CN1836334A - Full spectrum phosphor blends for white light generation with LED chips - Google Patents
Full spectrum phosphor blends for white light generation with LED chips Download PDFInfo
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- CN1836334A CN1836334A CN 200480021298 CN200480021298A CN1836334A CN 1836334 A CN1836334 A CN 1836334A CN 200480021298 CN200480021298 CN 200480021298 CN 200480021298 A CN200480021298 A CN 200480021298A CN 1836334 A CN1836334 A CN 1836334A
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Classifications
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- Y02B20/181—
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- Luminescent Compositions (AREA)
Abstract
A light emitting device including a phosphor blend including four or more phosphors emitting within a specific spectral range to optimize the color rendering index (CRI) for a given color coordinated temperature (CCT). The blend will include at least four phosphors selected from the following: a blue phosphor having an emission peak at 400-500 nm, a green phosphor having an emission peak at 500-575 nm, an orange phosphor having an emission peak from 575-615 nm, and a deep red phosphor having an emission peak at 615-680 nm. The preferred blends are used to make light sources with general CRI values (Ra) greater than 95 at CCT's from about 2500 to 8000 K.
Description
Technical field
Exemplary embodiments of the present invention relates to the phosphor blends that is used to change by the radiation of light emitted.It is found that the concrete application that converts the white light that is used for general illumination purposes about ultraviolet ray (UV), purple or the blue radiation that LED is generated to.Yet, should be appreciated that the present invention also can be applicable to convert the radiation from UV, purple and/or blue laser and other light source to white light.
Background technology
Light-emitting diode (LED) is a semiconductor light emitter, is used as the substitute of other light source (for example incandescent lamp) usually.They especially can be used as display lamp, warning lamp and indicator light, or are used for the application that other requires colourama.The color of the light that LED produced depends on the type of employed semi-conducting material in it is made.
Colored light emitting semiconductor device comprises light-emitting diode and laser (these two is generically and collectively referred to as LED) herein, by making such as the III-V family alloy of gallium nitride (GaN).In order to form LED, typically, with multilayer alloy extension be deposited on the substrate (for example carborundum or sapphire), and available various n type and p type doping impurity are to improve the characteristic such as luminous efficiency.About the LED based on GaN, the light of being launched is usually in the UV and/or blue spectrum of electromagnetic spectrum.Up to now and since light that LED produced intrinsic color, caused LED also not to be suitable for the lighting use that needs bright white light.
Recently, developed the technology that the light that is used for that LED is launched converts the using light that is used for lighting use to.In a technology, LED is applied or covers fluorescence coating.Fluorophor is a kind of luminescent material, and it absorbs the radiant energy in a part of electromagnetic spectrum, then with another part electromagnetic spectrum emitted energy.A kind of fluorophor of important class is the crystalline inorganic compound, and it has very high chemical purity, and has controlled composition, has added a small amount of other element (being called " activator ") in this composition, to be converted into fluorescent material efficiently.By the appropriate combination of activator and host inorganic compounds, can control the color of emission.The most useful well-known fluorophor, in response to exciting of the electromagnetic radiation outside the visible range, the radiation of the electromagnetic spectrum of emission visible part.
By proposing a kind of radiation institute excited fluorescent body that is generated by LED, can generate the light (for example in the visible range of spectrum) of different wave length.Color LED is generally used for toy, indicator light and other device.The new colour phosphor that is used for this LED is sought by manufacturer constantly, with the color of generation customization and the brightness of Geng Gao.
Except colored IED, the light that LED generates can be used for producing white light with the combining of light that fluorophor generates.The most general White LED is based on blue-light-emitting GaInN chip.The coated fluorophor of blue-light-emitting chip, it converts some blue radiations to complementary colours (for example yellow-green) and launches.Total amount from the light of fluorophor and led chip provides color dot, and it has corresponding color coordinates (x and y) and correlated colour temperature (CCT), and its spectral distribution provides the look ability of being measured by color rendering index (CRI) of drilling.
Although stipulate 14 standard color samples in the world and can calculate wideer CRI (R by its mean value people
1-14), but usually CRI is defined as 8 standard color sample (R
1-8) mean value, its so-called general colour rendering index, and be abbreviated as R
aEspecially, measure the R of red by force color rendering
9Value is very important for the application (especially medical circle) of some scope.
A kind of known white light emitting device comprises blue-light-emitting LED, in its peak emission wavelength blue spectrum (about 440nm to about 480nm), and with fluorophor (such as being doped with yttrium-aluminium-garnet Y
3Al
5O
12: Ce
3+The cerium of (" YAG ")) combines.This fluorophor absorbs a part from the LED radiation emitted, and the radiation that is absorbed is transformed into green-yellow light.Fluorophor is crossed in remainder transmission by the blue light of LED emission, and with yellow light mix by the fluorophor emission.The viewed person of the mixing of blue light and gold-tinted is felt as white light.
Above-mentioned blue led-YAG phosphor device typically produces white light, and this white light has the general colour rendering index (R of about 70-82
a), the adjustable color temperature scope of about 4000K to 8000K.Obtainable YAG fluorophor and the red-emitting phosphors (CaS:Eu of having used on the recent market
2+) the LED of mixture, 4000K is provided following colour temperature, have the R about 90
aAlthough this LED is suitable for some application, many user expectations are a kind of to have higher R
aLight source, this R
aThe value of being similar to is the R of the incandescent lamp of 95-100
a
Some White LED also, it has adopted UV transmitting chip and phosphor blends, and this phosphor blends comprises redness, green and the blue emission fluorophor that is designed to the UV radiation is converted to visible light.Its spectrum often in the dark red zone of spectrum, especially has gap (spectral intensity is 0 substantially) or bigger disappearance near 650nm, this has seriously reduced R
9The CRI value.
Therefore the new LED-based solution of expectation exploitation has full spectrum (be defined as between 400 to 700nm very close to each other, that is, do not exist intensity of emission spectra to be about 0 zone), and has high R
a, R
1-14, and R
9Value.The invention provides phosphor blends and formation method new and improvement, it has overcome above-mentioned and other problem.
Summary of the invention
In first aspect, a kind of light-emitting device that is used to launch white light is provided, comprising: semiconductor light sources, emission peak is in the radiation of about 250nm to about 450nm; And fluorescent material, be coupled to radiation light source, this fluorescent material comprises: at the green emission fluorescent body between about 500 to 575nm, peak emission blue emission fluorophor between about 400 to 500nm and the other fluorophor of filling up any residual gap in the gained spectrum as requested, described light-emitting device has the full spectrum between 400 to 700nm to peak emission in the orange emission fluorophor between about 575 to 615nm, peak emission in the red emission fluorophor between about 615 to 680nm, peak emission.
In second aspect, a kind of light-emitting device that is used to launch white light is provided, comprising: light source, emission peak is in the radiation of about 250nm to about 450nm; And fluorescent material, be coupled to radiation light source, this fluorescent material comprises: peak emission the red emission fluorophor between about 615 to 680nm, peak emission the orange emission fluorophor between about 575 to 615nm, peak emission at green emission fluorescent body between about 500 to 575nm and peak emission the blue emission fluorophor between about 400 to 500nm, described light source has the general CRI index (R greater than 95
a).
In the third aspect, a kind of light-emitting device that is used to launch white light is provided, comprising: light source, emission peak is in the radiation of about 250nm to about 450nm; And fluorescent material, be coupled to radiation light source, this fluorescent material comprises: peak emission the orange emission fluorophor between about 575 to 615nm, peak emission the blue emission fluorophor between about 400 to 500nm, peak emission between about 615 to 680nm the red emission fluorophor and be selected from by (Ca, Sr, Ba) Al
2O
4: Eu
2+, (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+, and composition thereof the green emission fluorescent body of the group that constitutes.
In fourth aspect, a kind of phosphor blends is provided, comprise (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+And at least three kinds of other fluorophor: the orange emission fluorophor of peak emission between about 575 to 61 5nm, the green emission fluorescent body of peak emission between about 500 to 575nm, and the blue emission fluorophor of peak emission between about 400 to 500nm.
Description of drawings
Fig. 1 is the cross-sectional schematic of luminescent system according to an embodiment of the invention;
Fig. 2 is the cross-sectional schematic of luminescent system according to a second embodiment of the present invention;
Fig. 3 is the cross-sectional schematic of the luminescent system of a third embodiment in accordance with the invention;
Fig. 4 is the cutaway side perspective view of the luminescent system of a fourth embodiment in accordance with the invention;
Fig. 5 be (Sr, Ba, Mg)
4Si
2O
8: Eu
2+, Mn
2+Emission and absorption spectrum;
Fig. 6 is SrAl
2O
4: Eu
2+Emission and absorption spectrum;
Fig. 7 is the table that the correlation properties of multiple phosphor blends according to an embodiment of the invention are shown;
Fig. 8 is the table that the correlation properties of multiple phosphor blends according to another embodiment of the present invention are shown;
Fig. 9 is that the CCT according to the prescription of Fig. 7 is the emission spectrum of a kind of phosphor blends of 4000K;
Figure 10 illustrates the curve chart that the color dot of the mixture of Fig. 7 is compared with the black body locus on the XYZ chromaticity diagram;
Figure 11 a-Figure 11 h is the emission spectrum according to the multiple phosphor blends with different CCT of the embodiment of Fig. 8; And
Figure 12 illustrates the curve chart that the color dot of the mixture of Fig. 8 is compared with the black body locus on the XYZ chromaticity diagram.
Embodiment
This paper has proposed novel phosphor blends, with and application in LED and other light source.The color of the visible light that is generated depends on the special component of fluorescent material.Unless otherwise mentioned, term " fluorophor " comprises a kind of phosphor compound and two kinds or more than the mixture of two kinds of fluorophor with then being meant in this article.
Clear and definite is that the LED lamp produces bright white light will realize that the quality of expectation has effect very much to the LED as light source.Therefore, in one embodiment of the invention, disclose a kind of led chip that is coated with luminescent material fluorophor transition material mixture (phosphor blends), be used to provide white light.Various fluorophor or comprise that the phosphor blends of various fluorophor converts the radiation of specified wavelength about radiation of 250 to 450nm of nearly UV or visible LED emission (for example by) to the different wave length visible light.The visible light that is provided by fluorescent material (and if led chip of visible emitting) comprises the bright white light with high strength and brightness.
With reference to Fig. 1, typical luminescence component or lamp 10 according to a preferred structure of the present invention are shown.Luminescence component 10 comprises semiconductor UV source or visible radiation source, and for example light-emitting diode (LED) chip 12, and the lead-in wire 14 that is electrically connected to led chip.Lead-in wire 14 can comprise the thin wire that is supported by thick lead frame 16, and perhaps this lead-in wire can comprise the self-supporting electrode and can save lead frame.The 14 pairs of led chips 12 that go between provide electric current, thereby make led chip 12 emitted radiations.
This lamp can comprise any semiconductor visible light source or UV light source, and when its radiation emitted was directed on the fluorophor, it can produce white light.The preferred emission of the led chip among the present invention will depend on the fluorophor itself among the disclosed embodiment, and can be distributed in for example 250-450nm.Yet in a preferred embodiment, the emission of LED will be at nearly UV to dark blue zone, and peak wavelength about 350 to about 430nm scope.So typically, semiconductor light sources comprises the LED that is doped with various impurity.Therefore, LED can comprise based on any suitable III-V, II-VI or the semiconductor diode of IV-IV family semiconductor layer, and have about emission wavelength of 250 to 450nm.
Preferably, LED can comprise the semiconductor layer that at least one comprises GaN, ZnSe or SiC.For example, LED can comprise nitride-based semiconductor, and this nitride-based semiconductor is expressed as molecular formula In
iGa
jAl
kN (0≤i wherein; 0≤j; 0≤k; And i+j+k=1), and have greater than about 250nm and less than the peak emission wavelength of about 450nm.This LED semiconductor is known in the present technique field.For convenience's sake, this paper is described as LED with radiation source.Yet this term is meant when using in this article and comprises all semiconductor radiant sources (comprising for example semiconductor laser diode).
Although it is at the light source based on inorganic LED that the summary of the typical structure of the present invention of this paper discussion is discussed, but should be appreciated that, unless otherwise mentioned, led chip can replace with organic emitting structural or other radiation source, and only is any suitable radiation source of representative to led chip or semi-conductive any quoting.
Led chip 12 is salable in housing 18, and housing is sealed led chip and encapsulant 20.Housing 18 can be for example glass or plastics.Preferably, LED 12 is located substantially on the center of sealant 20.Sealant 20 is preferably epoxy resin, plastics, low temperature glass, polymer, thermoplastics, thermosets, resin or other type LED encapsulant well known in the art.Alternatively, sealant 20 is spin-coating glass or certain other high-index material.Preferably, encapsulant 20 is epoxy resin or polymeric material, for example silicones.Housing 18 and sealant 20 be for the light wavelength that is produced by led chip 12 and fluorescent material 22 (back description), is preferably transparent or optical transmission basically.In another embodiment, lamp 10 can include only encapsulant, and does not have shell 18.Led chip 12 can be for example by lead frame 16, by the bottom of self-supporting electrode, housing 18 be installed in housing or lead frame on the base (not shown) support.
The structure of luminescent system is coupled to the fluorescent material 22 of led chip 12 with comprising radiation.The coupling of radiation ground is meant that a plurality of elements connect each other, and feasible radiation from an element is sent to another element.In a preferred embodiment, fluorescent material 22 is four kinds or more than the mixture of four kinds of fluorophor, will describe in detail this below.
This fluorescent material 22 is deposited on the LED 12 by any suitable method.For example, can form the fluorophor of water base suspension, and be applied to the LED surface as fluorescence coating.In a kind of such method, the silicones thin pulp that phosphor particles is wherein suspended at random is placed on around the LED.This method only is the example of the possible position of fluorescent material 22 and LED 12.Therefore, can be by above led chip 12, applying phosphor suspension and it being become dry, fluorescent material 22 is coated in the light-emitting area top of led chip 12 or directly is coated on above it.Housing 18 and sealant 20 all should be transparent, to allow light 24 transmissions by these elements.In one embodiment, the median particle size of fluorescent material can be about 1 to about 10 microns, but this and do not mean that restriction.
Fig. 2 illustrates second preferred structure of system according to a preferred aspect of the present invention.The similar of the embodiment of Fig. 2, except being is scattered in fluorescent material 122 in the encapsulant 120 rather than directly is formed on the led chip 112 in the structure of Fig. 1.Fluorescent material (with powder type) can be scattered in the single zone of encapsulant 120, or more preferably, is scattered in the whole volume of encapsulant.Mixed with the light of being launched by fluorescent material 122 by led chip 112 radiation emitted 126, mixed light is revealed as white light 124.If fluorophor will be scattered in the encapsulant 120, fluorophor powder can be added in the polymer precursor so, be loaded into around the led chip 112, polymer precursor is solidified so that polymeric material solidifies.Also can use other known fluorophor process for dispersing, for example shift and load (transfer loading).
Fig. 3 illustrates the 3rd preferred structure of system according to a preferred aspect of the present invention.Similar embodiment illustrated in fig. 3 is in the structure of Fig. 1, except fluorescent material 222 is coated on the surface of housing 218, rather than is formed at led chip 212 tops.Fluorescent material preferably is coated on the inner surface of housing 218, although if needed, fluorophor can be coated on the outer surface of housing.Fluorescent material 222 can be coated on the whole surface of housing or only be coated on the top on surface of housing.Mixed with the light of being launched by fluorescent material 222 by led chip 212 radiation emitted 226, mixed light is revealed as white light 224.Certainly, the structure of Fig. 1-Fig. 3 can make up, and fluorophor can be positioned at any two or all three positions, or is positioned at any other suitable position, for example is incorporated among the LED or with LED with housing and separates.
In any one said structure, lamp 10 also can comprise a plurality of scattering particles (not shown), and it embeds in the encapsulant.Scattering particles can comprise, for example the Al of alumina powder
2O
3Particle or TiO
2Particle.Scattering particles scattering effectively preferably has the absorption of negligible quantity from the coherent light of led chip emission.
Shown in the 4th preferred structure among Fig. 4, led chip 412 can be installed in the reflector 430.Reflecting material (for example aluminium oxide, titanium dioxide or other dielectric medium powder known in the art) be made or be coated with to cup 430 can by reflecting material.Preferred reflecting material is Al
2O
3The remainder of the structure of the embodiment of Fig. 4 is all identical with the structure of any width of cloth accompanying drawing in front, the lead 432 and the encapsulant 420 that comprise two lead-in wires 416, led chip 412 and second is gone between and to be electrically connected.
In one embodiment, the invention provides a kind of phosphor blends, it can be used in the fluorescent material 22 in the above-mentioned LED lamp, and wherein this fluorescent material is the mixture of red emission fluorophor, orange emission fluorophor, green emission fluorescent body and blue emission fluorophor.
Single concrete amount of planting fluorophor of using in fluorescent material 22 will depend on the colour temperature of expectation.The relative populations of every kind of fluorophor in phosphor blends can illustrate according to spectral weight (spectral weight).Spectral weight is the relative quantity of every kind of fluorophor to the contribution of the total emission spectrum of device.All are single plant the spectral weight of fluorophor and from the LED source any surplus of seepage will add up to 100%.In a preferred embodiment, to have scope be about spectral weight of 1% to 75% to the above-mentioned fluorophor of every kind in the mixture.
Suitable red emission fluorophor comprises that those emission bands have peaked fluorophor at about 615nm to (more preferably at about 625nm between the 660nm) between the 680nm.Especially, suitable red emission fluorophor preferably includes 3.5MgO
*0.5MgF
2 *GeO
2: Mn
4+(" MFG ") and/or (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, Mn
2+(SASI is red).Shown in Fig. 5 (Sr, Ba, Mg)
4Si
2O
8: Eu
2+, Mn
2+Excite and emission spectrum.
Suitable orange emission fluorophor comprises that those emission bands have peaked fluorophor at about 575nm to (more preferably at about 580nm between the 610nm) between the 615nm.Especially, suitable orange emission fluorophor prescription preferably include (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, Mn
2+(" HALO ") and/or (Mg, Ca, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+(" SPP ").
Suitable green emission fluorescent body comprise those emission bands about 500nm between the 575nm (more preferably at about 490nm between the 560nm, more preferably at about 515nm between the 545nm) have a peaked fluorophor.Especially, the optional freedom of suitable green emission fluorescent body (Ca, Sr, Ba) Al
2O
4: Eu
2+, (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+, and/or the group that constitutes of its mixture.SrAl shown in Fig. 6
2O
4: Eu
2+Excite and emission spectrum.
Suitable blue emission fluorophor comprises that those emission bands have peaked fluorophor at about 400nm to (more preferably at about 440nm between the 460nm) between the 500nm.Especially, suitable blue emission fluorophor can preferably be selected from by (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+(" SECA ") and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+(" BAM ") (wherein x is the integer between about 1 to 5, and y is the integer between about 5 to 25), and composition thereof the group that constitutes.
If necessary, in phosphor blends, can adopt other fluorophor, in the combination of wide region, fill up any residual gap in the emission spectrum of mixture.The suitable fluorophor that is used to fill up the gap can comprise, for example, and Sr
4Al
14O
25: and Eu
2+, (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, (Ba, Ca, Sr)
2MgAl
16O
27: Eu
2+, Mn
2+, and composition thereof.
It will be appreciated by those skilled in the art that, can adopt other fluorophor to replace the redness of any aforementioned suitable example, orange, green, blue or " gap filling " fluorophor, even the chemical molecular formula of this replacement may be different significantly with the chemical molecular formula listed in the previous examples with very approximate emission spectrum.
In addition, in case of necessity, can allow partial L ED irradiation to leak (bleed through), the spectrum of device is made contributions, be used to realize that full spectrum manifests.As routinely the White LED based on blue chip of industry being done, by changing the optical density of fluorescence coating, scalable LED leakage.Alternatively, further describe, can regulate by using suitable filter or pigment as the back.
Preferably, adopt above-mentioned phosphor blends will produce the full emission spectrum of gained and in 2500 to 8000K CCT scopes, be in light-emitting device between 400 to 700nm." full spectrum " is meant in designated wavelength range spectrum without any gap (that is, this place's spectral intensity is 0 substantially) at this.
In another preferred embodiment, fluorescent material comprises four kinds of fluorophor, these four kinds of fluorophor be selected from by (Mg, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+, (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, OH): Eu
2+, Mn
2+, 3.5MgO
*0.5MgF
2 *GeO
2: Mn
4+, Sr
4Al
14O
24: Eu
2+, (Sr, Ba, Ca)
5(PO
4)
3(Cl, OH): Eu
2+, (Ca, Sr, Ba) Al
2O
4: Eu
2+, (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+, (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, Mn
2+, and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+The group that (wherein x is an integer between about 1 to 5, and y is an integer between about 5 to 25) constitutes.The amount of the activator that mixes in every kind of fluorophor will change in the scope of 0.001 mole of % to 50 mole of % usually, preferably change in about scope of 0.01% to 30%.
Above-mentioned fluorophor can use the known solid state course of reaction to produce, and being used for by inciting somebody to action for example basic oxide, carbonate and/or hydroxide combinations is that raw material produce fluorophor.Other raw material can comprise nitrate, sulfate, acetate, citrate or oxalates.In an exemplary process, by do to mix handling or wet mixing is handled and made up raw material, and in air or reduced air in for example 900 to 1600 ℃ of following roastings.
Before the blend step or during, flux can be added in the mixture.This flux can be NH
4Cl or any other conventional flux for example are selected from the fluoride of at least a metal in the group that is made of terbium, aluminium, gallium and indium.The amount of flux is little more about 20% than the total weight of mixture on weight, and preferably little about 10%, this is applicable to the purpose of fluxing.
Raw material can mix by any mechanical means, include but not limited to stir in homogenizer or ribbon formula mixer or mix.Raw material can make up in ball mill, hammer-mill or jet mill and grind together.Especially when raw-material mixture will be made into to be used for the solution of precipitation subsequently, can realize mixing by wet-milling.If mixture wets, it can at first be dried, roasting under reducing atmosphere then, and temperature preferably from about 900 ℃ to about 1500 ℃, continues the enough time to convert all mixtures to final material from about 900 ℃ to about 1700 ℃.
Roasting can discontinuous technology or continuous processing carry out, preferably by stirring or immixture promotes good gas-solid contact.Roasting time depends on the speed and the gas in the roasting apparatus-solid contact amount of the amount of mixture that will roasting, the gas by the roasting apparatus conduction.Typically, it is just enough to reach 10 hours roasting time.Reducing atmosphere typically comprises the reducing gas such as hydrogen, carbon monoxide or its combination, uses the inert gas such as nitrogen, argon gas or its combination to dilute alternatively.Alternatively, the crucible that accommodates mixture can be filled in the second sealing crucible that the high purity carbon particle is housed, and roasting in air, so that the oxygen that exists in carbon particle and the air reacts, thereby generate the carbon monoxide that is used to provide reducing atmosphere.
In one embodiment, can and be dissolved in the salpeter solution these compound.The intensity of acid solution is chosen as quick dissolving oxygenatedchemicals, and this selection is in those skilled in the art's skill.Then ammonium hydroxide is incrementally added in the acid solution.Organic base, for example carbinolamine, monoethanolamine, Propanolamine, dimethanolamine, diethanol amine, dipropanolamine, trimethanolamine, triethanolamine or tripropanol amine can be used for replacing ammonium hydroxide.
Can be with sediment roasting, usefulness deionized water wash, dry then.Can be with the sediment ball milling of drying or otherwise mix up hill and dale, then in air, about 400 ℃ to about 1600 ℃ of calcining time enough down, to guarantee raw material dehydration fully basically.Calcining can be carried out under constant temperature.Alternatively, during calcining, calcining heat can rise to final temperature from room temperature is even, and remains on final temperature.With like the burnt material type 1000-1600 ℃, under reducing atmosphere the roasting time enough, all burnt materials are converted to the phosphor compound of expectation, this reducing atmosphere is for example H
2, a kind of and the mixture of inert gas or the air that generates by the reaction between coconut husk charcoal and raw-material catabolite in CO or these gas.
Pigment or filtering material can be added in the fluorescent material.Fluorescence coating 22 also can comprise calculate by weight (based on the total weight of fluorophor) from 0 to about 5% can absorbing wavelength at pigment or other the UV absorbing material of 250nm to the UV radiation the 450nm.
Suitable pigment or filtering material comprise as known in the art any, and it can be absorbed in 250nm to the radiation that generates between the 450nm.This pigment comprises, for example, and nickel titanate or zirconic acid praseodymium.The consumption of pigment is for effectively filtering 10% to 100% of the radiation that generates in 250nm to the 450nm scope.
By every kind of fluorophor is distributed suitable spectral weight, especially for white lamps, the spectrum that people can produce the appropriate section that covers colo(u)r space mixes.Instantiation about this situation is shown below.For CCT, CRI and the color dot of various expectations, people can determine will comprise the appropriate amount of every kind of fluorophor in mixture.Therefore, the customizable phosphor blends of people is to produce almost any CCT or color dot with corresponding high CRI.Shown example is the exemplary spectrum about every kind of fluorophor.Certainly, the color of every kind of fluorophor (for example will depend on its accurate composition, the relative quantity of Ba, Ca, Sr and Eu in the BAM fluorophor), it can may for example be green rather than blue by the degree of rename to it with the color change of fluorophor.In addition, for example SASI is red and some fluorophor HALO may (be Eu by activator promotor (Co-activator) here
2+) and launch second blue peak, it will be made contributions to the emission of mixture Smalt fluorophor (SECA or BAM).Yet, determine the variation in the spectral weight, must produce the light-emitting device of identical or similar characteristics by this variation, this is very common, and can make in all sorts of ways by those skilled in the art and realize for example experimental design (DOE) or other strategy.
The application of the invention, the particularly mixture of describing in embodiment two can be provided at general CRI (R in the whole reference color temperature (2500K to 8000K) of general illumination purposes
a) value is greater than 95 lamp.In some mixtures, for general CRI value (" R
a") and average CRI value (R
1-14), the CRI value is all near theoretical maximum 100.In addition, the R of these mixtures
9Value can surpass 90, also near theoretical maximum.
Example
Provide the various light sources of use below according to the phosphor blends of the foregoing description.Carry out two different tests with the result shown in the form of Fig. 7 and Fig. 8 respectively.The fluorophor that uses in the test of Fig. 7 is: 3.5MgO
*0.5MgF
2 *GeO2:Mn
4+(" MFG ") is as red, Ca
5(PO
4)
3Cl:Eu
2+, Mn
2+(" HALO ") is used for orange, SrAl
2O
4: Eu
2+Be used for green and (Ca, Sr, Ba)
5(PO
4)
3Cl:Eu
2+(" SECA ") is used for blueness.The fluorophor that uses in the test of Fig. 8 is: 3.5MgO
*0.5MgF
2 *GeO
2: Mn
4+(" MFG "), Ca
5(PO
4)
3Cl:Eu
2+, Mn
2+(" HALO "), SrAl
2O
4: Eu
2+, Sr
2P
2O
7: Eu
2+, Mn
2+(" SPP "), Sr
4Al
14O
24: Eu
2+(" SAE "), (Sr, Ba, Ca)
5(PO
4)
3Cl:Eu
2+(" SECA ") and (Sr, Ba, Mg)
4Si
2O
8: Eu
2+, Mn
2+(" SASI is red ").
Show the specified quantitative (percentage form) based on every kind of fluorophor of spectral weight and the spectral contribution of UV seepage in the table together.Calculate prediction color coordinates (x and y) and the brightness (Im/W), CRI value (R of these fluorophor on XYZ chromaticity diagram
1-R
14, R
a) and the coordinatograph colour temperature (CCT) of these mixtures.The result is shown in the table.
The emission spectrum that calculates of the 4000K mixture of Fig. 8 shown in Figure 9 (mixture 3).In addition, can Figure 10 find out Fig. 8 light source be transmitted in the whole color dot scope with XYZ chromaticity diagram on black body locus be complementary basically.
Can in Figure 11 a-11h, see the emission spectrum that calculates of every kind of mixture among Fig. 7.In addition, can in Figure 12, see in the whole color dot scope of being transmitted in of these fluorophor with XYZ chromaticity diagram on black body locus be complementary basically.Preferably, the color dot of fluorophor is in pact ± 0.01 of the black body locus on x and the y axle, more preferably in about ± 0.002.Therefore, use above-mentioned phosphor blends to make and to produce light source, the value that this CRI value is realized in whole useful CCT scope near reference illuminant, thereby alternative these luminous elements of the almost all available in any application LED of permission with high CRI value.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (49)
1. light-emitting device that is used to launch white light comprises:
Semiconductor light sources is launched the radiation of about 250nm to about 450nm; And
Fluorescent material, be coupled to radiation described light source, described fluorescent material comprises: peak emission at about 615nm to the red emission fluorophor between the 680nm, peak emission at about 575nm to the orange emission fluorophor between the 615nm, peak emission at about 500nm to the green emission fluorescent body between the 575nm, peak emission at about 400nm to the blue emission fluorophor between the 500nm and one or more other gap filling fluorophor, wherein, described light-emitting device has 400nm to the full spectrum between the 700nm.
2. light-emitting device according to claim 1, wherein, described light source comprises a kind of in LED and the organic emitting structural.
3. light-emitting device according to claim 1 also comprises the sealant that surrounds described light source.
4. light-emitting device according to claim 3, wherein, described fluorescent material is dispersed in the described sealant.
5. light-emitting device according to claim 1 also comprises reflector.
6. light-emitting device according to claim 1 also comprises being absorbed in pigment, filtering material or other absorbent of 250nm to the radiation that generates between the 450nm.
7. light-emitting device according to claim 1, wherein, described red-emitting phosphors comprise (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, Mn
2+, and 3.5MgO
*0.5MgF
2 *GeO
2: Mn
4+In at least a.
8. light-emitting device according to claim 1, wherein, described green-emitting phosphor comprises (Ca, Sr, Ba) Al
2O
4: Eu
2+, and (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+In at least a.
9. light-emitting device according to claim 1, wherein, described blue emitting phophor comprise (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+In at least a, wherein, x is an integer between about 1 to 5, y is an integer between about 5 to 25.
10. light-emitting device according to claim 1, wherein, described fluorescent orange body comprise (Mg, Ca, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+, and (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, Mn
2+In at least a.
11. light-emitting device according to claim 1, wherein, described gap filling fluorophor is selected from Sr
4Al
14O
25: and Eu
2+, (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, (Ba, Ca, Sr)
2MgAl
16O
27: Eu
2+, Mn
2+, and composition thereof in one or more.
12. light-emitting device according to claim 1, wherein, described blue emitting phophor accounts for about spectral weight of 1% to 45%, described green-emitting phosphor accounts for about spectral weight of 15% to 60%, described red-emitting phosphors accounts for about spectral weight of 5% to 55%, and described fluorescent orange body accounts for about spectral weight of 20% to 75%.
13. light-emitting device according to claim 1, wherein, described light-emitting device has the general CRI (R greater than 90
a).
14. light-emitting device according to claim 1, wherein, described light-emitting device has the average CRI (R greater than 90
1-R
14).
15. light-emitting device according to claim 1, wherein, described light-emitting device has the CRI (R greater than 80
9).
16. light-emitting device according to claim 1, wherein, the color dot of described fluorescent material is positioned at or is positioned at substantially on the black body locus of XYZ chromaticity diagram.
17. light-emitting device according to claim 1, wherein, described light-emitting device has the CCT of about 2500K to 8000K.
18. a light-emitting device that is used to launch white light comprises:
Light source is launched the radiation of about 250nm to about 450nm; And
Fluorescent material, be coupled to radiation described light source, described fluorescent material comprises: peak emission at about 500nm to the green emission fluorescent body between the 575nm, peak emission at about 615nm to the red emission fluorophor between the 680nm, peak emission at about 575nm to the orange emission fluorophor between the 615nm and peak emission at about 400nm to the blue emission fluorophor between the 500nm, wherein, described light-emitting device has the general CRI (R greater than 95
a).
19. light-emitting device according to claim 18, wherein, described light source comprises a kind of in LED and the organic emitting structural.
20. light-emitting device according to claim 18 also comprises the sealant that surrounds described light source.
21. light-emitting device according to claim 20, wherein, described fluorescent material is dispersed in the described sealant.
22. light-emitting device according to claim 18 also comprises reflector.
23. light-emitting device according to claim 18 also comprises being absorbed in pigment, filtering material or other absorbent of 250nm to the radiation that generates between the 450nm.
24. light-emitting device according to claim 18, wherein, described red-emitting phosphors comprise (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, Mn
2+, and 3.5MgO
*0.5MgF
2 *GeO
2: Mn
4+In at least a.
25. light-emitting device according to claim 18, wherein, described green-emitting phosphor comprises (Ca, Sr, Ba) Al
2O
4: Eu
2+, and (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+In at least a.
26. light-emitting device according to claim 18, wherein, described blue emitting phophor comprise (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+In at least a, wherein, x is an integer between about 1 to 5, y is an integer between about 5 to 25.
27. light-emitting device according to claim 18, wherein, described fluorescent orange body comprise (Mg, Ca, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+, and (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, Mn
2+In at least a.
28. light-emitting device according to claim 18 also comprises being selected from by Sr
4Al
14O
25: and Eu
2+, (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, (Ba, Ca, Sr)
2MgAl
16O
27: Eu
2+, Mn
2+, and composition thereof one or more the other fluorophor in the group that constitutes.
29. light-emitting device according to claim 18, wherein, described light-emitting device has the average CRI (R greater than 95
1-R
14).
30. light-emitting device according to claim 18, wherein, described light-emitting device has the CRI (R greater than 90
9).
31. light-emitting device according to claim 18, wherein, the color dot of described fluorescent material is positioned at or is positioned at substantially on the black body locus of XYZ chromaticity diagram.
32. light-emitting device according to claim 18, wherein, described light-emitting device has the CCT of about 2500K to 8000K.
33. a light-emitting device that is used to launch white light comprises:
Light source is launched the radiation of about 250nm to about 450nm; And
Fluorescent material, be coupled to radiation described light source, described fluorescent material comprise peak emission at about 575nm to the orange emission fluorophor between the 615nm, peak emission at about 400nm to the blue emission fluorophor between the 500nm, peak emission at about 615nm to the red emission fluorophor between the 680nm and comprise (Ca, Sr, Ba) Al
2O
4: Eu
2+, and (Ca, Sr, Ba, Zn)
2SiO
4: Eu
2+In at least a green emission fluorescent body.
34. light-emitting device according to claim 33, wherein, described blue emitting phophor comprise (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+In at least a, wherein, x is an integer between about 1 to 5, y is an integer between about 5 to 25.
35. light-emitting device according to claim 33, wherein, described fluorescent orange body comprise (Mg, Ca, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+, and (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, Mn
2+In at least a.
36. light-emitting device according to claim 33 also comprises being selected from by Sr
4Al
14O
25: and Eu
2+, (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+, (Ba, Ca, Sr)
2MgAl
16O
27: Eu
2+, Mn
2+, and composition thereof one or more the other fluorophor in the group that constitutes.
37. light-emitting device according to claim 33, wherein, described light-emitting device has the average CRI (R greater than 90
1-R
14).
38. light-emitting device according to claim 33, wherein, described light-emitting device has the general CRI (R greater than 90
a).
39. light-emitting device according to claim 33, wherein, described light-emitting device has the CRI (R greater than 80
9).
40. light-emitting device according to claim 33 also comprises being absorbed in pigment, filtering material or other absorbent of 250nm to the radiation that generates between the 450nm.
41. a phosphor blends, comprise (Mg, Ca, Sr, Ba, Zn)
4Si
2O
8: Eu
2+And at least three kinds of other fluorophor: peak emission at about 575nm to the orange emission fluorophor between the 615nm; Peak emission at about 500nm to the green emission fluorescent body between the 575nm; And peak emission at about 400nm to the blue emission fluorophor between the 500nm.
42. according to the described phosphor blends of claim 41, wherein, described fluorescent material can absorb by light emitted with the 250-450nm radiation emitted, and when with from the described radiation combination of described light source the time, emission produces the radiation of white light.
43. according to the described phosphor blends of claim 41, wherein, described fluorescent orange body comprise (Mg, Ca, Sr, Ba, Zn)
2P
2O
7: Eu
2+, Mn
2+, and (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, Mn
2+In at least a.
44. according to the described phosphor blends of claim 41, wherein, described blue emitting phophor comprise (Ca, Sr, Ba)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, and (Ca, Sr, Ba) Mg
xAl
yO
(1+x+1.5y): Eu
2+In at least a, wherein, x is an integer between about 1 to 5, y is an integer between about 5 to 25.
45. according to the described phosphor blends of claim 41, wherein, described light-emitting device has the general CRI (R greater than 90
a).
46. according to the described phosphor blends of claim 41, wherein, described light-emitting device has the average CRI (R greater than 90
1-R
14).
47. according to the described phosphor blends of claim 41, wherein, described light-emitting device has the CRI (R greater than 80
9).
48. according to the described phosphor blends of claim 41, wherein, the color dot of described fluorescent material is positioned at or is positioned at substantially on the black body locus of XYZ chromaticity diagram.
49. according to the described phosphor blends of claim 41, wherein, described light-emitting device has the CCT of about 2500K to 8000K.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48097503P | 2003-06-24 | 2003-06-24 | |
| US60/480,975 | 2003-06-24 | ||
| US60/545,445 | 2004-02-17 |
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| Publication Number | Publication Date |
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| CN1836334A true CN1836334A (en) | 2006-09-20 |
| CN100477256C CN100477256C (en) | 2009-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200480021298 Expired - Lifetime CN100477256C (en) | 2003-06-24 | 2004-06-23 | Full spectrum phosphor blends for white light generation of LED chips |
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| CN (1) | CN100477256C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101868086A (en) * | 2010-05-17 | 2010-10-20 | 中山大学佛山研究院 | LED light source module and method for improving color rendering index of LED light source module |
| CN102244154A (en) * | 2011-05-09 | 2011-11-16 | 宜兴环特光电科技有限公司 | Spectrum optimizing control method for white light LED (light-emitting diode) |
| CN102007195B (en) * | 2008-03-19 | 2013-07-31 | 国立大学法人新泻大学 | Fluorophores |
| CN104282828B (en) * | 2013-07-12 | 2017-06-23 | Lg伊诺特有限公司 | Luminescent device |
| CN108767097A (en) * | 2018-05-31 | 2018-11-06 | 旭宇光电（深圳）股份有限公司 | Burst of ultraviolel full-spectrum LED and its application |
| CN113054083A (en) * | 2019-12-27 | 2021-06-29 | 英特美光电（苏州）有限公司 | 5000k ultra-high display spectrum fluorescent powder |
| CN113178514A (en) * | 2016-05-20 | 2021-07-27 | 株式会社东芝 | White light source |
-
2004
- 2004-06-23 CN CN 200480021298 patent/CN100477256C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007195B (en) * | 2008-03-19 | 2013-07-31 | 国立大学法人新泻大学 | Fluorophores |
| CN101868086A (en) * | 2010-05-17 | 2010-10-20 | 中山大学佛山研究院 | LED light source module and method for improving color rendering index of LED light source module |
| CN101868086B (en) * | 2010-05-17 | 2014-03-05 | 王孟源 | LED light source module and method for improving color rendering index of LED light source module |
| CN102244154A (en) * | 2011-05-09 | 2011-11-16 | 宜兴环特光电科技有限公司 | Spectrum optimizing control method for white light LED (light-emitting diode) |
| CN104282828B (en) * | 2013-07-12 | 2017-06-23 | Lg伊诺特有限公司 | Luminescent device |
| CN113178514A (en) * | 2016-05-20 | 2021-07-27 | 株式会社东芝 | White light source |
| CN113178514B (en) * | 2016-05-20 | 2024-04-02 | 首尔半导体株式会社 | White light source |
| CN108767097A (en) * | 2018-05-31 | 2018-11-06 | 旭宇光电（深圳）股份有限公司 | Burst of ultraviolel full-spectrum LED and its application |
| CN108767097B (en) * | 2018-05-31 | 2019-05-07 | 旭宇光电（深圳）股份有限公司 | Burst of ultraviolel full-spectrum LED and its application |
| CN113054083A (en) * | 2019-12-27 | 2021-06-29 | 英特美光电（苏州）有限公司 | 5000k ultra-high display spectrum fluorescent powder |
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| Publication number | Publication date |
|---|---|
| CN100477256C (en) | 2009-04-08 |
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