Luminescent material

Abstract
This invention relates to luminescent materials for ultraviolet light or visible light excitation containing lead and/or copper doped chemical compounds. The luminescent material is composed of one or more than one compounds of aluminate type, silicate type, antimonate type, germanate/or germanate-silicate type, and/or phosphate type. Accordingly, the present invention is a good possibility to substitute earth alkaline ions by lead and copper for a shifting of the emission bands to longer or shorter wave length, respectively. Luminescent compounds containing copper and/or lead with improved luminescent properties and also with improved stability against water, humidity as well as other polar solvents are provided. The present invention is to provide lead and/or copper doped luminescent compounds, which has high color temperature range about 2,000K to 8,000K or 10,000K and CRI over 90.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


This invention relates generally to fluorescent materials containing rare earth elements and more particularly to such luminescent materials for exciting ultraviolet as well as visible light containing lead and/or copper doped compounds.


2. Description of the Related Art


Lead and copper activated materials are known for short wave excitation, e.g. from a low pressure mercury lamp, such as barium disilicate activated by lead (Keith H. Butler, The Pennsylvania State University Press, 1980, S 175, orthosilicate activated by lead (Keith H. Butler, The Pennsylvania State University Press, 1980, S. 181), akermanites activated by lead, or Ca-metasilicate activated by Pb2+.


Generally, the maxima of the emission bands of such lead activated phosphors are located between 290 nm and 370 nm at 254 nm excitation. Bariumdisilicate activated by lead is an U.V. emitting phosphor which currently is used in sun parlor lamps.


Lead has in the ground state 1S0 two outer electrons. The electron configuration of the ground state is d10s2, so that the lowest excited state has d10sp configuration. The excited sp configuration has four levels, 3P0, 3P1, 3P2 and 1P1, which can be achieved between 165.57 nm (3P0) and 104.88 nm (1P1) in the free ion. Transitions between 1S0 and 1P1 excited level are allowed by all selection rules. While transitions between 1S0 and 3P0 are only allowed with the lowest symmetry, transitions between 1S0 and 3P1 as well as 3P2 are allowed only under certain conditions. However, excitation between 180 and 370 nm has the same emission. Excitation with wavelength longer than 370 nm is not possible.


Otherwise, luminescent materials are known having lead as a host lattice component. Molybdate phosphors containing MoO42− centers are described in Bernhardt, H. J., Phys. Stat. Sol. (a), 91, 643, 1985. PbMoO4 shows at room temperature red emission with an emission maximum at 620 nm under photoexcitation at 360 nm.


However, such emission is not caused by lead itself. In molybdates the luminescence properties are not caused by the metal ion M2+ (M2+MoO4 where M2+=Ca, Sr, Cd, Zn, Ba, Pb etc). Here, defect centers of MoO42− ions coupled to O2−-ion vacancies seem to be the reason. Nevertheless, the Pb2+-ion influences the preferred emission properties because it stabilizes the host lattice.


As a familiar example, tungstates (Ca,Pb)WO4 as mixed crystals have a strong green emission with high quantum output of 75% (Blasse, G, Radiationless processes in luminescent materials, in Radiationless Processes, DiBartolo, B., Ed. Plenum Press, New York, 1980, 287). Under 250 nm excitation PbWO4 shows blue emission and under 313 nm excitation PbWO4 has an orange emission band, which can be caused by Schottky defects or by impurity ions (Phosphor Handbook, edited under the Auspice of Phosphor Research Society, CRC Press New York, 1998, S 205).


Copper was used as a monovalent activator in orthophosphates (Wanmaker, W. L. and Bakker, C., J. Electrochem. Soc., 106, 1027, 1959) with an emission maximum at 490 nm. The ground state of monovalent copper is a filled shell 3d10. That is the level 1S0. After exciting the lowest excited configuration is 3d94s. This configuration has two terms, 3D and 1D. The next higher configuration, 3d94p, gives 6 terms 3P°, 3F°, 3D°, 1F°, 1D° and 1P°. The transitions between the ground state 1S0 and the 1D or 3D are forbidden by parity or spin, respectively. In copper ions, the excitation to the crystal field levels of 4p terms are allowed. Emission will be got either by a direct return from the crystal field odd state to the ground state or by a combination of transitions first from the odd state to a crystal field level and after that a second transition from these 3D or 1D state of the 3d94s configuration to the ground state.


The ground state of bivalent copper has 3d9-configuration. That is the level 2D5/2. In the bivalent copper, one of the d-electrons can be excited to the 4s or 4p orbital. The lowest exciting configuration is the 3d84s with two quartet terms 4F, 4P and four doublet terms, 2F, 2D, 2P and 2G without emission caused by forbidden transitions. The higher exciting configuration is the 3d84p-configuration with four terms 4D°, 4G°, 4F°, and 4P°, where emission can occur.


Copper activated or co-activated sulphide-phosphors are well known and they are commercial used for cathode ray tubes. The green-emitting ZnS:Cu, Al (wherein, the copper is used as activator and Al is used as co-activator) is very important in CRT applications.


In zinc-sulphide phosphors, the luminescent materials can be classified into five kinds, depending on the relative ratio of the concentration of activators and co-activators (van Gool, W., Philips Res. Rept. Suppl., 3, 1, 1961). Here, the luminescent centers are formed from deep donors or deep acceptors, or by their association at the nearest-neighbor sites (Phosphor Handbook, edited under the Auspice of Phosphor Research Society, CRC Press New York, 1998, S. 238).


Orthophosphates activated by copper (Wanmaker, W. L., and Spier, H. L., JECS 109 (1962), 109), and pyrophosphates, alumosilicates, silicates, and tripolyphosphates all activated by copper are described in “Keith H. Butler, The Pennsylvania State University Press, 1980, S. 281”. However, such phosphors can only be used for a short wave U.V. excitation. Because of their unstable chemical properties and their temperature behavior, they cannot be used in fluorescent lamps.


The influence of lead and copper ions as host lattice component in oxygen dominated compounds, activated by rare earth ions such as Eu2+, Ce3+ and others, has not been yet described. It should to be expected that the incorporation of lead and/or copper as a host lattice component influences the preferred luminescent-optical properties regarding improved luminescent intensity as well as desirable shifting of emission maxima, color points, and shape of emission spectra and stabilizing of the lattice.


The influence of lead-ions and/or copper-ions as components in the host lattice should show improved luminescent properties for excitation wavelength higher than 360 nm. In this region of wavelength, both ions do not show own radiation transfers due to the energy levels of their electron configuration, so that any kind of exciting radiation cannot be lost.


Lead and copper doped luminescent materials show improved emission intensities compared to luminescent materials having not these components in the host lattice. Furthermore, as a desirable effect of lead and copper doped luminescent materials shows a shifting of the emission wavelength to higher or to lower energies. For compounds containing lead or copper, these ions do not react as activators in broadest sense. However, the use of these ions leads to an influence on the crystal field splitting as well as the covalency.


Lead ions having an ionic radius of 119 pm can substitute the alkaline earth ions Ca having an ionic radius of 100 pm and Sr having an ionic radius of 118 pm very easily. The electro negativity of lead with 1.55 is much higher than that of Ca (1.04) and Sr (0.99). The preparation of substances containing lead is complicated due to the possibility of an oxidation of these ions in reducing atmospheres. For the preparation of lead doped compounds, which need reducing atmosphere, special preparation processes are necessary.


The influence on lead in the crystal field is shown in a generally shifting the emission characteristics depending on the substituted ions. In cases of a substitution of Pb for Sr or Ba in Eu-activated aluminates and/or silicates, the emission maximum should be shifted to longer wavelength due to smaller ionic radii of Pb compared with Ba and Sr ionic radii. That leads to a stronger crystal field in the surrounding of the activator ion.


A similar effect shows the substitution of copper for alkaline earth ions. Here, an additional influence is effective. Due to the higher ionic potential of copper as a quotient of ionic charge and ionic radius compared to the bigger alkaline earth ions, the copper ions can attract the neighboring oxygen ions stronger than the alkaline earth ions. So the substitution of the bigger alkaline earth ions Ca, Sr and Ba by copper leads to a stronger crystal field in the surrounding of the activator ions, too. Thus, the shape of emission bands can be influenced, the shifting of the emission peak to longer wavelength is connected in a broadening of the emission curves for band emission. In addition, it should be possible to increase the intensity of emission by substitution of ions copper and lead. Generally, the shifts of emission peaks to longer as well as to shorter wavelength are desirable in the field of LED lighting. Here, it is necessary to realize a fine tuning to get a special wavelength for desired color points as well as for better brightness of optical devices. By using cations, copper and lead, such a fine tuning should be possible.


It is known that some luminescent materials and phosphors are unstable in water, air humidity, water steam or polar solvents. For instance, aluminates with spinell structure or silicates with orthorhomcic as well as akermanite structures show more or less high sensitivity to water, air humidity, water steam or polar solvents due to high basicity. However, due to a higher covalency and a lower basicity, the incorporation of lead and or copper in a host lattice should improve this behavior of luminescent materials against water, air humidity and polar solvents if substituted for cations having a high basicity.


SUMMARY OF THE INVENTION

In view of the prior art described above, it is an object of the present invention to provide lead and/or copper doped luminescent materials which have a very good possibility to substitute earth alkaline ions by lead and copper with a shifting of the emission bands to longer or shorter wave length, respectively.


Another object of the present invention is to provide luminescent materials containing copper and/or lead with improved luminescent properties and also with improved stability against water, humidity as well as other polar solvents.


An additional object of the present invention is to provide lead and/or copper doped luminescent materials, which give high color temperature range about 2,000K to 8,000K or 10,000K and CRI over 90 in LED.


To achieve these and other objects, as embodied and broadly described herein, luminescent materials for ultraviolet light or visible light excitation comprises lead and/or copper doped chemical compounds containing a rare earth element or other luminescent ions.


The luminescent materials may be composed of one or more compounds of aluminate, silicate, antimonate, germanate/or germanate-silicate, and phosphate.


The aluminate is expressed as follows:

a(M′O).b(M″2O).c(M″X).dAl2O3.e(M′″O).f(M″″2O3).g(M′″″oOp).h(M″″″xOy)
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)
and
a(M′O).b(M″O).c(Al2O3).d(M′″2O3).e(M″″O2).f(M′″″xOy)


The silicate is expressed as follows:

a(M′O).b(M″O).c(M′″X).d(M′″O2).e(M″″2O3).f(M′″″oOp).g(SiO2).h(M″″″xOy)


The antimonate is expressed as follows:

a(M′O).b(M″2O).c(M″X).d(Sb2O5).e(M′″O).f(M″″xOy)


The germanate/or germanate-silicate is expressed as follows:

a(M′O).b(M″2O).c(M″X).dGeO2.e(M′″O).f(M″″2O3).g(M″′″oOp).h(M″″″xOy)


The phosphate is expressed as follows:

a(M′O).b(M″2O).c(M″X).dP2O5.e(M′″O).f(M″″2O3).g(M′″″O2).h(M″″″xOy)


Meanwhile, the luminescent materials may be used as a converter for the primary long-wave ultraviolet in the range of 300-400 nm and/or blue radiation in the range of 380-500 nm generated from one or more single primary elements within a light emitting device to produce light in the visible region of the spectrum up to a high color rendering index Ra>90.


Furthermore, the luminescent materials may be used in LED as a single compound and/or a mixture of a plurality of single compounds for realizing white light with a color rendering up to Ia.







DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, the present invention will be described in detail.


Example 1

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped aluminates according to the formula as follows:

a(M′O).b(M″2O).c(M″X).dAl2O3.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, J, 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 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 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 doped Eu2+-activated aluminate compared with Eu2+-activated


aluminate without copper at about 400 nm excitation wavelength










Copper doped compound
Compound without copper



Cu0.02Sr3.98Al14O25:Eu
Sr4Al14O25:Eu













Luminous density
103.1
100


(%)


Wavelength (nm)
494
493









Preparation of the luminescent material having formula (4)

Pb0.05Sr3.95Al14O25:Eu(4)  (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 thermically 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 doped Eu2+-activated aluminate compared with Eu2+-activated


aluminate without lead at about 400 nm excitation wavelength










Lead doped compound
Compound without lead



Pb0.05Sr3.95Al14O25:Eu
Sr4Al14O25:Eu













Luminous density (%)
101.4
100


Wavelength (nm)
494.5
493
















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














Peak wave





Luminous density at 400 nm
length of



Possible
excitation compared
lead/copper
Peak wave length of



excitation
with copper/lead not doped
doped materials
materials without


Composition
range(nm)
compounds (%)
(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,
360-430
100.8
494
493


Dy


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









Example 2

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped aluminates according to the formula as follows:

a(M′O).b(M″O).c(Al2O3).d(M′″2O3).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≦1; 0≦b≦2; 0<c≦8; 0≦d≦1; 0≦e≦1; 0<f≦2; 1≦x≦2; and 1≦y≦5.


The luminous peak and density of Example 2 are described in Table 7, which will be shown below.


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 doped Eu2+-activated aluminate compared with Eu2+-activated


aluminate without copper at about 400 nm excitation wavelength











Compound



Copper doped compound
without copper



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













Luminous density (%)
106
100


Wavelength (nm)
521.5
519









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 doped Eu2+-activated aluminate compared with copper not


doped Eu2+-activated aluminate at 400 nm excitation wavelength











Comparison



Copper doped compound
without copper



Cu0.12BaMg1.88Al16O27:Eu
BaMg2Al16O27:Eu













Luminous density (%)
101
100


Wavelength (nm)
452
450









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 doped Eu2+-activated aluminate compared with Eu2+-activated


aluminate without lead at about 400 nm excitation wavelength










Lead doped compound
Compound without lead



Pb0.1Sr0.9Al2O4:Eu
SrAl2O4: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 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














Peak wave





Luminous density at
length of



Possible
400 nm excitation
lead/copper



excitation
compared with
doped
Peak wave length of



range
copper/lead not doped
materials
materials without


Composition
(nm)
compounds (%)
(nm)
lead/copper (nm)














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


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


Dy


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,
360-400
100.8
448
450


Dy


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


Pb0.3Ba0.7Cu0.1Mg1.9Al16O27:Eu,
360-400
100.4
452, 515
450, 515


Mn









Example 3

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped silicates according to the formula as follows:

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 superior luminous density of Example 3 can be seen below.


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 doped Eu2+-activated silicate compared with Eu2+-activated


silicate without copper at about 400 nm excitation wavelength











Compound



Copper doped compound
without copper



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













Luminous density (%)
104
100


Wavelength (nm)
592
588









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 doped Eu2+-activated silicate compared with Eu2+-activated


silicate without copper at 400 nm excitation wavelength











Compound



Copper doped compound
without copper



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













Luminous
101.5
100


density (%)


Wavelength (nm)
467
465









Preparation of the luminescent material having formula (12)

Pb0.1BaO0.95Sr0.95Si0.998Ge0.002O4: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 doped Eu2+-activated silicate compared with Eu2+-activated


silicate without lead at about 400 nm excitation wavelength











Compound




without



Lead doped compound
lead



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













Luminous density
101.3
100


(%)


Wavelength (nm)
527
525









Preparation of the luminescent material having formula (13)

Pb0.25Sr3.75Si3O8Cl4:Eu  (13)


Starting materials: PbO, SrCO3, SrCl2, SiO2, 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 doped Eu2+-activated chlorosilicate compared with Eu2+-activated


chlorosilicate without lead at 400 nm excitation wavelength











Compound



Lead doped compound
without lead



Pb0.25Sr3.75Si3O8Cl4:Eu
Sr4Si3O8Cl4: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 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













Luminous density at
Peak wave




Possible
400 nm excitation
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)














Pb0.1Ba0.95Sr0.95Si0.998Ge0.002O4: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,
360-470
102.5
557
555


Eu


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


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


Mn


Pb0.25Sr3.75Si3O8Cl4:Eu
360-470
100.6
492
490


Cu0.2Ba2.2Sr0.75Pb0.05Zn0.8Si2O8: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









Example 4

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped antimonates according to the formula as follows:

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 doped antimonate compared with antimonate without copper at


about 400 nm excitation wavelength











Comparison without



Copper doped compound
copper



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













Luminous density (%)
101.8
100


Wavelength (nm)
652
650









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 doped antimonate compared with antimonate without lead at


400 nm excitation wavelength











Compound



Lead doped compound
without lead



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













Luminous density (%)
102
100


Wavelength (nm)
637
638









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









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 400 nm

Peak wave




excitation

length of




compared with
Peak wave length
materials



Possible
copper/lead not
of lead/copper
without



excitation
doped compounds
doped materials
lead/copper


Composition
range (nm)
(%)
(nm)
(nm)














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


Cu0.15Ca1.845Sr0.005Sb1.998Si0.002O7: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









Example 5

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped germanates and/or a germanate-silicates according to the formula as follows:

a(M′O).b(M″2O).c(M″X).dGeO2.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 doped Mn-activated germanate compared with Mn-activated


germinate without lead at about 400 nm excitation wavelength










Copper doped compound
Comparison without copper



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













Luminous density (%)
101.5
100


Wavelength (nm)
655
657









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 doped Mn-activated germanate-silicate compared with Mn-


activated germanate-silicate without copper at 400 nm


excitation wavelength











Compound



Copper doped compound
without copper



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













Luminous density (%)
103
100


Wavelength (nm)
658
655
















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 at






400 nm excitation
Peak wave
Peak wave



Possible
compared with
length of
length of materials



excitation
copper/lead not
lead/copper
without



range
doped
doped
lead/copper


Composition
(nm)
compounds (%)
materials (nm)
(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









Example 6

Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped phosphates according to the formula as follows:

a(M′O).b(M″2O).c(M″X).dP2O5.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, Tb, 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.


The luminescent materials comprising the lead and/or copper doped phosphates may be used as compounds for ultraviolet light in a light emitting device.


Examples of Preparation

Preparation of the luminescent material having formula (21)

Cu0.02Ca4.98(PO4)3Cl:Eu  (21)


Starting materials: CuO, CaCO3, CaCO3(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 doped Eu+2-activated chlorophosphate compared with Eu+2-


activated chlorophosphate without copper at about 400 nm


excitation wavelength











Compound



Copper doped compound
without copper



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













Luminous density (%)
101.5
100


Wavelength (nm)
450
447
















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




excitation compared
Peak wave length
Peak wave length



Possible
with copper/lead not
of lead/copper
of materials



excitation
doped compounds
doped materials
without


Composition
range (nm)
(%)
(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)4.95P3O12Cl:Eu,
360-410
101.5
438, 641
435, 640


Mn


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









Lead and/or copper doped luminescent materials can be act as converter for light emitting devices, such as ultraviolet as well as blue emitting LEDs, back lights and painting pigments. They can convert the excitation wavelength from the ultraviolet and blue light to longer visible wavelength. For all color temperatures as well as for all color coordinates inside of the white light coordinates color mixture can be found. That is caused by the different emission colors corresponding to the RGB principle by using different kinds of luminescent materials.

Claims
  • 1. A luminescent material for an LED, comprising: a compound including a host lattice,wherein the host lattice comprises first group ions and oxygen,wherein the first group includes at least one of Be, Mg, Ca, Sr, Ba, Zn, Cd, and Mn,wherein a first portion of the first group ions is substituted by divalent copper ions,wherein a second portion of the first group ions is substituted by lead ions, andwherein the compound has the formula a(M′O).b(M″2O).c(M″X).d(Sb2O5).e(M′″O).f(M″″xOy),wherein:M′ is 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 Bi, Sn, Sc, Y, La, Pr, Sm, Eu, Tb, Dy, Gd, or any combination thereof;X is F, CI, Br, I, 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; and1≦y≦5.
  • 2. A luminescent material for an LED, comprising: a compound including a host lattice,wherein the host lattice comprises first group ions and oxygen,wherein the first group includes at least one of Be, Mg, Ca, Sr, Ba, Zn, and Cd,wherein a first portion of the first group ions is substituted by divalent copper ions,wherein a second portion of the first group ions is substituted by lead ions, andwherein the compound has the formula a(M′O).b(M″2O).c(M″X).d(GeO2).e(M′″O).f(M″″2O3).g(M″″′oOp). h(M″″″xOy),wherein:M′ is 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, or any combination thereof;M″″ is Sc, Y, B, Al, La, Ga, In, or any combination thereof;M″″′ is Si, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or any combination thereof;M″″″ is Bi, Sn, Pr, Sm, Eu, Gd, Dy, or any combination thereof;X is F, CI, Br, I, 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;0≦o≦2;1≦p≦5;1≦x≦2; and1≦y≦5.
  • 3. A luminescent material for an LED, comprising: a compound including a host lattice,wherein the host lattice comprises first group ions and oxygen,wherein the first group includes at least one of Be, Mg, Ca, Sr, Ba, Zn, Cd, and Mn,wherein a first portion of the first group ions is substituted by divalent copper ions,wherein a second portion of the first group ions is substituted by lead ions, andwherein the compound has the formula a(M′O).b(M″2O).c(M″X).d(P2O5).e(M′″O).f(M″″2O3).g(M′″″O2). h(M″″″xOy),wherein:M′ is 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, Y, B, AI, La, Ga, In, or any combination thereof;M″′″ is Si, Ge, Ti, Zr, Hf; V, Nb, Ta, W, Mo, or any combination thereof;M″″″ is Bi, Sn, Pr, Sm, Eu, Gd, Dy, Ce, Tb or any combination thereof;X is F, CI, Br, I, 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; and1≦y≦5.
  • 4. The luminescent material according to claim 1, wherein the compound comprises Eu.
  • 5. The luminescent material according to claim 2, wherein the compound comprises Eu.
  • 6. The luminescent material according to claim 3, wherein the compound comprises Eu.
Priority Claims (1)
Number Date Country Kind
10-2004-0042397 Jun 2004 KR national
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent application Ser. No. 11/024,722 filed on Dec. 30, 2004, and claims priority from and the benefit of Korean Patent Application No. 10-2004-0042397 filed on Jun. 10, 2004, all of which are hereby incorporated by reference for all purposes as if fully set forth herein.

US Referenced Citations (91)
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 Wanmaker et al. 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, Jr. 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
5433295 Hao et al. 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 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
20020015013 Ragle Feb 2002 A1
20030038295 Koda Feb 2003 A1
20030168636 Dobson et al. Sep 2003 A1
20040051111 Ota et al. Mar 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 et al. 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 (109)
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
10233050 Feb 2004 DE
10259946 Jul 2004 DE
0 094 132 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
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
2002-97466 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
2003-152229 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
2004-127988 Apr 2004 JP
2004-134699 Apr 2004 JP
2004-192833 Jul 2004 JP
2005-167177 Jun 2005 JP
2006-073656 Mar 2006 JP
2006-173433 Jun 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
1996-32457 Oct 1996 WO
98-05078 Feb 1998 WO
98-12757 Mar 1998 WO
98-39805 Sep 1998 WO
98-42798 Oct 1998 WO
00-19546 Apr 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
2004-85570 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
20100176342 A1 Jul 2010 US
Continuations (1)
Number Date Country
Parent 11024722 Dec 2004 US
Child 12731811 US