Red-emitting nitride-based calcium-stabilized phosphors

Abstract

Red-emitting phosphors may comprise 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 at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0c5.0; 0d1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. Furthermore, nitride-based red-emitting phosphor compositions may be represented by the chemical formula M.sub.xM.sub.2Si.sub.5-yAl.sub.yN.sub.8:A, wherein: M is Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M is at least one of Mg, Ca, Sr, Ba, and Zn; 0y0.15; and A is at least one of Eu, Ce, Tb, Pr, and Mn; wherein x>y/v and v is the valence of M, and wherein the red-emitting phosphors have the general crystalline structure of M.sub.2Si.sub.5N.sub.8:A.

Claims

1. A calcium-stabilized red-emitting phosphor comprising Ca, Sr, Si, Al, N and Eu, wherein said red-emitting phosphor absorbs radiation at a wavelength ranging from about 200 nm to about 550 nm and emits light with a photoluminescence peak emission wavelength greater than 620.0 nm, wherein said red-emitting phosphor has the general crystalline structure of Sr.sub.2Si.sub.5N.sub.8:Eu with Ca and Al incorporated therein, and wherein said red-emitting phosphor is configured such that under excitation by a blue LED the reduction in photoluminescent intensity after 800 hours of aging at about 85 C. and about 85% humidity is no greater than about 15%.

2. The calcium-stabilized red-emitting phosphor of claim 1, further comprising at least one of F, Cl, Br and O.

3. The calcium-stabilized red-emitting phosphor of claim 1, wherein said red-emitting phosphor is Eu.sub.0.05Ca.sub.0.2Sr.sub.1.95Si.sub.4.9Al.sub.0.1N.sub.8.

4. The calcium-stabilized red-emitting phosphor of claim 1, wherein said red-emitting phosphor has chromaticity coordinates CIE (x) of 0.6470 and CIE (y) of 0.3526.

5. The calcium-stabilized red-emitting phosphor of claim 1, wherein said red-emitting phosphor is Eu.sub.0.05Ca.sub.0.2Sr.sub.1.95Si.sub.4.88Al.sub.0.12N.sub.8.

6. The calcium-stabilized red-emitting phosphor of claim 1, wherein said red-emitting phosphor has chromaticity coordinates CIE (x) of 0.6478 and CIE (y) of 0.3518.

7. A calcium-stabilized red-emitting phosphor comprising Ca, Sr, Si, Al, N and Eu, wherein said red-emitting phosphor absorbs radiation at a wavelength ranging from about 200 nm to about 550 nm and emits light with a photoluminescence peak emission wavelength greater than 620.0 nm, wherein said red-emitting phosphor has the general crystalline structure of Sr.sub.2Si.sub.5N.sub.8:Eu with Ca and Al incorporated therein, and wherein said red-emitting phosphor is configured such that the deviation in chromaticity coordinates CIE x and CIE y after 800 hours of aging at about 85 C. and about 85% relative humidity is less than or equal to about 0.015 for each coordinate.

8. The calcium-stabilized red-emitting phosphor of claim 7, wherein the deviation in chromaticity coordinates CIE x and CIE y is less than or equal to about 0.005 for each coordinate.

9. The calcium-stabilized red-emitting phosphor of claim 7, further comprising at least one of F, Cl, Br and O.

10. The calcium-stabilized red-emitting phosphor of claim 7, wherein said red-emitting phosphor is Eu.sub.0.05Ca.sub.0.2Sr.sub.1.95Si.sub.4.9Al.sub.0.1N.sub.8.

11. The calcium-stabilized red-emitting phosphor of claim 7, wherein said red-emitting phosphor has chromaticity coordinates CIE (x) of 0.6470 and CIE (y) of 0.3526.

12. The calcium-stabilized red-emitting phosphor of claim 7, wherein said red-emitting phosphor is Eu.sub.0.05Ca.sub.0.2Sr.sub.1.95Si.sub.4.88Al.sub.0.12N.sub.8.

13. The calcium-stabilized red-emitting phosphor of claim 7, wherein said red-emitting phosphor has chromaticity coordinates CIE (x) of 0.6478 and CIE (y) of 0.3518.

14. A white light emitting device comprising: a solid state excitation source with emission wavelength within a range from 200 nm to 480 nm; a calcium-stabilized red-emitting phosphor according to claim 1, said red-emitting phosphor being configured to absorb excitation radiation from said excitation source and to emit light having a peak emission wavelength in the range from 620 nm to about 650 nm; and a yellow/green-emitting phosphor having a peak emission wavelength in the range from about 500 nm to about 580 nm.

15. The white light emitting device of claim 14, wherein said calcium-stabilized red-emitting phosphor is configured to absorb excitation radiation from said excitation source and to emit light having a peak emission wavelength in the range from about 624 nm to about 632 nm.

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, wherein:

(2) FIG. 1 shows emission spectra of the red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 5, according to some embodiments of the present invention, and Sample 1 is a prior art red-emitting nitride-based 2-5-8 phosphor shown for comparison;

(3) FIG. 2 shows emission spectra of the red-emitting nitride-based calcium-stabilized phosphors Samples 6 through 8, according to some embodiments of the present invention, and Sample 1 is shown for comparison;

(4) FIG. 3 shows emission spectra of the red-emitting nitride-based calcium-stabilized phosphors Samples 9 through 12, according to some embodiments of the present invention;

(5) FIG. 4 shows emission spectra of the red-emitting nitride-based calcium-stabilized phosphors Samples 13 through 15, according to some embodiments of the present invention;

(6) FIGS. 5A-5D show trends with phosphor calcium content of the peak emission wavelength, peak photoluminescence intensity (PL) and CIE x and y chromaticity coordinates, for red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 5 (no aluminum) and 9 through 12 (aluminum containing), according to some embodiments of the present invention;

(7) FIGS. 6A-6D show trends with phosphor calcium content of the peak emission wavelength, peak photoluminescence intensity (PL) and CIE x and y chromaticity coordinates, for red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 4 (additional calcium) and 6 through 8 (substitutional calcium), according to some embodiments of the present invention;

(8) FIGS. 7A-7C show the results of reliability testing under the conditions of 85 C. and 85% relative humidity of the red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 4, where FIG. 7A is the change in photoluminescent intensity (brightness) with time, FIG. 7B is the change in CIE x chromaticity coordinate with time, and FIG. 7C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention;

(9) FIGS. 8A-8C show the results of reliability testing under the conditions of 85 C. and 85% relative humidity of the red-emitting nitride-based calcium-stabilized phosphors Samples 3 (additional calcium) and 7 (substitutional calcium), where FIG. 8A is the change in photoluminescent intensity (brightness) with time, FIG. 8B is the change in CIE x chromaticity coordinate with time, and FIG. 8C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention, and reliability data for prior art red-emitting nitride-based 2-5-8 phosphor Sample 1 is shown for comparison;

(10) FIGS. 9A-9C show the results of reliability testing under the conditions of 85 C. and 85% relative humidity of the red-emitting nitride-based calcium-stabilized phosphors Samples 3 (no aluminum) and 10 (aluminum containing), where FIG. 9A is the change in photoluminescent intensity (brightness) with time, FIG. 9B is the change in CIE x chromaticity coordinate with time, and FIG. 9C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention, and reliability data for prior art red-emitting nitride-based 2-5-8 phosphor Sample 1 is shown for comparison;

(11) FIGS. 10A-10C show the results of reliability testing under the conditions of 85 C. and 85% relative humidity of the red-emitting nitride-based calcium-stabilized phosphors Samples 13 through 15, where FIG. 10A is the change in photoluminescent intensity (brightness) with time, FIG. 10B is the change in CIE x chromaticity coordinate with time, and FIG. 10C is the change in CIE y chromaticity coordinate with time, according to some embodiments of the present invention;

(12) FIG. 11 shows x-ray diffraction (XRD) patterns of the red-emitting nitride-based calcium-stabilized phosphor Samples 2 through 5, according to some embodiments of the present invention, the XRD pattern for Sample 1 is shown for comparison;

(13) FIG. 12 shows x-ray diffraction patterns of the red-emitting nitride-based calcium-stabilized phosphor Samples 6 through 8, according to some embodiments of the present invention, the XRD pattern for Sample 1 is shown for comparison;

(14) FIG. 13 shows x-ray diffraction patterns of the red-emitting nitride-based calcium-stabilized phosphors Samples 9 through 12, according to some embodiments of the present invention, the XRD pattern for Sample 1 is shown for comparison;

(15) FIG. 14 shows x-ray diffraction patterns of the red-emitting nitride-based calcium-stabilized phosphors Samples 13 through 15, according to some embodiments of the present invention, the XRD pattern for Sample 1 is shown for comparison;

(16) FIGS. 15-17 show SEM micrographs of red-emitting nitride-based calcium-stabilized phosphors Sample 3 (FIG. 16) (additional calcium) and Sample 7 (FIG. 17) (substitutional calcium), according to some embodiments of the present invention, and prior art red-emitting nitride-based 2-5-8 phosphor Sample 1 (FIG. 15) is shown for comparison;

(17) FIG. 18 shows a light emitting device, according to some embodiments of the present invention;

(18) FIGS. 19A & 19B show a solid-state light emitting device, according to some embodiments of the present invention; and

(19) FIG. 20 shows the emission spectrum from a white LED (3000K) comprising a blue InGaN LED, a red phosphor having the composition of Sample 14, and a yellow/green phosphor, according to some embodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(20) 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.

(21) Some embodiments of the present invention are directed to a red-emitting phosphor which may comprise a nitride-based composition represented by the chemical formula M.sub.xM.sub.2Si.sub.5-yAl.sub.yN.sub.8:A, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M is at least one of Mg, Ca, Sr, Ba, Y, Li and Zn; 0y1.0; and A is at least one of Eu, Ce, Tb, Pr, Sin and Mn; wherein x>y/v and v is the valence of Mthe latter reflecting the presence of an excess of M for stabilization of the phosphor and a larger amount of M than needed for charge balance of any Al substituting for Si. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, the red-emitting phosphor may have the general crystalline structure of M.sub.2Si.sub.5N.sub.8:A; although embodiments of the red-emitting phosphor may exist with other crystalline structures. Furthermore, Al may substitute for Si within the general crystalline structure and M may be located within the general crystalline structure substantially at interstitial sites.

(22) According to some further embodiments of the present invention, nitride-based calcium-stabilized phosphors may have a composition given by the formula Ca.sub.xSr.sub.2Si.sub.5-yAl.sub.yN.sub.8 where x>0 and 0y1, wherein the Ca is present in an amount greater than is required to charge balance the substitution of Si by Al, in other words where 2x>y, and wherein the phosphors exhibit good stability under heat and humidity, as specified herein.

(23) According to further embodiments of the present invention, a red-emitting phosphor may comprise 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 at least one of Mg, Ca, Sr, Ba, Y Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0c5.0; 0d1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of Mthe latter reflecting the presence of an excess of M for stabilization of the phosphor and a larger amount of M than needed for charge balance of any Al substituting for Si. Furthermore, the red-emitting phosphor may comprise at least one of F, Cl, Br and O. Yet furthermore, M may be Ca, d=0 and 0.1a0.4, and in some embodiments M may be Ca, d=0 and 0.15a0.25. Furthermore, M may be Ca, 0.1d0.15 and 0.1a0.4, and in some embodiments M may be Ca, 0.1d0.15 and 0.15a0.25.

(24) Some embodiments of the present invention are directed to a nitride-based phosphor composition represented by the general formula M.sub.xM.sub.2A.sub.5-yD.sub.yE.sub.8:A, where M is a modifier cation. Advantages of the modification to the 2-5-8 phosphor include an increase in peak emission wavelength towards the deep red end of the spectrum, and an enhanced stability in elevated thermal and humidity conditions.

(25) M is at least one of a 1+ cation, a 2+ cation, and a 3+ cation, and M is at least one of Mg, Ca, Sr, Ba, and Zn, used either individually or in combinations. A is at least one of C, Si and Ge, used either individually or in combinations. The element D replaces the A component substitutionally, where D is selected from the group consisting of column IIIB elements of the periodic table of elements. (The labeling of the columns of the periodic table in this disclosure follow the old IUPAC (International Union of Pure and Applied Chemistry) system. See http://en.wikipedia.org/wiki/Group_(periodic_table), last viewed Jan. 15, 2013.) In one embodiment, D is at least one of B, Al, and Ga, used either individually or in combinations. E in the general formula of the present phosphor is at least one of a 3 anion, a 2 anion, and a 1 anion. Specifically, E may be at least one of O.sup.2, N.sup.3, F.sup.1, Cl.sup.1, Br.sup., and I.sup., used either individually or in combinations. The activator, A, is at least one of Eu, Ce, Tb, Pr, Sm and Mn. Herein A represents a phosphor activator and the notation :A represents doping by a rare earth and/or Mn which is generally substitutional, but may also include doping at grain boundaries, on particle surfaces and in interstitial sites within the crystalline structure of the phosphor material. The parameter y is given by 0y1.0 and the value of the parameter x may be defined as being greater than the value of y divided by the valence of M, such that M is present in an amount greater than required for charge balance of any substitution of A by D.

(26) The modifier cation M is added to the phosphor in an amount which is greater than is required to charge compensate for the substitution of D for A. Specifically, M may be at least one of Li.sup.1+, Na.sup.1+, K.sup.1+, Sc.sup.3+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Zn.sup.2+, B.sup.3+ and Y.sup.3+, used either individually or in combinations. M is an extra cation, utilized in addition to the stoichiometric amount of the divalent metal M in the formula M.sub.2Si.sub.5N.sub.8, and as such, it is expected that this modifier cation might be inserted into the phosphor substantially interstitially, although M may occupy other positions within the host lattice.

(27) Interstitial sites are cavities, holes, or channels that exist in the crystalline lattice by virtue of the manner in which the host's constituent atoms are arranged (packed, or stacked). Dopant atoms that occupy the interstices of a crystal are to be distinguished from such atoms introduced substitutionally; in this latter mechanism, the dopant atoms replace host atoms residing on crystal lattice sites. Support for the proposed interstitial placement of modifier cations within the structure of the phosphor material is found in the literature for ceramic materials with an -silicon nitride crystal structure. For example, see Hampshire et al. -Sialon ceramics, Nature 274, 880 (1978) and Huang et al. Formation of -Si.sub.3N.sub.4 Solid Solutions in the System Si.sub.3N.sub.4AlNY.sub.2O.sub.3 J. Amer. Ceram. Soc. 66 (6), C-96 (1983). These articles state that it is known that the -silicon nitride unit cell contains two interstitial sites large enough to accommodate other atoms or ions. Furthermore, the -sialon structure is derived from the -silicon nitride structure by partial replacement of Si with Al, and valency compensation is effected by cationssuch as Li, Ca, Mg and Yoccupying the interstices of the (Si, Al)N network, and also by oxygen replacing nitrogen when an oxide is used. (The -sialon structure is represented by M.sub.x(Si, Al).sub.12(O, N).sub.16, where x is not greater than 2.) Yet furthermore, it is accepted that the a r-sialon structure requires the equivalent of at least half a cationic valency in each of the two interstices within the unit cell to stabilize the structure.

(28) Generally, the crystalline structures of the 2-5-8 nitride-based compounds as described herein may have a space group selected from Pmn2.sub.1, Cc, derivatives thereof, or mixtures thereof. In some examples, the space group is Pmn2.sub.1. Furthermore, it should be noted that in materials science theory the vacancy density of a pure crystalline material may be on the order of a hundred parts per million of the existing lattice sites depending on the thermal equilibrium conditions of the crystal. As such, a small percentage of the modifier ions, M, may end up in vacant metal ion sites, rather than the interstitial sitesthe modifier ions filling the vacancies before the interstitial sites.

(29) Furthermore, the modifier ions may also be involved in charge balancing to compensate for the presence of anions of elements such as F, Cl, Br and O within the phosphor, either substituting for N within the M.sub.2Si.sub.5N.sub.8 crystal lattice, or filling interstitial positions within the crystal lattice. These anions may either be present in the phosphor material intentionally, or as contaminants. Contaminants, such as oxygen, may be from environmental sources. According to some embodiments, the phosphor may have halide and/or oxygen intentionally introduced in a range from 0 to about 6 mole percent. Halide may be added by using one or more starting materials comprising a halide, for example: EuCl.sub.3, EuF.sub.3, EuBr.sub.3, NH.sub.4F, etc. Oxygen may be added by using one or more starting materials comprising an oxide, for example: Eu.sub.2O.sub.3, SiO.sub.2, etc. Furthermore, the methods for controllably incorporating oxygen in to the phosphor material that are described in U.S. patent application Ser. No. 13/871,961, incorporated herein by reference in its entirety, may be used for incorporation of oxygen into the phosphors of the present invention.

(30) Next the disclosure will present phosphors based on the present modifier cation-stabilized M.sub.xM.sub.2A.sub.5-yD.sub.yE.sub.8:A embodiments, giving their advantages and properties, and how these phosphors differ from the prior art. Specific examples will be given, including a phosphor wherein the column IIIB element substituting for Si.sup.4+ is Al.sup.3+, and wherein the modifying cation is Ca.sup.2+, and other examples in which y=0. Accelerated aging results will be discussed which show the superior thermal and chemical stability of the phosphors of the present invention over other prior art 2-5-8 based phosphors. Finally, SEM micrographs will show the change in morphology of the phosphor crystals as the amount of Ca is increased beyond the amount used to charge balance the substitution of Si by Al.

(31) Discussion of the Present Phosphors Based on Ca.sub.xSr.sub.2Si.sub.5-yAl.sub.yN.sub.8:A

(32) Fifteen different phosphor samples were prepared as described in more detail below with reference to Tables 1A, 1B, 2A, 2B, 3A, 3B, 4A and 4B. PL spectra, CIE coordinates, XRD and SEM data were collected for samples, as discussed in more detail below.

(33) Sample 1 is a well-known 2-5-8 red-emitting nitride phosphor used herein as a control; it has the composition Sr.sub.1.95Si.sub.5N.sub.8Eu.sub.0.05. Samples 2 through 5 are based on the composition of Sample 1, but with increasing amounts of calcium added as modifier cations; in these samples the modifier cations do not have a charge compensation role to play, for Si substitution at least. These samples have a composition represented by the formula Ca.sub.xSr.sub.1.95Si.sub.5N.sub.8Eu.sub.0.05.

(34) Samples 6 through 8 are based on the composition of Sample 1, but with calcium substituting for strontium in increasing amounts; in these samples the modifier cations do not have a charge compensation role to play. These samples have a composition represented by the formula Ca.sub.xSr.sub.1.95-xSi.sub.5N.sub.8Eu.sub.0.05. These Samples are compared with Samples 2 through 4 which have the same amount of calcium added, but in Samples 2 through 4 the calcium does not substitute for strontiumit is in addition to the strontium and is expected to be present in the phosphor crystal in interstitial lattice positions.

(35) Samples 9 through 12 are based on the composition of Sample 1, but with (1) some aluminum substituted for silicon, and (2) with increasing amounts of calcium added as modifier cations, where the calcium is BOTH playing the role of charge compensation for the substitution of aluminum for silicon, and is present in amounts beyond what is needed for charge compensation and may result in improved phosphor stability under conditions of heat and humidity. These samples have a composition represented by the formula Ca.sub.xSr.sub.1.95Si.sub.4.9 Al.sub.0.1N.sub.8Eu.sub.0.05.

(36) Samples 13 through 15 are similar to Samples 9 through 12, except for the amount of aluminum being slightly greater in Samples 13 through 15. These samples have a composition represented by the formula Ca.sub.xSr.sub.1.95Si.sub.4.88Al.sub.0.12N.sub.8Eu.sub.0.05. Furthermore, Sample 13 has only enough additional calcium to charge compensate the substitution of aluminum for silicon, whereas Samples 14 & 15 have amounts of calcium beyond what is needed for charge compensation.

(37) According to some embodiments, the phosphors, under blue excitation, may be configured to emit light having a peak emission wavelength greater than about 620 nm, in embodiments greater than 623 nm, and in further embodiments greater than about 626 nm, where blue may be defined as light having a wavelength ranging from about 420 nm to about 470 nm. The present phosphors may also be excited by radiation having shorter wavelengths; e.g., from about 200 nm to about 420 nm, but when the excitation radiation is in the x-ray or UV, a separate blue-emitting phosphor is provided to contribute a blue component to the desired white light for a white light source. Furthermore, the present phosphors may also be excited by radiation having longer wavelengths, wherein the wavelength ranges from about 200 nm to about 550 nm. A common blue excitation source is an InGaN LED, or GaN LED, emitting with a peak at about 460 nm. According to some embodiments, a solid state excitation source is provided, having an emission wavelength within a range from 200 nm to 480 nm, and a red-emitting phosphor is configured to absorb excitation radiation from that excitation source and to emit light having a peak emission wavelength in the range from 620 nm to 650 nm. According to other embodiments, a red-emitting phosphor is configured to absorb excitation radiation from that excitation source and to emit light having a peak emission wavelength in the range of 624 nm to 632 nm.

(38) FIGS. 5A-5D show trends based on the phosphor calcium content of the peak emission wavelength, peak photoluminescence intensity (PL) and CIE x and y chromaticity coordinates, for red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 5 (no aluminum) and 9 through 12 (aluminum containing), according to some embodiments of the present invention. All of these phosphors have excess calcium, beyond what is required for charge balance in the case of the aluminum-containing samples; and all of these phosphors are assumed to have the calcium present in the crystal structure at interstitial sites. The trends for the no aluminum and the aluminum-containing samples are very similar, suggesting that the trends may be dominated by the interstitial calcium content.

(39) FIGS. 6A-6D show trends with phosphor calcium content of the peak emission wavelength, peak photoluminescence intensity (PL) and CIE x and y chromaticity coordinates, for red-emitting nitride-based calcium-stabilized phosphors Samples 2 through 4 (additional calcium) and 6 through 8 (substitutional calcium), according to some embodiments of the present invention. There is an appreciable difference in the trends between the additional (assumed interstitial) calcium and the substitutional calcium, suggesting the location of the calcium within the crystal lattice may be significant.

(40) Reliability Testing

(41) Within many territories including the United States, regulatory bodies set performance criteria for replacement LED lamps. For example the US Environmental Protection Agency (EPA) in conjunction with the US Department of Energy (DOE) promulgates performance specifications under which a lamp may be designated as an ENERGY STAR compliant product, e.g. identifying the power usage requirements, minimum light output requirements, luminous intensity distribution requirements, luminous efficacy requirements, life expectancy, etc. The ENERGY STAR Program Requirements for Integral LED Lamps requires that for all LED lamps the change of chromaticity over the minimum lumen maintenance test period (6000 hours) shall be within 0.007 on the CIE 1976 (u,v) diagram and depending on lamp type, the lamp must have 70% lumen maintenance (L70) at 15,000 or 25,000 hours of operation. The ENERGY STAR requirements are for the lamp performance and include all components of the lamp such as the LEDs, phosphor, electronic driver circuitry, optics and mechanical components. In principal, the degradation in brightness of a white LED with aging can be due not only to the phosphor, but also to the blue LED chip. Additional sources of degradation can come from the packaging materials (such as the substrate), the bond wires and other components encapsulated with silicone. In contrast, the factors affecting the change in color coordination are dominated primarily by phosphor degradation. In terms of phosphor performance it is believed that in order to comply with ENERGY STAR requirements would require a change in chromaticity (CIE x, CIE y) of 0.01 for each coordinate over 1000 hours for the phosphor under accelerated testing at 85 C. and 85% relative humidity. The accelerated testing is done on phosphor coated 3000K white LEDs prepared as follows: phosphor particles are combined with a binder, such as epoxy or silicone, and then applied to the LED chip. The coated LED is placed in an oven at the specified temperature and humidity and operated continuously for the testing period.

(42) FIGS. 7A-7C, 8A-8C, 9A-9C and 10A-10C show the results of reliability testing under the conditions of 85 C. and 85% relative humidity of phosphor Samples 2 through 4, Samples 1, 3 and 7, Samples 1, 3 and 10 and Samples 13 through 15, respectively. The figures show the change in photoluminescent intensity (brightness) with time, the change in CIE x chromaticity coordinate with time, and the change in CIE y chromaticity coordinate with time. The Sr.sub.2Si.sub.5N.sub.8:Eu control sample (Sample 1) showed results that would typically be unacceptable to the industryall other Samples showed different levels of improvement over the control, the best performance being shown by Samples 10 & 15 which will most likely satisfy the typical industry heat and humidity stability requirement.

(43) In more detail, FIGS. 7A-7C show an improvement in reliability with increase in additional calcium content of the no aluminum-content phosphors. FIGS. 8A-8C compare the control with a substitutional calcium phosphor and an additional calcium phosphorall phosphors without aluminum and where the two calcium-containing phosphors differ in composition only in that Sample 3 has more strontium than Sample 7, since in Sample 7 the calcium has substituted for strontium; the best reliability is seen for the phosphor with additional calcium. FIGS. 9A-9C compare the control with an additional calcium phosphor without aluminum and an additional calcium phosphor with aluminumthe two calcium-containing phosphors differ in composition only in that Sample 10 contains aluminum and Sample 3 does not; the best reliability is seen for the phosphor containing aluminum. FIGS. 10A-10C show an improvement in reliability for the additional calcium phosphors with increase in calcium content. In summary, the most significant improvement in stability over the control (Sample 1), as defined by maintaining intensity and chromaticity, is realized by Ca interstitial charge balancing and Al substituting for Si, plus excess interstitial Ca (beyond what is required for charge balance of the Al); the best stability results are seen for the higher Ca/Al ratio materials, as exemplified by Samples 10 & 15 (see Tables 3B & 4B). It should be noted that Samples 10 & 15 are uncoated phosphors, and yet shows excellent stabilitystability data is shown for up to 800 hours for Sample 15 and it is expected that after 1000 hours Sample 15 will meet the accelerated testing criteria used to establish ENERGY STAR compliance. Even though Samples 10 & 15 show excellent stability without coating, Samples 10 & 15 can be coated to provide expected further stability improvement. Similarly, other Samples can be coated to improve stability.

(44) To provide a potential further improvement in performance the particles of the phosphor with the composition of the Samples of the present invention can be coated with one or more coatings of, for example, SiO2, AhO3 and/or TiO2, as taught in commonly-owned U.S. Pat. No. 9,006,966 for COATINGS FOR PHOTOLUMINESCENT MATERIALS and U.S. Pat. App. Pub. No. 2013/0092964 for HIGHLY RELIABLE PHOTOLUMINESCENT MATERIALS HAVING A THICK AND UNIFORM TITANIUM DIOXIDE COATING, the content of each of which is incorporated in its entirety herein by way of reference thereto.

(45) XRD of the Present Phosphor Compositions

(46) FIGS. 11-14 show XRD patterns of red-emitting nitride-based phosphors of the present invention; the XRD pattern for sample 1 is shown for comparison.

(47) Morphology of Phosphor Particles of the Present Phosphor Compositions

(48) FIGS. 15-17 show secondary electron micrographs of as prepared red-emitting nitride-based calcium-stabilized phosphors Sample 3 (FIG. 16) (additional calcium) and Sample 7 (FIG. 17) (substitutional calcium), according to some embodiments of the present invention, and prior art red-emitting nitride-based 2-5-8 phosphor Sample 1 (FIG. 15) is shown for comparison. All of FIGS. 15-17 show some particles with a higher aspect ratio (length to width)in excess of 3. Furthermore, a comparison of FIGS. 15-17 suggests that the percentage of high aspect ratio particles is greater for the control (FIG. 15) than for the samples of the phosphors of the present invention.

(49) Synthesis of the Present Phosphors

(50) For each of the examples and comparative examples described herein, the starting materials included at least one of the compounds Si.sub.3N.sub.4, AlN, Ca.sub.3N.sub.2, Sr.sub.3N.sub.2, BN, GaN, SiO.sub.2, Al.sub.2O.sub.3, and EuCl.sub.3.

(51) Samples 1 Through 5

(52) To obtain desired compositions of the phosphors exemplified in Samples 1 through 5, solid powders were weighed according to the compositions listed in Table 1A. This mixture of raw materials were then loaded into a plastic milling bottle together with milling beads, sealed in a glove box, followed by a ball milling process for about 2 hours. The mixed powders were then loaded into a molybdenum crucible having an inner diameter of 30 mm and a height of 30 mm; the loaded crucible was covered with a molybdenum lid and placed into a gas sintering furnace equipped with a graphite heater.

(53) After loading the crucible, the furnace was evacuated to 10.sup.2 Pa, and the sample heated to 150 C. under these vacuum conditions. At the 150 C. temperature, a high purity N.sub.2 gas was introduced into the chamber; the temperature of the furnace was then increased to about 1700 C. at a substantially constant heating rate of 4 C./min. The samples were maintained at 1700 C. for about 7 hours.

(54) After firing, the power was shut off and the samples allowed to cool in the furnace. The as-sintered phosphor was ground slightly, ball milled to a certain particle size, followed by a wash, dry and sieve procedure. The final product was tested using an Ocean Optics USB4000 spectrometer for photoluminescence intensity (PL) and chromaticity (CIE coordinates x and y). The x-ray diffraction (XRD) patterns of the phosphors were measured using the K.sub. line of a Cu target. The test results are listed in Table 1B.

(55) A flux, such as ammonium chloride, may also be used in the fabrication of the phosphors of the present invention.

(56) FIG. 1 is the emission spectra of the phosphors from Samples 1 through 5. Powder x-ray diffraction measurements using the K.sub. line of a Cu target are shown in FIG. 11 for the phosphors of Samples 1 through 5.

(57) TABLE-US-00001 TABLE 1A Composition of starting raw materials for Samples 1 through 5 Compound EuCl.sub.3 Sr.sub.3N.sub.2 Ca.sub.3N.sub.2 Si.sub.3N.sub.4 AlN Sample 1 5.166 75.62 0 93.52 0 Sample 2 2.583 37.81 0.988 46.76 0 Sample 3 2.583 37.81 1.976 46.76 0 Sample 4 2.583 37.81 2.964 46.76 0 Sample 5 2.583 37.81 3.952 46.76 0

(58) TABLE-US-00002 TABLE 1B Emission Peak wavelength, Intensity and CIE of Samples 1 through 5 with Composition Ca.sub.xSr.sub.1.95Si.sub.5N.sub.8Eu.sub.0.05 Test Results Emission Ca Peak PL Content, Al Wavelength Intensity CIE CIE Sample x Content (nm) (a.u.) (x) (y) 1 0 0 622.77 1.56 0.6423 0.3573 2 0.1 0 624.10 1.62 0.6449 0.3547 3 0.2 0 626.29 1.61 0.6584 0.3511 4 0.3 0 628.64 1.60 0.6493 0.3502 5 0.4 0 630.16 1.56 0.6517 0.3477

(59) Samples 6 Through 8

(60) To obtain the desired compositions of the phosphors of Samples 6 through 8, solid powders were weighed according to the compositions listed in Table 2A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 2B.

(61) The emission spectra of phosphor Samples 6 through 8 are shown in FIG. 2. X-ray diffraction measurements using the K.sub. line of a Cu target were obtained, and the XRD patterns of Samples 6 through 8 are shown in FIG. 12.

(62) TABLE-US-00003 TABLE 2A Composition of starting raw materialsfor Samples 6 through 8 Compound EuCl.sub.3 Sr.sub.3N.sub.2 Ca.sub.3N.sub.2 Si.sub.3N.sub.4 AlN Sample 6 2.583 35.87 0.988 46.76 0 Sample 7 2.583 33.93 1.976 46.76 0 Sample 8 2.583 31.99 2.964 46.76 0

(63) TABLE-US-00004 TABLE 2B Emission Peak wavelength, Intensity and CIE of Samples 6 through 8 with Composition Ca.sub.xSr.sub.1.95-xSi.sub.5-yAl.sub.yN.sub.8Eu.sub.0.05 Test Results Emission Ca Al Peak PL Content, Content, Wavelength Intensity CIE CIE Sample x y (nm) (a.u.) (x) (y) 6 0.1 0 624.54 1.66 0.6443 0.355 7 0.2 0 627.86 1.57 0.6476 0.352 8 0.3 0 631.08 1.51 0.6500 0.350

(64) Samples 9 Through 12

(65) To obtain the desired compositions of the phosphors of Samples 9 through 12, solid powders were weighed according to the compositions listed in Table 3A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 3B.

(66) FIG. 3 is the emission spectra of the phosphors from Samples 9 through 12. X-ray diffraction measurements using the K.sub. line of a Cu target were obtained, and the XRD patterns of Samples 9-12 are shown in FIG. 13.

(67) TABLE-US-00005 TABLE 3A Composition of starting raw materials for Samples 9 through 12 Compound EuCl.sub.3 Sr.sub.3N.sub.2 Ca.sub.3N.sub.2 Si.sub.3N.sub.4 AlN Sample 9 2.583 37.81 0.988 45.83 0.82 Sample 10 2.583 37.81 1.976 45.83 0.82 Sample 11 2.583 37.81 2.964 45.83 0.82 Sample 12 2.583 37.81 3.952 45.83 0.82

(68) TABLE-US-00006 TABLE 3B Emission Peak wavelength, Intensity and CIE of Samples 9 through 12 with Composition Ca.sub.xSr.sub.1.95Si.sub.4.9Al.sub.0.1N.sub.8Eu.sub.0.05 Test Results Emission Ca Peak PL Content, Al Wavelength Intensity CIE CIE Sample x Content (nm) (a.u.) (x) (y) 9 0.1 0.1 626.50 1.56 0.6442 0.3554 10 0.2 0.1 628.42 1.52 0.6470 0.3526 11 0.3 0.1 630.75 1.46 0.6476 0.3520 12 0.4 0.1 632.71 1.41 0.6504 0.3492

(69) Samples 13 Through 15

(70) To obtain the desired compositions of the phosphors of Samples 13 through 15, solid powders were weighed according to the compositions listed in Table 4A. The same synthesis procedure as that used for Samples 1 through 5 was used. The test results are listed in Table 4B.

(71) FIG. 4 is the emission spectra of the phosphors from Samples 13 through 15. X-ray diffraction measurements using the K.sub. line of a Cu target were obtained, and the XRD patterns of Samples 13-15 are shown in FIG. 14.

(72) TABLE-US-00007 TABLE 4A Composition of starting raw materials for Samples 13 through 15 Compound EuCl.sub.3 Sr.sub.3N.sub.2 Ca.sub.3N.sub.2 Si.sub.3N.sub.4 AlN Sample 13 5.166 75.622 1.186 91.28 1.968 Sample 14 5.166 75.622 1.976 91.28 1.968 Sample 15 5.166 75.622 3.592 91.28 1.968

(73) TABLE-US-00008 TABLE 4B Emission Peak wavelength, Intensity and CIE of Samples 13 through 15 with Composition Ca.sub.xSr.sub.1.95Si.sub.4.88Al.sub.0.12N.sub.8Eu.sub.0.05 Test Results Emission Ca Peak Content, Al Wavelength Intensity CIE CIE Sample x Content (nm) (a.u.) (x) (y) 13 0.06 0.12 625 1.66 0.6450 0.3540 (charge balanced) 14 0.1 0.12 626 1.59 0.6459 0.3538 (Ca excess) 15 0.2 0.12 629 1.52 0.6478 0.3518 (Ca excess)

(74) Those of ordinary skill in the art will appreciate that compositions beyond those specifically described above may be made using the methods described above with some different choices of elements. For example, phosphor compositions may be made which are represented by the chemical formula M.sub.aSr.sub.bSi.sub.cAl.sub.dN.sub.eEu.sub.f, wherein: M is at least one of Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and 0<a<1.0; 1.5<b<2.5; 4.0c5.0; 0d1.0; 7.5<e<8.5; and 0<f<0.1; wherein a+b+f>2+d/v and v is the valence of M. Furthermore, phosphor compositions may be made which are represented by the chemical formula M.sub.xM.sub.2Si.sub.5-yAl.sub.yN.sub.8:A, wherein: M is Mg, Ca, Sr, Ba, Y, Li, Na, K and Zn, and x>0; M is at least one of Mg, Ca, Sr, Ba, and Zn; 0y0.15; and A is at least one of Eu, Ce, Tb, Pr, and Mn; wherein x>y/v and v is the valence of M, and wherein the phosphors have the general crystalline structure of M.sub.2Si.sub.5N.sub.8:A.

(75) FIG. 18 illustrates a light emitting device, according to some embodiments. The device 10 can comprise a blue light emitting, within the range of 450 nm to 470 nm, GaN (gallium nitride) LED chip 12, for example, housed within a package. The package, which can for example comprise a low temperature co-fired ceramic (LTCC) or high temperature polymer, comprises upper and lower body parts 16, 18. The upper body part 16 defines a recess 20, often circular in shape, which is configured to receive the LED chips 12. The package further comprises electrical connectors 22 and 24 that also define corresponding electrode contact pads 26 and 28 on the floor of the recess 20. Using adhesive or solder, the LED chip 12 can be mounted to a thermally conductive pad located on the floor of the recess 20. The LED chip's electrode pads are electrically connected to corresponding electrode contact pads 26 and 28 on the floor of the package using bond wires 30 and 32 and the recess 20 is completely filled with a transparent polymer material 34, typically a silicone, which is loaded with a mixture of a yellow and/or green phosphor and a red phosphor material of the present invention such that the exposed surfaces of the LED chip 12 are covered by the phosphor/polymer material mixture. To enhance the emission brightness of the device the walls of the recess are inclined and have a light reflective surface.

(76) FIGS. 19A and 19B illustrate a solid-state light emitting device, according to some embodiments. The device 100 is configured to generate warm white light with a CCT (Correlated Color Temperature) of approximately 3000K and a luminous flux of approximately 1000 lumens and can be used as a part of a downlight or other lighting fixture. The device 100 comprises a hollow cylindrical body 102 composed of a circular disc-shaped base 104, a hollow cylindrical wall portion 106 and a detachable annular top 108. To aid in the dissipation of heat, the base 104 is preferably fabricated from aluminum, an alloy of aluminum or any material with a high thermal conductivity. The base 104 can be attached to the wall portion 106 by screws or bolts or by other fasteners or by means of an adhesive.

(77) The device 100 further comprises a plurality (four in the example illustrated) of blue light emitting LEDs 112 (blue LEDs) that are mounted in thermal communication with a circular-shaped MCPCB (metal core printed circuit board) 114. The blue LEDs 112 can comprise a ceramic packaged array of twelve 0.4 W GaN-based (gallium nitride-based) blue LED chips that are configured as a rectangular array 3 rows by 4 columns.

(78) To maximize the emission of light, the device 100 can further comprise light reflective surfaces 116 and 118 that respectively cover the face of the MCPCB 114 and the inner curved surface of the top 108. The device 100 further comprises a photoluminescent wavelength conversion component 120 that is operable to absorb a proportion of the blue light generated by the LEDs 112 and convert it to light of a different wavelength by a process of photoluminescence. The emission product of the device 100 comprises the combined light generated by the LEDs 112 and the photoluminescent wavelength conversion component 120. The wavelength conversion component is positioned remotely to the LEDs 112 and is spatially separated from the LEDs. In this patent specification remotely and remote means in a spaced or separated relationship. The wavelength conversion component 120 is configured to completely cover the housing opening such that all light emitted by the lamp passes through the component 120. As shown the wavelength conversion component 120 can be detachably mounted to the top of the wall portion 106 using the top 108 enabling the component and emission color of the lamp to be readily changed.

(79) FIG. 20 shows the emission spectrum from a white light emitting device, such as described above with reference to FIGS. 18, 19A & 19B, comprising a blue-emitting InGaN LED, a red phosphor having the composition of Sample 14, and one or more yellow/green phosphors with peak emission within the range of 500 mn to 580 mn, such as a phosphor described in commonly-owned U.S. Pat. No. 8,529,791 and U.S. Pat. No. 8,475,683, both incorporated by reference herein in their entirety. In further embodiments, the yellow/green phosphor may be a silicate. Yet furthermore, the white LED may further comprise another phosphor as may be needed to achieve a desired emission spectrum, for example an orange aluminate.

(80) Although the present invention has been particularly described with reference to certain embodiments thereof, it should be readily apparent to those of ordinary skill in the art that changes and modifications in the form and details may be made without departing from the spirit and scope of the invention.