Phosphors with narrow green emission

Abstract

A luminescent composition of matter is characterized by the formula REM.sub.2+xE.sub.y, where RE may be one or more Rare Earth elements (for example, Eu or Gd), M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu, and Y; E is one or more elements selected from the group S, Se, O, and Te; x is greater than zero; and y has the value that achieves charge balance in the formula assuming that E has a charge of 2.

Claims

1. A luminescent composition of matter characterized by the formula REM.sub.2+xE.sub.y, wherein: RE is one or more rare earth elements; M is one or more elements selected from the group Al, Ga, B, In, Sc, Lu, and Y; E is one or more elements selected from the group S, Se, O, and Te; x is greater than or equal to 0.1 and less than or equal to 0.9; and y has the value that achieves charge balance in the formula assuming that E has a charge of 2.

2. The luminescent composition of matter of claim 1, wherein x is greater than or equal to 0.3.

3. The luminescent composition of matter of claim 1, wherein x is greater than or equal to 0.7.

4. The luminescent composition of matter of claim 1, having exclusively an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure.

5. The luminescent composition of matter of claim 1, having a mixture of predominantly an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.

6. The luminescent composition of matter of claim 1, wherein RE is Eu.

7. The luminescent composition of matter of claim 6, wherein x is greater than or equal to 0.3.

8. The luminescent composition of matter of claim 6, wherein x is greater than or equal to 0.7.

9. The luminescent composition of matter of claim 6, having exclusively an EuM.sub.2E.sub.4. pseudoorthorhombic crystal structure.

10. The luminescent composition of matter of claim 6, having a mixture of predominantly an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.

11. The luminescent composition of matter of claim 1, wherein RE comprises Eu and Gd.

12. The luminescent composition of matter of claim 11, wherein x is greater than or equal to 0.3.

13. The luminescent composition of matter of claim 11, wherein x is greater than or equal to 0.7.

14. The luminescent composition of matter of claim 1, wherein the composition is characterized by the formula Eu(Al,Ga).sub.2+xS.sub.y.

15. The luminescent composition of matter of claim 14, wherein the ratio of Al to Ga is between about 1:3 and about 2:1.

16. The luminescent composition of matter of claim 14, wherein x is greater than or equal to 0.3.

17. The luminescent composition of matter of claim 14, wherein x is greater than or equal to 0.7.

18. The luminescent composition of matter of claim 14, having exclusively an EuM.sub.2E.sub.4. pseudoorthorhombic crystal structure.

19. The luminescent composition of matter of claim 14, having a mixture of predominantly an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.

20. The luminescent composition of matter of claim 17 wherein the composition is characterized by the formula EuAl.sub.1.08Ga.sub.1.02S.sub.5.05.

21. The luminescent composition of matter of claim 1, wherein the composition is characterized by the formula EuAl.sub.2+xE.sub.y. where E is selected from the group S and Se.

22. The luminescent composition of matter of claim 21, wherein x is greater than or equal to 0.3.

23. The luminescent composition of matter of claim 21, wherein x is greater than or equal to 0.7.

24. The luminescent composition of matter of claim 21, having exclusively an EuM.sub.2E.sub.4. pseudoorthorhombic crystal structure.

25. The luminescent composition of matter of claim 21, having a mixture of predominantly an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.

26. The luminescent composition of matter of claim 21, wherein the composition is characterized by the formula EuAl.sub.2.7Se.sub.5.05.

27. The luminescent composition of matter of claim 21, wherein the composition is characterized by the formula EuAl.sub.2.7S.sub.5.05.

28. A light emitting device comprising: a light emitting diode emitting light over a first wavelength range; and a luminescent composition of matter arranged to be excited by emission from the light emitting diode and in response emit light over a second wavelength range; wherein the luminescent composition of matter is characterized by the formula REM.sub.2+xE.sub.y, wherein: RE is one or more rare earth elements; M is one or more elements selected from the group Al, Ga, B, In, Sc, Lu, and Y; E is one or more elements selected from the group S, Se, O, and Te; x is greater than or equal to zero and less than or equal to 0.9; and y has the value that achieves charge balance in the formula assuming that E has a charge of 2.

29. The light emitting device of claim 28, wherein RE is Eu and x is greater than or equal to 0.3.

30. The light emitting device of claim 28, wherein RE is Eu and x is greater than or equal to 0.7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a plot showing CIE xy color points of example commercially available phosphors, the green gamut points from the NTSC color gamut and the DCI-P3 color gamut, and emission from example phosphors of the present invention peaked at 530 nm and 537 nm.

(2) FIGS. 2A-2C show, respectively, an emission spectrum, an excitation spectrum, and a powder x-ray diffraction pattern for EuAl.sub.2.133B.sub.0.567S.sub.5.05.

(3) FIGS. 3A-3B show, respectively, an emission spectrum and an excitation spectrum for EuAl.sub.2.322Lu.sub.0.378S.sub.5.05.

(4) FIGS. 4A-4C show, respectively, emission spectra, excitation spectra, and powder x-ray diffraction patterns for Eu(Al.sub.0.4Ga.sub.0.6).sub.2+xS.sub.y with x=0, 0.1, 0.3, 0.5, 0.7, and 0.9.

(5) FIGS. 5A-5B show, respectively, emission spectra and excitation spectra for EuAl.sub.2Se.sub.4, EuAl.sub.2.4Se.sub.4-6, EuAl.sub.2.4Se.sub.3.6S, and EuAl.sub.2.7Se.sub.5.05.

(6) FIG. 6 shows an emission spectrum for EuAl.sub.2.07In.sub.0.23S.sub.4.45.

(7) FIG. 7 shows an emission spectrum for EuAl.sub.1.84In.sub.0.46S.sub.4.45.

(8) FIG. 8 shows an emission spectrum for EuAl.sub.1.61Ga.sub.0.23In.sub.0.46S.sub.4.45.

(9) FIG. 9 shows an emission spectrum for an example phosphor converted LED.

(10) FIG. 10 shows an emission spectrum for another example phosphor converted LED.

(11) FIG. 11 shows an emission spectrum for another example phosphor converted LED.

(12) FIG. 12 shows the emission spectrum for the example phosphor converted LED of FIG. 11 overlaid with example color filters.

DETAILED DESCRIPTION

(13) The following detailed description should be read with reference to the drawings, which depict selective embodiments and are not intended to limit the scope of the invention. The detailed description illustrates by way of example, not by way of limitation, the principles of the invention. This description will clearly enable one skilled in the art to make and use the invention, and describes several embodiments, adaptations, variations, alternatives and uses of the invention, including what is presently believed to be the best mode of carrying out the invention. As used in this specification and the appended claims, the singular forms a, an, and the include plural referents unless the context clearly indicates otherwise.

(14) Phosphors of the present invention emit green light over a relatively narrow range of emission wavelengths in response to excitation with, for example, ultraviolet, violet, blue, or short wavelength green light. Their narrow emission may appear more saturated and widen the green vertex of the color gamut compared to commercially available green phosphors. As an example of this advantage, FIG. 1 shows the CIE xy color points of example commercially available phosphors such as LuAGs and silicates peaked at 525 nm, 530 nm, and 540 nm (such as available for example from Intematix Corporation, Fremont, Calif., under product numbers GAL525, GAL530, GAL540, EG2762, EG3261, and EG3759), the green gamut points from the NTSC color gamut and the DCI-P3 color gamut, and emission from example phosphors of the present invention peaked at 530 nm and 537 nm.

(15) Phosphors of the present invention have the empirical composition REM.sub.2+xE.sub.y, where RE may be one or more Rare Earth elements (for example, Eu or Gd), M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y, E may be one or more elements selected from the group S, Se, O, or Te, x is greater than zero, or greater than or equal to 0.1, or greater than or equal to 0.3, or greater than or equal to 0.7, and less than or equal to 0.9, and y has the value that achieves charge balance in the formula assuming that E has a charge of 2. (In the experimental examples described in this specification, reactions are always run with an excess of chalcogen, allowing the reaction to utilize what is needed to form the charge balanced composition). Some minor compositional substitutions may also occur from the use of reaction promoters including but not limited to AlCl.sub.3 or I.sub.2. The phosphors may have the same basic pseudoorthorhombic crystal structure as REM.sub.2E.sub.4 (e.g., EuGa.sub.2S.sub.4). The phosphors may comprise a mixture of a REM.sub.2E.sub.4 crystal phase and one or more binary chalcogenide crystals phases such as for example an M.sub.2E.sub.3 (e.g., Ga.sub.2S.sub.3) crystal phase or an ME (e.g., GaS) crystal phase. In some variations the composition is characterized by the formula Eu(Al,Ga).sub.2+xS.sub.y, and the ratio of Al to Ga is between about 1:3 and about 2:1.

(16) Phosphors of the present invention may show an improvement over known alkaline earth thiogallate phosphors by providing a narrower emission spectrum than is provided by state of the art thiogallate phosphors. Phosphors of the present invention may show an improvement in brightness over EuM.sub.2E.sub.4 compositions such as, for example, EuAl.sub.2S.sub.4, EuAl.sub.2Se.sub.4, and EuGa.sub.2S.sub.4 disclosed by Thi et al. Materials Science & Engineering B14 (1992), No 4, pp. 393-397, Donohue U.S. Pat. No. 3,801,702 (issued Apr. 2, 1974), and Donohue and Hanlon, Journal of the Electrochemical Society: Solid-State Science and Technology (1974), Vol. 121, No. 1, pp. 137-142.

(17) In particular, phosphors having the empirical formula REM.sub.2+xE.sub.y with x>0 described above may provide a significant increase in the relative intensity of the phosphor's emission peak, in some cases greater than two-fold, compared to phosphors having the composition REM.sub.2E.sub.4. The optimal value of x may vary with the exact composition of the system. However, x=0.7 appears to be at or near an optimal value for many choices of M, such as for example for RE=Eu and M=1/3 Al, 2/3 Ga.

(18) Phosphors of the present invention may be tuned through a wavelength range based upon application requirements by varying the M and E components of the composition. For example, for phosphors having the empirical formula Eu(Al,Ga).sub.2+x(S,Se).sub.y, the emission wavelength range can extend for example from a peak emission wavelength around 490 nm for EuAl.sub.2+xSe.sub.y to a peak emission wavelength around 550 nm for EuGa.sub.2+xS.sub.y. Even longer wavelengths of emission can be obtained by incorporating indium or oxygen. For phosphors having the empirical formula Eu(Al,Ga).sub.2+xS.sub.y, the peak emission wavelength may vary with percent Ga approximately as follows: 0% Ga, 505 nm; 5% Ga, 509 nm; 14% Ga, 512 nm; 25% Ga, 517 nm; 50% Ga, 527 nm; 55% Ga, 530 nm; 60% Ga, 533 nm; 65% Ga, 533 nm; 70% Ga, 535 nm; 75% Ga, 541 nm; 100% Ga, 545 nm. For phosphors having the empirical formula Eu(Al,Ga).sub.2+x(S,Se).sub.y, the percent Ga may be, for example, 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 0% to 5%, 5% to 10%, 10%, to 15%, 15% to 20%, 20% to 25%, 25% to 30%, 30% to 35%, 35% to 40%, 40% to 45%, 45% to 50%, 50% to 55%, 55% to 60%, 60% to 65%, 65% to 70%, 70% to 75%, 75% to 80%, 80% to 85%, 85% to 90%, 90%, 95%, 95% to 100%, or 50% to 75%.

(19) A number of fluxes/reaction promoters have been investigated, such as for example I.sub.2, AlF.sub.3, AlCl.sub.3, AlBr.sub.3, GaCl.sub.3, GaBr.sub.3, BaF.sub.2, EuCl.sub.3, EuI.sub.2, and Na.sub.2S. Use of promoters with cations other than those in the targeted final product (e.g., Ba and Na) resulted in the formation of alternative phases, not meeting the desired properties of the invention.

(20) The phosphors of the present invention may be optically coupled with an excitation source in any conventional manner. One of the more common methods is to combine phosphors, such as the green phosphor disclosed here, with a red phosphor and optional blue and/or yellow phosphors. The phosphors may be combined together and then added to an encapsulant, such as silicone, epoxy, or some other polymer, or the phosphors may be combined during their addition to the encapsulant. The phosphor loaded encapsulant may then be placed in the optical path of an excitation source. One common method is to deposit the slurry of phosphor or phosphors into an LED (light emitting diode) package which contains an LED die. The slurry is then cured forming an encapsulated LED package. Other methods include forming the encapsulant into a shape or coating the encapsulant onto a substrate which may already be in a particular shape, or may be subsequently formed into a particular shape. Additionally, the phosphor containing encapsulant may be coated on the in-coupling region of a light guide, or on the out-coupling region of a light guide, such as a light guide intended for use in a display. The combination of an excitation source and the phosphors of the present invention may be used in general lighting, niche lighting applications, display backlighting, or other lighting applications.

(21) Applicant has prepared and characterized a number of example phosphor samples having the empirical composition REM.sub.2+xE.sub.y described above. Preparation and characterization of these examples is described below and summarized in Table 1. For some samples one or more crystal phases observed by powder x-ray diffraction are reported in addition to the empirical composition. Emission spectra were measured using a Fluorolog-3 spectrofluorometer with xenon lamp or an Ocean Optics spectrometer used in conjunction with an external blue or violet LED excitation source. Excitation spectra were measured using a Fluorolog-3 spectrofluorometer with xenon lamp. Powder x-ray diffraction spectra were measured using a Rigaku MiniFlex600.

Example 1 EuAl2.133B0.567S5.05 (Sample Number KB3-063-406), x=0.7

(22) A 1:2.133:0.567:4.4 ratio of Eu:Al:B:S was ground in an argon filled glovebox and sealed in a fused silica tube. The sample was heated at 400 C. for 6 hours, then the temperature was increased and held at 800 C. for 12 hours. The sample was cooled to room temperature at about 130 C./hour. The sample was opened in an argon filled glovebox, ground with an additional 10 wt % sulfur and sealed in a fused silica tube and heated a second time with the same heating profile.

(23) FIG. 2A shows an emission spectrum from this sample with excitation at 395 nm. FIG. 2B shows an excitation spectrum for this sample with emission detected at 510 nm. FIG. 2C shows a powder x-ray diffraction (XRD) measurement for this sample, which matches the XRD pattern for EuAl.sub.2S.sub.4 (standard PDF #01-081-2821). This suggests that some of the excess Al, excess B, and excess S may be present in one or more a binary chalcogenide phases.

Example 2 EuAl2.322Lu0.378S5.05 (Sample Number KB3-059-399), x=0.7

(24) A 1:2.322:0.378:4.4 ratio of Eu:Al:Lu:S was ground in an argon filled glovebox and sealed in a fused silica tube. The sample was heated at 400 C. for 6 hours, then the temperature was increased and held at 800 C. for 12 hours. The sample was cooled to room temperature at about 130 C./hour. The sample was opened in an argon filled glovebox, ground with an additional 10 wt % sulfur and sealed in a fused silica tube and heated a second time with the same heating profile.

(25) FIG. 3A shows an emission spectrum from this sample with excitation at 395 nm. FIG. 3B shows an excitation spectrum for this sample with emission detected at 505 nm.

Example 3 EuAl08Ga1.2S4, (Sample Number KB3-125-488), x=0, Comparative Example

(26) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S were mixed in a stoichiometric ratio and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.116 g Eu, 0.046 g Al.sub.2S.sub.3, 0.108 g Ga.sub.2S.sub.3, 0.031 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(27) FIG. 4A shows the emission spectrum for this sample (labeled x=0) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.

Example 4 EuAl0.84Ga1.26S4.15, (Sample Number KB3-125-489), x=0.1

(28) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S were mixed in a stoichiometric ratio and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.113 g Eu, 0.047 g Al.sub.2S.sub.3, 0.110 g Ga.sub.2S.sub.3, 0.030 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(29) FIG. 4A shows the emission spectrum for this sample (labeled x=0.1) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0.1) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.1.

Example 5 EuAl0.02Ga1.38S4.45, (Sample Number KB3-125-490), x=0.3

(30) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S were mixed in a stoichiometric ratio, and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.108 g Eu, 0.049 g, Al.sub.2S.sub.3, 0.115 g Ga.sub.2S.sub.3, 0.028 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(31) FIG. 4A shows the emission spectrum for this sample (labeled x=0.3) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0.3) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.3.

Example 6 EuAlGa1.5S4.75, (Sample Number KB3-125-491), x=0.5

(32) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S were mixed in a stoichiometric ratio, and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.103 g Eu, 0.051 g Al.sub.2S.sub.3, 0.120 g Ga.sub.2S.sub.3, 0.027 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(33) FIG. 4A shows the emission spectrum for this sample (labeled x=0.5) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0.5) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.5.

Example 7 EuAl1.08Ga1.62S5.05, (Sample Number KB3-126-492), x=0.7

(34) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S were mixed in a stoichiometric ratio, and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.098 g Eu, 0.052 g Al.sub.2S.sub.3, 0.124 g Ga.sub.2S.sub.3, 0.026 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(35) FIG. 4A shows the emission spectrum for this sample (labeled x=0.7) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0.7) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.7.

Example 8 EuAl1.16Ga1.74S5.35 (Sample Number KB3-126-493), x=0.9

(36) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S, were mixed in a stoichiometric ratio and an additional 0.25 sulfur per formula unit and 7.5 wt % AlCl.sub.3 were added (0.094 g Eu, 0.054 g Al.sub.2S.sub.3, 0.127 g Ga.sub.2S.sub.3, 0.025 g S, 0.023 g AlCl.sub.3). The mixture was ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The sample was cooled to room temperature at 50 C./hour.

(37) FIG. 4A shows the emission spectrum for this sample (labeled x=0.9) with excitation at 395 nm. FIG. 4B shows the excitation spectrum for this sample (labeled x=0.9) with emission detected at 535 nm. FIG. 4C shows a powder x-ray diffraction (XRD) measurement for this sample, labeled x=0.9.

(38) XRD Data for Examples 3-8

(39) In FIG. 4C the major phase in each XRD pattern matches EuGa.sub.2S.sub.4 (standard PDF#01-071-0588). Ga.sub.2S.sub.3 (PDF #00-054-0415) is also present (peaks are marked with stars), and the amount increases as x increases. The peaks for both phases are shifted to slightly higher angle than the database patterns, likely due to incorporation of aluminum.

Example 9 EuAl1.08Ga1.62S5.05 (Sample Number KB3-132-506), x=0.7

(40) This sample was prepared using an AlF.sub.3 flux, rather than an AlCl.sub.3 flux as in example 7. Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S, were mixed in a stoichiometric ratio. An additional 0.25 sulfur per formula unit and 7.5 wt % AlF.sub.3 were added. The mixture was ground in an argon filled glovebox and sealed in a carbon coated fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 800 C. for 6 hours. The samples were cooled to room temperature at 50 C./hour.

Example 10 EuAl0.8Ga1.2S4 (Sample Number KB3-133-507), x=0

(41) This sample was prepared using an AlF.sub.3 flux, rather than an AlCl.sub.3 flux as in example 3. Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, and S, were mixed in a stoichiometric ratio. An additional 0.25 sulfur per formula unit and 7.5 wt % AlF.sub.3 were added. The mixture was ground in an argon filled glovebox and sealed in a carbon coated fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 800 C. for 6 hours. The samples were cooled to room temperature at 50 C./hour.

Example 11 EuAl2Se4, (Sample Number YBG-170419-1), x=0, Comparative Example

(42) Stoichiometric amounts of Eu, Al, and Se were thoroughly ground in a mortar with a pestle in the glove box. The mixture was placed in dried, carbon coated silica tubes, which were evacuated and sealed at a length of about 5 in. The reaction was carried out in a box furnace. The temperature was raised to 400 C. and held for 6 hours and raised again to 800 C. and held for 6 hours, then cooled to room temperature for 6 hours.

(43) FIG. 5A shows the emission spectrum for this sample (labeled a) for excitation at 395 nm. The relative intensity of the emission peak is 100% compared to the other emission spectra in this figure. FIG. 5B shows the excitation spectrum for this sample (labeled a) with emission detected at 490 nm.

Example 12 EuAl2.4Se4.6 (Sample Number YBG-170419-2), x=0.4

(44) Stoichiometric amounts of Eu, Al, and Se were thoroughly ground in a mortar with a pestle in the glove box. The mixture was placed in dried, carbon coated silica tubes, which were evacuated and sealed at a length of about 5 in. The reaction was carried out in a box furnace. The temperature was raised to 400 C. and held for 6 hours and raised again to 800 C. and held for 6 hours, then cooled to room temperature for 6 hours.

(45) FIG. 5A shows the emission spectrum for this sample (labeled b) for excitation at 395 nm. The relative intensity of the emission peak is 144% compared to the other emission spectra in this figure. FIG. 5B shows the excitation spectrum for this sample (labeled b) with emission detected at 490 nm.

Example 13 EuAl2.4Se3.6S (Sample Number YBG-170419-4), x=0.4

(46) Stoichiometric amounts of Eu, Al, Se, and S were thoroughly ground in a mortar with a pestle in the glove box. The mixture was placed in dried, carbon coated silica tubes, which were evacuated and sealed at a length of about 5 in. The reaction was carried out in a box furnace. The temperature was raised to 400 C. and held for 6 hours and raised again to 800 C. and held for 6 hours, then cooled to room temperature for 6 hours.

(47) FIG. 5A shows the emission spectrum for this sample (labeled c) for excitation at 395 nm. The relative intensity of the emission peak is 117% compared to the other emission spectra in this figure. FIG. 5B shows the excitation spectrum for this sample (labeled c) with emission detected at 490 nm.

Example 14 EuAl2.7Se5.05 (Sample Number YBG-170419-5), x=0.7

(48) Stoichiometric amounts of Eu, Al, and Se were thoroughly ground in a mortar with a pestle in the glove box. The mixture was placed in dried, carbon coated silica tubes, which were evacuated and sealed at a length of about 5 in. The reaction was carried out in a box furnace. The temperature was raised to 400 C. and held for 6 hours and raised again to 800 C. and held for 6 hours, then cooled to room temperature for 6 hours.

(49) FIG. 5A shows the emission spectrum for this sample (labeled d) for excitation at 395 nm. The relative intensity of the emission peak is 224% compared to the other emission spectra in this figure. FIG. 5B shows the excitation spectrum for this sample (labeled d) with emission detected at 490 nm.

Example 15 EuAl2.07In0.23S4.45 (Sample Number KB3-132-503)

(50) Eu, Al.sub.2S.sub.3, In.sub.2S.sub.3, and S were mixed in a stoichiometric ratio. The mixtures were ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The samples were cooled to room temperature at 50 C./hour.

(51) FIG. 6 shows the emission spectrum for this sample for excitation at 405 nm.

Example 16 EuAl1.84In0.46S4.45 (Sample Number KB3-132-504)

(52) Eu, Al.sub.2S.sub.3, In.sub.2S.sub.3, and S were mixed in a stoichiometric ratio. The mixtures were ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The samples were cooled to room temperature at 50 C./hour.

(53) FIG. 7 shows the emission spectrum for this sample for excitation at 405 nm.

Example 17 EuAl1.61Ga0.23In0.46S445 (Sample Number KB3-132-505)

(54) Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3, In.sub.2S.sub.3, and S were mixed in a stoichiometric ratio. The mixtures were ground in an argon filled glovebox and sealed in a fused silica tube. The samples were heated at 400 C. for 1 hour, then the temperature was increased and held at 900 C. for 6 hours. The samples were cooled to room temperature at 50 C./hour.

(55) FIG. 8 shows the emission spectrum for this sample for excitation at 405 nm.

Example 18 EuAlGa1.5S4.75 (Sample Number ELTAlS-056A)

(56) A 1.2 g mixture of stoichiometric amounts of Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3 and S was prepared under Ar. The mixture was combined with 20 wt % excess S, and separated into five 200 mg portions for use in this example and in examples 19-22. For this example one 200 mg portion of the mixture was thoroughly mixed with 30 mg (15 wt %) of an AlBr.sub.3 flux and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 2 hours, dwelled for 1 hour at that temperature, and then was heated to 900 C. over 1.5 hours and dwelled at that temperature for 6 h before being slowly cooled to room temperature at 50 C./hr.

Example 19 EuAlGa1.5S4.75 (Sample Number ELTAlS-056B)

(57) A 200 mg portion of the 1.2 g mixture of stoichiometric amounts of Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3 and S prepared in Example 18 was thoroughly mixed with 30 mg (15 wt %) of a GaBr.sub.3 flux and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 2 hours, dwelled for 1 hour at that temperature, and then was heated to 900 C. over 1.5 hours and dwelled at that temperature for 6 h before being slowly cooled to room temperature at 50 C./hr.

Example 20 EuAlGa1.5S4.75 (Sample Number ELTAlS-056C)

(58) A 200 mg portion of the 1.2 g mixture of stoichiometric amounts of Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3 and S prepared in Example 18 was thoroughly mixed with 30 mg (15 wt %) of a GaCl.sub.3 flux and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 2 hours, dwelled for 1 hour at that temperature, and then was heated to 900 C. over 1.5 hours and dwelled at that temperature for 6 h before being slowly cooled to room temperature at 50 C./hr.

Example 21 EuAlGa1.5S4.75 (Sample Number ELTAlS-056D)

(59) A 200 mg portion of the 1.2 g mixture of stoichiometric amounts of Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3 and S prepared in Example 18 was thoroughly mixed with 30 mg (15 wt %) of a EuCl.sub.3 flux and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 2 hours, dwelled for 1 hour at that temperature, and then was heated to 900 C. over 1.5 hours and dwelled at that temperature for 6 h before being slowly cooled to room temperature at 50 C./hr.

Example 22 EuAlGa1.5S4.75 (Sample Number ELTAlS-056E)

(60) A 200 mg portion of the 1.2 g mixture of stoichiometric amounts of Eu, Al.sub.2S.sub.3, Ga.sub.2S.sub.3 and S prepared in Example 18 was thoroughly mixed with 30 mg (15 wt %) of a EuI.sub.2 flux and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 2 hours, dwelled for 1 hour at that temperature, and then was heated to 900 C. over 1.5 hours and dwelled at that temperature for 6 h before being slowly cooled to room temperature at 50 C./hr.

Example 23 Eu0.97Gd0.03Al0.92Ga1.38S4.45 (Sample Number YBG-170424-2)

(61) Stoichiometric amount of Eu, Al, Ga.sub.2S.sub.3, Gd.sub.2O.sub.3, S, and 5 wt % excess S were thoroughly ground in a mortar with a pestle in the glove box. The mixtures were placed in dried silica tubes, which were evacuated and sealed at a length of about 5 in. Reactions were carried out in a box furnace. The temperature was raised to 900 C. for 4 hours and held for 12 hours then cooled to room temperature for 6 hours.

Example 24 EuAl2S4 (Sample Number ELTAlS-006C), Comparative Example

(62) A mixture of stoichiometric amounts of Eu, Al, S, and a few wt. % excess of S was thoroughly mixed under argon and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 6 hours, dwelled for 6 hours at that temperature, and then was heated to 800 C. and dwelled at that temperature for 24 hours before being cooled to room temperature over 9 hours. The sample was thoroughly mixed under argon and sealed in an evacuated quartz tube. The heating step was repeated.

Example 25 EuAl2.33S4.28 (Sample Number ELTAlS-016C)

(63) A mixture of stoichiometric amounts of Eu, Al, S, and a few wt. % excess of S was thoroughly mixed under argon and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 6 hours, dwelled for 6 hours at that temperature, and then was heated to 800 C. and dwelled at that temperature for 24 hours before being cooled to room temperature over 6 hours. The sample was thoroughly mixed under argon and sealed in an evacuated quartz tube. The heating step was repeated.

Example 26 EuAl2.7S5.05 (Sample Number ELTAlS-016E)

(64) A mixture of stoichiometric amounts of Eu, Al, S, and a few wt. % excess of S was thoroughly mixed under argon and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 6 hours, dwelled for 6 hours at that temperature, and then was heated to 800 C. and dwelled at that temperature for 120 hours before being cooled to room temperature over 6 hours. The sample was thoroughly mixed under argon and sealed in an evacuated quartz tube. The heating step was repeated with the dwell step at 800 C. for 48 hours.

Example 27 EuAl2.9S5.35 (Sample Number ELTAlS-016F)

(65) A mixture of stoichiometric amounts of Eu, Al, S, and a few wt. % excess of S was thoroughly mixed under argon and sealed in an evacuated quartz tube. The ampoule was heated to 400 C. over 6 hours, dwelled for 6 hours at that temperature, and then was heated to 800 C. and dwelled at that temperature for 48 hours before being cooled to room temperature over 6 hours. The sample was thoroughly mixed under argon and sealed in an evacuated quartz tube. The heating step was repeated.

(66) Relative photoluminescent intensities were compared for EuAl.sub.2S.sub.4, EuAl.sub.2.33S.sub.4.28, EuAl.sub.2.7S.sub.5.05, and EuAl.sub.2.9S.sub.5.35 using 395 nm excitation. Setting EuAl.sub.2S.sub.4 as 100%, EuAl.sub.2.33S.sub.4.28 was more intense at 109%, EuAl.sub.2.7S.sub.5.05 was the most intense at 378% and EuAl.sub.2.9S.sub.5.35 was also more intense than the comparative example by 292%.

Example 28 EuGa2S4 (Sample Number ELTAlS-062A), Comparative Example

(67) Stoichiometric amounts of Eu, Ga.sub.2S.sub.3 and S, with 20 wt % excess S were homogenized under argon. The mixture was combined with 136 mg (6 mg/cm.sup.3) I.sub.2 prior to sealing in an approx. 8 in evacuated quartz tube. The ampoule was placed in a horizontal tube furnace with a natural gradient and heated to 400 C. over 6 h, dwelled for 6 h, then heated to 900 C. over 2.5 h and dwelled for 72 h before being slowly cooled to room temperature over 24 h. The phosphor powder had a peak emission wavelength of 549 nm and a full width at half maximum of 43 nm when excited with 405 nm light from an LED.

Example 29 EuGa2S4 (Sample Number ELTAlS-062B), Comparative Example

(68) Stoichiometric amounts of Eu, Ga.sub.2S.sub.3 and S, with 20 wt % excess S were homogenized under argon. The mixture was combined with 60 mg (15 wt %) GaCl.sub.3 prior to sealing in an approx. 8 in evacuated quartz tube. The ampoule was placed in a horizontal tube furnace with a natural gradient and heated to 400 C. over 6 h, dwelled for 6 h, then heated to 900 C. over 2.5 h and dwelled for 72 h before being slowly cooled to room temperature over 24 h. The phosphor powder had a peak emission wavelength of 551 nm and a full width at half maximum of 39 nm when excited with 405 nm light from an LED.

Example 30 EuGa2.7S5.05 (Sample Number ELTAlS-063A)

(69) Stoichiometric amounts of Eu, Ga.sub.2S.sub.3 and S, with 20 wt % excess S were homogenized under argon. The mixture was combined with 136 mg (6 mg/cm.sup.3) I.sub.2 prior to sealing in an approx. 8 in evacuated quartz tube. The ampoule was placed in a horizontal tube furnace with a natural gradient and heated to 400 C. over 6 h, dwelled for 6 h, then heated to 900 C. over 2.5 h and dwelled for 72 h before being slowly cooled to room temperature over 24 h. The phosphor powder had a peak emission wavelength of 549 nm and a full width at half maximum of 41 nm when excited with 405 nm light from an LED, and appeared visibly brighter than the comparative example 28.

Example 31 EuGa2.7S5.05 (Sample Number ELTAlS-063B)

(70) Stoichiometric amounts of Eu, Ga.sub.2S.sub.3 and S, with 20 wt % excess S were homogenized under argon. The mixture was combined with 60 mg (15 wt %) GaCl.sub.3 prior to sealing in an approx. 8 in evacuated quartz tube. The ampoule was placed in a horizontal tube furnace with a natural gradient and heated to 400 C. over 6 h, dwelled for 6 h, then heated to 900 C. over 2.5 h and dwelled for 72 h before being slowly cooled to room temperature over 24 h. The phosphor powder had a peak emission wavelength of 550 nm and a full width at half maximum of 39 nm when excited with 405 nm light from an LED, and appeared visibly brighter than the comparative example 29.

(71) Phosphor Converted LED Examples

(72) A phosphor slurry was created by combining 21.40 mg Dow Corning OE-6550 2 part silicone, 0.98 mg red phosphor, BR101J and 2.67 mg of a green phosphor of the present invention (example 5, EuAl.sub.0.92Ga.sub.1.38S.sub.4.45, x=0.3). Phosphor converted LEDs 1-3 (examples 24-26 below) were fabricated using portions of this slurry, and vary from each other only in the amount of slurry deposited on the LED.

Example 32 Phosphor Converted LED 1

(73) The phosphor slurry described above was applied on top of a blue emitting InGaN based LED mounted in a 2835 PLCC package from Power Opto Co., and the silicone was cured overnight at ca. 100 C. The emission spectrum of this LED, shown in FIG. 9, was measured with an Ocean Optics spectrometer. The phosphor converted LED of this example was measured to have a correlated color temperature (CCT) of 4625K, a duv of 0.0046, and a CRI of 83, corresponding to a neutral white.

Example 33 Phosphor Converted LED 2

(74) The phosphor slurry described above was applied on top of a blue emitting InGaN based LED mounted in a 2835 PLCC package from Power Opto Co., and the silicone was cured overnight at ca. 100 C. The emission spectrum of this LED, shown in FIG. 10, was measured with an Ocean Optics spectrometer. The cured layer of slurry on the LED in this example was thinner than that in Example 25 (phosphor converted LED 1). The phosphor converted LED of this example was measured to have a correlated color temperature (CCT) of 6575K, a duv of 0.0045, and a CRI of 85, corresponding to a cool white.

Example 34 Phosphor Converted LED 3

(75) The phosphor slurry described above was applied on top of a blue emitting InGaN based LED mounted in a 2835 PLCC package from Power Opto Co., and the silicone was cured overnight at ca. 100 C. The emission spectrum of this LED, shown in FIG. 11, was measured with an Ocean Optics spectrometer. The cured layer of slurry on the LED in this example was thinner than that in Example 26 (phosphor converted LED 2). The phosphor converted LED of this example was measured to have CIE xy coordinates of 0.253, 0.250, suitable for backlighting applications. FIG. 12 shows the emission (solid line) from this phosphor converted LED overlaid with an example set of LCD color filters: blue (long dash), green (alternating dash and dot), and red (short dash). The emission spectrum is a good match for the example color filters shown in the figure.

(76) Various embodiments are described in the following clauses.

(77) Clause 1. A luminescent composition of matter characterized by the formula REM.sub.2+xE.sub.y, wherein:

(78) RE is one or more rare earth elements;

(79) M is one or more elements selected from the group Al, Ga, B, In, Sc, Lu, and Y;

(80) E is one or more elements selected from the group S, Se, O, and Te;

(81) x is greater than zero; and

(82) y has the value that achieves charge balance in the formula assuming that E has a charge of 2.

(83) Clause 2. The luminescent composition of matter of clause 1, wherein RE is Eu.

(84) Clause 3. The luminescent composition of matter of clause 1, wherein RE comprises Eu and Gd.

(85) Clause 4. The luminescent composition of matter of clause 1, having exclusively an EuM.sub.2E.sub.4. pseudoorthorhombic crystal structure.

(86) Clause 5. The luminescent composition of matter of clause 1, having a mixture of predominantly an EuM.sub.2E.sub.4 pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.

(87) Clause 6. The luminescent composition of matter of any of clauses 1-5, wherein the composition is characterized by the formula Eu(Al.sub.0.4Ga.sub.0.6).sub.2+xS.sub.y, where x is greater than zero.

(88) Clause 7. The luminescent composition of matter of any of clauses 1-5, wherein:

(89) M is Al; and

(90) E is S, Se, or a mixture of S and Se.

(91) Clause 8. The luminescent composition of matter of any of clauses 1-7, wherein x is greater than or equal to 0.5.

(92) Clause 9. The luminescent composition of matter of any of clauses 1-8, wherein x is greater than or equal to 0.7.

(93) Clause 10. The luminescent composition of matter of any of clauses 1-5, wherein the composition is characterized by the formula EuAl.sub.1.08Ga.sub.1.62S.sub.5.05.

(94) Clause 11. A light emitting device comprising a phosphor of any of clauses 1-10.

(95) Clause 12. A phosphor converted light emitting diode comprising:

(96) a light emitting diode emitting light over a first wavelength range; and

(97) a phosphor of any of clauses 1-10 arranged to be excited by emission from the light emitting diode and in response emit light over a second wavelength range.

(98) This disclosure is illustrative and not limiting. Further modifications will be apparent to one skilled in the art in light of this disclosure and are intended to fall within the scope of the appended claims.

(99) TABLE-US-00001 TABLE 1 Summary of experimental examples compositions and spectral properties Peak emission Phases Observed wavelength/ FWHM/ Example Sample Empirical Composition in PXRD nm nm 1 KB3-063-406 EuAl.sub.2.133B.sub.0.567S.sub.5.05 Eu(Al.sub.0.79B.sub.0.21).sub.2S.sub.4 505 34 2 KB3-059-399 EuAl.sub.2.322Lu.sub.0.378S.sub.5.05 501 35 3 KB3-125-488 EuAl.sub.0.8Ga.sub.1.2S.sub.4 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 535 42 AlCl.sub.3 flux 4 KB3-125-489 EuAl.sub.0.84Ga.sub.1.26S.sub.4.15 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 534 43 AlCl.sub.3 flux (Ga,Al).sub.2S.sub.3 5 KB3-125-490 EuAl.sub.0.92Ga.sub.1.38S.sub.4.45 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 539 44 AlCl.sub.3 flux (Ga,Al).sub.2S.sub.3 6 KB3-125-491 EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 535 43 AlCl.sub.3 flux (Ga,Al).sub.2S.sub.3 7 KB3-126-492 EuAl.sub.1.08Ga.sub.1.62S.sub.5.05 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 535 43 AlCl.sub.3 flux (Ga,Al).sub.2S.sub.3 8 KB3-126-493 EuAl.sub.1.16Ga.sub.1.74S.sub.5.35 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 533 43 AlCl.sub.3 flux (Ga,Al).sub.2S.sub.3 9 KB3-132-506 EuAl.sub.1.08Ga.sub.1.62S.sub.5.05 530 48 AlF.sub.3 flux 10 KB3-133-507 EuAl.sub.0.8Ga.sub.1.2S.sub.4 532 47 AlF.sub.3 flux 11 YBG-170419-1 EuAl.sub.2Se.sub.4 EuAl.sub.2Se.sub.4 + EuSe + 486 34 Al.sub.1.33Se.sub.2 12 YBG-170419-2 EuAl.sub.2.4Se.sub.4.6 EuAl.sub.2Se.sub.4 + EuSe 488 34 13 YBG-170419-4 EuAl.sub.2.4Se.sub.3.6S EuAl.sub.2Se.sub.4 + EuSe 496 37 14 YBG-170419-5 EuAl.sub.2.7Se.sub.5.05 EuAl.sub.2Se.sub.4 488 33 15 KB3-132-503 EuAl.sub.2.07In.sub.0.23S.sub.4.45 508 31 16 KB3-132-504 EuAl.sub.1.84In.sub.0.46S.sub.4.45 511 37 17 KB3-132-505 EuAl.sub.1.61Ga.sub.0.23In.sub.0.46S.sub.4.45 517 45 18 ELTAlS-056A EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 533 43 AlBr.sub.3 flux (Ga,Al).sub.2S.sub.3 19 ELTAlS-056B EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 541 44 GaBr.sub.3 flux (Ga,Al).sub.2S.sub.3 20 ELTAlS-056C EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 541 45 GaCl.sub.3 flux (Ga,Al).sub.2S.sub.3 21 ELTAlS-056D EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 + 537 44 EuCl.sub.3 flux (Ga,Al).sub.2S.sub.3 + (Ga,Al)S 22 ELTAlS-056E EuAlGa.sub.1.5S.sub.4.75 Eu(Ga.sub.0.6Al.sub.0.4).sub.2S.sub.4 536 47 EuI.sub.2 flux 23 YBG-170424-2 Eu.sub.0.97Gd.sub.0.03Al.sub.0.92Ga.sub.1.38S.sub.4.45 EuAl.sub.0.8Ga.sub.1.2S.sub.4 537 50 24 ELTAlS-006C EuAl.sub.2S.sub.4 EuAl.sub.2S.sub.4 503 30 25 ELTAlS-016C EuAl.sub.2.33S.sub.4.28 EuAl.sub.2S.sub.4 509 31 26 ELTAlS-016E EuAl.sub.2.7S.sub.5.05 EuAl.sub.2S.sub.4 508 32 27 ELTAlS-016F EuAl.sub.2.9S.sub.5.35 EuAl.sub.2S.sub.4 507 31 28 ELTAlS-062A EuGa.sub.2S.sub.4 549 43 I.sub.2 flux 29 ELTAlS-062B EuGa.sub.2S.sub.4 551 39 GaCl.sub.3 flux 30 ELTAlS-063A EuGa.sub.2.7S.sub.5.05 549 41 I.sub.2 flux 31 ELTAlS-063B EuGa.sub.2.7S.sub.5.05 550 39 GaCl.sub.3 flux