Light emitting device

Abstract
A light emitting device is disclosed. The light emitting device may include a light emitting diode (LED) for emitting light and phosphor adjacent to the LED. The phosphor may be excitable by light emitted by the LED and may include a first compound having a host lattice comprising first ions and oxygen. In one embodiment, the host lattice may include silicon, the copper ions may be divalent copper ions and first compound may have an Olivin crystal structure, a β-K2SO4 crystal structure, a trigonal Glaserite (K3Na(SO4)2) or monoclinic Merwinite crystal structure, a tetragonal Ackermanite crystal structure, a tetragonal crystal structure or an orthorhombic crystal structure. In another embodiment, the copper ions do not act as luminescent ions upon excitation with the light emitted by the LED.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


Embodiments of the present invention relate generally to light emitting devices and, more particularly, to light emitting devices including at least one light-emitting diode and phosphor including lead- and/or copper-containing chemical compounds and converting the wavelength 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 emitting devices 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 and the 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, which absorbs light from the blue light emitting diode and emits yellowish light (mostly), which may have different wavelength from that of the absorbed light. However, phosphors which are used for white LEDs are usually unstable in the water, vapor or polar solvent, and this unstableness may cause changes in the emitting characteristics of white LED.


SUMMARY OF THE INVENTION

One embodiment exemplarily described herein can be generally characterized as a light emitting device that includes a light emitting diode (LED) for emitting light and a phosphor adjacent to the LED. The phosphor is excitable by light emitted by the LED and may include a first compound having a host lattice comprising first ions, silicon and oxygen. A first portion of the first ions may be substituted by divalent copper ions and the first compound may have one of an Olivin crystal structure, a β-K2SO4 crystal structure, a trigonal Glaserite (K3Na(SO4)2) or monoclinic Merwinite crystal structure, a tetragonal Ackermanite crystal structure, a tetragonal crystal structure and an orthorhombic crystal structure.


Another embodiment exemplarily described herein can be generally characterized as a light emitting device that includes a light emitting diode (LED) for emitting light and a phosphor adjacent to the LED. The phosphor is excitable by light emitted by the LED and may include a first compound having a host lattice comprising first ions and oxygen. A first portion of the first ions may be substituted by copper ions and the copper ions do not act as luminescent ions upon excitation with the light emitted by the LED.





BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments 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;



FIG. 2 shows a side cross-sectional view of an illustrative embodiment of a portion of a top-type package light emitting device;



FIG. 3 shows a side cross-sectional view of an illustrative embodiment of a portion of a lamp-type package light emitting device;



FIG. 4 shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power;



FIG. 5 shows a side cross-sectional view of another illustrative embodiment of a portion of a light emitting device for high power;



FIG. 6 shows emitting spectrum of a light emitting device with luminescent material; and



FIG. 7 shows emitting spectrum of the light emitting device with luminescent material according to another embodiment.





DETAILED DESCRIPTION

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. The chip-type package light emitting device may comprise at least one light emitting diode 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 electrically conductive paste 9. An electrode of light emitting diode 6 may be connected to electrode pattern 5 via an electrically conductive wire 2. A plurality of electrodes 5 may be arranged on the substrate 1, an electrically conductive device may connect the light emitting diode 6 with one of the plurality of electrodes 5, and the light emitting diode 6 may be mounted on another of the plurality of electrodes 5.


Light emitting diodes may emit light with a wide range of wavelengths, for example, from ultraviolet light to visible light. In one embodiment, a UV light emitting diode and/or blue light emitting diode may be used.


Phosphor, i.e., a phosphorescent substance, 3 may be placed on the top and side faces of the light emitting diode 6. In some embodiments, the phosphor may include lead- and/or copper containing chemical compounds. In some embodiments, the chemical compounds may comprise aluminates, silicates, antimonates, germanates, germanate-silicates, phosphates, or the like, or a combination thereof. Phosphor 3 converts the wavelength of the light from the light emitting diode 6 to another wavelength or other wavelengths. In one embodiment, the light is in a visible light range after the conversion. Phosphor 3 may be applied to light emitting diode 6 after mixing phosphor 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 sealing material 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 one or more lead- and/or copper containing chemical compounds. Phosphor 3 may include one or more single chemical compounds. Each single compound may have an emission peak of, for example, from about 440 nm to about 500 nm, from about 500 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 primary light 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 may be emitted from light emitting diode 6. In one embodiment, more than one light emitting diodes that have different emission peaks can be mounted together. In some embodiments, a mixture ratio of different phosphors can be adjusted to achieve a desired color of light, color temperature, and CRI.


As described above, if the light emitting diode 6 and the compound(s) included in phosphor 3 are properly controlled then the desired color temperature or specific color coordination can be provided, especially, wide range of color temperature, for example, from about 2,000K to about 8,000K or about 10,000K and/or color rendering index of greater than about 60. In some embodiments, the compound(s) included in the phosphor 3 can be controlled to have a color rendering index between about 50 and about 90. In some embodiments, the compound(s) included in the phosphor 3 can be controlled to have a color rendering index greater than about 90. In some embodiments, the compound(s) included in the phosphor 3 can be controlled to have a color rendering index between about 90 and about 95. Therefore, the light emitting devices exemplarily described herein may be used for electronic devices such as home appliances, stereos, telecommunication devices, and for interior/exterior custom displays. The light emitting devices exemplarily described herein may also be used for automobiles and illumination products because they provide similar color temperatures and CRI to those of 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. A top-type package light emitting device may have a similar 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 single compounds with different emission peaks. 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. As explained more fully below, the phosphor may include lead- and/or copper containing aluminate type compounds, lead- and/or copper containing silicates, lead- and/or copper containing antimonates, lead- and/or copper containing germanates, lead- and/or copper containing germanate-silicates, lead and/or copper containing phosphates, or any combination thereof.


In one embodiment, 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 light emitting 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. Lamp type light emitting device 60 may have a pair of leads 51, 52, and a diode holder 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 of them 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 containing 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. The sealing material may cover the light emitting diode 6 and the phosphor 3.


In one embodiment, the lamp type package light emitting device may have more than one pair of electrode pair leads. The light emitting device may include a plurality of leads, and a diode holder 53 may be arranged at the end of one of the plurality of leads. An electrically conductive device may connect the light emitting diode 6 with another of the plurality of leads, and the light emitting diode 6 may be arranged in the diode holder 53 and comprise a plurality of electrodes.



FIG. 4 shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power. Heat sink 71 may be provided inside of housing 73 of the light emitting device for high power 70, and it may be partially exposed to outside. A pair of lead frames 74 may protrude from housing 73.


One or more light emitting diodes may be mounted directly on 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. In another embodiment, one or more light emitting diodes may be mounted directly on the heat sink 71, as opposed to directly on the lead frame 74, via thermally conductive adhesive. Electrically conductive pate 9 may be provided between 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.


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. In one embodiment, one or more light emitting diodes 6, 7 may be mounted directly on one or more of the heat sinks 61, 62 via thermally conductive adhesive. In one or more of the lead frames 64. The lead frames 64 may receive power from a power supplier and may protrude from housing 63. The light emitting device 80 may include a housing 63, a heat sink 61 or 62 at least partially provided in the housing 63, a plurality of lead frames 64 arranged on or around the heat sink 61 or 62, and an electrically conductive device to connect the light emitting diode 6 or 7 with one of the plurality of lead frames 64. The light emitting diode 6 or 7 may be arranged on the heat sink 61 or 62.


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, 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, the phosphor may include lead and/or copper containing components.


A light emitting device for high power 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 exemplarily described herein are 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 also applications. Moreover, new part can be added to the structures.


Exemplary embodiments of the phosphor 3 are described as follows.


(Phosphor)


According to some embodiments, the phosphor 3 may include one or more lead- and/or copper containing chemical compounds. The phosphor 3 may be excited by UV and/or visible (e.g., blue) light, and emit light due to transitions of the direct type, f-d transitions, or charge transfer transitions. In some embodiments, the lead- and/or copper-containing chemical compounds may be generally characterized as including a host lattice having anions and cations. In some embodiments, at least a portion of the cations are divalent cations. In some embodiments, the divalent cations include alkaline earth ions. In some embodiments, at least a portion of the divalent cations of the host lattice are substituted by divalent lead and/or divalent copper ions.


The phosphor 3 may include a first compound including a host material including divalent copper ions and oxygen, and a second compound including a different composition than the first compound. The first compound may include an aluminate containing copper, an antimonate containing copper, a germanate containing copper, a germanate-silicate containing copper, a phosphate containing copper, or any combination thereof.


As mentioned above, conventional luminescent materials and phosphors are generally unstable in water, air humidity, water steam and polar solvents. However, due to a higher covalency and a lower basicity, the substitutionally-incorporated divalent lead and/or divalent copper ions in the host lattice of the chemical compound yields luminescent materials have improved resistance against water, air humidity and polar solvents. Moreover, it will be appreciated that the divalent lead and/or divalent copper ions within the host lattice do not act as activators (also referred to herein as “luminescent center ions”) and, therefore do not luminesce.


As described above, the phosphor 3 may include one or more chemical compounds such as, for example, aluminates, silicates, antimonates, germanates, germanate-silicates, and/or phosphates. Exemplary embodiments of these chemical compounds are described in greater detail below.


In some embodiments, the lead- and/or copper-containing aluminates may be generally characterized according to formulas (1), (2), and (5)

a(M′O).b(M″2O).c(M″X).d(Al2O3).e(M′″O).f(M″″2O3).g(M′″″oOp).h(M″″″xOy)  (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 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, and/or any combination thereof; 0<a≦2; 0≦b≦2; 0≦c≦2; 0<d≦8; 0<e≦4; 0≦f≦3; 0≦g≦8; 0<h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.

a(M′O)b(M″2O)c(M″X)4-a-b
c(M′″O)7(Al2O3)d(B2O3)e(Ga2O3)f(SiO2)g(GeO2)h(M″″xOy)  (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≦4; 0≦b≦2; 0≦c≦2; 0≦d≦1; 0≦e≦1; 0≦f≦1; 0≦g≦1; 0<h≦2; 1≦x≦2; and 1≦y≦5.


The preparation of copper—as well as lead containing 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 a heating process may be used to form oxygen dominated phosphors.


Examples of Preparation

Preparation of the luminescent material having formula (3)

Cu0.02Sr3.98Al14O25:Eu  (3)


Starting materials: CuO, SrCO3, Al(OH)3, Eu2O3, and/or any combination thereof.


The starting materials in the form of oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, e.g., H3BO3. The mixture may be fired in an alumina crucible in a first step at about 1,200° C. for about one hour. After milling the pre-fired materials a second firing step at about 1,450° C. in a reduced atmosphere for about 4 hours may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 494 nm.









TABLE 1







copper-containing Eu2+-activated aluminate compared with Eu2+-activated


aluminate without copper at about 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.02Sr3.98Al14O25:
Sr4Al14O25:



Eu
Eu















Luminous
103.1
100



density (%)



Wavelength
494
493



(nm)










Preparation of the luminescent material having formula (4)

Pb0.05Sr3.95Al14O25:Eu  (4)


Starting materials: PbO, SrCO3, Al2O3, Eu2O3, and/or any combination thereof.


The starting materials in form of very pure oxides, carbonates, or other components which may decompose thermally into oxides, may be mixed in stoichiometric proportion together with small amounts of flux, for example, H3BO3. The mixture may be fired in an alumina crucible at about 1,200° C. for about one hour in the air. After milling the pre-fired materials a second firing step at about 1,450° C. in air for about 2 hours and in a reduced atmosphere for about 2 hours 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 2







lead-containing Eu2+-activated aluminate compared with Eu2+-activated


aluminate without lead at about 400 nm excitation wavelength










Lead-containing
Compound without



compound
lead



Pb0.05Sr3.95Al14O25:
Sr4Al14O25:



Eu
Eu















Luminous
101.4
100



density (%)



Wavelength
494.5
493



(nm)

















TABLE 3







optical properties of some copper- and/or lead-containing aluminates excitable by long wave ultraviolet


and/or by visible light and their luminous density in % at 400 nm excitation wavelength













Luminous density at






400 nm excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range(nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














Cu0.5Sr3.5Al14O25: Eu
360-430
101.2
495
493


Cu0.02Sr3.98Al14O25: Eu
360-430
103.1
494
493


Pb0.05Sr3.95Al14O25: Eu
360-430
101.4
494.5
493


CU0.01Sr3.99Al13.995Si0.005O25: Eu
360-430
103
494
492


Cu0.01Sr3.395Ba0.595Al14O25: Eu,Dy
360-430
100.8
494
493


Pb0.05Sr3.95Al13.95Ga0.05O25: Eu
360-430
101.5
494
494











a(M′O).b(M″O).c(Al2O3).d(M′″O2).e(M″″O2).f(M′″″xOy)  (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 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; 0<a≦; 0≦b≦2; 0<c≦8; 0≦d≦1; 0≦e≦1; 0<f≦2; 1≦x≦2; and 1≦y≦5.


Example of Preparation

Preparation of the luminescent material having formula (6)

Cu0.05Sr0.95Al1.9997Si0.0003O4:Eu  (6)


Starting materials: CuO, SrCO3, Al2O3, SiO2, Eu2O3, 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, AlF3. The mixture may be fired in an alumina crucible at about 1,250° 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 4







copper-containing Eu2+-activated aluminate compared with Eu2+-activated


aluminate without copper at about 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.05Sr0.95Al1.9997Si0.0003O4:
SrAl2O4:



Eu
Eu













Luminous
106
100


density (%)


Wavelength
521.5
519


(nm)









Preparation of the luminescent material having formula (7)

Cu0.12BaMg1.88Al16O27:Eu  (7)


Starting materials: CuO, MgO, BaCO3, Al(OH)3, Eu2O3, 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, AlF3. The mixture may be fired in an alumina crucible at about 1,420° 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 5







copper-containing Eu2+-activated aluminate compared with copper not


doped Eu2+-activated aluminate at 400 nm excitation wavelength










Copper-containing
Comparison without



compound
copper



Cu0.12BaMg1.88Al16O27:
BaMg2Al16O27:



Eu
Eu















Luminous
101
100



density (%)



Wavelength
452
450



(nm)










Preparation of the luminescent material having formula (8)

Pb0.1Sr0.9Al2O4:Eu  (8)


Starting materials: PbO, SrCO3, Al(OH)3, Eu2O3, and/or any combination thereof.


The starting materials in form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, H3BO3. The mixture may be fired in an alumina crucible at about 1,000° C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,420° C. in the air for about 1 hour and in a reduced atmosphere for about 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 of about 521 nm.









TABLE 6







lead-containing Eu2+-activated aluminate compared with Eu2+-activated


aluminate without lead at about 400 nm excitation wavelength










Lead-containing
Compound without



compound
lead



Pb0.1Sr0.9Al2O4:
SrAl2O4:



Eu
Eu















Luminous
102
100



density (%)



Wavelength
521
519



(nm)










Results obtained in regard to copper- and/or lead doped aluminates are shown in table 7.









TABLE 7







optical properties of some copper- and/or lead-containing aluminates excitable by long wave ultraviolet


and/or by visible light and their luminous density in % at 400 nm excitation wavelength













Luminous density at






400 nm excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range (nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














Cu0.05Sr0.95Al1.9997Si0.0003O4: Eu
360-440
106
  521.5
519


Cu0.2Mg0.7995Li0.0005Al1.9Ga0.1O4: Eu,Dy
360-440
101.2
482
480


Pb0.1Sr0.9Al2O4: Eu
360-440
102
521
519


Cu0.05BaMg1.95Al16O27: Eu,Mn
360-400
100.5
451, 515
450, 515


Cu0.12BaMg1.88Al16O27: Eu
360-400
101
452
450


Cu0.01BaMg0.99Al10O17: Eu
360-400
102.5
451
449


Pb0.1BaMg0.9Al9.5Ga0.5O17: Eu,Dy
360-400
100.8
448
450


Pb0.08Sr0.902Al2O4: Eu,Dy
360-440
102.4
521
519


Pb0.2Sr0.8Al2O4: Mn
360-440
100.8
658
655


Cu0.06Sr0.94Al2O4: Eu
360-440
102.3
521
519


Cu0.05Ba0.94Pb0.06Mg0.95Al10O17: Eu
360-440
100.4
451
449


Pb0.3Ba0.7Cu0.1Mg1.9Al16O27: Eu
360-400
100.8
452
450


Pb0.3Ba0.7Cu1.9Mg1.9Al16O27: Eu,Mn
360-400
100.4
452, 515
450, 515









In some embodiments, the lead- and/or copper-containing silicates may be generally characterized according to formula (9)

a(M′O).b(M″O).c(M″X).d(M′″2O).e(M″″2O3).f(M′″″oOp).g(SiO2).h(M″″″xOy)  (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 any combination 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, and any combination thereof; 0<a≦2; 0<b≦8; 0≦c≦4; 0≦d≦2; 0≦e≦2; 0≦f≦2; 0<g≦10; 0<h≦5; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.


The copper-containing silicates exemplarily described herein may, in some embodiments, contain SiO4 and can be characterized as having an Olivin structure (orthorhombic) or β-K2SO4 structure (orthorhombic); contain Si2O8 and be characterized as having a trigonal Glaserite (K3Na(SO4)2) or monoclinic Merwinite structure; contain Si2O7 and be characterized as having a tetragonal Ackermanite structure; contain SiO5 and be characterized as having a tetragonal structure; and/or contain Si2O5 and be characterized as having an orthorhombic structure.


Example of Preparation

Preparation of the luminescent material having formula (10)

Cu0.05Sr1.7Ca0.25SiO4:Eu  (10)


Starting materials: CuO, SrCO3, CaCO3, SiO2, Eu2O3, 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 NH4Cl. The mixture may be fired in an alumina crucible at about 1,200° C. in an inert gas atmosphere (e.g., N2 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° 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 8







copper-containing Eu2+-activated silicate compared with Eu2+-activated


silicate without copper at about 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.05Sr1.7Ca0.25SiO4:
Sr1.7Ca0.3SiO4:



Eu
Eu















Luminous
104
100



density (%)



Wavelength
592
588



(nm)










Preparation of the luminescent material having formula (11):

Cu0.2Ba2Zn0.2Mg0.6Si2O7:Eu  (11)


Starting materials: CuO, BaCO3, ZnO, MgO, SiO2, Eu2O3, 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, NH4Cl. In a first step the mixture may be fired in an alumina crucible at about 1,100° 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° C. in a reduced atmosphere for about 2 hours. Then that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 467 nm.









TABLE 9







copper-containing Eu2+-activated silicate compared with Eu2+-activated


silicate without copper at 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.2Sr2Zn0.2Mg0.6Si2O7:
Sr2Zn2Mg0.6Si2O7:



Eu
Eu















Luminous
101.5
100



density (%)



Wavelength
467
465



(nm)










Preparation of the luminescent material having formula (12)

Pb0.1Ba0.95Sr0.95Si0.998Ge0.002O4:Eu  (12)


Starting materials: PbO, SrCO3, BaCO3, SiO2, GeO2, Eu2O3, 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, NH4Cl. The mixture may be fired in an alumina crucible at about 1,000° C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at 1,220° 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 10







lead-containing Eu2+-activated silicate compared with Eu2+-activated


silicate without lead at about 400 nm excitation wavelength










Lead-containing
Compound without



compound
lead



Pb0.1Ba0.95Sr0.95Si0.998Ge0.002O4:
BaSrSiO4:



Eu
Eu













Luminous
101.3
100


density (%)


Wavelength
527
525


(nm)









Preparation of the luminescent material having formula (13)

Pb0.25Sr3.75Si3O8Cl4:Eu  (13)


Starting materials: PbO, SrCO3, SrCl2SiO2, Eu2O3, 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, NH4Cl. The mixture may be fired in an alumina crucible in a first step at about 1,100° C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,220° C. in the air for about 4 hours and in a reduced atmosphere for about 1 hour 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 492 nm.









TABLE 11







lead-containing Eu2+-activated chlorosilicate compared with Eu2+-activated


chlorosilicate without lead at 400 nm excitation wavelength










Lead-containing
Compound without



compound
lead



Pb0.25Sr3.75Si3O8C14:
Sr4Si3O8C4:



Eu
Eu















Luminous
100.6
100



density (%)



Wavelength
492
490



(nm)










Results obtained with respect to copper- and/or lead-containing silicates are shown in table 12.









TABLE 12







optical properties of some copper- and/or lead-containing 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













Luminous density at






400 nm excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range (nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














P0.1Ba0.95Sr0.95Si0.998Ge0.002O4: Eu
360-470
101.3
527
525


Cu0.02(Ba,Sr,Ca,Zn)1.98SiO4: Eu
360-500
108.2
565
560


Cu0.05Sr1.7Ca0.25SiO4: Eu
360-470
104
592
588


Cu0.05Li0.002Sr1.5Ba0.448SiO4: Gd,Eu
360-470
102.5
557
555


Cu0.2Sr2Zn0.2Mg0.6Si2O7: Eu
360-450
101.5
467
465


Cu0.02Ba2.8Sr0.2Mg0.98Si2O8: Eu,Mn
360-420
100.8
440, 660
438, 660


Pb0.025Sr3.75Si3O8Cl4: Eu
360-470
100.6
492
490


C0.2Ba2.2Sr0.75Pb0.05Zn0.8Si2O8: Eu
360-430
100.8
448
445


Cu0.2Ba3Mg0.8Si1.99Ge0.01O8: Eu
360-430
101
444
440


Cu0.5Zn0.5Ba2Ge0.2Si1.8O7: Eu
360-420
102.5
435
433


Cu0.8Mg0.2Ba3Si2O8: Eu,Mn
360-430
103
438, 670
435, 670


Pb0.15Ba1.84Zn0.01Si0.99Zr0.01O4: Eu
360-500
101
512
510


Cu0.2Ba5Ca2.8Si4O16: Eu
360-470
101.8
495
491









In some embodiments, the lead- and/or copper-containing antimonates may be generally characterized according to formula (14)

a(M′O).b(M″2O).c(M″X).d(Sb2O5).e(M′″O).f(M″″xOy)  (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≦2; 0≦b≦2; 0≦c≦4; 0<d≦8; 0≦e≦8; 0≦f≦2; 1≦x≦2; and 1≦y≦5.


Examples of Preparation

Preparation of the luminescent material having formula (15)

Cu0.2Mg1.7Li0.2Sb2O7:Mn  (15)


Starting materials: CuO, MgO, Li2O, Sb2O5, MnCO3, 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° 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° C. in an atmosphere containing oxygen for about 8 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 626 nm.









TABLE 13







copper-containing antimonate compared with antimonate


without copper at about 400 nm excitation wavelength










Copper-containing
Comparison without



compound
copper



Cu0.2Mg1.7Li0.2Sb2O7:
Mg2Li0.2Sb2O7:



Mn
Mn















Luminous
101.8
100



density (%)



Wavelength
652
650



(nm)










Preparation of the luminescent material having formula (16)

Pb0.006Ca0.6Sr0.394Sb2O6  (16)


Starting materials: PbO, CaCO3, SrCO3, Sb2O5, 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° 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 1,175° C. in the air for about 4 hours and then in an oxygen-containing atmosphere for about 4 hours. 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 14







lead-containing antimonate compared with antimonate


without lead at 400 nm excitation wavelength










Lead-containing
Compound without



compound
lead



Pb0.006Ca0.6Sr0.394Sb2O6
Ca0.6Sr0.4Sb2O6















Luminous
102
100



density (%)



Wavelength
637
638



(nm)










Results obtained in respect to copper- and/or lead-containing antimonates are shown in table 15.









TABLE 15







optical properties of some copper- and/or lead-containing 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






400 nm excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range (nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














Pb0.2Mg0.002Ca1.798Sb2O6F2: Mn
360-400
102
645
649


Cu0.15Ca1.845Sr0.0005Sb1.998Si0.002O7: Mn
360-400
101.5
660
658


Cu0.2Mg1.7Li0.2Sb2O7: Mn
360-400
101.8
652
650


Cu0.2Pb0.01Ca0.79Sb1.98Nb0.02O6: Mn
360-400
98.5
658
658


Cu0.01Ca1.99Sb1.9995V0.0005O7: Mn
360-400
100.5
660
657


Pb0.006Ca0.6Sr0.394Sb2O6
360-400
102
637
638


Cu0.02Ca0.9Sr0.5Ba0.4Mg0.18Sb2O7
360-400
102.5
649
645


Pb0.198Mg0.004Ca1.798Sb2O6F2
360-400
101.8
628
630









In some embodiments, the lead- and/or copper-containing germanates and/or germanate-silicates may be generally characterized according to formula (17)

a(M′O).b(M″2O)c(M″X).d(GeO2).e(M′″O).f(M″″2O3).g(M′″″oOp).h(M″″″xOy)  (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/or any 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≦2; 0≦b≦2; 0≦c≦10; 0<d≦10; 0≦e≦14; 0≦f≦14; 0≦g≦10; 0≦h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.


Example of Preparation

Preparation of the luminescent material having formula (18)

Pb0.004Ca1.99Zn0.006Ge0.8Si0.2O4:Mn  (18)


Starting materials: PbO, CaCO3, ZnO, GeO2, SiO2, MnCO3, 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, NH4Cl. In a first step the mixture may be fired in an alumina crucible at about 1,200° 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° C. in oxygen containing 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 at about 655 nm.









TABLE 16







lead-containing Mn-activated germanate compared with Mn-activated


germanate without lead at about 400 nm excitation wavelength










Copper-containing
Comparison without



compound
copper



Pb0.004Ca1.99Zn0.006Ge0.8Si0.2O4:
Ca1.99Zn0.01Ge0.8Si0.2O4:



Mn
Mn













Luminous
101.5
100


density (%)


Wavelength
655
657


(nm)









Preparation of the luminescent material having formula (19)

Cu0.46Sr0.54Ge0.6Si0.4O3:Mn  (19)


Starting materials: CuO, SrCO3, GeO2, SiO2, MnCO3, 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, NH4Cl. In a first step the mixture may be fired in an alumina crucible at about 1,100° 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° C. in an oxygen-containing atmosphere for about 4 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 658 nm.









TABLE 17







copper-containing Mn-activated germanate-silicate


compared with Mn-activated germanate-silicate without


copper at 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.46Sr0.54Ge0.6Si0.4O3:
SrGe0.6Si0.4O3:



Mn
Mn















Luminous
103
100



density (%)



Wavelength
658
655



(nm)

















TABLE 18







optical properties of some copper- and/or lead-containing 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 at






400 nm excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range (nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














Pb0.004Ca1.99Zn0.006Ge0.8Si0.2O4: Mn
360-400
101.5
655
657


Pb0.002Sr0.954Ca1.044Ge0.93Si0.07O4: Mn
360-400
101.5
660
661


Cu0.46Sr0.54Ge0.6Si0.4O3: Mn
360-400
103
658
655


Cu0.002Sr0.998Ba0.99Ca0.01Si0.98Ge0.02O4: Eu
360-470
102
538
533


Cu1.45Mg26.55Ge9.4Si0.6O48: Mn
360-400
102
660
657


Cu1.2Mg26.8Ge8.9Si1.1O48: Mn
360-400
103.8
670
656


Cu4Mg20Zn4Ge5Si2.5O38F10: Mn
360-400
101.5
658
655


Pb0.001Ba0.849Zn0.05Sr1.1Ge0.04Si0.96O4: Eu
360-470
101.8
550
545


Cu0.05Mg4.95GeO6F2: Mn
360-400
100.5
655
653


Cu0.05Mg3.95GeO5.5F: Mn
360-400
100.8
657
653









In some embodiments, the lead- and/or copper-containing phosphates may be generally characterized according to formula (20)

a(M′O).b(M″2O).c(M″X).d(P2O5).e(M′″O).f(M″″2O3).g(M′″″O2).h(M″″″xOy)  (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, Th, and/or any combination thereof, X may be F, Cl, Br, I, and/or any combination thereof; 0<a≦2; 0≦b≦12; 0≦c≦16; 0<d≦3; 0≦e≦5; 0≦f≦3; 0≦g≦2; 0<h≦2; 1≦x≦2; and 1≦y≦5.


Examples of Preparation

Preparation of the luminescent material having formula (21)

Cu0.02Ca4.98(PO4)3Cl:Eu  (21)


Starting materials: CuO, CaCO3, Ca3(PO4)2, CaCl2, Eu2O3, 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° 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 19







copper-containing Eu2+-activated chlorophosphate


compared with Eu2+- activated chlorophosphate


without copper at about 400 nm excitation wavelength










Copper-containing
Compound without



compound
copper



Cu0.02Ca4.98(PO4)3Cl:
Ca5(PO4)3Cl:



Eu
Eu















Luminous
101.5
100



density (%)



Wavelength
450
447



(nm)

















TABLE 20







copper- and/or lead-containing 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 excitation
Peak wavelength of



Possible
compared with compounds
lead-/copper-
Peak wavelength of



excitation
not containing
containing
materials without


Composition
range (nm)
copper/lead (%)
materials (nm)
lead/copper (nm)














Cu0.02Sr4.98(PO4)3Cl: Eu
360-410
101.5
450
447


Cu0.2Mg0.8BaP2O7: Eu,Mn
360-400
102
638
635


Pb0.5Sr1.5P1.84B0.16O6.84: Eu
360-400
102
425
420


Cu0.5Mg0.5Ba2(P,Si)2O8: Eu
360-400
101
573
570


Cu0.5Sr9.5(P,B)6O24Cl2: Eu
360-410
102
460
456


Cu0.5Ba3Sr6.5P6O24(F,Cl)2: Eu
360-410
102
443
442


Cu0.05(Ca,Sr,Ba)04.95P3O12Cl: Eu,Mn
360-410
101.5
438, 641
435, 640


Pb0.1Ba2.9P2O8: Eu
360-400
103
421
419









Meanwhile, the phosphor of the light emitting device can comprise aluminate, silicate, antimonate, germanate, phosphate type chemical compound, and any combination thereof.



FIG. 6 is 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 mixture of the selected multiple chemical compounds in proper ratio. The phosphor may be composed of Cu0.05BaMg1.95Al16O27:Eu which may have peak wavelength at about 451 nm, Cu0.03Sr1.5Ca0.47SiO4:Eu which may have peak wavelength at 586 nm, Pb0.006Ca0.6Sr0.394Sb2O6:Mn4+ which may have peak wavelength at about 637 nm, Pb0.15Ba1.84Zn0.01Si0.99Zr0.01O4:Eu which may have peak wavelength at around 512 nm, and Cu0.2Sr3.8Al14O25: 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 2nd wavelength. The 1st and 2nd light is mixed together and the desire emission is produced. As the shown FIG. 6, the light emitting device convert the 1st 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 and CRI is about 90 to about 95.



FIG. 7 is another embodiment's emission spectrum, 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 is mixture of the selected multiple chemical compounds in proper ratio.


The phosphor is composed of Cu0.05Sr1.7Ca0.25SiO4:Eu which may have peak wavelength at about 592 nm, Pb0.1Ba0.95Sr0.95Si0.998Ge0.002O4:Eu which may have peak wavelength at about 527 nm, and Cu0.05Li0.002Sr1.5Ba0.448SiO4: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 2nd wavelength. The 1st and 2nd light is mixed together and the desire emission is produced. As the shown FIG. 7, the light emitting device convert the 1st 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 about 4,000K to about 6,500K and CRI is about 86 to about 93.


The phosphor of the light emitting device exemplarily described herein 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 explained above.


According to the description above, light emitting device with wide range of color temperature about 2,000K to about 8,000K or about 10,000K and superior color rendering index of greater than about 60 (e.g., between about 60 and about 90, or greater than about 90, or between about 90 and about 95) can be realized by using the lead- and/or copper-containing chemical compounds.


In such a wavelength conversion, the light emitting device exemplarily described herein is capable of use in mobile phones, note book computers and electronic devices such as home appliance, stereo, telecommunication products, as well as in custom display's key pad and back light applications. Moreover, the light emitting device exemplarily described herein can be applied in automobiles, medical instruments and illumination products.


In addition, the chemical compounds exemplarily described herein can be incorporated within paint as a pigment capable of converting wavelengths of light.


According to the embodiments exemplarily described above, the chemical can increase the stability of the light emitting device 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 claimed invention 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 hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.

Claims
  • 1. A light emitting device, comprising: a light emitting diode to emit light; anda phosphor to change a wavelength of the light, the phosphor covering at least a portion of the light emitting diode;wherein the phosphor comprises a first compound comprising a host material comprising divalent copper ions and oxygen, and a second compound comprising a different composition than the first compound.
  • 2. The light emitting device according to claim 1, wherein the first compound comprises an aluminate containing copper, an antimonate containing copper, a germanate containing copper, a germanate-silicate containing copper, a phosphate containing copper, or any combination thereof.
  • 3. The light emitting device according to claim 1, wherein the first compound has the formula a(M′O).b(M″O).c(M″X).d(M′″2O).e(M″″2O3).f(M′″″oOp).g(SiO2).h(M″″″xOy)whereinM′ is Cu, or a combination of Cu and Pb;M″ is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof;M′″ is Li, Na, K, Rb, Cs, Au, Ag, or any combination thereof;M″″ is Al, Ga, In, or any combination thereof;M′″″ is Ge, V, Nb, Ta, W, Mo, Ti, Zr, Hf, 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, CI, Br, I, or any combination thereof; 0<a≦2;0<b≦8;0≦c≦4;0≦d≦2;0≦e≦2;0≦f≦2;0<g≦10;0<h≦5;1≦o≦2;1≦p≦5;1≦x≦2; and1≦y≦5.
  • 4. The light emitting device according to claim 1, further comprising a sealing material to cover the light emitting diode and the phosphor.
  • 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, further comprising: a substrate;a plurality of electrodes arranged on the substrate; andan electrically conductive device to connect the light emitting diode with one of the plurality of electrodes;wherein the light emitting diode is provided on another of the plurality of electrodes.
  • 7. The light emitting device according to claim 1, further comprising: a plurality of leads;a diode holder arranged at the end of one of the plurality of leads; andan electrically conductive device to connect the light emitting diode with another of the plurality of leads,wherein the light emitting diode is arranged in the diode holder and comprises a plurality of electrodes.
  • 8. 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 arranged on or around the heat sink; andan electrically conductive device to connect the light emitting diode with one of the plurality of lead frames,wherein the light emitting diode is arranged on the heat sink.
  • 9. The light emitting device according to claim 1, wherein the light emitting diode is to emit ultraviolet light or blue light.
Priority Claims (1)
Number Date Country Kind
10-2004-042396 Jun 2004 KR national
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 12/491,457, filed on Jun. 25, 2009, which is a continuation-in-part of U.S. patent application Ser. No. 11/948,845, filed on Nov. 30, 2007 (issued as U.S. Pat. No. 8,066,909), which is a continuation-in-part of U.S. patent application Ser. No. 11/024,702, filed on Dec. 30, 2004 (issued as U.S. Pat. No. 7,554,129), the disclosures of which are incorporated by reference herein in their entirety, which claim priority of Korean Patent Application No. 10-2004-042396, filed Jun. 10, 2004, the disclosure of which is incorporated by reference herein in its entirety.

US Referenced Citations (100)
Number Name Date Kind
2110162 Leverenz Mar 1938 A
2402760 Leverenz Jun 1946 A
2570136 Lyon Oct 1951 A
2617773 Nagy et al. Nov 1952 A
2719128 Kressin Sep 1955 A
2780600 Wollentin Feb 1957 A
3143510 Bakker Aug 1964 A
3598752 Sisneros et al. Aug 1971 A
3644212 McAllister et al. Feb 1972 A
3893939 DeKalb et al. Jul 1975 A
3905911 Kelsey et al. Sep 1975 A
4215289 De Hair et al. Jul 1980 A
4770950 Ohnishi Sep 1988 A
4972086 Bryan et al. Nov 1990 A
5032316 Takahashi et al. Jul 1991 A
5060118 Penrod et al. Oct 1991 A
5188763 Chenot et al. Feb 1993 A
5433295 Murphy Jul 1995 A
5472636 Forster et al. Dec 1995 A
5518808 Bruno et al. May 1996 A
5770110 Schrell et al. Jun 1998 A
5770111 Moriyama et al. Jun 1998 A
5853614 Hao et al. Dec 1998 A
5952681 Chen Sep 1999 A
5965192 Potter Oct 1999 A
5998925 Shimizu et al. Dec 1999 A
6045722 Leblans et al. Apr 2000 A
6066861 Hohn et al. May 2000 A
6084250 Justel et al. Jul 2000 A
6373184 Suh et al. Apr 2002 B1
6472765 Sano et al. Oct 2002 B1
6482664 Lee et al. Nov 2002 B1
6565771 Ono et al. May 2003 B1
6670751 Song et al. Dec 2003 B2
6686691 Mueller Feb 2004 B1
6842664 Harada Jan 2005 B2
6982045 Menkara et al. Jan 2006 B2
6982048 Atwater Jan 2006 B1
6987353 Menkara et al. Jan 2006 B2
7019335 Suenaga Mar 2006 B2
7029602 Oshio Apr 2006 B2
7045078 Choi May 2006 B2
7138770 Uang et al. Nov 2006 B2
7189340 Shimomura et al. Mar 2007 B2
7206507 Lee et al. Apr 2007 B2
7229571 Ezuhara et al. Jun 2007 B2
7244965 Andrews et al. Jul 2007 B2
7332746 Takahashi et al. Feb 2008 B1
7468147 Shida et al. Dec 2008 B2
7554129 Roth et al. Jun 2009 B2
7608200 Seto et al. Oct 2009 B2
7679101 Ota et al. Mar 2010 B2
7679281 Kim et al. Mar 2010 B2
8066909 Roth et al. Nov 2011 B2
8070983 Roth et al. Dec 2011 B2
8070984 Roth et al. Dec 2011 B2
8075802 Roth et al. Dec 2011 B2
8089084 Roth et al. Jan 2012 B2
20020015013 Ragle Feb 2002 A1
20030030063 Sosniak et al. Feb 2003 A1
20030038295 Koda Feb 2003 A1
20030168636 Dobson et al. Sep 2003 A1
20040051111 Ota et al. Mar 2004 A1
20040079957 Andrews et al. Apr 2004 A1
20040104391 Maeda et al. Jun 2004 A1
20040135504 Tamaki et al. Jul 2004 A1
20040136891 Kijima et al. Jul 2004 A1
20040206970 Martin Oct 2004 A1
20040251809 Shimomura Dec 2004 A1
20050001225 Yoshimura et al. Jan 2005 A1
20050001537 West et al. Jan 2005 A1
20050029927 Setlur et al. Feb 2005 A1
20050117334 Lee et al. Jun 2005 A1
20050139846 Park et al. Jun 2005 A1
20050141048 Mizutani Jun 2005 A1
20050239227 Aanegola et al. Oct 2005 A1
20050264161 Oaku et al. Dec 2005 A1
20050274930 Roth et al. Dec 2005 A1
20050274972 Roth et al. Dec 2005 A1
20060076883 Himaki et al. Apr 2006 A1
20060158090 Wang et al. Jul 2006 A1
20060261309 Li et al. Nov 2006 A1
20060261350 Kawazoe et al. Nov 2006 A1
20060267042 Izuno et al. Nov 2006 A1
20070029526 Cheng et al. Feb 2007 A1
20070247051 Kuze et al. Oct 2007 A1
20070284563 Lee et al. Dec 2007 A1
20080036364 Li et al. Feb 2008 A1
20080067472 Roth et al. Mar 2008 A1
20080067920 Roth et al. Mar 2008 A1
20080224163 Roth et al. Sep 2008 A1
20090050847 Xu et al. Feb 2009 A1
20090050849 Lee et al. Feb 2009 A1
20090134413 Roth et al. May 2009 A1
20090152496 Roth et al. Jun 2009 A1
20090262515 Lee et al. Oct 2009 A1
20090303694 Roth Dec 2009 A1
20100002454 Lee et al. Jan 2010 A1
20100165645 Lee et al. Jul 2010 A1
20100207132 Lee et al. Aug 2010 A1
Foreign Referenced Citations (132)
Number Date Country
410266 Mar 2003 AT
1218084 Jun 1999 CN
1289454 Mar 2001 CN
1317537 Oct 2001 CN
1344777 Apr 2002 CN
1434521 Aug 2003 CN
2624578 Jul 2004 CN
1581503 Feb 2005 CN
2690724 Apr 2005 CN
1702809 Nov 2005 CN
1706043 Dec 2005 CN
1707819 Dec 2005 CN
10233050 Feb 2004 DE
10259946 Jul 2004 DE
0094132 Nov 1983 EP
0382295 Aug 1993 EP
0862794 Sep 1998 EP
0 896 994 Feb 1999 EP
1249873 Oct 2002 EP
1605030 Dec 2005 EP
2031038 Mar 2009 EP
1336053 Nov 1973 GB
2016034 Sep 1979 GB
31-1118 Feb 1956 JP
33-8177 Sep 1958 JP
38-6082 May 1963 JP
39-8803 May 1964 JP
47-6258 Apr 1972 JP
49-38994 Oct 1974 JP
55-135190 Oct 1980 JP
57-109886 Jul 1982 JP
61-258892 Nov 1986 JP
62-197487 Sep 1987 JP
5-78659 Mar 1993 JP
9-40946 Feb 1997 JP
9-153644 Jun 1997 JP
9-279140 Oct 1997 JP
10-321914 Dec 1998 JP
11-177143 Jul 1999 JP
2000-260580 Sep 2000 JP
2000-294387 Oct 2000 JP
2001-115157 Apr 2001 JP
2001-308393 Nov 2001 JP
2001-524163 Nov 2001 JP
2002-50795 Feb 2002 JP
2002-057376 Feb 2002 JP
2002-094122 Mar 2002 JP
2002-97465 Apr 2002 JP
2002-97466 Apr 2002 JP
2002-173677 Jun 2002 JP
2002-335019 Nov 2002 JP
2002-359403 Dec 2002 JP
2002-368277 Dec 2002 JP
2003-064358 Mar 2003 JP
2003-133595 May 2003 JP
2003-152229 May 2003 JP
2003-183649 Jul 2003 JP
2003-224306 Aug 2003 JP
2003-321675 Nov 2003 JP
2004-006582 Jan 2004 JP
2004-010786 Jan 2004 JP
2004-505470 Feb 2004 JP
2004-71726 Mar 2004 JP
2004-71807 Mar 2004 JP
2004-079867 Mar 2004 JP
2004-88011 Mar 2004 JP
2004-127988 Apr 2004 JP
2004-134699 Apr 2004 JP
2004-192833 Jul 2004 JP
2005-100799 Apr 2005 JP
2005-100800 Apr 2005 JP
2005-101296 Apr 2005 JP
2005-153606 Jun 2005 JP
2005-167177 Jun 2005 JP
2005-354027 Dec 2005 JP
2006-073656 Mar 2006 JP
2006-173433 Jun 2006 JP
2006-252944 Sep 2006 JP
2007-186674 Jul 2007 JP
2009-007545 Jan 2009 JP
10-232395 Dec 1999 KR
20010032450 Apr 2001 KR
10-2001-0050839 Jun 2001 KR
20010101910 Nov 2001 KR
10-2002-0000835 Jan 2002 KR
10-2002-0053975 Jul 2002 KR
10-392363 Jul 2002 KR
10-2002-0079513 Oct 2002 KR
2003-0063211 Jul 2003 KR
10-2003-0082395 Oct 2003 KR
10-0426034 Jul 2004 KR
10-2004-0088418 Oct 2004 KR
10-2005-0008426 Jan 2005 KR
10-2005-0070349 Jul 2005 KR
10-2005-0098462 Oct 2005 KR
10-2005-0106945 Nov 2005 KR
10-2005-0117164 Dec 2005 KR
10-2005-0117165 Dec 2005 KR
10-2006-0034056 Apr 2006 KR
10-0626272 Sep 2006 KR
10-2006-0134728 Dec 2006 KR
10-2007-0016900 Feb 2007 KR
10-2008-0046789 May 2008 KR
1328885 Mar 1999 TW
96-32457 Oct 1996 WO
98-05078 Feb 1998 WO
98-12757 Mar 1998 WO
98-42798 Oct 1998 WO
98-39805 Nov 1998 WO
00-19546 Apr 2000 WO
0033390 Jun 2000 WO
01-41215 Jun 2001 WO
2002-054502 Jul 2002 WO
2002-054503 Jul 2002 WO
02-089219 Nov 2002 WO
03-021691 Mar 2003 WO
03030274 Apr 2003 WO
2004036962 Apr 2004 WO
2004-085570 Oct 2004 WO
2004-111156 Dec 2004 WO
2005068584 Jul 2005 WO
2005-109532 Nov 2005 WO
2005-112137 Nov 2005 WO
2006-043682 Apr 2006 WO
2006-68359 Jun 2006 WO
2006-081803 Aug 2006 WO
2006109659 Oct 2006 WO
2007-035026 Mar 2007 WO
2007-055538 May 2007 WO
2007-069869 Jun 2007 WO
2007-114614 Nov 2007 WO
2009-028818 Mar 2009 WO
Related Publications (1)
Number Date Country
20100165645 A1 Jul 2010 US
Continuations (1)
Number Date Country
Parent 12491457 Jun 2009 US
Child 12491780 US
Continuation in Parts (2)
Number Date Country
Parent 11948845 Nov 2007 US
Child 12491457 US
Parent 11024702 Dec 2004 US
Child 11948845 US