Dimmable solid-state light emitting devices
10568172 ยท 2020-02-18
Assignee
Inventors
Cpc classification
F21K9/232
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H01L33/504
ELECTRICITY
F21Y2115/10
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H01L25/13
ELECTRICITY
C09K11/77348
CHEMISTRY; METALLURGY
H05B47/11
ELECTRICITY
H05B33/14
ELECTRICITY
Y02B20/00
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
H01L25/13
ELECTRICITY
F21K9/232
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
A white light emitting device or LED-filament comprises: a solid-state light emitter (LED) operable to generate excitation light; a first phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 500 nm to 575 nm; and a second phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 600 nm to 650 nm, wherein a percentage decrease in conversion efficiency corresponding to an increase in excitation light photon density exhibited by the second phosphor is larger than a percentage decrease in conversion efficiency corresponding to the same increase in excitation light photon density exhibited by the first phosphor.
Claims
1. A white light emitting device comprising: a solid-state light emitter operable to generate excitation light upon application of electrical power thereto; a first phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 500 nm to 575 nm; and a second phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 600 nm to 650 nm, wherein a percentage decrease in conversion efficiency corresponding to an increase in excitation light photon density exhibited by the second phosphor is larger than a percentage decrease in conversion efficiency corresponding to the same increase in excitation light photon density exhibited by the first phosphor.
2. The white light emitting device of claim 1, wherein the percentage conversion efficiency of the second phosphor decreases by at least 8% in response to a 95% increase in excitation light photon density.
3. The white light emitting device of claim 1, wherein a percentage decrease in peak emission intensity corresponding to an increase in temperature exhibited by the second phosphor is larger than a percentage decrease in peak emission intensity corresponding to the same increase in temperature exhibited by the first phosphor.
4. The white light emitting device of claim 3, wherein the percentage decrease in peak emission intensity of the second phosphor decreases by at least 18% in response to an increase in temperature from 25 C. to 200 C.
5. The white light emitting device of claim 1, wherein the second phosphor comprises a Group IIA/IIB selenide sulfide-based phosphor material.
6. The white light emitting device of claim 5, wherein said Group IIA/IIB selenide sulfide-based phosphor material has a composition MSe.sub.1-xS.sub.x:Eu.sub.y, wherein M is at least one of Mg, Ca, Sr, Ba and Zn, 0<x<1.0 and 0.0005y<0.005.
7. The white light emitting device of claim 6, wherein M is calcium.
8. The white light emitting device of claim 1, wherein in operation a decrease in electrical power to the solid-state light emitter of about 90% results in a decrease in CCT of emitted light of at least one of: of at least 400K, of at least 700K, and of at least 1500K.
9. The white light emitting device of claim 1, comprising a light transmissive substrate for at least mounting said solid-state light emitter thereon.
10. An LED-filament comprising: a solid-state light emitter operable to generate blue light with a dominant wavelength in a range 440 nm to 470 nm upon application of electrical power thereto; a light transmissive substrate for at least mounting said solid-state light emitter; a yellow to green-emitting phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 500 nm to 575 nm; and a red-emitting phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 600 nm to 650 nm, wherein a percentage decrease in conversion efficiency corresponding to an increase in blue light photon density exhibited by the red-emitting phosphor is larger than a percentage decrease in conversion efficiency corresponding to the same increase in excitation light photon density exhibited by the yellow to green-emitting phosphor.
11. The LED-filament of claim 10, wherein the percentage conversion efficiency of the red-emitting phosphor decreases by at least 8% in response to a 95% increase in blue light photon density.
12. The LED-filament of claim 10, wherein a percentage decrease in peak emission intensity corresponding to an increase in temperature exhibited by the red-emitting phosphor is larger than a percentage decrease in peak emission intensity corresponding to the same increase in temperature exhibited by the yellow to green-emitting phosphor.
13. The LED-filament of claim 12, wherein the percentage decrease in peak emission intensity of the red-emitting phosphor decreases by at least 18% in response to an increase in temperature from 25 C. to 200 C.
14. The LED-filament of claim 10, wherein the red-emitting phosphor comprises a Group IIA/IIB selenide sulfide-based phosphor material.
15. The LED-filament of claim 14, wherein said Group IIA/IIB selenide sulfide-based phosphor material has a composition MSe.sub.1-xS.sub.x:Eu.sub.y, wherein M is at least one of Mg, Ca, Sr, Ba and Zn, 0<x<1.0 and 0.0005y<0.005.
16. The LED-filament of claim 15, wherein M is calcium.
17. The LED-filament of claim 10, wherein in operation a decrease in electrical power to the solid-state light emitter of about 90% results in a decrease in CCT of emitted light of at least one of: of at least 400K, of at least 700K, and of at least 1500K.
18. A white light emitting device or an LED-filament comprising: a solid-state light emitter to generate blue excitation light with a dominant wavelength in a range 440 nm to 470 nm; a yellow to green-emitting phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 500 nm to 575 nm; and a red-emitting phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 600 nm to 650 nm, wherein the red-emitting phosphor comprises a Group IIA/IIB selenide sulfide-based phosphor material, and wherein the white light emitting device is configured such that in operation a reduction in electrical power to the solid-state light emitter of about 90% results in a reduction in CCT of emitted light of at least 700K.
19. A method of dimming a white light emitting device or LED-filament comprising the steps of: providing a solid-state light emitter to generate excitation light with a dominant wavelength in a range 440 nm to 470 nm; supplying electrical power to the solid-state light emitter; providing a first phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 500 nm to 575 nm; providing a second phosphor associated with the solid-state light emitter to generate light with a peak emission wavelength in a range 600 nm to 650 nm; wherein a percentage decrease in conversion efficiency corresponding to an increase in excitation light photon density exhibited by the second phosphor is larger than a percentage decrease in conversion efficiency corresponding to the same increase in excitation light photon density exhibited by the first phosphor; and decreasing the electrical power to the solid-state light emitter to decrease the excitation light photon density.
20. The method of claim 19, wherein decreasing the electrical power to the solid-state light emitter by about 90% results in decreasing the CCT of emitted light by at least one of: by at least 400K and by at least 700K.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) These and other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures, in which:
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DETAILED DESCRIPTION OF THE INVENTION
(25) Embodiments of the present invention will now be described in detail with reference to the drawings, which are provided as illustrative examples of the invention so as to enable those skilled in the art to practice the invention. Notably, the figures and examples below are not meant to limit the scope of the present invention to a single embodiment, but other embodiments are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present invention can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present invention will be described, and detailed descriptions of other portions of such known components will be omitted so as not to obscure the invention. In the present specification, an embodiment showing a singular component should not be considered limiting; rather, the invention is intended to encompass other embodiments including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, applicants do not intend for any term in the specification or claims to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present invention encompasses present and future known equivalents to the known components referred to herein by way of illustration.
(26) Embodiments of the invention are directed to solid-state light emitting devices comprising solid-state light emitters, typically LEDs, that are operable to generate excitation light (typically blue light) which is used to excite a photoluminescence material, such as a blue light excitable phosphor material. In particular, embodiments of the invention concern solid-state light emitting devices that at least in part overcome the limitations of the known devices and whose color temperature of emitted light decreases on dimming. In this specification, the characteristic of a light emitting device whose color temperature decreases (i.e. moves towards a warmer color temperature) as it is dimmed will be referred to as warm dimming.
(27) LED-Filament Lamp: A-Series (A19) Lamp
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(29) The LED-filament lamp 100 comprises a connector base 110, a light-transmissive envelope 120; an LED-filament support 130 and four LED-filaments 140a, 140b, 140c, 140d.
(30) In some embodiments, the LED-filament lamp 100 can be configured for operation with a 110V (r.m.s.) AC (60 Hz) mains power supply as used in North America. For example, and as illustrated, the LED-filament lamp 100 can comprise an E26 (26 mm) connector base (Edison screw lamp base) 110 enabling the lamp to be directly connected to a mains power supply using a standard electrical lighting screw socket. It will be appreciated that depending on the intended application other connector bases can be used such as, for example, a double contact bayonet connector (i.e. B22d or BC) as is commonly used in the United Kingdom, Ireland, Australia, New Zealand and various parts of the British Commonwealth or an E27 (27 mm) screw base (Edison screw lamp base) as used in Europe. The connector base 110 can house rectifier or other driver circuitry (not shown) for operating the LED-filament lamp.
(31) The light-transmissive envelope 120 is attached to the connector 110. The light-transmissive envelope 120 and LED-filament support 130 can comprise glass such that the envelope defines a hermetically sealed volume 150 in which the LED-filaments 140a to 140d are located. The envelope 120 can additionally incorporate or include a layer of a light diffusive (scattering) material such as for example particles of Zinc Oxide (ZnO), titanium dioxide (TiO.sub.2), barium sulfate (BaSO.sub.4), magnesium oxide (MgO), silicon dioxide (SiO.sub.2) or aluminum oxide (Al.sub.2O.sub.3).
(32) The LED-filaments 140a to 140d, which are linear (strip or elongate) in form, are oriented such that their direction of elongation is generally parallel to an axis 250 of the lamp 100. The LED-filaments 140a to 140b can be equally circumferentially spaced around the glass filament support 130 (
(33) An LED-filament 140 according to an embodiment of the invention is now described with reference to
(34) The substrate 200 can further comprise respective electrical contacts 230a, 230b at its first and second ends for electrical connection to a respective one of the conducting wires 160, 170 (
(35) When the LED-filament 140 is used as a part of an energy efficient bulb, an elongate configuration may be preferred since the appearance and emission characteristics of the device more closely resembles a traditional filament of an incandescent bulb. Depending on the application, the substrate 200 can comprise other forms such as for example being square or circular and the LED chips configured as other arrays or configurations. It should be noted that the LED chips 210 are mounted directly to the substrate 200 and are not packaged. Such packaging would otherwise block the emission of light in a backward direction towards and through the substrate 200.
(36) The substrate 200 can comprise any light-transmissive material which is at least translucent and preferably has a transmittance to visible light of 50% or greater. Accordingly, the substrate can comprise a glass or a plastics material such as polypropylene, silicone or an acrylic. To aid in the dissipation of heat generated by the LED chips 210, the substrate 200 is not only light-transmissive but is advantageously also thermally conductive to aid in the dissipation of heat generated by the LED chips. Examples of suitable light-transmissive thermally conductive materials include: magnesium oxide, sapphire, aluminum oxide, quartz glass, aluminum nitride and diamond. The transmittance of the thermally conductive substrate can be increased by making the substrate thin. To increase mechanical strength, the substrate can comprise a laminated structure with the thermally conductive layer mounted on a light-transmissive support such as a glass or plastics material. To further assist in the dissipation of heat, the volume within the glass envelope is preferably filled with a thermally conductive gas such as helium, hydrogen or a mixture thereof.
(37) The LED-filament 140 further comprises a photoluminescence wavelength conversion material 240 comprising a mixture of a yellow to green-emitting photoluminescence material (eg. Phosphor) and a red-emitting photoluminescence material (eg. Phosphor) that is applied directly to the LEDs chips 210 in the form of an encapsulating layer.
(38) The yellow to green-emitting photoluminescence material (eg. Phosphor) can comprise any photoluminescence material which, when excited by excitation light (typically blue excitation light), generates light with a peak emission wavelength .sub.p in a range 500 nm to 575 nm and can include for example silicate-based phosphors, a garnet-based phosphor such as YAG or LuAG phosphors. Examples of such phosphors are given in TABLE 1. In an embodiment, the yellow to green-emitting phosphor comprises a green-emitting LuAG-based phosphor as taught in U.S. Pat. No. 8,529,791 entitled Green-Emitting, Garnet-Based Phosphors in General and Backlighting Applications which is hereby incorporated in its entirety. Such a green-emitting phosphor comprises a cerium-activated, green-emitting lutetium aluminate phosphor consisting of lutetium, cerium, at least one alkaline earth metal, aluminum, oxygen, and at least one halogen, wherein the phosphor is configured to absorb excitation radiation having a wavelength ranging from about 380 nm to about 480 nm, and to emit light having a peak emission wavelength .sub.p ranging from about 500 nm to about 550 nm. An example of such a phosphor is GAL535 phosphor from Intematix Corporation, Fremont Calif., USA which has a peak emission wavelength of 535 nm.
(39) TABLE-US-00001 TABLE 1 Example yellow to green-emitting phosphors Wavelength Phosphor General Composition .sub.p (nm) YAG Y.sub.3x(Al.sub.1yGa.sub.y).sub.5O.sub.12:Ce.sub.x 0.01 < x < 0.2 & 520-550 0 < y < 2.5 LuAG Lu.sub.3x(Al.sub.1yM.sub.y).sub.5O.sub.12:Ce.sub.x 0.01 < x < 0.2 & 500-575 0 < y < 1.5 M = Mg, Ca, Sr, Ba, Ga, Silicate A.sub.2SiO.sub.4:Eu A = Mg, Ca, Sr, Ba 500-550 Silicate (Sr.sub.1xBa.sub.x).sub.2SiO.sub.4:Eu 0.3 < x < 0.9 500-550
(40) The red-emitting photoluminescence material (eg. Phosphor) can comprise any photoluminescence material which, when excited by excitation light (typically blue light), emits light with a peak emission wavelength .sub.p in a range 600 nm to 650 nm. As described below and in accordance with an embodiment of the invention, the red-emitting photoluminescence material exhibits a blue quench characteristic in which its emission intensity decreases as the excitation photon density increases.
(41) Optionally, the photoluminescence wavelength conversion material can further comprise an orange to red-emitting photoluminescence material (eg. Phosphor) material, for example, for increasing CRI and/or reducing color temperature. The orange to red-emitting photoluminescence material can comprise any photoluminescence material which, when excited by blue light, emits light with a peak emission wavelength .sub.p in a range 580 nm to 620 nm and can include for example a silicate, europium activated silicon nitride-based phosphor or -SiAlON phosphor. Examples of such orange to red-emitting phosphors are given in TABLE 2. In one embodiment, the orange-emitting phosphor comprises a red-emitting phosphor as taught in U.S. Pat. No. 8,597,545 entitled Red-Emitting Nitride-Based Calcium-Stabilized Phosphors which is hereby incorporated in its entirety. Such a red emitting phosphor comprises a nitride-based composition represented by the chemical formula M.sub.aSr.sub.bSi.sub.cAl.sub.dN.sub.eEu.sub.f, wherein: M is Ca, and 0.1a0.4; 1.5<b<2.5; 4.0c5.0; 0.1d0.15; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. Alternatively, the red-emitting phosphor comprises a red light emitting nitride-based phosphor comprises a as taught in U.S. Pat. No. 8,663,502 entitled Red-Emitting Nitride-Based Phosphors which is hereby incorporated in its entirety. Such a red emitting phosphor comprising a nitride-based composition represented by the chemical formula M.sub.(x/v)M.sub.2Si.sub.5-xAl.sub.xN.sub.8:RE, wherein: M is at least one monovalent, divalent or trivalent metal with valence v; M is at least one of Mg, Ca, Sr, Ba, and Zn; and RE is at least one of Eu, Ce, Tb, Pr, and Mn; wherein x satisfies 0.1x<0.4, and wherein said red-emitting phosphor has the general crystalline structure of M.sub.2Si.sub.5N.sub.8:RE, Al substitutes for Si within said general crystalline structure, and M is located within said general crystalline structure substantially at the interstitial sites. An example of one such a phosphor is XR600 red nitride phosphor from Intematix Corporation, Fremont Calif., USA which has a peak emission wavelength of 600 nm.
(42) TABLE-US-00002 TABLE 2 Example orange to red-emitting phosphors Wavelength Phosphor General Composition .sub.p (nm) -SiAlON Ca.sub.(x/2)Si.sub.12xAl.sub.xN.sub.16:Eu 0 < x < 6 580-610 -SiAlON M.sub.xSi.sub.12-(m+n)Al.sub.m+nO.sub.nN.sub.16n:Eu M = Ca, Sr, Y..; x<2 580-600 CASN (Ca.sub.1xSr.sub.x)AlSiN.sub.3:Eu 0.5 < x 1 600-660 258 nitride Ba.sub.2xSr.sub.xSi.sub.5N.sub.8:Eu 0 x 2 580-620 Silicate (Ba.sub.xSr.sub.1x).sub.3SiO.sub.5:Eu 0 x 0.2 586-600 Silicate (Ba.sub.xY.sub.ySr.sub.1xy).sub.3(Al.sub.ySi)O.sub.5:Eu 0 x 0.2, 0 y 0.4 600-615
(43) In operation, blue excitation light generated by the LED chips 210 excites the photoluminescence wavelength conversion material 240 to generate yellow to green and red photoluminescence light. The emission product of the LED-filament 140 which appears white in color comprises the combined photoluminescence light and unconverted blue excitation light. Since the photoluminescence light generation process is isotropic, phosphor light is generated equally in all directions and light emitted in a direction towards the substrate can pass through the substrate and be emitted from the rear of the LED-Filament. Use of a light-transmissive substrate thus enables the LED-filament to achieve a generally omnidirectional emission characteristic. Additionally, particles of a light reflective material can be combined with the phosphor material to reduce the quantity of phosphor required to generate a given emission product color. Furthermore, it should be understood that the color of the light generated by the LED-filament can be changed by including additional phosphors.
(44) In other embodiments, the LED chip can comprise surface mountable or flip-chip devices. The LED chips 210 can be mounted to the substrate board by soldering, a thermally conductive adhesive or by other fixing methods which will be apparent to those skilled in the art.
(45) Where the light-transmissive substrate 200 comprises a thermally conductive material, the LED chips 210 are advantageously mounted in thermal communication with the circuit board. A heat sink compound such as beryllium oxide can be used to aid in thermal coupling of the LED chips to the circuit board.
(46) LED-Filament Lamps: B-Series (B11) Bullet Lamp
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(48) As illustrated, the LED-filament lamp 300 can comprise an E12 (12 mm) connector base (Edison screw lamp base) 110. If practicable, the connector base 110 can house driver circuitry (not shown) for operating the LED-filaments. Where it is impracticable to house the driver circuitry in the connector base 110 the LED-filament lamp 300 can further comprise an extender (not shown) disposed between the envelope 120 and connector base 110. The extender can comprise for example a hollow frusto-conical element comprising a plastics material.
(49) Light emitting devices of the present invention have been described herein as LED-filaments including a light-transmissive substrate which is elongate in form and also as devices with LED chips mounted on only one side of the substrate. However, in other embodiments the light-transmissive substrate may be circular, square, or one of many other shapes, the device may have LED chips may be mounted on both or several sides of a light-transmissive substrate.
(50) LED-Based Light Emitting DevicesWhite LED
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(52) The device 400 can comprise one or more blue-emitting GaN (gallium nitride)-based LED chips 210 that are housed within a package 402. The one or more LED chips are operable to generate blue light with a dominant wavelength within a range of 440 nm to 470 nm, typically 450 nm to 455 nm. The package, which can for example comprise a Surface Mountable Device (SMD) such as an SMD 5630 LED package, comprises upper and lower body portions 404 and 406. The upper body portion 404 defines a rectangular-shaped recess (cavity) 408 which is configured to receive the one or more LED chips 210. The package further comprises electrical connectors 410 and 412 on the base that are electrically connected to corresponding electrode contact pads 414 and 416 on the floor of the recess 408. Using adhesive or solder, the LED chip(s) 110 can be mounted to a thermally conductive pad 418 located on the floor of the recess 408. The thermally conductive pad 418 is thermally connected to a thermally conductive pad 420 on the base of the package. The LED chip's electrode pads are electrically connected to corresponding electrode contact pads 414 and 416 on the floor of the package using bond wires 422 and 424 and the recess 418 is completely filled with a transparent silicone 426 which is loaded with a mixture of a yellow to green-emitting phosphor, optionally an orange to red-emitting phosphor, and a red-emitting phosphor such that the exposed surfaces of the LED chip 210 are covered by the phosphor/silicone material mixture. To enhance the emission brightness of the device, the walls of the recess 408 are inclined and have a light reflective surface.
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(54) Red-Emitting Phosphor
(55) As described above, the inventors have discovered that use of a red-emitting phosphor having a photoluminescence characteristic with an enhanced level of blue quenching, compared with known phosphors, in particular yellow to green emitting phosphors, enables LED-based devices and LED-filaments to be implemented that exhibit levels of warm dimming that resemble those of a traditional incandescent light source. More particularly, the inventors postulate that it is the reduction of conversion efficiency (CE) with increasing excitation energy (blue photon density) that has the biggest effect, though enhanced changes of chromaticity CIE x and CIE y of light generated by the red phosphor with increasing excitation (blue) photon density also contribute to the warm dimming effect. In addition, the red-emitting phosphor of the invention can also show enhanced levels of thermal quenchingdecrease of emission intensity and/or chromaticity CIE x and CIE y change with an increase in temperatureand by careful thermal management of the device/filament thermal quenching can be used to increase the CCT change on dimming.
(56) Group IIA/IIB Selenide Sulfide-Based Red-Emitting Phosphors
(57) Examples of red-emitting phosphors that exhibit blue quenching and are suitable for the invention are Group IIA/IIB selenide sulfide-based phosphor materials having a composition M.sub.1-ySe.sub.1-xS.sub.x:Eu.sub.y, wherein M is at least one of Mg, Ca, Sr, Ba and Zn, 0<x<1.0 and 0.0005y<0.005. A particular example of this phosphor material is CSS phosphor (CaSe.sub.1-xS.sub.x:Eu.sub.y). Details of CSS phosphors are provided in co-pending U.S. patent application Ser. No. 15/282,551 filed 30 Sep. 2016, which is hereby incorporated by reference in its entirety. It is envisaged that the CSS narrow-band red phosphors described in U.S. patent application Ser. No. 15/282,551 can be used in the present invention.
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(59) CSS phosphor particles can be synthesized from purified CaSeO.sub.4 and CaSO.sub.4 in a mild H.sub.2 (gas) environment (for example 5% H.sub.2/N.sub.2).
(60) The CSS phosphor particles can be coated with one or more oxides, for example: aluminum oxide (Al.sub.2O.sub.3), silicon oxide (SiO.sub.2), titanium oxide (TiO.sub.2), zinc oxide (ZnO), magnesium oxide (MgO), zirconium oxide (ZrO.sub.2), boron oxide (B.sub.2O.sub.3) or chromium oxide (CrO). Alternatively and/or in addition, the narrow-band red phosphor particles may be coated with one or more flourides, for example: calcium fluoride (CaF.sub.2), magnesium fluoride (MgF.sub.2), zinc fluoride (ZnF.sub.2), aluminum fluoride (AlF.sub.3) or titanium fluoride (TiF.sub.4). In embodiments, the coatings may be a single layer, or multiple layers with combinations of the aforesaid coatings. The combination coatings may be coatings with an abrupt transition between the first and second materials, or may be coatings in which there is a gradual transition from the first material to the second material thus forming a zone with mixed composition that varies through the thickness of the coating. The thickness of the coating may typically be in the ranges 100 nm to 5 m, 50 nm to 100 nm, 100 nm to 500 nm, 500 nm to 1 m, or 1 m to 2 m. Coated CSS narrow-band red phosphor particle samples used in the examples herein are coated with approximately 1 m of amorphous alumina (Al.sub.2O.sub.3).
(61) The particles can be coated by a CVD process in a fluidized bed reactor. In a typical coating process, the phosphor powder is loaded into the reactor and heated to 100-250 C., preferably 200 C., under N.sub.2 gas flow. When an oxide coating is to be deposited, a metal organic oxide precursor MO such as TrimethylAluminum (TMA), Titanium tetra-chloride (TiCl.sub.4), Silicon tetra-chloride (SiCl.sub.4), or DimethylZinc (DMZ) was introduced in to the reactor with a N.sub.2 carrier gas through a bubbler. H.sub.2O vapor was also introduced into the reactor to react with the metal oxide precursor to form oxide coating layers on phosphor particles. Complete fluidization of the particles being coated (from gas flow optimization, etc.) without any dead space is important to ensure homogeneous coating of all phosphor particles. In a typical coating conducted at 200 C., for a 250 g phosphor particle loading of the reactor, the coating was produced with a metal oxide precursor feeding rate of 1 to 10 g/hour for 4 hours, while feeding H.sub.2O at a rate of 2 to 7 g/hour. These conditions can produce dense and pinhole free coatings and these conditions are able to produce dense substantially pin-hole free coatings of uniform thickness, with a theorized percentage solid space (percentage bulk density) of greater than 95% and in embodiments greater than 97% and in embodiments greater than 99%. In this patent specification, percentage solid space=(bulk density of the coating/density of the material within a single particle)100. It will be understood that the percentage solid space (% solid space) provides a measure of the porosity of the coating resulting from pinholes.
(62) The inventors have found that the amount of blue quenching and thermal quenching can be altered (tuned) by changing the amount of activator (Eu). TABLE 3 tabulates compositions of various sample red-emitting CSS phosphors of the invention.
(63) TABLE-US-00003 TABLE 3 Red-emitting CSS (Ca.sub.1ySe.sub.1xS.sub.x:Eu.sub.y) phosphors Composition Wavelength .sub.p Name x y (nm) CSS627H 0.4 0.0040 627 1.5 CSS630L 0.5 0.0015 630 1.5 CSS630M 0.5 0.0020 630 1.5 CSS630H 0.5 0.0030 630 1.5 CSS634L 0.6 0.0015 634 1.5 CSS634H 0.6 0.0030 634 1.5
(64) Test DataRed-Emitting Phosphor Blue Quenching
(65) Phosphor Blue Quenching was measured using a phosphor cavity test. The cavity test method involves mixing phosphor powder with an uncurable optical encapsulant (Silicone) and placing the mixture in a 5630 cavity (5.6 mm3.0 mm) containing a 0.5 W blue LED (dominant wavelength 454 nm) and measuring total light emission in an integrating sphere.
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(67) Table 4 tabulates measured cavity test data of relative CE (%) as a function of LED DC Power (W) for red-emitting phosphors: (i) CSS627H, (ii) CSS630L, (iii) CSS630H, (iv) CSS634L, (v) CSS634M, (vi) CSS634H, (vii) CASN650 and (viii) green-emitting phosphor GAL535.
(68) TABLE-US-00004 TABLE 4 Measured 5630 cavity test data of relative CE (%) with LED DC Power (W) Reduction in CE from 2.5% LED DC Power (W) power to full 0.013 0.055 0.180 0.320 0.508 power (%) CASN650 100.0 97.2 96.3 95.5 95.4 4.6 CSS627H 100.0 89.1 78.6 72.4 67.4 32.6 CSS630H 100.0 96.6 91.9 88.3 84.8 15.2 CSS630L 100.0 95.7 91.8 88.9 86.3 13.7 CSS634H 100.0 97.2 92.4 88.8 85.5 14.5 CC634M 100.0 97.8 94.4 91.7 89.7 10.3 CSS634L 100.0 98.2 95.6 93.4 91.5 8.5 GAL535 100.0 99.2 98.8 97.9 97.7 2.3
(69) As can be seen from TABLE 4 and
(70) TABLE 5 tabulates measured cavity test data of change in chromaticity CIE x (CIE x)relative to CIE x at the lowest power (0.013 W)as a function of LED DC Power (W) for red-emitting phosphors: (i) CSS627H, (ii) CSS630L, (iii) CSS630H, (iv) CSS634L, (v) CSS634M, (vi) CSS634H, (vii) CASN650 and (viii) green-emitting phosphor GAL535.
(71) TABLE-US-00005 TABLE 5 Measured cavity test data of change in chromaticity CIE x (CIE x) with LED DC Power (W) LED DC Power (W) Phosphor 0.013 0.055 0.180 0.320 0.508 CASN650 0 0.0025 0.0023 0.0013 0.0002 CSS627H 0 0.0170 0.0351 0.0474 0.0601 CSS630H 0 0.0123 0.0202 0.0270 0.0338 CSS630L 0 0.0081 0.0170 0.0240 0.0318 CSS634H 0 0.0108 0.0207 0.0276 0.0349 CC634M 0 0.0080 0.0171 0.0229 0.0277 CSS634L 0 0.0068 0.0143 0.0192 0.0238 GAL535 0 0.0016 0.0024 0.0025 0.0036
(72) As can be seen from TABLE 5 and
(73) TABLE 6 tabulates measured cavity test data of change in chromaticity CIE y (CIE y)relative to CIE y at the lowest power (0.013 W)as a function of LED DC Power (W) for red-emitting phosphors: (i) CSS627H, (ii) CSS630L, (iii) CSS630H, (iv) CSS634L, (v) CSS634M, (vi) CSS634H, (vii) CASN650 and (viii) green-emitting phosphor GAL535.
(74) TABLE-US-00006 TABLE 6 Measured cavity test data of change of chromaticity CIE y (CIE y) with LED DC Power (W) LED DC Power (W) Phosphor 0.013 0.055 0.180 0.320 0.508 CASN650 0 0.0020 0.0025 0.0026 0.0027 CSS627H 0 0.0100 0.0206 0.0276 0.0345 CSS630H 0 0.0067 0.0112 0.0146 0.0179 CSS630L 0 0.0044 0.0093 0.0129 0.0166 CSS634H 0 0.0056 0.0112 0.0146 0.0179 CC634M 0 0.0043 0.0094 0.0125 0.0147 CSS634L 0 0.0035 0.0074 0.0099 0.0118 GAL535 0 0.0061 0.0074 0.0086 0.0101
(75) As can be seen from TABLE 6 and
(76) Test DataRed-Emitting PhosphorThermal Quenching
(77) Phosphor Thermal quenching was measured using a phosphor powder test. The phosphor powder test involves placing phosphor powder on a temperature controllable stage and illuminating the phosphor powder with blue LED light of a constant power (dominant wavelength 454 nm) and measuring the emitted light.
(78)
(79) As can be seen from
(80) As can be seen from
(81) As can be seen from
(82) Test DataLED-Filament
(83) Test data for an LED-filament in accordance with the invention will now be described. The LED-filament comprises a 38 mm0.8 mm glass substrate comprising 31 serially connected LED chips (chip size 921 one thousandths of an inch, dominant wavelength 455 to 460 nm). The phosphor encapsulant comprises a mixture of GAL53 (92 wt %) and CSS630H (8 wt %).
(84) TABLE 7 tabulates measured test data for an LED-filament in accordance with the invention. All data are measured at steady state conditions.
(85) TABLE-US-00007 TABLE 7 Measured test data for nominal 2700K LED-filament comprising GAL535 + CSS630L DC drive Voltage Current Power Flux Efficacy Chromaticity CCT CRI CCT (V) (mA) (W) (lm) (lm/W) CIE x CIE y (K) Ra R8 R9 (K) 80.10 1.4 0.11 18.7 166.8 0.5115 0.4056 2082 87.2 70.6 45.7 712 80.81 2.4 0.20 31.3 160.1 0.5095 0.4070 2109 88.0 69.9 44.4 685 81.61 4.4 0.36 55.2 154.4 0.5063 0.4087 2150 88.5 68.7 41.3 644 82.03 6.4 0.52 77.0 147.8 0.5026 0.4101 2195 88.5 67.3 36.8 599 82.25 8.4 0.69 96.1 139.8 0.4978 0.4120 2256 88.5 66.5 34.3 538 82.32 10.4 0.85 112.4 131.5 0.4924 0.4138 2326 88.5 65.8 32.5 468 82.29 12.4 1.02 125.3 123.2 0.4866 0.4158 2402 88.3 65.4 30.6 392 82.11 15.4 1.26 139.0 110.3 0.4771 0.4186 2536 88.1 64.9 27.9 258 81.79 18.4 1.50 145.5 96.9 0.4668 0.4213 2687 87.7 64.6 24.8 107 81.55 20.4 1.66 145.6 87.6 0.4599 0.4230 2794 87.6 64.4 23.8 0
(86)
(87) As can be seen from
(88) Comparing the emission spectra of
(89) Test DataWhite LED
(90) Test data for a white LED in accordance with the invention will now be described. The white LED comprises a Kaistar 2835 (28 mm35 mm) cavity comprising a single blue LED chip (chip size 2240 one thousandths of an inchdominant wavelength 445 to 450 nm). The phosphor encapsulant comprises a mixture of GAL535 (89 wt %) and CSS630H (11 wt %). All data were tested using a pulse current arrangement to separate the effects of blue quenching and thermal quenching.
(91) TABLE 8 tabulates measured test data for a nominal 2700 K 2835 white LED in accordance with the invention.
(92) TABLE-US-00008 TABLE 8 Measured test data for nominal 2700K 2835 white LED comprising GAL535 + CSS627H DC drive Voltage Current Power Flux Efficacy Chromaticity CCT CRI CCT (V) (mA) (W) (lm) (lm/W) CIE x CIE y (K) Ra R8 R9 (K) 2.61 0.001 0.003 1.0 147.6 0.5001 0.4053 2187 87.5 61.6 23.3 435 2.62 0.005 0.013 2.4 145.6 0.4991 0.4060 2202 87.6 61.7 23.4 420 2.64 0.010 0.026 4.0 143.1 0.4977 0.4070 2223 87.8 61.9 23.5 399 2.66 0.015 0.040 5.7 140.6 0.4964 0.4079 2242 87.9 62.0 23.6 380 2.68 0.020 0.054 7.4 138.0 0.4950 0.4088 2262 88.0 62.1 23.7 360 2.75 0.040 0.110 14.1 127.9 0.4896 0.4125 2346 88.5 62.6 24.1 276 2.88 0.080 0.230 26.1 113.3 0.4804 0.4148 2467 88.2 62.7 20.5 155 2.93 0.100 0.293 31.5 107.4 0.4768 0.4156 2516 87.8 62.6 19.7 106 2.99 0.120 0.359 36.6 102.1 0.4736 0.4162 2561 87.6 62.4 18.3 61 3.07 0.150 0.460 43.7 95.0 0.4691 0.4167 2622 87.9 62.3 18.0 0
(93)
(94) As can be seen from
(95) Similar to LED-filament data described above (
(96) As described above, the white LED test data were conducted using a pulsed current such that only the effects of blue quenching are being measured. As a result, the reason for the reduction in red light is due to blue quenching. Thermal measurements of the white indicate that a further 300K of warm dimming may be possible for a temperature change of 25 C. to 100 C. For comparison,
(97) To summarize, it is postulated that the invention is realized by the provision of a white light emitting device or LED-filament having a red-emitting phosphor and a yellow to green-emitting phosphor that are excitable by blue light (blue-light excitable) and in which blue quenching occurs in the red-emitting phosphor to a greater extent than the yellow to green-emitting phosphor. More particularly, the red phosphor exhibits a change in conversion efficiency with increasing powermore specifically, an increase in excitation (blue) photon densitythat is substantially larger than the change in conversion efficiency of the yellow to green-emitting phosphor with increasing power. Such an arrangement has the effect that the relative proportion of green and red light in the emission spectrum will change with power and it is this change in the emission spectrum which results in a change in color temperature of emitted light in response to the change in power.
(98) It will be appreciated that light emitting devices in accordance with the invention are not limited to the exemplary embodiments described and that variations can be made within the scope of the invention. For example whilst the invention has been described in relation to LED-based light emitting devices the invention also applies to devices based on other solid-state light emitters including solid-state lasers and laser diodes.