ=538～548nm and spectral region λ=548～760nm that fluorescent material is inspired the yellow spectrum maximum.Must be pointed out that the fluorescent material of mentioning is in the inferior green that gives off in spectrum, yellow green, orange and red spectral region spectral hand.
The present invention is in the x-ray radiofluorescence powder course of work, for their special cubic crystal, the parameter of lattice
Relative garnet chemistry formula Y
3Al
5O
12The lattice parameter value be
Cation has large-size particle diameter ion, for example: yttrium, gadolinium, cerium, it is on every side round eight oxonium ions, but fluorescent material partial oxygen ion proposed by the invention is replaced by fluorine ion, causes ionic radius numerical value difference, as the oxonium ion radius
Fluorine ion radius τ
Less because of the fluorine ion radius thus, cause the static field of force grow of fluorescent material, forming the cerium ion radiation intensity increases.Another characteristics, the special static field of force has heterogeneity, connects oxygen, the such filling of fluorine ion radius with different size, and fluorine ion has independent filling than oxonium ion, and is the replacement of non-equivalence.Fluorine ion replacement oxonium ion with different size causes: reduce the inside combination of the spacing 2. minimizing crystal inside between the garnet crystal lattice intermediate ion 1.; 3. the symmetry of crystal inside in the destruction garnet.
Except the cerium ion radiation intensity increased, the curve form of luminescent spectrum also produced change, produced to reduce the wide radiation curve of half-wave and the asymmetric curve of spectrum, and as partly comparing with the longwave optical spectral curve of itself, its shortwave part area should be less.Yttrium aluminium garnet fluorescent powder Y for standard
3Al
5O
12; when temperature was heated to 125 ℃, its conversion efficiency that is excited reduced by 25%, but fluorescent material proposed by the invention is when wanting temperature to reach 175 ℃; its conversion efficiency that is excited just can reduce by 25%, therefore we can say the better heat stability of the new material that the present invention of institute proposes.In addition, new material is introduced optium concentration [Ce]=0.015～0.04 atomic fraction of cerium ion, and be ζ=810 persistence
-8Second.So-called ' the sunset glow time ' be meant that fluorescent material is stimulated the back generation required time of luminescence generated by light, the sunset glow time is short more, the number of times that expression fluorescent material can be excited in same period is many more, then its radiation-curable brightness is just high more. and the fluorescent material sunset glow time that the present invention created is very short, therefore can create very high radiance.
Point out that in front the light-emitting diode that the present invention obtained, luminous power are that 1 watt-hour radiates 100～106 lumens.We can say, at the electrical power W=2 of light-emitting diode watt-hour, electric current I=700mA, luminous flux 170～180 lumens.High like this luminous flux is in single light-emitting diode, and the present invention reaches first.In new fluorescent material building-up process of the present invention work, the solid phase response temperature can obtain the fluorescent powder grain than small particle diameter at 1400 ℃, median particle diameter 1.2≤d
Cp≤ 2.8 microns, fluorescent powder grain has natural multi-angular 12 polygons (or more polygon), and particle has very strong gloss, has high transparent.In the preparation process of luminescent conversion layer, can make extremely thin conversion layer, thickness is 80～120 microns.The standard thickness layer of luminescent conversion layer generally all exceeds 200 microns, the present invention also finds a superperformance of fluorescent material, portion has very high bulk density within it, and the composition that the link of each inorganic fluorescent powder depends on atom constitutes, and has single independently density feature.This numerical value is determined with the method for ray that normally for connecting garnet chemical composition, density is ρ=4.60g/cm
3, and the yttrium aluminium garnet fluorescent powder density of standard is ρ=2～2.25g/cm
3, fluorescent material proposed by the invention produce thinner conversion layer.
Really, the light-emitting diode that the present invention proposes has very high luminous flux F＞100 lumens/watt, high distribute power, and preserved the change for a long time of this parameter.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when the change that can do a little and retouching, so protection scope of the present invention is when looking being as the criterion that accompanying Claim defines.
Claims (16)
1. white light emitting diode, it is that the nitride heterojunction of being made up of In-Ga-N is the basis, it is characterized in that: have the first blue ray radiation and a luminescent conversion layer of specific wavelength on this light-emitting diode, produce white light thus, wherein this specific wavelength is λ=450 ± 2nm.
2. white light emitting diode as claimed in claim 1, wherein the colour temperature of this white light is 5500～6600K, the luminous flux that gross power equals 1 watt-hour is F＞100 lumens.
3. white light emitting diode as claimed in claim 1, wherein when the gross area of this nitride heterojunction is 1.0～1.2 square millimeters, this luminescent conversion layer forms light at radiating surface, chromaticity coordinate value in the radiation of integrated form white light is: 0.31＜x≤0.34,0.316 under≤y≤0.354 situation, light flux values F/y surpasses 310 lumens.
4. white light emitting diode as claimed in claim 1, wherein be enclosed in the profile that radiating surface around this luminescent conversion layer and faceted pebble have same thickness, the symmetrical centre of profile conforms to the diagonal crosspoint on head-on radiation surface, and the optical thickness on this each limit of luminescent conversion layer is 80～120 microns.
5. white light emitting diode as claimed in claim 1 is under the situation of 2 θ=60 ° in the half-power angle wherein, its luminous intensity 1 〉=102cd.
6. white light emitting diode as claimed in claim 1, its luminous efficiency η 〉=106 lumens/watt, after the continual work through 1000 hours, the variation of numerical value Δ η is no more than 1～2%.
7. white light emitting diode as claimed in claim 1, it drills colour index is Ra 〉=82.
8. white light emitting diode as claimed in claim 1, wherein these luminescent conversion series of strata are matrix with the fluorescent material that is activated by cerium, add the oxygen atom of fluorine ion replacement in lattice in the composition of this fluorescent material, form chemometric equation and are: (∑ Ln)
3Al
5O
12-xF
2x, wherein ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr, 0.001≤x≤1.5.
9. luminescent conversion layer, it can be used in the white light emitting diode, convert white light in order to blue light with In-Ga-N heterojunction institute radiation, it is characterized in that: these luminescent conversion series of strata are matrix with fluorescent material, the organosilicon polymer that also comprises molecular mass M=15000～25000 carbosilane units, polymer quality ratio at this inorganic fluorescent powder is between 15～55%, and make its curing in a following a period of time of specified temp, wherein this specified temp is T 〉=110 ℃, and this section period is more than 1 hour.
10. luminescent conversion layer as claimed in claim 9, wherein this fluorescent material is an inorganic fluorescent powder, it is activated by cerium, adds the oxygen atom of fluorine ion replacement in lattice during it is formed, and forms chemometric equation and is: (∑ Ln)
3Al
5O
12-xF
2x, wherein ∑ Ln=Y and/or Gd and/or Lu and/or Tb and/or Ce and/or Pr, 0.001≤x≤1.5.
11. luminescent conversion layer as claimed in claim 9, wherein the material component of this fluorescent material is Y
2.87Lu
0.1Ce
0.03Al
5O
11.95F
0.1, the λ=450 ± 5nm blue ray radiation that has guaranteed at this In-Ga-N heterojunction excites down, is inspired the spectral radiance maximum λ=538～548nm of gold-tinted radiation.
12. luminescent conversion layer as claimed in claim 9 wherein further adds fluorine ion in this fluorescent material, this fluorescent material is had
The cubic lattice parameter value.
13. luminescent conversion layer as claimed in claim 9 wherein has two different anions element O in the aluminium cations coordination valence
-2And F
-1Guaranteed the very narrow spectral radiance of this fluorescent material, its spectrum maximum is λ
Max=538～556nm is distributed on the sub-band, and half-wave is wide only λ
0.5=112nm.
14. luminescent conversion layer as claimed in claim 10, wherein the concentration of this fluorine ion is 0.015～0.04 atomic fraction, at this moment, and τ persistence of this fluorescent material
e＜8x10
-8Second.
15. luminescent conversion layer as claimed in claim 9, wherein this fluorescent material is the ellipse grains shape, and the neutrality line diameter is 1.2≤d
50≤ 2.8 μ m, each particle is independently, and is natural, the crystalline form of dodecahedron.
16. luminescent conversion layer as claimed in claim 9, wherein this fluorescent material has
Density.
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| CN101621103B (en) * | 2009-07-31 | 2011-05-11 | 苏州纳维科技有限公司 | Light-emitting diode (LED) and growing method thereof |
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| CN101475800B (en) * | 2009-01-23 | 2012-07-18 | 罗维鸿 | Fluorescent powder with gadolinium-lutetium-cerium as substrate and warm white light emitting diode using the same |
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