LED cap containing quantum dot phosphors

Abstract

An LED device has a cap containing one or more quantum dot (QD) phosphors. The cap may be sized and configured to be integrated with standard LED packages. The QD phosphor may be held within the well of the LED package, so as to absorb the maximum amount of light emitted by the LED, but arranged in spaced-apart relation from the LED chip to avoid excessive heat that can lead to degradation of the QD phosphor(s). The packages may be manufactured and stored for subsequent assembly onto an LED device.

Claims

1. A cap for an LED package having a central well containing an LED and an upper surface surrounding the central well, said cap comprising: a peripheral portion sized and configured to engage the upper surface of the LED package; a central portion depressed from the peripheral portion and comprising a side wall and a base wall, the side wall and the base wall lining a cap well; a phosphor incorporated in the base wall of the cap; and a plurality of quantum dots in the cap well, wherein the side wall of the cap is configured to abut the central well of the LED package.

2. The cap recited in claim 1, further comprising: a lid attached to the peripheral portion and covering the cap well.

3. The cap recited in claim 2, wherein the lid is transparent.

4. The cap recited in claim 2, wherein the lid is translucent.

5. The cap recited in claim 2, wherein the lid is shaped to provide a lens array.

6. The cap recited in claim 2, wherein the lid comprises a light diffuser.

7. The cap recited in claim 1, wherein the cap well is spaced apart from the LED when the cap is engaged with the LED package.

8. The cap recited in claim 1, wherein the plurality of quantum dots comprise a first type of quantum dots that emit secondary light having a first wavelength and a second type of quantum dots that emit secondary light having a second wavelength.

9. The cap recited in claim 8, wherein the first type of quantum dots emit green light when excited by blue light and the second type of quantum dots emit red light when excited by blue light.

10. The cap recited in claim 1, wherein the quantum dots comprise a central core surrounded by at least one shell.

11. The cap recited in claim 10, wherein the shell material is different from the core material.

12. The cap recited in claim 1, wherein the quantum dots comprise a core comprising indium and phosphorus surrounded by a first shell comprising ZnS surrounded by a second shell comprising ZnO.

13. The cap recited in claim 1, wherein the quantum dots are cadmium-free quantum dots.

14. The cap recited in claim 1, wherein the quantum dots are suspended in a matrix.

15. The cap recited in claim 14, wherein the matrix comprises an acrylate polymer.

16. The cap recited in claim 14, wherein the matrix comprises an epoxy polymer.

17. The cap recited in claim 1, wherein the quantum dots are incorporated into beads.

18. The light-emitting device recited in claim 1, wherein the phosphor is a broad-emitting, inorganic yellow-green phosphor.

19. The light-emitting device recited in claim 1, wherein the phosphor comprises Ce:YAG or Ce:LuAG.

20. A light-emitting device comprising: a package having a central well and an upper surface; an LED within the central well; and a cap comprising: a peripheral portion configured to engage the upper surface of the package; and a central portion depressed from the peripheral portion, the central portion comprising a side wall extending into the central well and a base wall, the side wall and the base wall lining a cap well; a phosphor incorporated in the base wall of the cap: and a plurality of quantum dots in the cap well, wherein the side wall of the cap abuts at least a portion of the central well.

21. The light-emitting device recited in claim 20, wherein the peripheral portion of the cap is attached to the upper surface of the package with an adhesive that is substantially impervious to oxygen.

22. The light-emitting device recited in claim 20, wherein the phosphor is an inorganic phosphor.

23. The light-emitting device recited in claim 20, wherein the phosphor is a broad-emitting, yellow-green phosphor.

24. The light-emitting device recited in claim 20, wherein the phosphor comprises Ce:YAG.

25. The light-emitting device recited in claim 20, wherein the phosphor comprises Ce:LuAG.

26. A light-emitting device comprising: a package having a central well and an upper surface; an LED within the central well; and a cap comprising: a peripheral portion attached to the upper surface of the package; a central portion depressed from the peripheral portion, the central portion comprising a side wall extending into the central well and a base wall, the side wall and base wall lining a cap well; a phosphor incorporated in the base wall of the cap well; and a plurality of quantum dots in the cap well, wherein the side wall of the cap abuts the central well of the package.

27. The light-emitting device recited in claim 26 wherein the LED is a blue LED, the phosphor is a broad-emitting, yellow-green phosphor, and the quantum dots are red-fluorescing quantum dots.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

(1) FIG. 1 illustrates a QD-containing LED device known in the art.

(2) FIG. 2 illustrates an LED device equipped with a pre-assembled QD-containing cap.

(3) FIGS. 3A and 3B illustrate an alternative embodiment of an LED device equipped with a pre-assembled QD-containing cap.

(4) FIG. 4 is the spectral power distributions of the empty cap with Merck Isophor phosphor embedded into the base (blue line) and same cap with containing red QDs suspended in acrylate resin (red line).

(5) FIG. 5 is a schematic illustration of a pre-assembled QD-containing cap, showing dimensions.

(6) FIG. 6A illustrates light rays emanating from an LED package of the prior art.

(7) FIG. 6B shows a conventional LED package equipped with a QD-containing cap according to the embodiment illustrated in FIG. 2.

(8) FIG. 6C shows light rays emanating from a cap according to the embodiments of the invention illustrated in FIGS. 3A and 3B.

DETAILED DESCRIPTION OF THE INVENTION

(9) FIG. 1 illustrates a LED device 100, wherein solid-state LED 101 is arranged to emit blue primary light 102 upon the application of current. Solid-state LED is submerged in a commercially available LED encapsulant 103, in which is embedded a plurality of quantum dot-containing silica beads 104 and 105. Some of the beads 104 contain quantum dots that emit red secondary light 106 upon excitation by the blue primary light from the LED 101, and the remaining beads 105 contain quantum dots that emit green secondary light 107 upon excitation by the blue primary light from the LED 101. LED devices, as illustrated in FIG. 1, are described in more detail in commonly-owned U.S. patent application Ser. No. 12/888,982 filed Sep. 23, 2010, (published as U.S. 2011/0068322), the entire contents of which is hereby incorporated by reference.

(10) Challenges with adapting quantum dots as light converting materials in LED-based lighting solutions stem from their air sensitivity, heat instability and reduction in light conversion efficiencies at higher temperatures. One method of reducing the air sensitivity is incorporating the QDs into beads, such as beads 104 and 105. However, the embodiment illustrated in FIG. 1 can still suffer from heat-related problems because the QDs are proximate the LED junction, which is typically the hottest-running part of an LED device.

(11) FIG. 2 illustrates an improvement on the embodiment illustrated in FIG. 1. The LED device 200 of FIG. 2 includes a standard LED package 201 having an LED chip 202, disposed within a well 203. Well 203 may be filled with an LED encapsulant, as is known in the art. LED device 200 also includes a lid 204 having a cap well 205 (the term cap well is used herein to distinguish the well of the lid 205 from the well 203 of the LED package 201). QDs 206 are deposited within cap well 205. Well 205 may be equipped with a cover 207.

(12) Lid 204 may be made of essentially any transparent material, such as polymer, ceramic, glass, or the like, and may be constructed using molding, casting, etc. Optionally, lid 204 may be shaped to provide a lens, a lens array, diffuser elements, and or other optical elements as are known in the art. Likewise, cover 207 may be made of glass, polymer, ceramic, or the like, and may be sealed to lid 204 by adhesion using a suitable UV curing epoxy resin, e.g. Optocast 3553 or other resin, as known in the art. Advantageously, the seal between cover 207 and lid 204 can form an oxygen impermeable barrier, thereby protecting QDs 206 from oxidation.

(13) QDs 206 are typically semiconductor material that may incorporate ions from any one or more of groups 2 through 16 of the periodic table, and may include binary, ternary and quaternary materials, that is, materials incorporating two, three or four different ions respectively. By way of example, the nanoparticle may incorporate a semiconductor material, such as, but not limited to, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge and combinations thereof. According to various embodiments, nanoparticles may have diameters of less than around 100 nm, less than around 50 nm, less than around 20 nm, less than around 15 nm and/or may be in the range of around 2 to 10 nm in diameter.

(14) Nanoparticles that include a single semiconductor material, e.g., CdS, CdSe, ZnS, ZnSe, InP, GaN, etc. may have relatively low quantum efficiencies because of non-radiative electron-hole recombination that occurs at defects and dangling bonds at the surface of the nanoparticles. In order to at least partially address these issues, the nanoparticle cores may be at least partially coated with one or more layers (also referred to herein as shells) of a material different than that of the core, for example a different semiconductor material than that of the core. The material included in the, or each, shell may incorporate ions from any one or more of groups 2 to 16 of the periodic table. When a nanoparticle has two or more shells, each shell may be formed of a different material. In an exemplary core/shell material, the core is formed from one of the materials specified above and the shell includes a semiconductor material of larger band-gap energy and similar lattice dimensions as the core material. Exemplary shell materials include, but are not limited to, ZnS, ZnO, MgS, MgSe, MgTe and GaN. An exemplary multi-shell nanoparticle is InP/ZnS/ZnO. The confinement of charge carriers within the core and away from surface states provides nanoparticles of greater stability and higher quantum yield.

(15) While the disclosed methods are not limited to any particular nanoparticle material, nanoparticles comprising materials that do not contain cadmium are particularly preferred. Examples of cadmium free nanoparticles include nanoparticles comprising semiconductor materials, e.g., ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge, including alloys and doped derivatives thereof, and, particularly, nanoparticles comprising cores of one of these materials and one or more shells of another of these materials. Particularly suitable QDs are CFQD? heavy metal-free quantum dots (Nanoco Technologies, Manchester, U.K.).

(16) QDs 206 may be suspended in a matrix material such as a polymer such as an acrylate or epoxy polymer or a combination thereof. Bare QDs may be suspended in the matrix, or alternatively, the QDs may first be incorporated into beads, as described in U.S. Pub. Nos. 2011/0068322 and 2010/0123155, the entire contents of which are hereby incorporated by reference.

(17) An advantage of the LED device 200 is that the lid 204 containing QDs 206 can have an appreciable shelf life prior to being incorporated onto the LED device. Thus, it is not critical that the LED device be made immediately following the construction of lid 204. This is in contrast to devices having the QDs deposited directly into the well of the LED package, because in those devices the QDs are typically not covered and isolated from the atmosphere until the entire package is assembled. LED device 200 thus provides greater flexibility of manufacture workflow. Moreover, during operation, the QDs 206 of LED device 200 are remote from LED chip 202 and are therefore not as susceptible to complications due to heating as they would be if they were proximate to the LED chip, as in the device of FIG. 1.

(18) FIG. 3A illustrates an alternative embodiment of an LED device 300, having an LED package 301 with an LED chip 302 and a well 303. Device 300 is provided with a cap 304 having a cap well part 305 that is designed to fit into well 303. Cap 304 also has a cap lid part 306 and a cavity 307, within which QDs 308 are contained. All of the materials discussed above in reference to the embodiment illustrated in FIG. 2 are also suitable for the embodiment illustrated in FIG. 3.

(19) FIG. 3B illustrates a larger view of cap 304. According to one embodiment, an additional inorganic phosphor can be incorporated into the base wall 309 of cap 304. Exemplary phosphors include Ce:YAG, Ce:LuAG, and other broad emitting yellow-green phosphors. The combination of broad emitting yellow-green phosphors with red CFQD? heavy metal-free quantum dots in conjunction with a blue LED can produce a very high-quality light source. Thus, one embodiment is a single optical element combining both QD phosphors and conventional bulk phosphors.

(20) As with the embodiment illustrated in FIG. 2, cap 304 can be constructed by molding, casting, etc. In the case of caps incorporating phosphor, a multi-step casting process may be necessary. Furthermore, a multistage casting process using a resin filled with white reflective material may be used for the walls and top of the cap while using a transparent colorless resin for the base to allow light from the LED to enter the cap.

(21) A potential advantage of the embodiment illustrated in FIG. 3 over that of FIG. 2, is that the QD phosphor is situated closer to the LED chip in the FIG. 3 embodiment, and therefore absorbs more light. Consequently, less QD phosphor can be used. The QD phosphor is still protected from heat-caused deterioration by the base wall of the cap.

(22) Table 1 compares measured optical performance data for an empty cap, as illustrated in FIG. 3B, the base of which is impregnated with Merck Isophor phosphor and the same cap containing red CFQD? heavy metal-free quantum dots (Nanoco Technologies Ltd., Manchester, U.K.) suspended in acrylate resin:

(23) TABLE-US-00001 TABLE 1 Phosphor Only Phosphor + QD Radiant Flux (Watts) 0.016 0.016 Luminous Flux (lumens) 4.6 4.2 Chromaticity x coord 0.249 0.383 Chromaticity y coord 0.324 0.332 Efficacy 76 70 CRI 65 82

(24) FIG. 4 illustrates the spectral power distributions of the empty cap with Merck Isophor phosphor embedded into the base (blue [or solid] line) and the same cap containing red QDs suspended in acrylate resin (red [or dashed] line).

(25) Caps were prepared as described below to fit standard 3528 and 5050 LED packages.

EXAMPLE 1

(26) Caps, as illustrated in FIG. 3, were prepared using a casting method utilizing pairs (male/female) of silicone molds. Into a female mold, 6 microliters of Optocast 3553 epoxy resin were dispensed. The male mold was then put in place with care to ensure the locator points were aligned. During this stage any excess resin is expelled from the cap mold reservoir and leaks into the space between the mold pair. The mold was then irradiated with UV light to cure the epoxy resin. The conditions for the cure are as follows: 360 nm, 170 mW/cm.sup.2, 72 seconds. After curing, the caps were de-molded and stored for 24 hours at room temperature after which excess flashing was removed using a scalpel. The caps were transparent and could be used with QD phosphor.

EXAMPLE 2

(27) Caps with a phosphor-impregnated base were prepared using a two-stage process. Firstly, the base was prepared by mixing the appropriate amount of phosphor into uncured Optocast 3553 epoxy resin. 3 microliters was dispensed into mold, which is of the same width dimensions as the base of the cap but 50 microns thinner. The epoxy was cured by irradiating with UV light. The conditions for the cure were as follows: 360 nm, 170 mW/cm.sup.2, 72 seconds. To fabricate the finished cap, the phosphor base was incorporated into the final cap as follows: 15 microliters of uncured Optocast 3553 epoxy resin were deposited into the female 5050 silicone mold. The phosphor base was then introduced and pushed carefully to the bottom of the mold taking care not to entrap any air. The male 5050 silicone mold was then introduced with care to ensure the locator points were aligned. Excess epoxy resin is expelled from the mold and forms flashing once cured. The cure conditions used were as described above. Most dimensions are determined by the LED package. The wall thickness of the caps used in these examples of the 5050 cap was 350 microns, as shown in FIG. 5.

EXAMPLE 3

(28) Caps for 5050 packages with phosphor-impregnated bases were prepared as described above. In an inert atmosphere glove box, these were filled with 7 microliters of CFQD-containing acrylate resin and cured (360 nm, 170 mW/cm.sup.2, 180 seconds). A lid prepared from 150-micron-thick borosilicate glass was applied by depositing 5 microliters of Optocast 3553 epoxy resin onto the acrylate resin then pushing the lid down firmly in place. The epoxy was cured by UV light (360 nm, 170 mW/cm.sup.2, 72 seconds). These caps were used to generate the data in FIG. 4 and Table 1, above.

(29) An important aspect of the invention is that a cap design according to the invention allows the color-converting material to be situated within the package of the LED and take advantage of the package reflectors for improved light output and beam shaping.

(30) FIG. 6A illustrates a blue-emitting LED 600 in a package 602 of the prior art. Some of the light rays emitted by the LED reflect off the walls 604 of the package well 602 within which LED 600 is situated. White wall material may be used if Lambertian reflection is desired. In applications requiring specular reflection, the walls may be silvered. Due to beam shaping by LED package 602, there is little blue intensity at wide angles.

(31) FIG. 6B shows a conventional LED package (as 602 in FIG. 6A) equipped with a QD-containing cap according to the embodiment illustrated in FIG. 2. Cap well 608 contains green- and red-emitting quantum dots that fluoresce by means of excitation by blue-emitting LED 600. Due to beam shaping by the LED package, there is little blue intensity at wide angles. As indicated by rays 610, photoluminescence from the quantum dots within cap well 608 emitted in a lateral direction can be directly observed at wide angles. However, the absence of blue light (from LED 600) in rays 610 results in a different color being observed and the color uniformity over angle is thereby compromised.

(32) FIG. 6C shows how a cap according to the embodiments of the invention illustrated in FIGS. 3A and 3B overcome the color-uniformity-over-angle problem illustrated in FIG. 6B and discussed above. Photoluminescence from the quantum dots within recessed cap well 616 can reflect off the walls of the LED package before escaping the device. This results in less QD-only photoluminescence (rays 614) being observed at wide angles thereby leading to improved color uniformity over angle (rays 612 comprising red, green, and blue light).

(33) Although particular embodiments of the present invention have been shown and described, they are not intended to limit what this patent covers. One skilled in the art will understand that various changes and modifications may be made without departing from the scope of the present invention as literally and equivalently covered by the following claims.