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Light emitting device |
| 7399998 |
Light emitting device
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| Patent Drawings: | |
| Inventor: |
Roth, et al. |
| Date Issued: |
July 15, 2008 |
| Application: |
11/024,702 |
| Filed: |
December 30, 2004 |
| Inventors: |
Roth; Gundula (Dorfstrasse, DE)
Tews; Walter (Rudolf-Petershagen-Allee, DE)
Lee; Chung Hoon (Seoul, KR)
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| Assignee: |
Seoul Semiconductor Co., Ltd. (Seoul, KR) |
| Primary Examiner: |
Nguyen; Joseph |
| Assistant Examiner: |
|
| Attorney Or Agent: |
Marger Johnson & McCollom PC |
| U.S. Class: |
257/100; 252/301.4F; 252/301.4R; 252/301.6R; 257/103; 257/79; 313/502; 313/503 |
| Field Of Search: |
257/81; 257/88; 257/98; 257/99; 257/100; 257/E33.058; 257/79; 257/103; 313/498; 313/499; 313/500; 313/502; 313/503; 438/22; 438/24; 252/301.4R; 252/301.4P; 252/301.6R |
| International Class: |
H01L 27/15; H01L 29/24 |
| U.S Patent Documents: |
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| Foreign Patent Documents: |
1218084; 1317537; 1344777; WO9812757; 1249873; 1336053; 2016034; 38-6082; 47-6258; 55135190; 57109886; 61258892; 5-78659; 9-40946; WO9805078; 2002094122; 2002-97466; 2002173677; 2002335019; 2002368277; 2003183649; 2003321675; 2004010786; 2004071726; 2004127988; 2002-0053975; 10-0392363; WO96/32457; WO9632457 |
| Other References: |
WL. Wanmaker, et al. "Luminescence of Phosphors Based on the Host Lattice ABGe206 (A, B=Ca, Sr, Ba)" Journeal of Solid State Chemistry 3,(1971), pp. 194-196. cited by other.
X. W. Sun, et al. "Pulsed Laser Deposition of Silicate Phosphor Thin Films", Appl. Phys. A 69, 1999, 5 pages. cited by other.
Takashi Hase, et al., "Phosphor Handbook", CRC Press, 3 pages. cited by other.
Shenstone, A.G., "The Third Spectrum of Copper (Cu III)", Journal of Research of the National Bureau of Standards - A. Physics and Chemistry, vol. 79A, No. 3, May-Jun. 1975, pp. 497-521. cited by other.
Lever, A.B.P., "Inorganic Electronics Spectroscopy", 2nd ed., Elsevier, 1984, pp. 355 and 557-559. cited by other.
Dubicki, Lujcan et al., "The First d-d Fluorescence of a Six-Coordinate Copper (II) Ion", J. Am. Chem. Soc., 1989, No. 111, pp. 3452-3454. cited by other.
Scacco, A., et al., "Optical Spectra of Cu2+ Ions in LiF Crystals", Radiation Effects and Defects in Solids, vol. 134, 1995, pp. 333-336. cited by other.
Shionoya, S., et al. (Eds.), "Principal phosphor materials and their optical properties" in Phosphor Handbook CRC Press, 1999, pp. 231-255. cited by other.
Yang, Ping et al., "Photoluminescence of Cu+-doped and Cu2+-doped ZnS nanocrystallites", Journal of Physics and Chemistry of Solids, No. 63, 2002, pp. 639-643. cited by other.
Suyver, J.F., et al., "Luminescence of nanocrystalline ZnSe:Cu", Applied Physics Letters, vol. 79, No. 25, Dec. 17, 2001, pp. 4222-4224. cited by other.
Bol, Ageeth A., et al., "Luminescence of nanocrystalline ZnS:Cu2+", Journal of Luminescence, No. 99, 2002, pp. 325-334. cited by other.
Non-Final Office Action mailed May 23, 2007 for U.S. Appl. No. 11/024,722, filed Dec. 30, 2004, entitled "Luminescent Material", Examiner Carol M. Koslow. cited by other.
Amendment and Declaration under 37 CFR 1.132 filed in response to the Non-Final Office Action mailed May 23, 2007 for U.S. Appl. No. 11/024,722, filed Dec. 30, 2004, entitled "Luminescent Material". cited by other.
Shionoya, S., et al. (Eds.), "Principal phosphor materials and their optical properties" in Phosphor Handbook, CRC Press, 1999, p. 826. cited by other.
Final Office Action dated Oct. 22, 2007 isued in U.S. Appl. No. 11/024,722 filed Dec. 30, 2004. cited by other.
"Phosphors for Mercury Lamps" https:/www.lamptech.co.uk/Docuemnts/M14%20Phosphors.htm 2003 (2 pages). cited by other.
Butler, "Flourescent Lamp Phosphors", The Pennsylvania State University Press, 1980, pp. 281-284. cited by other.
Wanmaker, Luminescence of Copper-Activated Orthophosphates of the Type ABPO (A=Ca, Sr, or Ba and B=Li, Na or K, Journal of the Electrochemical Society, pp. 109-113. cited by other.
Shinoya, "Phosphor Handbook", edited under the auspice of Phosphor Research Society, CRC Press, 1999, pp. 238-231. cited by other.
van Gool, Philips Res. Rept. Suppl., 3, 1, 1961 (2 pages). cited by other.
Wanmaker, "Luminescence of Copper-Activated Calcium and Strontium Orthophosphates", Journal of the Electromagnetic Society, pp. 1027-1031. cited by other.
Shinonoya, "Phosphor Handbook", edited under the auspice of Phosphor Research Society, CRC Press, 1999, pp. 204-205. cited by other.
Blasse, "Radiationless Processes in Luminescent Materials", Radiationless Processes, 1980, pp. 287-289, 283. cited by other.
Butler, "Fluorescent Lamp Phosphors", The Pennsylvania State University Press, 1980, pp. 181-182. cited by other.
Butler, "Flourescent Lamp Phosphors", The Pennsylvania State University Press, 1980, pp. 175-176. cited by other.
Bernhardt, Investigations of the Orange Luminescence of PbMo04 Crystals, Phys. Stat. Sol. (2), 91, 643, 1985, pp. 643-647. cited by other.
Yang, Conversion Fluorescence in Er3 + Yb3 + Co- Doped Oxy - Fluoride Compound Materials' Based on GeO2, Natural Science Journal of Xiangtan University, vol. 23, No. 2, 2001, pp. 37-41. cited by other.
First Office Action of the State Intellectual Property Office of the PRC corresponding to Chinese Patent Application No. 20051002304.2 dated Feb. 15, 2008. cited by other.
Shinoya, "Phosphor Handbook", edited under the auspice of Phosphor Research Society, CRC Press, 1998, pp. 238-239, 241. cited by other.
Shinoya, "Phosphor Handbook", edited under the auspice of Phosphor Research Society, CRC Press, 1998, pp. 204-205. cited by other.
Blasse, "Radiatonless Processes in Luminescent Materials", Radiationless Processes, 1980, pp. 287-289, 293. cited by other. |
|
| Abstract: |
A light emitting device can include a substrate, electrodes provided on the substrate, a light emitting diode configured to emit light, the light emitting diode being provided on one of the electrodes, phosphors configured to change a wavelength of the light, and an electrically conductive device configured to connect the light emitting diode with another of the plurality of electrodes. The phosphors can substantially cove at least a portion of the light emitting diode. The phosphor may include aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof. |
| Claim: |
What is claimed is:
1. A light emitting device, comprising: a light emitting diode configured to emit light; and a phosphor configured to change a wavelength of the light, the phosphorsubstantially covering at least a portion of the light emitting diode; wherein said phosphor comprises a compound including a host material, wherein divalent copper ions and oxygen are components of the host material, wherein the compound has theformula a(M'O).b(M''.sub.2O).c(M''X).d(Al.sub.2O.sub.3).e(M'''O).f(M.sub.''''.sub- .2O.sub.3).g(M'''''.sub.oO.sub.p).h(M''''''.sub.xO.sub.y) wherein M' is Cu, or a combination of Cu and Pb; M'' is Li, Na, K, Rb, Cs, Au, Ag or any combination thereof; M''' is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn or any combination thereof; M'''' is Sc, B, Ga, In, or any combination thereof; M''''' is Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or any combination thereof; M'''''' is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof; X is F, Cl, Br, I, or any combination thereof; 0<a.ltoreq.2; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2; 0<d.ltoreq.8; 0<e.ltoreq.4; 0.ltoreq.f.ltoreq.3; 0.ltoreq.g.ltoreq.8; 0<h.ltoreq.2; 1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
2. The light emitting device according to claim 1, wherein the phosphor includes one or more single compounds or any combination thereof.
3. The light emitting device according to claim 1, further comprising a sealing material configured to cover the light emitting diode and the phosphor.
4. The light emitting device according to claim 3, wherein the phosphor is distributed in the sealing material.
5. The light emitting device according to claim 1, wherein the phosphor is mixed with a hardening material.
6. The light emitting device according to claim 1, wherein the light emitting diode comprises a plurality of light emitting diodes.
7. The light emitting device according to claim 1, wherein the phosphor further comprises an aluminate containing copper, an antimonate containing copper, a germinate containing copper, a germanate-silicate containing copper, a phosphatecontaining copper, or any combination thereof.
8. The light emitting device according to claim 1, further comprising: a substrate; a plurality of electrodes provided on the substrate; and an electrically conductive device configured to connect the light emitting diode with one of theplurality of electrodes; wherein the light emitting diode is provided on another of the plurality of electrodes.
9. The light emitting device according to claim 8, further comprising electrically conductive paste provided between the light emitting diode and one of the plurality of electrodes.
10. The light emitting device according to claim 8, further comprising a reflector configured to reflect the light from the light emitting diode.
11. The light emitting device according to claim 1, further comprising: a plurality of leads; a diode holder provided at the end of one of the plurality of leads; and an electrically conductive device configured to connect the light emittingdiode with another of the plurality of leads, wherein the light emitting diode is provided in the diode holder and includes a plurality of electrodes.
12. The light emitting device according to claim 11, further comprising electrically conductive paste provided between the light emitting diode and one of the plurality of electrodes.
13. The light emitting device according to claim 1, further comprising: a housing; a heat sink at least partially provided in the housing; a plurality of lead frames provided on or around the heat sink; and an electrically conductive deviceconfigured to connect the light emitting diode with one of the plurality of lead frames, wherein the light emitting diode is disposed over the heat sink.
14. The light emitting device according to claim 13, further comprising electrically conductive paste provided between the light emitting diode and the heat sink.
15. The light emitting device according to claim 13, wherein at least one of the plurality of lead frames protrudes from the housing.
16. The light emitting device according to claim 13, wherein the heat sink comprises a plurality of heat sinks.
17. The light emitting device according to claim 1, wherein lead is a component of the host material.
18. A light emitting device, comprising: a light emitting diode configured to emit light: and a phosphor configured to change a wavelength of the light, the phosphor substantially covering at least a portion of the light emitting diode: whereinsaid phosphor comprises a compound including a host material, wherein divalent copper ions and oxygen are components of the host material, wherein the compound has the formula a(M'O)b(M''.sub.2O)c(M''X)4-a-b-c(M'''O)7(Al.sub.2O.sub.3)d(B.su-b.2O.sub.3)e(Ga.sub.2O.sub.3)f(SiO.sub.2)g(GeO.sub.2)h (M''''.sub.xO.sub.y) wherein M' is Cu, or a combination of Cu and Pb; M'' is Li, Na, K, Rb, Cs, Au, Ag, or any combination thereof; M''' is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combinationthereof; M'''' is Bi, Sn, Sb, Sc, Y, La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof; X is F, Cl, Br, I, or any combination thereof; 0<a.ltoreq.4; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2; 0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1; 0.ltoreq.f.ltoreq.1; 0.ltoreq.g.ltoreq.1; 0<h.ltoreq.2; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5. |
| Description: |
This case is related to copending U.S. patent application Ser. No. 11/024,722, filed Dec. 30, 2004.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to light emitting devices and more particularly to light emitting devices including at least one light-emitting diode and phosphor, the phosphor including lead and/or copper doped chemical compounds and converting thewavelength of light.
2. Description of the Related Art
Light emitting devices (LEDs), which used to be used for electronic devices, are now used for automobiles and illumination products. Since light emitting devices have superior electrical and mechanical characteristics, demands for light emittingdevices have been increased. In connection to this, interests in white LEDs are increasing as an alternative to fluorescent lamps and incandescent lamps.
In LED technology, solution for realization of white light is proposed variously. Normally, realization of white LED technology is to put the phosphor on the light-emitting diode, and mix the primary emission from the light emitting diode andthe secondary emission from the phosphor, which converts the wavelength. For example, as shown in WO 98/05078 and WO 98/12757, use a blue light emitting diode, which is capable of emitting a peak wavelength at 450-490 nm, and YAG group material, whichabsorbs light from the blue light emitting diode and emits yellowish light (mostly), which may have different wavelength from that of the absorbed light.
However, in such a usual white LED, color temperature range is narrow which is between about 6,000-8,000K, and CRI (Color Rendering Index) is about 60 to 75. Therefore, it is hard to produce the white LED with color coordination and colortemperature that are similar to those of the visible light. It is one of the reasons why only white light color with a cold feeling could be realized. Moreover, phosphors which are used for white LEDs are usually unstable in the water, vapor or polarsolvent, and this unstableness may cause changes in the emitting characteristics of white LED.
SUMMARY OF THE INVENTION
Wavelength conversion light emitting device are provided. In one embodiment consistent with this invention, a device is provided for emitting light. The device can include a substrate, a plurality of electrodes provided on the substrate, alight emitting diode configured to emit light, the light emitting diode being provided on one of the plurality of electrodes, phosphors configured to change a wavelength of the light, the phosphors substantially covering at least a portion of the lightemitting diode, and an electrically conductive device configured to connect the light emitting diode with another of the plurality of electrodes.
In another embodiment consistent with this invention, a light emitting device can include a plurality of leads, a diode holder provided at the end of one of the plurality of lead, a light emitting diode provided in the diode holder, the lightemitting diode including a plurality of electrodes, phosphors configured to change a wavelength of the light, the phosphors substantially covering at least a portion of the light emitting diode; and an electrically conductive device configured to connectthe light emitting device with another of the plurality of leads.
In another embodiment consistent with this invention, a light emitting device may include a housing, a heat sink at least partially provided in the housing, a plurality of lead frames provided on the heat sink, a light emitting diode mounted onone of the plurality of lead frames, phosphors configured to change a wavelength of the light, the phosphors substantially covering at least a portion of the light emitting diode, and an electrically conductive device configured to connect the lightemitting diode with another of the plurality of lead frames.
The phosphor in consistent with this invention may include aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, leadand/or copper doped phosphates, or any combination thereof. Formulas for phosphors consistent with this invention are also provided.
BRIEF DESCRIPTION OF THE DRAWINGS
Further aspects of the invention may be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:
FIG. 1 shows a side cross-sectional view of an illustrative embodiment of a portion of a chip-type package light emitting device consistent with this invention;
FIG. 2 shows a side cross-sectional view of an illustrative embodiment of a portion of a top-type package light emitting device consistent with this invention;
FIG. 3 shows a side cross-sectional view of an illustrative embodiment of a portion of a lamp-type package light emitting device consistent with this invention;
FIG. 4 shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power consistent with this invention;
FIG. 5 shows a side cross-sectional view of another illustrative embodiment of a portion of a light emitting device for high power consistent with this invention;
FIG. 6 shows emitting spectrum of a light emitting device with luminescent material consistent with this invention; and
FIG. 7 shows emitting spectrum of the light emitting device with luminescent material according to another embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Refer to the attached drawing, the wavelength conversion light emitting device is going to be explained in detail, and the light emitting device and the phosphor are separately explained for easiness of explanation as below.
(Light Emitting Device)
FIG. 1 shows a side cross-sectional view of an illustrative embodiment of a portion of a chip-type package light emitting device consistent with this invention. The chip-type package light emitting device may comprise at least one light emittingdiode and a phosphorescent substance. Electrodes 5 may be formed on both sides of substrate 1. Light emitting diode 6 emitting light may be mounted on one of the electrodes 5. Light emitting diode 6 may be mounted on electrode 5 through electricallyconductive paste 9. An electrode of light emitting diode 6 may be connected to electrode pattern 5 via an electrically conductive wire 2.
Light emitting diodes may emit light with a wide range of wavelengths, for example, from ultraviolet light to visible light. In one embodiment consistent with this invention, a UV light emitting diode and/or blue light emitting diode may be use.
Phosphor, i.e., a phosphorescent substance, 3 may be placed on the top and side faces of the light emitting diode 6. The phosphor in consistent with this invention may include lead and/or copper doped aluminate type compounds, lead and/or copperdoped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof. Phosphor 3 converts the wavelength of the lightfrom the light emitting diode 6 to another wavelength or other wavelengths. In one embodiment consistent with this invention, the light is in a visible light range after the conversion. Phosphor 3 may be applied to light emitting diode 6 after mixingphosphor 3 with a hardening resin. The hardening resin including phosphor 3 may also be applied to the bottom of light emitting diode 6 after mixing phosphor 3 with electrically conductive paste 9.
The light emitting diode 6 mounted on substrate 1 may be sealed with one or more sealing materials 10. Phosphor 3 may be placed on the top and side faces of light emitting diode 6. Phosphor 3 can also be distributed in the hardened sealingmaterial during the production. Such a manufacturing method is described in U.S. Pat. No. 6,482,664, which is hereby incorporated by reference in its entirety.
Phosphor 3 may comprise lead and/or copper doped chemical compound(s). Phosphor 3 may include one or more single chemical compounds. The single compound may have an emission peak of, for example, from about 440 nm to about 500 nm, from about500 nm to about 590 nm, or from about 580 nm to 700 nm. Phosphor 3 may include one or more single phosphors, which may have an emission peak as exemplified above.
In regard to light emitting device 40, light emitting diode 6 may emit primary light when light emitting diode 6 receives power from a power supply. The primary light then may stimulate phosphor(s) 3, and phosphor(s) 3 may convert the primarylight to a light with longer wavelength(s) (a secondary light). The primary light from the light emitting diode 6 and the secondary light from the phosphors 3 are diffused and mixed together so that a predetermined color of light in visible spectrum maybe emitted from light emitting diode 6. In one embodiment consistent with this invention, more than one light emitting diodes that have different emission peaks can be mounted together. Moreover, if the mixture ratio of phosphors is adjusted properly,specific color of light, color temperature, and CRI can be provided.
As described above, if the light emitting diode 6 and the compound included in phosphor 3 are properly controlled then desired color temperature or specific color coordination can be provided, especially, wide range of color temperature, forexample, from about 2,000K to about 8,000K or about 10,000K and/or color rendering index of greater than about 90. Therefore, the light emitting devices consistent with this invention may be used for electronic devices such as home appliances, stereos,telecommunication devices, and for interior/exterior custom displays. The light emitting devices consistent with this invention may also be used for automobiles and illumination products because they provide similar color temperatures and CRI to thoseof the visible light.
FIG. 2 shows a side cross-sectional view of an illustrative embodiment of a portion of a top-type package light emitting device consistent with this invention. A top-type package light emitting device consistent with this invention may have asimilar structure as that of the chip type package light emitting device 40 of FIG. 1. The top-type package device may have reflector 31 which may reflect the light from the light emitting diode 6 to the desire direction.
In top-type package light emitting device 50, more than one light emitting diodes can be mounted. Each of such light emitting diodes may have a different peak wavelength from that of others. Phosphor 3 may comprise a plurality of singlecompounds with different emission peak. The proportion of each of such plurality of compounds may be regulated. Such a phosphor may be applied to the light emitting diode and/or uniformly distributed in the hardening material of the reflector 31. Asexplained more fully below, the phosphor in consistent with this invention may include lead and/or copper doped aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, leadand/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof.
In one embodiment consistent with this invention, the light emitting device of the FIG. 1 or FIG. 2 can include a metal substrate, which may have good heat conductivity. Such a light emitting device may easily dissipate the heat from the lightemitting diode. Therefore, light emitting devices for high power may be manufactured. If a heat sink is provided beneath the metal substrate, the heat from the light emitting diode may be dissipated more effectively.
FIG. 3 shows a side cross-sectional view of an illustrative embodiment of a portion of a lamp-type package light emitting device consistent with this invention. Lamp type light emitting device 60 may have a pair of leads 51, 52, and a diodeholder 53 may be formed at the end of one lead. Diode holder 53 may have a shape of cup, and one or more light emitting diodes 6 may provided in the diode holder 53. When a number of light emitting diodes are provided in the diode holder 53, each ofthem may have a different peak wavelength from that of others. An electrode of light emitting diode 6 may be connected to lead 52 by, for example, electrically conductive wire 2.
Regular volume of phosphor 3, which may be mixed in the epoxy resin, may be provided in diode holder 53. As explained more fully below, phosphor 3 may include lead and/or copper doped components.
Moreover, the diode holder may include the light emitting diode 6 and the phosphor 3 may be sealed with hardening material such as epoxy resin or silicon resin.
In one embodiment consistent with this invention, the lamp type package light emitting device may have more than one pair of electrode pair leads.
FIG. 4 shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power consistent with this invention. Heat sink 71 may be provided inside of housing 73 of the light emitting device for highpower 70, and it may be partially exposed to outside. A pair of lead frame 74 may protrude from housing 73.
One or more light emitting diodes may be mounted one lead frame 74, and an electrode of the light emitting diode 6 and another lead frame 74 may be connected via electrically conductive wire. Electrically conductive pate 9 may be providedbetween light emitting diode 6 and lead frame 74. The phosphor 3 may be placed on top and side faces of light emitting diode 6.
FIG. 5 shows a side cross-sectional view of another illustrative embodiment of a portion of a light emitting device for high power consistent with this invention.
Light emitting device for high power 80 may have housing 63, which may contain light emitting diodes 6, 7, phosphor 3 arranged on the top and side faces of light emitting diodes 6, 7, one or more heat sinks 61, 62, and one or more lead frames 64. The lead frames 64 may receive power from a power supplier and may protrude from housing 63.
In the light emitting devices for high power 70, 80 in the FIGS. 4 and 5, the phosphor 3 can be added to the paste, which may be provided between heat sink and light emitting devices. A lens may be combined with housing 63, 73.
In a light emitting device for high power consistent with this invention, one or more light emitting diodes can be used selectively and the phosphor can be regulated depending on the light emitting diode. As explained more fully below, thephosphor may include lead and/or copper doped components.
A light emitting device for high power consistent with this invention may have a radiator (not shown) and/or heat sink(s). Air or a fan may be used to cool the radiator.
The light emitting devices consistent with this invention is not limited to the structures described above, and the structures can be modified depending on the characteristics of light emitting diodes, phosphor, wavelength of light, and alsoapplications. Moreover, new part can be added to the structures.
An exemplary phosphor consistent with this invention is as follows.
(Phosphor)
Phosphor in consistence with this invention may include lead and/or copper doped chemical compounds. The phosphor may be excited by UV and/or visible light, for example, blue light. The compound may include Aluminate, Silicate, Antimonate,Germanate, Germanate-silicate, or Phosphate type compounds.
Aluminate type compounds may comprise compounds having formula (1), (2), and/or (5) a(M'O).b(M''.sub.2O).c(M''X).d(Al.sub.2O.sub.3).e(M'''O).f(M''''.sub.2O.s- ub.3). g(M'''''.sub.oO.sub.p).h(M''''''.sub.xO.sub.y) (1)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be one or more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be one or more divalent elements, for example, Be, Mg, Ca, Sr,Ba, Zn, Cd, Mn, and/or any combination thereof; M'''' may be one or more trivalent elements, for example, Sc, B, Ga, In, and/or any combination thereof; M''''' may be Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, and/or any combination thereof; M'''''' may beBi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; X may be F, Cl, Br, I, and/or any combination thereof; 0<a.ltoreq.2; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2; 0<d.ltoreq.8;0<e.ltoreq.4; 0.ltoreq.f.ltoreq.3; 0.ltoreq.g.ltoreq.8; 0<h.ltoreq.2; 1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5. a(M'O).b(M''.sub.2O).c(M''X).4-a-b-c(M'''O).7(Al.sub.2O.sub.3).d(B.sub.2O-.sub.3).e(Ga.sub.2O.sub.3).f(SiO.sub.2).g(GeO.sub.2).h(M''''.sub.xO.sub.y) (2)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be one or more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be one or more divalent elements, for example, Be, Mg, Ca, Sr,Ba, Zn, Cd, Mn, and/or any combination thereof; M'''' may be Bi, Sn, Sb, Sc, Y. La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and any combination thereof; X may be F, Cl, Br, I, and any combination thereof; 0<a.ltoreq.4;0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.2; 0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1; 0.ltoreq.f.ltoreq.1; 0.ltoreq.g.ltoreq.1; 0<h.ltoreq.2; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
The preparation of copper as well as lead doped luminescent materials may be a basic solid state reaction. Pure starting materials without any impurities, e.g. iron, may be used. Any starting material which may transfer into oxides via aheating process may be used to form oxygen dominated phosphors.
EXAMPLES OF PREPARATION
Preparation of the Luminescent Material Having Formula (3) Cu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu (3)
Starting materials: CuO, SrCO.sub.3, Al(OH).sub.3, Eu.sub.2O.sub.3, and/or any combination thereof.
As shown above, it will be appreciated that, in formula (3), the composition Cu.sub.0.02SR.sub.3.98Al.sub.14Q.sub.25 represents the host material of the luminescent material and Eu represents the activator of the luminescent material. Thestarting materials in the form of oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, e.g., H.sub.3BO.sub.3. The mixture may be fired in an alumina crucible in a first step at about1,200.degree. C. for about one hour. After milling the pre-fired materials a second firing step at about 1,450.degree. C. in a reduced atmosphere for about 4 hours may be followed. After that the material may be milled, washed, dried and sieved. Theresulting luminescent material may have an emission maximum of about 494 nm.
TABLE-US-00001 TABLE 1 copper doped Eu.sup.2+-activated aluminate compared with Eu.sup.2+-activated aluminate without copper at about 400 nm excitation wavelength Compound Copper doped compound without copperCu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu Sr.sub.4Al.sub.14O.sub.25:Eu Luminous density (%) 103.1 100 Wavelength (nm) 494 493
Preparation of the Luminescent Material Having Formula (4) Pb.sub.0.05Sr.sub.3.95Al.sub.14O.sub.25:Eu (4)
Starting materials: PbO, SrCO.sub.3, Al.sub.2O.sub.3, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in form of very pure oxides, carbonates, or other components which may decompose thermically into oxides, may be mixed in stoichiometric proportion together with small amounts of flux, for example, H.sub.3BO.sub.3. Themixture may be fired in an alumina crucible at about 1,200.degree. C. for about one hour in the air. After milling the pre-fired materials a second firing step at about 1,450.degree. C. in air for about 2 hours and in a reduced atmosphere for about 2hours may be followed. Then the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum of from about 494.5 nm.
TABLE-US-00002 TABLE 2 lead doped Eu.sup.2+-activated aluminate compared with Eu.sup.2+-activated aluminate without lead at about 400 nm excitation wavelength Lead doped compound Compound without lead Pb.sub.0.05Sr.sub.3.95Al.sub.14O.sub.25:EuSr.sub.4Al.sub.14O.sub.25:Eu Luminous density (%) 101.4 100 Wavelength (nm) 494.5 493
TABLE-US-00003 TABLE 3 optical properties of some copper and/or lead doped aluminates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at 400 nm excitation wavelength Luminous density at Peak wave 400 nmexcitation length of Possible compared with lead/copper Peak wave length of excitation copper/lead not doped doped materials materials without Composition range(nm) compounds (%) (nm) lead/copper (nm) Cu.sub.0.5Sr.sub.3.5Al.sub.14O.sub.25:Eu 360-430101.2 495 493 Cu.sub.0.02Sr.sub.3.98Al.sub.14O.sub.25:Eu 360-430 103.1 494 493 Pb.sub.0.05Sr.sub.3.95Al.sub.14O.sub.25:Eu 360-430 101.4 494.5 493 Cu.sub.0.01Sr.sub.3.99Al.sub.13.995Si.sub.0.005O.sub.25:Eu 360-430 103 494- 492Cu.sub.0.01Sr.sub.3.395Ba.sub.0.595Al.sub.14O.sub.25:Eu, 360-430 100.8 494- 493 Dy Pb.sub.0.05Sr.sub.3.95Al.sub.13.95Ga.sub.0.05O.sub.25:Eu 360-430 101.5 494- 494
a(M'O).b(M''O).c(Al.sub.2O.sub.3).d(M'''.sub.2O.sub.3).e(M''''O.sub.2).f(- M'''''.sub.xO.sub.y) (5)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M''' may be B, Ga, In, and/or any combination thereof; M'''' may be Si, Ge, Ti, Zr, Hf, and/or any combinationthereof; M''''' may be Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; 0<a.ltoreq.1; 0.ltoreq.b.ltoreq.2; 0<c.ltoreq.8; 0.ltoreq.d.ltoreq.1; 0.ltoreq.e.ltoreq.1; 0<f.ltoreq.2;1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
EXAMPLE OF PREPARATION
Preparation of the Luminescent Material Having Formula (6) Cu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu (6)
Starting materials: CuO, SrCO.sub.3, Al.sub.2O.sub.3, SiO.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of, for example, pure oxides and/or as carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, AlF.sub.3. The mixture may be fired in an alumina crucible at about1,250.degree. C. in a reduced atmosphere for about 3 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 521.5 nm.
TABLE-US-00004 TABLE 4 copper doped Eu.sup.2+-activated aluminate compared with Eu.sup.2+-activated aluminate without copper at about 400 nm excitation wavelength Compound without Copper doped compound copperCu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu SrAl.sub.2O.su- b.4:Eu Luminous density (%) 106 100 Wavelength (nm) 521.5 519
Preparation of the Luminescent Material Having Formula (7) Cu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu (7)
Starting materials: CuO, MgO, BaCO.sub.3, Al(OH).sub.3, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, AlF.sub.3. The mixture may be fired in an aluminacrucible at about 1,420.degree. C. in a reduced atmosphere for about 2 hours. After that the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum of about 452 nm.
TABLE-US-00005 TABLE 5 copper doped Eu.sup.2+-activated aluminate compared with copper not doped Eu.sup.2+-activated aluminate at 400 nm excitation wavelength Comparison Copper doped compound without copperCu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu BaMg.sub.2Al.sub.16O.sub.27:- Eu Luminous density (%) 101 100 Wavelength (nm) 452 450
Preparation of the Luminescent Material Having Formula (8) Pb.sub.0.1Sr.sub.0.9Al.sub.2O.sub.4:Eu (8)
Starting materials: PbO, SrCO.sub.3, Al(OH).sub.3, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stochiometric proportions together with small amounts of flux, for example, H.sub.3BO.sub.3. The mixture may be fired in an aluminacrucible at about 1,000.degree. C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,420.degree. C. in the air for about 1 hour and in a reduced atmosphere for about 2 hours may be followed. Afterthat the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 521 nm.
TABLE-US-00006 TABLE 6 lead doped Eu.sup.2+-activated aluminate compared with Eu.sup.2+-activated aluminate without lead at about 400 nm excitation wavelength Lead doped compound Compound without lead Pb.sub.0.1Sr.sub.0.9Al.sub.2O.sub.4:EuSrAl.sub.2O.sub.4:Eu Luminous density (%) 102 100 Wavelength (nm) 521 519
Results obtained in regard to copper and/or lead doped aluminates are shown in table 7.
TABLE-US-00007 TABLE 7 optical properties of some copper and/or lead doped aluminates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at 400 nm excitation wavelength Luminous density at Peak wavePossible 400 nm excitation length of excitation compared with lead/copper Peak wave length of range copper/lead not doped doped materials without Composition (nm) compounds (%) materials (nm) lead/copper (nm)Cu.sub.0.05Sr.sub.0.95Al.sub.1.9997Si.sub.0.0003O.sub.4:Eu 360-440 106 521.5 519 Cu.sub.0.2Mg.sub.0.7995Li.sub.0.0005Al.sub.1.9Ga.sub.0.1O.sub.4:Eu, Dy 360-440 101.2 482 480 Pb.sub.0.1Sr.sub.0.9Al.sub.2O.sub.4:Eu 360-440 102 521 519Cu.sub.0.05BaMg.sub.1.95Al.sub.16O.sub.27:Eu, Mn 360-400 100.5 451, 515 450, 515 Cu.sub.0.12BaMg.sub.1.88Al.sub.16O.sub.27:Eu 360-400 101 452 450 Cu.sub.0.01BaMg.sub.0.99Al.sub.10O.sub.17:Eu 360-400 102.5 451 449Pb.sub.0.1BaMg.sub.0.9Al.sub.9.5Ga.sub.0.5O.sub.17:Eu, Dy 360-400 100.8 448 450 Pb.sub.0.08Sr.sub.0.902Al.sub.2O.sub.4:Eu, Dy 360-440 102.4 521 519 Pb.sub.0.2Sr.sub.0.8Al.sub.2O.sub.4:Mn 360-440 100.8 658 655 Cu.sub.0.06Sr.sub.0.94Al.sub.2O.sub.4:Eu360-440 102.3 521 519 Cu.sub.0.05Ba.sub.0.94Pb.sub.0.06Mg.sub.0.95Al.sub.10O.sub.17:Eu 360-440 1- 00.4 451 449 Pb.sub.0.3Ba.sub.0.7Cu.sub.0.1Mg.sub.1.9Al.sub.16O.sub.27:Eu 360-400 100.8- 452 450Pb.sub.0.3Ba.sub.0.7Cu.sub.0.1Mg.sub.1.9Al.sub.16O.sub.27:Eu, Mn 360-400 100.4 452, 515 450, 515
Lead and/or copper doped silicates having formula (9) a(M'O).b(M''O).c(M'''X).d(M'''.sub.2O).e(M''''.sub.2O.sub.3).f(M'''''.sub- .oO.sub.p).g(SiO.sub.2).h(M''''''.sub.xO.sub.y) (9)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M''' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M'''' may be Al, Ga, In, and/or anycombination thereof; M''''' may be Ge, V, Nb, Ta, W, Mo, Ti, Zr, Hf, and/or any combination thereof; M'''''' may be Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; X may be F; Cl, Br, I, andany combination thereof; 0<a.ltoreq.; 0<b.ltoreq.8; 0.ltoreq.c.ltoreq.4; 0.ltoreq.d.ltoreq.2; 0.ltoreq.e.ltoreq.2; 0.ltoreq.f.ltoreq.2; 0<g.ltoreq.10; 0<h.ltoreq.5; 1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and1.ltoreq.y.ltoreq.5.
EXAMPLE OF PREPARATION
Preparation of the Luminescent Material Having Formula (10) Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu (10)
Starting materials: CuO, SrCO.sub.3, CaCO.sub.3, SiO.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of pure oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. The mixture may be fired in an alumina crucible at about 1,200.degree. C. in an inert gas atmosphere (e.g., N.sub.2 or noble gas) for about 2 hours. Then the material may be milled. After that, the material may be fired in an alumina crucible at about 1,200.degree. C. in a slightly reduced atmosphere for about 2 hours. Then, the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum at about 592 nm.
TABLE-US-00008 TABLE 8 copper doped Eu.sup.2+-activated silicate compared with Eu.sup.2+-activated silicate without copper at about 400 nm excitation wavelength Compound Copper doped compound without copperCu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu Sr.sub.1.7Ca.sub.0.3SiO.sub.- 4:Eu Luminous density (%) 104 100 Wavelength (nm) 592 588
Preparation of the Luminescent Material Having Formula (11) Cu.sub.0.2Ba.sub.2Zn.sub.0.2Mg.sub.0.6Si.sub.2O.sub.7:Eu (1)
Starting materials: CuO, BaCO.sub.3, ZnO, MgO, SiO.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of very pure oxides and carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. In a first step the mixture may be fired in an alumina crucible atabout 1,100.degree. C. in a reduced atmosphere for about 2 hours. Then the material may be milled. After that the material may be fired in an alumina crucible at about 1,235.degree. C. in a reduced atmosphere for about 2 hours. Then that thematerial may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 467 nm.
TABLE-US-00009 TABLE 9 copper doped Eu.sup.2+-activated silicate compared with Eu.sup.2+-activated silicate without copper at 400 nm excitation wavelength Compound Copper doped compound without copperCu.sub.0.2Sr.sub.2Zn.sub.0.2Mg.sub.0.6Si.sub.2O.sub.7:Eu Sr.sub.2Zn.sub.2- Mg.sub.0.6Si.sub.2O.sub.7:Eu Luminous 101.5 100 density (%) Wavelength (nm) 467 465
Preparation of the Luminescent Material Having Formula (12) Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu (12)
Starting materials: PbO, SrCO.sub.3, BaCO.sub.3, SiO.sub.2, GeO.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. The mixture may be fired in an alumina crucible at about 1,000.degree. C.for about 2 hours in the air. After milling the pre-fired materials a second firing step at 1,220.degree. C. in air for 4 hours and in reducing atmosphere for 2 hours may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 527 nm.
TABLE-US-00010 TABLE 10 lead doped Eu.sup.2+-activated silicate compared with Eu.sup.2+-activated silicate without lead at about 400 nm excitation wavelength Compound without Lead doped compound leadPb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu BaSrSi- O.sub.4:Eu Luminous density 101.3 100 (%) Wavelength (nm) 527 525
Preparation of the Luminescent Material Having Formula (13) Pb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu (13)
Starting materials: PbO, SrCO.sub.3, SrCl.sub.2, SiO.sub.2, Eu.sub.2O.sub.3, and any combination thereof.
The starting materials in the form of oxides, chlorides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. The mixture may be fired in an alumina crucible in a first stepat about 1,100.degree. C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,220.degree. C. in the air for about 4 hours and in a reduced atmosphere for about 1 hour may be followed. After that thematerial may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 492 nm.
TABLE-US-00011 TABLE 11 lead doped Eu.sup.2+-activated chlorosilicate compared with Eu.sup.2+-activated chlorosilicate without lead at 400 nm excitation wavelength Compound Lead doped compound without leadPb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu Sr.sub.4Si.sub.3O.sub.8C- l.sub.4:Eu Luminous density (%) 100.6 100 Wavelength (nm) 492 490
Results obtained with respect to copper and/or lead doped silicates are shown in table 12.
TABLE-US-00012 TABLE 12 optical properties of some copper and/or lead doped rare earth activated silicates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength Luminousdensity at Possible 400 nm excitation Peak wave length Peak wave length excitation compared with of lead/copper of materials range copper/lead not doped doped materials without Composition (nm) compounds (%) (nm) lead/copper (nm)Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu 360-470- 101.3 527 525 Cu.sub.0.02(Ba,Sr,Ca,Zn).sub.1.98SiO.sub.4:Eu 360-500 108.2 565 560 Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu 360-470 104 592 588Cu.sub.0.05Li.sub.0.002Sr.sub.1.5Ba.sub.0.448SiO.sub.4:Gd, Eu 360-470 102.5 557 555 Cu.sub.0.2Sr.sub.2Zn.sub.0.2Mg.sub.0.6Si.sub.2O.sub.7:Eu 360-450 101.5 467- 465 Cu.sub.0.02Ba.sub.2.8Sr.sub.0.2Mg.sub.0.98Si.sub.2O.sub.8:Eu, Mn 360-420 100.8 440, 660438, 660 Pb.sub.0.25Sr.sub.3.75Si.sub.3O.sub.8Cl.sub.4:Eu 360-470 100.6 492 490 Cu.sub.0.2Ba.sub.2.2Sr.sub.0.75Pb.sub.0.05Zn.sub.0.8Si.sub.2O.sub.8:Eu 360- -430 100.8 448 445 Cu.sub.0.2Ba.sub.3Mg.sub.0.8Si.sub.1.99Ge.sub.0.01O.sub.8:Eu 360-430 101 4- 44440 Cu.sub.0.5Zn.sub.0.5Ba.sub.2Ge.sub.0.2Si.sub.1.8O.sub.7:Eu 360-420 102.5 4- 35 433 Cu.sub.0.8Mg.sub.0.2Ba.sub.3Si.sub.2O.sub.8:Eu, Mn 360-430 103 438, 670 435, 670 Pb.sub.0.15Ba.sub.1.84Zn.sub.0.01Si.sub.0.99Zr.sub.0.01O.sub.4:Eu 360-500 - 101 512510 Cu.sub.0.2Ba.sub.5Ca.sub.2.8Si.sub.4O.sub.16:Eu 360-470 101.8 495 491
With lead and/or copper doped antimonates having formula (14) a(M'O).b(M''.sub.2O).c(M''X).d(Sb.sub.2O.sub.5).e(M'''O).f(M''''.sub.xO.s- ub.y) (14)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M'''' may be Bi, Sn, Sc, Y, La, Pr, Sm,Eu, Tb, Dy, Gd, and/or any combination thereof; X may be F; Cl, Br, I, and/or any combination thereof; 0<a.ltoreq.2; 0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.4; 0<d.ltoreq.8; 0-e.ltoreq.8; 0.ltoreq.f.ltoreq.2; 1.ltoreq.x.ltoreq.2; and1.ltoreq.y.ltoreq.5.
EXAMPLES OF PREPARATION
Preparation of the Luminescent Material Having Formula (15) Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:Mn (15)
Starting materials: CuO, MgO, Li.sub.2O, Sb.sub.2O.sub.5, MnCO.sub.3, and/or any combination thereof.
The starting materials in the form of oxides may be mixed in stoichiometric proportion together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 985.degree. C. in the air for about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,200.degree. C. in an atmosphere containing oxygen for about 8 hours. After that the material may be milled, washed, driedand sieved. The resulting luminescent material may have an emission maximum at about 626 nm.
TABLE-US-00013 TABLE 13 copper doped antimonate compared with antimonate without copper at about 400 nm excitation wavelength Comparison Copper doped compound without copper Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:MnMg.sub.2Li.sub.0.2Sb.sub- .2O.sub.7:Mn Luminous density (%) 101.8 100 Wavelength (nm) 652 650
Preparation of the Luminescent Material Having Formula (16) Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6 (16)
Starting materials: PbO, CaCO.sub.3, SrCO.sub.3, Sb.sub.2O.sub.5, and/or any combination thereof.
The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 975.degree. C. in the airfor about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,175.degree. C. in the air for about 4 hours and then in an oxygen-containing atmosphere for about 4hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 637 nm.
TABLE-US-00014 TABLE 14 lead doped antimonate compared with antimonate without lead at 400 nm excitation wavelength Compound Lead doped compound without lead Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6 Ca.sub.0.6Sr.sub.0.4Sb.- sub.2O.sub.6Luminous density (%) 102 100 Wavelength (nm) 637 638
Results obtained in respect to copper and/or lead doped antimonates are shown in table 15.
TABLE-US-00015 TABLE 15 optical properties of some copper and/or lead doped antimonates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength Luminous density at Peakwave 400 nm excitation length of Peak wave length Possible compared with lead/copper of materials excitation copper/lead not doped doped materials without Composition range (nm) compounds (%) (nm) lead/copper (nm)Pb.sub.0.2Mg.sub.0.002Ca.sub.1.798Sb.sub.2O.sub.6F.sub.2:Mn 360-400 102 64- 5 649 Cu.sub.0.15Ca.sub.1.845Sr.sub.0.005Sb.sub.1.998Si.sub.0.002O.sub.7:Mn 360-- 400 101.5 660 658 Cu.sub.0.2Mg.sub.1.7Li.sub.0.2Sb.sub.2O.sub.7:Mn 360-400 101.8 652 650Cu.sub.0.2Pb.sub.0.01Ca.sub.0.79Sb.sub.1.98Nb.sub.0.02O.sub.6:Mn 360-400 9- 8.5 658 658 Cu.sub.0.01Ca.sub.1.99Sb.sub.1.9995V.sub.0.0005O.sub.7:Mn 360-400 100.5 66- 0 657 Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6 360-400 102 637 638Cu.sub.0.02Ca.sub.0.9Sr.sub.0.5Ba.sub.0.4Mg.sub.0.18Sb.sub.2O.sub.7 360-40- 0 102.5 649 645 Pb.sub.0.198Mg.sub.0.004Ca.sub.1.798Sb.sub.2O.sub.6F.sub.2 360-400 101.8 6- 28 630
Lead and/or copper doped germanates and/or a germanate-silicates having formula (17) a(M'O).b(M''.sub.2O).c(M''X)d(GeO.sub.2).e(M'''O).f(M''''.sub.2O.sub.3).g (M'''''.sub.oO.sub.p).h(M''''''.sub.xO.sub.y) (17)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, and/or any combination thereof; M'''' may be Sc, Y, B, Al, La, Ga, In, and/orany combination thereof; M''''' may be Si, Ti, Zr, Mn, V, Nb, Ta, W, Mo, and/or any combination thereof; M'''''' may be Bi, Sn, Pr, Sm, Eu, Gd, Dy, and/or any combination thereof; X may be F, Cl, Br, I, and/or any combination thereof; 0<a.ltoreq.2;0.ltoreq.b.ltoreq.2; 0.ltoreq.c.ltoreq.10; 0<d.ltoreq.10; 0.ltoreq.e.ltoreq.14; 0.ltoreq.f.ltoreq.14; 0.ltoreq.g.ltoreq.10; 0.ltoreq.h.ltoreq.2; 1.ltoreq.o.ltoreq.2; 1.ltoreq.p.ltoreq.5; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
EXAMPLE OF PREPARATION
Preparation of the Luminescent Material Having Formula (18) Pb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn (18)
Starting materials: PbO, CaCO.sub.3, ZnO, GeO.sub.2, SiO.sub.2, MnCO.sub.3, and/or any combination thereof.
The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. In a first step the mixture may be fired in an alumina crucible at about1,200.degree. C. in an oxygen-containing atmosphere for about 2 hours. Then, the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,200.degree. C. in oxygen containing atmosphere for about 2hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 655 nm.
TABLE-US-00016 TABLE 16 lead doped Mn-activated germanate compared with Mn-activated germanate without lead at about 400 nm excitation wavelength Copper doped compound Comparison without copperPb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn Ca.sub.- 1.99Zn.sub.0.01Ge.sub.0.8Si.sub.0.2O.sub.4:Mn Luminous density (%) 101.5 100 Wavelength (nm) 655 657
Preparation of the Luminescent Material Having Formula (19) Cu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn (19)
Starting materials: CuO, SrCO.sub.3, GeO.sub.2, SiO.sub.2, MnCO.sub.3, and/or any combination thereof.
The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH.sub.4Cl. In a first step the mixture may be fired in an alumina crucible at about1,100.degree. C. in an oxygen-containing atmosphere for about 2 hours. Then, the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,180.degree. C. in an oxygen-containing atmosphere for about 4hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 658 mm.
TABLE-US-00017 TABLE 17 copper doped Mn-activated germanate-silicate compared with Mn-activated germanate-silicate without copper at 400 nm excitation wavelength Compound Copper doped compound without copperCu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn SrGe.sub.0.6Si.sub.0- .4O.sub.3:Mn Luminous density (%) 103 100 Wavelength (nm) 658 655
TABLE-US-00018 TABLE 18 optical properties of some copper and/or lead doped germanate-silicates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength Luminous density atPeak wave Peak wave Possible 400 nm excitation length of length of excitation compared with lead/copper materials without range copper/lead not doped doped lead/copper Composition (nm) compounds (%) materials (nm) (nm)Pb.sub.0.004Ca.sub.1.99Zn.sub.0.006Ge.sub.0.8Si.sub.0.2O.sub.4:Mn 360-400 - 101.5 655 657 Pb.sub.0.002Sr.sub.0.954Ca.sub.1.044Ge.sub.0.93Si.sub.0.07O.sub.4:Mn 360-4- 00 101.5 660 661 Cu.sub.0.46Sr.sub.0.54Ge.sub.0.6Si.sub.0.4O.sub.3:Mn 360-400 103 658655 Cu.sub.0.002Sr.sub.0.998Ba.sub.0.99Ca.sub.0.01Si.sub.0.98Ge.sub.0.02O.sub.- 4:Eu 360-470 102 538 533 Cu.sub.1.45Mg.sub.26.55Ge.sub.9.4Si.sub.0.6O.sub.48:Mn 360-400 102 660 657- Cu.sub.1.2Mg.sub.26.8Ge.sub.8.9Si.sub.1.1O.sub.48:Mn 360-400 103.8 670656- Cu.sub.4Mg.sub.20Zn.sub.4Ge.sub.5Si.sub.2.5O.sub.38F.sub.10:Mn 360-400 101- .5 658 655 Pb.sub.0.001Ba.sub.0.849Zn.sub.0.05Sr.sub.1.1Ge.sub.0.04Si.sub.0.96O.sub.4- :Eu 360-470 101.8 550 545 Cu.sub.0.05Mg.sub.4.95GeO.sub.6F.sub.2:Mn 360-400 100.5 655653 Cu.sub.0.05Mg.sub.3.95GeO.sub.5.5F:Mn 360-400 100.8 657 653
Lead and/or copper doped phosphates having formula (20) a(M'O).b(M''.sub.2O).c(M''X).d(P.sub.2O.sub.5).e(M'''O).f(M''''.sub.2O.su- b.3).g(M'''''O.sub.2).h(M''''''.sub.xO.sub.y) (20)
wherein M' may be Pb, Cu, and/or any combination thereof; M'' may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M''' may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M'''' may be Sc, Y, B, Al, La, Ga, In,and/or any combination thereof; M''''' may be Si, Ge, Ti, Zr, Hf. V, Nb, Ta, W, Mo, and/or any combination thereof; M'''''' may be Bi, Sn, Pr, Sm, Eu, Gd, Dy, Ce, Tb, and/or any combination thereof; X may be F, Cl, Br, I, and/or any combination thereof;0<a.ltoreq.2; 0.ltoreq.b.ltoreq.12; 0.ltoreq.c.ltoreq.16; 0<d.ltoreq.3; 0.ltoreq.e.ltoreq.5; 0.ltoreq.f.ltoreq.3; 0.ltoreq.g.ltoreq.2; 0<h.ltoreq.2; 1.ltoreq.x.ltoreq.2; and 1.ltoreq.y.ltoreq.5.
EXAMPLES OF PREPARATION
Preparation of the Luminescent Material Having Formula (21) Cu.sub.0.02Ca.sub.4.98(PO.sub.4).sub.3Cl:Eu (21)
Starting materials: CuO, CaCO.sub.3, Ca.sub.3(PO.sub.4).sub.2, CaCl.sub.2, Eu.sub.2O.sub.3, and/or any combination thereof.
The starting materials in the form of oxides, phosphates, and/or carbonates and chlorides may be mixed in stoichiometric proportions together with small amounts of flux. The mixture may be fired in an alumina crucible at about 1,240.degree. C.in reducing atmosphere for about 2 hours. After that the material may be milled, washed, dried and sieved. The luminescent material may have an emission maximum at about 450 nm.
TABLE-US-00019 TABLE 19 copper doped Eu.sup.2+-activated chlorophosphate compared with Eu.sup.2+-activated chlorophosphate without copper at about 400 nm excitation wavelength Copper doped compound Compound without copperCu.sub.0.02Ca.sub.4.98(PO.sub.4).sub.3Cl:Eu Ca.sub.5(PO.sub.4).sub.3Cl:Eu- Luminous 101.5 100 density (%) Wavelength (nm) 450 447
TABLE-US-00020 TABLE 20 copper and/or lead doped phosphates excitable by long wave ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength Luminous density at 400 nm Peak wave length Peak wavelength Possible excitation compared of lead/copper of materials excitation with copper/lead not doped materials without Composition range (nm) doped compounds (%) (nm) lead/copper (nm) Cu.sub.0.02Sr.sub.4.98(PO.sub.4).sub.3Cl:Eu 360-410 101.5 450 447Cu.sub.0.2Mg.sub.0.8BaP.sub.2O.sub.7:Eu, Mn 360-400 102 638 635 Pb.sub.0.5Sr.sub.1.5P.sub.1.84B.sub.0.16O.sub.6.84:Eu 360-400 102 425 420 Cu.sub.0.5Mg.sub.0.5Ba.sub.2(P,Si).sub.2O.sub.8:Eu 360-400 101 573 570Cu.sub.0.5Sr.sub.9.5(P,B).sub.6O.sub.24Cl.sub.2:Eu 360-410 102 460 456 Cu.sub.0.5Ba.sub.3Sr.sub.6.5P.sub.6O.sub.24(F,Cl).sub.2:Eu 360-410 102 443- 442 Cu.sub.0.05(Ca,Sr,Ba).sub.4.95P.sub.3O.sub.12Cl:Eu, Mn 360-410 101.5 438, 641 435, 640Pb.sub.0.1Ba.sub.2.9P.sub.2O.sub.8:Eu 360-400 103 421 419
Meanwhile, the phosphor of the light emitting device consistent with this invention can comprise aluminate, silicate, antimonate, germanate, phosphate type chemical compound, and any combination thereof.
FIG. 6 is a one of the embodiment's emission spectrum according to the invention, which the phosphor is used for the light emitting device. The embodiment may have a light emitting diode with 405 nm wavelength and the phosphor, which is mixtureof the selected multiple chemical compounds in proper ratio. The phosphor may be composed of Cu.sub.0.05BaMg.sub.1.95Al.sub.16O.sub.27:Eu which may have peak wavelength at about 451 nm, Cu.sub.0.03Sr.sub.1.5Ca.sub.0.47SiO.sub.4:Eu which may have peakwavelength at 586 nm, Pb.sub.0.006Ca.sub.0.6Sr.sub.0.394Sb.sub.2O.sub.6:Mn.sup.4+ which may have peak wavelength at about 637 nm, Pb.sub.0.15Ba.sub.1.84Zn.sub.0.01Si.sub.0.99Zr.sub.0.01O.sub.4:Eu which may have peak wavelength at around 512 nm, andCu.sub.0.2Sr.sub.3.8Al.sub.14O.sub.25:Eu which may have peak wavelength at about 494 nm.
In such an embodiment, part of the initial about 405 nm wavelength emission light from the light emitting diode is absorbed by the phosphor, and it is converted to longer 2.sup.nd wavelength. The 1.sup.st and 2.sup.nd light is mixed together andthe desire emission is produced. As the shown FIG. 6, the light emitting device convert the 1.sup.st UV light of 405 nm wavelength to wide spectral range of visible light, that is, white light, and at this time the color temperature is about 3,000K andCRI is about 90 to about 95.
FIG. 7 is another embodiment's emission spectrum according to the invention, which the phosphor is applied for the light emitting device. The embodiment may have a light emitting diode with about 455 nm wavelength and the phosphor, which ismixture of the selected multiple chemical compounds in proper ratio.
The phosphor is composed of Cu.sub.0.05Sr.sub.1.7Ca.sub.0.25SiO.sub.4:Eu which may have peak wavelength at about 592 nm, Pb.sub.0.1Ba.sub.0.95Sr.sub.0.95Si.sub.0.998Ge.sub.0.002O.sub.4:Eu which may have peak wavelength at about 527 nm, andCu.sub.0.05Li.sub.0.002Sr.sub.1.5Ba.sub.0.448SiO.sub.4:Gd, Eu which may have peak wavelength at about 557 nm.
In such an embodiment, part of the initial about 455 nm wavelength emission light from the light emitting diode is absorbed by the phosphor, and it is converted to longer 2.sup.nd wavelength. The 1.sup.st and 2.sup.nd light is mixed together andthe desire emission is produced. As the shown FIG. 7, the light emitting device convert the 1.sup.st blue light of about 455 nm wavelength to wide spectral range of visible light, that is, white light, and at this time the color temperature is about4,000K to about 6,500K and CRI is about 86 to about 93.
The phosphor of the light emitting device according to the invention can be applied by single chemical compound or mixture of plurality of single chemical compound besides the embodiments in relation to FIG. 6 and FIG. 7, which are explainedabove.
According to the description above, light emitting device with wide range of color temperature about 2,000K or about 8,000K or about 10,000K and superior color rendering index more than about 90 can be realized by using the lead and/or copperdoped chemical compounds containing rare earth elements.
In such a wavelength conversion light emitting device is capable of applying on mobile phone, note book and electronic devices such as home appliance, stereo, telecommunication products, but also for custom display's key pad and back lightapplication. Moreover, it can be applied for automobile, medical instrument and illumination products.
According to the invention, it is also able to provide a wavelength conversion light emitting device with stability against water, humidity, vapor as well as other polar solvents.
In the foregoing described embodiments, various features are grouped together in a single embodiment for purposes of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimedinvention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are herebyincorporated into this Detailed Description of Embodiments, with each claim standing on its own as a separate preferred embodiment of the invention.
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