Wavelength conversion materials are extensively used in the solid state lighting applications. Wavelength conversion materials or luminescent elements will convert light of a first color or wavelength into light of a second color or wavelength.
Typically powder phosphors are mixed with an organic binder system to form a luminescent element and deposited on the LED directly or at a distance as discussed by various authors as “phosphor at a distance”. While this approach is sufficient for low level light outputs, the luminescent element has significant shortcomings at high flux levels. The binder degrades due to photochemical effects especially in the presence of moisture. Thermal quenching effects on the converted light becomes important as the flux levels increase.
U.S. Pending patent application Ser. No. 12/380,439 for “Fixtures for Large Area Directional and Isotropic Solid State Lighting Panels” and U.S. Pending patent application Ser. No. 12/383,567 for “High Quality Luminescent Materials for Solid State Lighting Applications”, commonly assigned as the present application and herein incorporated by reference, have demonstrated that the formation of thermally conductive luminescent elements can be used to increase the useful range of the phosphors by providing a thermal conduction pathway for maintaining the wavelength conversion material at a lower temperature. It is desirable that the wavelength spectrum of these solid state lighting sources be controllable. At high current levels, the LEDs themselves shift their spectrum of the light they emit.
Wavelength conversion materials change their efficiency as a function of temperature. These effects are typically not seen in low level flux applications. However at high flux levels, especially for powders with little thermal conductivity or means of cooling, these effects can be as significant as the efficiency and color shifts associated with the LED itself. The present invention discloses methods and light sources whereby these color shifts caused by temperature changes to the wavelength conversion materials in the luminescent elements can be controlled or eliminated and stabilize the color of light emitted by the light source.
As an example, a blue LED with a yellow Ce:Yag powder phosphor contained within an organic binder typically has an increasing color temperature with increasing current level to the LED. This color shift is a function of the Ce:Yag experiencing a reduction in lumen output due to thermal quenching effects. Most luminescent materials, including quantum dots, isolated ions, organic and inorganic phosphors, exhibit thermal spectrum and output level changes versus temperature. The LED in this example is a GaN based LED which exhibits a blue shift with increasing current level. As such, the blue lumens are decreasing as the current increases. If the phosphor output level were stable, one would expect a decreasing color temperature. This decreasing color temperature typically is not the case because the rate at which the phosphor lumen output is decreasing is much higher than the rate at which the blue LED lumen output is decreasing, which leads to an overall increase in color temperature.
The present invention teaches methods and light sources which increase efficiency of the overall light source by controlling backscatter within the solid luminescent element such that a more optimum dopant concentration can be used with less concentration quenching.
The present invention discloses a color stabilized light source, which has a thermally conductive luminescent element in conjunction with a light emitting diode. This color stabilized light source does not color shift in the same manner as powder based wavelength conversion material at high flux levels.
The present invention teaches that the output level of the thermally conductive luminescent element can be maintained even at high flux levels if a thermal conduction path, either through the LED or through some other thermal pathway, is provided.
The thermal conduction path enhances the efficiency of the light source and also affects the color temperature shift that occurs within the light source. Thermally conductive luminescent elements can enhance efficiency and/or color temperature control at high flux levels. Even more preferably the combination of LED color shift and phosphor intensity changes leads to inherently stable color temperature sources over an extended current drive level.
Alternately, the combination of LED color shift and phosphor intensity changes to create a particular color temperature change versus drive level. These color stabilized light sources can be used in general illumination, display cases, food displays, museums and other color critical illumination applications. The dynamic control of the color temperature is based on using at least one stabilized color source and at least one other color source. More preferably, dynamically controlled color sources in projection application can reduce the binning requirements for LEDs. Even more preferably, passively or dynamically controlled color sources can create green/yellow, orange/red, and/or cyan/blue sources to extend or provide adjustable color gamut for displays including but not limited to projection, LCD backlights, LED displays, and fixed format.
The thermally conductive luminescent element 22 is formed from wavelength conversion materials. The wavelength conversion materials absorb light in a first wavelength range and emit light in a second wavelength range, where the light of a second wavelength range has longer wavelengths than the light of a first wavelength range. The wavelength conversion materials may be, for example, phosphor materials or quantum dot materials. The thermally conductive luminescent element may be formed from two or more different wavelength conversion materials. The thermally conductive luminescent element may also include optically inert host materials for the wavelength conversion materials of phosphors or quantum dots. Any optically inert host material must be transparent to ultraviolet and visible light.
Phosphor materials are typically optical inorganic materials doped with ions of lanthanide (rare earth) elements or, alternatively, ions such as chromium, titanium, vanadium, cobalt or neodymium. The lanthanide elements are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Optical inorganic materials include, but are not limited to, sapphire (Al.sub.2O.sub.3), gallium arsenide (GaAs), beryllium aluminum oxide (BeAl.sub.2O.sub.4), magnesium fluoride (MgF.sub.2), indium phosphide (InP), gallium phosphide (GaP), yttrium aluminum garnet (YAG or Y.sub.3Al.sub.5O.sub.12), terbium-containing garnet, yttrium-aluminum-lanthanide oxide compounds, yttrium-aluminum-lanthanide-gallium oxide compounds, yttrium oxide (Y.sub.2O.sub.3), calcium or strontium or barium halophosphates (Ca,Sr,Ba).sub.5(PO.sub.4).sub.3(Cl,F), the compound CeMgAl.sub.11O.sub.19, lanthanum phosphate (LaPO.sub.4), lanthanide pentaborate materials ((lanthanide)(Mg,Zn)B.sub.5O.sub.10), the compound BaMgAl.sub.10O.sub.17, the compound SrGa.sub.2S.sub.4, the compounds (Sr,Mg,Ca,Ba)(Ga,Al,In).sub.2S.sub.4, the compound SrS, the compound ZnS and nitridosilicate. There are several exemplary phosphors that can be excited at 250 nm or thereabouts. An exemplary red emitting phosphor is Y.sub.2O.sub.3:Eu.sup.3+. An exemplary yellow emitting phosphor is YAG:Ce.sup.3+. Exemplary green emitting phosphors include CeMgAl.sub.11O.sub.19:Tb.sup.3+, ((lanthanide)PO.sub.4:Ce.sup.3+,Tb.sup.3+) and GdMgB.sub.5O.sub.10:Ce.sup.3+,Tb.sup.3+. Exemplary blue emitting phosphors are BaMgAl.sub.10O.sub.17:Eu.sup.2+ and (Sr,Ba,Ca).sub.5(PO.sub.4).sub.3Cl:Eu.sup.2+. For longer wavelength LED excitation in the 400-450 nm wavelength region or thereabouts, exemplary optical inorganic materials include yttrium aluminum garnet (YAG or Y.sub.3Al.sub.5O.sub.12), terbium-containing garnet, yttrium oxide (Y.sub.2O.sub.3), YVO.sub.4, SrGa.sub.2S.sub.4, (Sr,Mg,Ca,Ba)(Ga,Al,In).sub.2S.sub.4, SrS, and nitridosilicate. Exemplary phosphors for LED excitation in the 400-450 nm wavelength region include YAG:Ce.sup.3+, YAG:Ho.sup.3+, YAG:Pr.sup.3+, YAG:Tb.sup.3+, YAG:Cr.sup.3+, YAG:Cr.sup.4+, SrGa.sub.2S.sub.4:Eu.sup.2+, SrGa.sub.2S.sub.4:Ce.sup.3+, SrS:Eu.sup.2+ and nitridosilicates doped with Eu.sup.2+.
Luminescent materials based on ZnO and its alloys with Mg, Cd, Al are preferred. More preferred are doped luminescent materials of ZnO and its alloys with Mg, Cd, Al which contain rare earths, Bi, Li, Zn, as well as other luminescent dopants. Even more preferred is the use of luminescent elements which are also electrically conductive, such a rare earth doped AlZnO, InZnO, GaZnO, InGaZnO, and other transparent conductive oxides of indium, tin, zinc, cadmium, aluminum, and gallium. The use of these transparent conductive oxides, oxynitrides and nitrides which are also luminescent as both interconnect means and/or wavelength conversion means is also an embodiment of this invention. Other phosphor materials not listed here are also within the scope of this invention.
Quantum dot materials are small particles of inorganic semiconductors having particle sizes less than about 30 nanometers. Exemplary quantum dot materials include, but are not limited to, small particles of CdS, CdSe, ZnSe, InAs, GaAs and GaN. Quantum dot materials can absorb light at first wavelength and then emit light at a second wavelength, where the second wavelength is longer than the first wavelength. The wavelength of the emitted light depends on the particle size, the particle surface properties, and the inorganic semiconductor material.
The transparent and optically inert host materials are especially useful to spatially separate quantum dots. Host materials include polymer materials and inorganic materials. The polymer materials include, but are not limited to, acrylates, polystyrene, polycarbonate, fluoroacrylates, chlorofluoroacrylates, perfluoroacrylates, fluorophosphinate polymers, fluorinated polyimides, polytetrafluoroethylene, fluorosilicones, sol-gels, epoxies, thermoplastics, thermosetting plastics and silicones. Fluorinated polymers are especially useful at ultraviolet wavelengths less than 400 nanometers and infrared wavelengths greater than 700 nanometers owing to their low light absorption in those wavelength ranges. Exemplary inorganic materials include, but are not limited to, silicon dioxide, optical glasses and chalcogenide glasses.
The light emitting diode 24 can be fabricated by epitaxially growing multiple layers of semiconductors on a growth substrate. Inorganic light-emitting diodes can be fabricated from GaN-based semiconductor materials containing gallium nitride (GaN), aluminum nitride (AIN), aluminum gallium nitride (AlGaN), indium nitride (InN), indium gallium nitride (InGaN) and aluminum indium gallium nitride (AlInGaN). Other appropriate materials for LEDs include, for example, aluminum gallium indium phosphide (AlGaInP), gallium arsenide (GaAs), indium gallium arsenide (InGaAs), indium gallium arsenide phosphide (InGaAsP), diamond or zinc oxide (ZnO).
Especially important LEDs for this invention are GaN-based LEDs that emit light in the ultraviolet, blue, cyan and green regions of the optical spectrum. The growth substrate for GaN-based LEDs is typically sapphire (Al.sub.2O.sub.3), silicon carbide (SiC), bulk gallium nitride or bulk aluminum nitride.
The color stabilized light source 20 can be a blue or ultraviolet emitting LED used in conjunction with a thermally conductive luminescent element one or more wavelength conversion materials such as phosphors or quantum dots that convert at least some of the blue or ultraviolet light to other wavelengths. For example, combining a yellow phosphor with a blue emitting LED can result in a white light source. The yellow phosphor converts a portion of the blue light into yellow light. Another portion of the blue light bypasses the yellow phosphor. The combination of blue and yellow light appears white to the human eye. Alternatively, combining a green phosphor and a red phosphor with a blue LED can also form a white light source. The green phosphor converts a first portion of the blue light into green light. The red phosphor converts a second portion of the blue light into green light. A third portion of the blue light bypasses the green and red phosphors. The combination of blue, green and red light appears white to the human eye. A third way to produce a white light source is to combine blue, green and red phosphors with an ultraviolet LED. The blue, green and red phosphors convert portions of the ultraviolet light into, respectively, blue, green and red light. The combination of the blue, green and red light appears white to the human eye.
The color stabilized white light source 20 of
Heat will flow from the thermally conductive luminescent element 22 through the adjacent LED. The combination of the light shift of the LED and the maintenance of the intensity of the thermally conductive luminescent element can be used to control color temperature and efficiency of a blue LED with a yellow phosphor. In this particular example, the color temperature of the combined blue and yellow spectrum versus current is determined by the rate of change in the blue spectrum and yellow spectrum. The thermal, electrical, and combinations of sources can stabilize the color temperature over a range of currents. The articles that perform those functions are embodiments of this invention.
The thermal impedance of the heatsink to ambient is also depicted. Combinations or arrays of elements such as two heatsink can be used. Both steady state and transient thermal responses are embodiments of this invention. More preferably the thermal impedance of sources in high current pulsed mode are also embodiments of this invention.
Unlike powder phosphor approaches, the thermally conductive luminescent element source can maintain high output levels at high excitation levels. This enables the formation of very high brightness sources with combined lumens/mm2 at 1 A exceeding 200 lumens/mm2 with dominate wavelengths well into the classic “green gap” which is known in the art. This technique to creates sources with high output both in the visible, UV and infrared. In the case of red sources, AlinGaP as well as other red LED sources tend to exhibit a shift towards longer wavelength.
Conversely, the radiance efficiency of AlinGap LED in particular increases at longer wavelengths but the luminous efficiency decreases due to the eye response dropping off at longer wavelengths. In this case, a more efficient source can be created by combining an efficient long wavelength AlinGap source with a thermally conductive luminescent element source at shorter wavelength where the combination creates a dominate wavelength at a longer wavelength than typically possible with the thermally conductive luminescent element source. The longer the wavelength of the thermally conductive luminescent element source the larger the stokes shift losses. In addition, a very limited set of efficient red phosphors presently exists in solid state lighting. This technique overcomes the red deficiency in solid state lighting. More preferably, orange/red thermally conductive luminescent elements will form combined sources in the spectrum range. The orange/red thermally conductive luminescent element can be used to correct for the shift to longer wavelength. Similar techniques can be used in all ranges of the visible, UV and infrared spectrum. The use of these techniques both dynamically or statically are embodiments of this invention.
Photoresponsive device 204, which may consist of but not limited to photodiodes, phototransistors, and other devices which change electrical parameters upon exposure to light, are also connected to control module 212 via control interconnect 220 and 222.
Photoresponsive devices 206, which may consist of but not limited to photodiodes, phototransistors, and other devices which change electrical parameters upon exposure to light, are also connected to control module 218 via control interconnect 224 and 226.
The output of at least one photoresponsive device 204 and/or 206 are used to control the drive levels of one and/or both sources 202 and 200. The use of pulse width modulation, amplitude modulation, and/or a combination of both to increase or decrease the intensity of sources 33 and/or 35 is an embodiment of this invention.
While the invention has been described with the inclusion of specific embodiments and examples, it is evident to those skilled in the art that many alternatives, modifications and variations will be evident in light of the foregoing descriptions. Accordingly, the invention is intended to embrace all such alternatives, modifications and variations that fall within the spirit and scope of the appended claims.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/189,652, which was filed on Aug. 21, 2008, which is herein incorporated by reference.
Number | Date | Country | |
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61189652 | Aug 2008 | US |