Luminescent materials
10533132 ยท 2020-01-14
Assignee
Inventors
Cpc classification
H01L33/504
ELECTRICITY
International classification
Abstract
Embodiments of the invention include a semiconductor light emitting device with a light emitting layer disposed between an n-type region and a p-type region. The light emitting layer emits first light. The device further includes AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x, wherein AE=one or more of Sr, Ba, Ca, disposed in the path of the first light. The AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x absorbs first light and emits second light. In some embodiments, the first light and second light may be blue.
Claims
1. A luminescent material comprising AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x, wherein AE=one or more of Sr, Ba, Ca and 0.002<x0.4.
2. The luminescent material of claim 1 wherein the luminescent material emits light having a peak wavelength in the range 440-470 nm.
3. The luminescent material of claim 1 wherein the luminescent material has a spectral widths of full width half maximum (FWHM) of 25-26 nm.
4. The luminescent material of claim 1 wherein the luminescent material has a crystal structure that is isotypic with M.sub.1-x-y-zZ.sub.zA.sub.aB.sub.bC.sub.cD.sub.dE.sub.eN.sub.6-nO.sub.n:ES.sub.x,RE.sub.y, wherein: a. M is a divalent element selected from Ca (calcium), Sr (strontium), and Ba (barium); b. Z is a monovalent element selected from Na (sodium), K (potassium), and Rb (rubidium); c. A is a monovalent element selected from Li (lithium), and Cu (copper); d. B is a divalent element selected from Mg (magnesium), Mn (manganese), Zn (zinc), and Cd (cadmium); e. C is a trivalent element selected from B (boron), Al (aluminum), and Ga (gallium); f. D is a tetravalent element selected from Si (silicon), Ge (germanium), Ti (titanium), and Hf (hafnium); g. E is a pentavalent element selected from P (phosphorous), V (vanadium), Nb (niobium), and Ta (tantalum); h. ES is a divalent rare earth element selected from Eu (europium), Sm (samarium) and Yb (ytterbium); i. RE is a trivalent rare earth element selected from Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), and Tm (thulium); j. 0x0.2; k. 0y0.2; l. 0<x+y0.4; m. 0z<1; n. x+y+z<1; o. 0n<0.75; p. a+b=2; q. c+d+e=4l and r. a+2b+3c+4d+5e+yz=16n.
5. The luminescent material of claim 1 wherein the luminescent material has a lattice structure comprising a single site populated by the Eu(II) activator ions with an eightfold coordination.
6. A device comprising: a. a semiconductor light emitting device comprising a light emitting layer disposed between an n-type region and a p-type region, the light emitting layer emitting first light; and b. the luminescent material according to claim 1 disposed in the path of the first light, wherein the luminescent material absorbs first light and emits second light.
7. The device of claim 6 wherein the first light is blue light.
8. The device of claim 6 wherein the second light is blue light.
9. The device of claim 6 further comprising a green emitting luminescent material and a red emitting luminescent material disposed in the path of the first light.
10. The device of claim 9 wherein the red emitting luminescent material is disposed in the path of the second light.
11. The device of claim 6 wherein the AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x is a ceramic body.
12. The device of claim 6 wherein the AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x is a powder disposed in a transparent matrix.
13. The device of claim 12 wherein the transparent matrix is selected from the group consisting of a crystalline material, an alkaline earth halide, and calcium.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(10) Embodiments of the invention include blue emitting phosphors AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x (AE=one or more of Sr, Ba, Ca; 0.002<x0.4). These narrow-band blue emitting phosphors may emit blue light, light having a peak wavelength of at least 440 nm in some embodiments, at least 450 nm in some embodiments, and no more than 470 nm in some embodiments, with spectral widths of full width half maximum (FWHM) of 25-26 nm. The narrow band width is caused by a very small Stokes shift that allows excitation of the claimed phosphors by light having a peak wavelength in the range UV-blue, up to wavelengths of 440 nm.
(11) The blue emitting phosphors may be used, for example, in a phosphor converted LED. For example, a UV- or blue-emitting LED may be used to pump, for example, red, green, and blue emitting phosphor mixtures including AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x. Such a device may have benefits. First, when compared with a conventional blue emitting LED combined with red and green phosphors, in some embodiments the overall efficiency may be increased by minimizing the down conversion loss while providing the advantage of a high color point stability regardless of variation of the pump LED emission wavelength. Second, in some embodiments, the amount of blue phosphor needed is reduced in devices including a Ce doped garnet phosphor (for emitting, for example, yellow-green light), because a pump LED emitting at or near 440 nm can also excite the garnet phosphors.
(12) In some embodiments, AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x crystallizes in a crystal structure that is isotypic with green emitting nitride phosphors described in US 20160244664, which is incorporated herein by reference. Paragraph 5 of US 20160244664 teaches A new class of phosphor materials described by the general composition M.sub.1-x-y-zZ.sub.zA.sub.aB.sub.bC.sub.cD.sub.dE.sub.eN.sub.6-nO.sub.n:ES.sub.x,RE.sub.y, where M is a divalent element selected from Ca (calcium), Sr (strontium), Ba (barium), Z is a monovalent element selected from Na (sodium), K (potassium), Rb (rubidium), A is a monovalent element selected from Li (lithium), Cu (copper), B is a divalent element selected from Mg (magnesium), Mn (manganese), Zn (zinc), Cd (cadmium), C is a trivalent element selected from B (boron), Al (aluminum), Ga (gallium), D is a tetravalent element selected from Si (silicon), Ge (germanium), Ti (titanium), Hf (hafnium), E is a pentavalent element selected from P (phosphorous), V (vanadium), Nb (niobium), Ta (tantalum), ES is a divalent rare earth element selected from Eu (europium), Sm (samarium) and Yb (ytterbium), RE is a trivalent rare earth element selected from Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium) has been found. The compositional range is further especially defined by 0x0.2, 0y0.2, especially 0<x+y0.4, 0z<1, x+y+z<1, especially 0n<0.75, a+b=2, c+d+e=4, and a+2b+3c+4d+5e+yz=16n.
(13) Paragraph 6 of US 20160244664 teaches These compounds crystallize in a new crystal structure . . . that has hitherto not been described in the literature. The crystal structure is illustrated in
(14) The narrow emission and small Stokes shift of AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x is a consequence of the highly condensed, rigid host lattice structure that creates a single site populated by the Eu(II) activator ions with an eightfold coordination that effectively restricts geometric relaxation in the excited activator state. Furthermore, AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x does not show an inhomogeneous broadening of the emission as consequence of a statistical occupation of host lattice cation sites observed for the isotypic nitridoalumosilicates described in US 20160244664.
(15) The emission band position of AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu may be tuned to some extent by replacing a larger alkaline earth cation AE by a smaller one (Ba is larger than Sr while Sr is larger than Ca) which leads to a spectroscopic red shift of absorption and emission bands in the 450-470 nm range.
(16) AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x (AE=Sr, Ba, Ca) can be prepared from any suitable commercially available starting compounds including, for example, alkaline earth (AE) carbonates, lithium carbonate and beryllium oxide. The dopant Eu can be introduced by any suitable material including, for example, Eu.sub.2O.sub.3, EuF.sub.3 or EuCl.sub.3. Any suitable additives such as fluxes and/or sintering aids can be added, such as, for example, boron oxide, BaF.sub.2 or LiF.
(17) AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x may be processed in powder form in some embodiments. The properties of AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu in powder form may be engineered by application of particle coatings, for example to enhance the light absorption properties and/or to increase the stability of the powder (i.e., to reduce or eliminate degradation of the luminescence function). The powder phosphor may be disposed in a transparent matrix (described below) that is amorphous, such as silicone or glass, or crystalline, such as an alkaline earth halide such as calcium fluoride.
(18) AE.sub.1-xLi.sub.2Be.sub.4O.sub.6:Eu.sub.x powders may be processed into polycrystalline luminescent ceramic bodies in some embodiments. As used herein, luminescent ceramic refers to a phosphor formed into a structure that is monolithic slab or tile that is self supporting (i.e., a self supporting structure can be formed and handled separately from the light source). The phosphor may be, for example, powder pressed and sintered, such that other than the phosphor itself, no binder material is necessary to form the tile. The luminescent ceramic may be a dense, polycrystalline structure. In some embodiments, the luminescent ceramic is so dense that porosity in the luminescent ceramic is limited to no more than 1 volume-%.
(19) In some embodiments, a luminescent ceramic is formed as follows: powder phosphor is predensified to a green body and sintered to a polycrystalline ceramic. The predensification to the green body may be done by any suitable method including, for example, pressing or tape casting, while the sintering may be done under normal pressure conditions or under gas pressure conditions, both in an inert gas atmosphere like nitrogen or forming gas. The luminescent ceramic may be fired at temperatures in the 800-1500 C. range in some embodiments, in the 10001350 C. range in some embodiments, and in the 1100-1250 C. range in some embodiments.
(20) The phosphors described herein may be used, for example, in a light source including a light emitting diode. Light emitted by the light emitting diode is absorbed by the phosphor according to embodiments of the invention and emitted at a different wavelength.
(21) Though in the example below the semiconductor light emitting device is a III-nitride LED that emits blue or UV light, semiconductor light emitting devices besides LEDs such as laser diodes and semiconductor light emitting devices made from other materials systems such as other III-V materials, III-phosphide, III-arsenide, II-VI materials, ZnO, or Si-based materials may be used.
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(23) The semiconductor structure includes a light emitting or active region sandwiched between n- and p-type regions. An n-type region 16 may be grown first and may include multiple layers of different compositions and dopant concentration including, for example, preparation layers such as buffer layers or nucleation layers, and/or layers designed to facilitate removal of the growth substrate, which may be n-type or not intentionally doped, and n- or even p-type device layers designed for particular optical, material, or electrical properties desirable for the light emitting region to efficiently emit light. A light emitting or active region 18 is grown over the n-type region. Examples of suitable light emitting regions include a single thick or thin light emitting layer, or a multiple quantum well light emitting region including multiple thin or thick light emitting layers separated by barrier layers. A p-type region 20 may then be grown over the light emitting region. Like the n-type region, the p-type region may include multiple layers of different composition, thickness, and dopant concentration, including layers that are not intentionally doped, or n-type layers.
(24) After growth, a p-contact is formed on the surface of the p-type region. The p-contact 21 often includes multiple conductive layers such as a reflective metal and a guard metal which may prevent or reduce electromigration of the reflective metal. The reflective metal is often silver but any suitable material or materials may be used. After forming the p-contact 21, a portion of the p-contact 21, the p-type region 20, and the active region 18 is removed to expose a portion of the n-type region 16 on which an n-contact 22 is formed. The n- and p-contacts 22 and 21 are electrically isolated from each other by a gap 25 which may be filled with a dielectric such as an oxide of silicon or any other suitable material. Multiple n-contact vias may be formed; the n- and p-contacts 22 and 21 are not limited to the arrangement illustrated in
(25) In order to form electrical connections to the LED 1, one or more interconnects 26 and 28 are formed on or electrically connected to the n- and p-contacts 22 and 21. Interconnect 26 is electrically connected to n-contact 22 in
(26) The substrate 10 may be thinned or entirely removed. In some embodiments, the surface of substrate 10 exposed by thinning is patterned, textured, or roughened to improve light extraction.
(27) Any suitable light emitting device may be used in light sources according to embodiments of the invention. The invention is not limited to the particular LED illustrated in
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(29) In
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(32) The wavelength converting structure 30 may be square, rectangular, polygonal, hexagonal, circular, or any other suitable shape. The wavelength converting structure may be the same size as LED 1, larger than LED 1, or smaller than LED 1.
(33) Examples of suitable wavelength converting structures include structures that are formed separately from LED 1, such the luminescent ceramic described above, powder phosphors that are disposed in transparent material such as silicone or glass and rolled, cast, or otherwise formed into a sheet, then singulated into individual wavelength converting structures, and wavelength converting materials such as powder phosphors that are disposed in a transparent material such as silicone that is formed into a flexible sheet, which may be laminated or otherwise disposed over an LED 1.
(34) Examples of suitable wavelength converting structures include structures that are formed in situ with LED 1 or with the luminescent ceramics described above, such as powder phosphors that are mixed with a transparent material such as silicone and dispensed, screen printed, stenciled, molded, or otherwise disposed over LED 1, a luminescent ceramic, or any other suitable structure, and wavelength converting materials that are coated on LED 1, a luminescent ceramic, or any other suitable structure by electrophoretic, vapor, or any other suitable type of deposition.
(35) In addition to the phosphors described herein, the wavelength converting structure 30 may also include, for example, other phosphors, organic phosphors, quantum dots, organic semiconductors, II-VI or III-V semiconductors, II-VI or III-V semiconductor quantum dots or nanocrystals, dyes, polymers, or other materials that luminesce.
(36) The wavelength converting structure absorbs light emitted by the LED and emits light of one or more different wavelengths. Unconverted light emitted by the LED may be part of the final spectrum of light extracted from the structure, though it need not be. In addition to the blue emitting phosphors described herein, for a device that emits light that appears white, the wavelength converting structure may include, for example, one or more of a yellow-emitting wavelength converting material, a green-emitting wavelength converting material, and a red-emitting wavelength converting material. Wavelength converting materials emitting other colors of light may be added to tailor the spectrum of light extracted from the structure.
(37) In some embodiments, other materials may be added to the wavelength converting structure or applied to the LED 1, such as, for example, materials that improve optical performance, materials that encourage scattering, and/or materials that improve thermal performance.
(38) The wavelength converting structure may include a single or multiple wavelength converting layers. For example, in some embodiments, the blue emitting phosphors described herein may be mixed with other phosphors and formed into a wavelength converting structure with a single layer of mixed phosphor. In some embodiments, the blue emitting phosphors described herein is part of wavelength converting structure where different phosphors are disposed in discrete layers. The discrete layers may be the same type of wavelength converting layer, or different types of layers may be combined. For example, the discrete layers may all be luminescent ceramics or powders disposed in a transparent matrix, or one discrete layer may be a luminescent ceramic combined with, for example, a second discrete layer that is a powder disposed in a transparent matrix. In some embodiments, in a wavelength converting structure with discrete layers, the layer including the blue emitting phosphors described herein is disposed closest to the LED 1, as the blue light emitted by the phosphor may pump the other wavelength converting material(s).
(39) In some embodiments, small Stokes shift, saturated blue emitting phosphors such as those described herein may be used as off-state white coatings. An off-state coating alters the appearance of a phosphor converted LED when the device is not operating. LEDs are often coated with yellow and red emitting phosphors which may absorb ambient light and emit yellow or red light, which may be unappealing to a user viewing the LED in the off-state.
EXAMPLES
(40) In some embodiments, the blue emitting phosphor is BaLi.sub.2Be.sub.4O.sub.6:Eu(l %).
(41) BaLi.sub.2Be.sub.4O.sub.6:Eu(1%) may be synthesized as follows: 230.0 g (1.5 mole) BaO, 151.6 g (6.06 mole) BeO, 45.3 g (1.52 mole) Li.sub.2O, and 2.7 g (0.008 mole) Eu.sub.2O.sub.3 are mixed and sintered under Ar atmosphere at 1100 C. for 1 h. The material shows block-like particles that may be de-aggregated or milled into powder form by any suitable technique including, for example, ball milling.
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(43) BaLi.sub.2Be.sub.4O.sub.6:Eu crystallizes in space group P4/ncc (No. 130) with the cell parameters a=7.2770 and c=8.8872 . P4/ncc is the symbol of the crystallographic space group that describes the symmetry of the crystal lattice according to INTERNATIONAL TABLES FOR CRYSTALLOGRAPHY, Volume A1, SYMMETRY RELATIONS BETWEEN SPACE GROUPS. Eds. H. Wondratscheck and U. Mueller, Kluwer Academic Publishers, Dordrecht (2004). Table 1 summarizes the atomic parameters of the BaLi.sub.2Be.sub.4O.sub.6 crystal structure. Atom is the species that occupies a lattice site with a specific Wyckoff position (Wyck.). Headings x/a, y/b and z/c refer to the coordinates of the atomic positions in the crystal lattice that is defined by the lattice constants a, b and c. In the tetragonal lattice system a=bc and ===90.
(44) TABLE-US-00001 TABLE 1 Atom Wyck. x/a y/b z/c Ba1 4c 0.32551(2) Be1 16g 0.1207(3) 0.5337(3) 0.0766(2) Li1 8f 0.3665(4) 0.6335(4) O1 16g 0.50530(15) 0.15991(16) 0.04538(12) O2 8f 0.59636(15) 0.40364(15)
(45) The crystal structure of AELi.sub.2Be.sub.4O.sub.6 (AE=Sr,Ba) is isotypic to BaLi.sub.2Al.sub.2Si.sub.2N.sub.6. N-ligands are exchanged by O, the mixed-occupied Al/Si site is exchanged by Be. Corner- and edge-sharing BeO.sub.4-tetrahedra build a rigid network, forming two different channels. The first channel is filled with Li atoms. Li atoms are in a 4+1 coordination by O. The second channel is filled by AE (AE=Sr,Ba) atoms. AE is coordinated 8-fold, the coordination sphere can be described as a truncated square pyramid.
(46) Energy-dispersive X-ray spectroscopy (EDS) scans of BaLi.sub.2Be.sub.4O.sub.6:Eu show a Ba:O ratio of 1:6. Inductively coupled plasma mass spectrometry (ICP) analysis of BaLi.sub.2Be.sub.4O.sub.6:Eu shows a ratio of Ba:Li:Be of 1.8:2:4.4.
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(48) In some embodiments, the blue emitting phosphor is SrLi.sub.2Be.sub.4O.sub.6:Eu(1%).
(49) SrLi.sub.2Be.sub.4O.sub.6:Eu(1%) may be synthesized as follows: 155.4 g (1.5 mole) SrO, 151.6 g (6.06 mole) BeO, 45.3 g (1.52 mole) Li.sub.2O, and 2.7 g (0.008 mole) Eu.sub.2O.sub.3 are mixed and sintered under Ar atmosphere at 1100 C. for 0.5 h.
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(51) SrLi.sub.2Be.sub.4O.sub.6:Eu crystallizes in space group P4/ncc (No. 130) with the cell parameters a=7.1659 and c=8.9085 and is isotypic to BaLi.sub.2Be.sub.4O.sub.6:Eu.
(52) Table 2 summarizes the atomic parameters of the SrLi.sub.2Be.sub.4O.sub.6:Eu crystal structure.
(53) TABLE-US-00002 TABLE 2 Atom Wyck. x/a y/b z/c Sr1 4c 0.34572(3) Be1 16g 0.1197(3) 0.5311(3) 0.0776(2) Li1 8f 0.3697(4) 0.6303(4) O1 16g 0.50309(13) 0.16231(15) 0.04168(10) O2 8f 0.59096(15) 0.40904(15)
(54) EDS scans of SrLi.sub.2Be.sub.4O.sub.6:Eu show a Sr:O:Eu ratio of 1:4.7:0.007. ICP analysis shows a ratio of Sr:Li:Be of 1:1.5:3.6.
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(56) Having described the invention in detail, those skilled in the art will appreciate that, given the present disclosure, modifications may be made to the invention without departing from the spirit of the inventive concept described herein. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described.