Patent Grant
8883040
1. Field of the Invention
Embodiments of the present invention relate 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-containing 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)Wa4 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 16p°. 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.
It has been observed that conventional luminescent materials are generally unstable in water, air humidity, water steam and polar solvents.
One embodiment exemplarily described herein can be generally characterized as a luminescent material for a light emitting diode (LED) that includes a first compound including a host lattice and a luminescent ion within the host lattice. The host lattice may include first ions and oxygen. A first portion of the first ions may be substituted by divalent copper ions. The first compound may emit light upon excitation with ultraviolet light or visible light emitted by the LED. The first compound may have an Olivine 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. According to another embodiment, the luminescent ion includes at least one of Bi, Sn, Sb, Sc, Y, La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. According to another embodiment, the first compound includes Ge. According to another embodiment, the luminescent material further includes at least one second compound selected from the group consisting of an aluminate, a silicate, an antimonite, a germinate, a germinate-silicate and a phosphate. According to another embodiment, the luminescent material emits white light upon excitation with ultraviolet light or visible light.
Another embodiment exemplarily described herein can be generally characterized as a luminescent material for a light emitting diode (LED) that includes a first compound including a host lattice and a luminescent ion within the host lattice. The host lattice may include first ions and oxygen. A first portion of the first ions may be substituted by copper ions. The first compound may emit light upon excitation with ultraviolet light or visible light emitted by the LED. However, the copper ions do not act as luminescent ions upon excitation with the ultraviolet light or visible light. 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.
According to embodiments exemplarily described herein, a luminescent material may include one or more lead- and/or copper-containing chemical compounds. The luminescent material may be excited by UV and/or visible (e.g., blue) light. 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.
As mentioned above, conventional luminescent materials 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 having improved resistance against water, air humidity and polar solvents.
The divalent lead and/or divalent copper ions within the host lattice do not act as activators (also referred to herein as “luminescent ions”) and, therefore do not luminance. Rather, it has been found that these ions tend to influence the crystal field splitting as well as the covalency of the chemical compound. As a result, the substitutional incorporation of divalent lead and/or copper ions within the host lattice tends to influence luminescent-optical properties of the chemical compounds so as to improve luminescent intensity and desirably shift the emission maxima, color points, and shape of emission spectra.
It has been found that phosphors having chemical compounds that contain substitutionally-incorporated divalent lead and/or divalent copper ions show improved emission intensities as compared with phosphors having chemical compounds that do not contain substitutionally-incorporated divalent lead and/or divalent copper ions.
In addition, it has been found that phosphors having chemical compounds that contain substitutionally-incorporated divalent lead and/or divalent copper ions tend to show improved luminescent properties for excitation wavelength higher than about 360 nm. At excitation wavelengths higher than about 360 nm, the divalent lead and/or divalent copper ions do not exhibit their own radiation transfers due to the energy levels of their electron configuration, so that any kind of exciting radiation cannot be lost. Furthermore, by substitutionally incorporating divalent lead and/or divalent copper ions, the emission wavelength can be shifted to higher or lower energies as desired.
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-containing compounds, which need reducing atmosphere, special preparation processes are necessary.
The influence of substitutionally-incorporated divalent lead ions in the crystal field on the shifting of emission characteristics depends upon the substituted ions. When divalent lead ions substitute Sr or Ba in Eu-activated aluminates and/or silicates, the emission maximum tends to be shifted to longer wavelengths due to smaller ionic radii of Pb as compared with the ionic radii of Ba and Sr. That leads to a stronger crystal field surrounding the activator ion.
A similar effect shows the substitution of divalent copper ions 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 shifting of emission peaks to longer or shorter wavelengths 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.
As described above, the luminescent material may include one or more chemical compounds such as, for example, aluminates, silicates, antimonates, germinates, germinate-silicates, and/or phosphates. Exemplary embodiments of these luminescent materials are described in greater detail below.
Luminescent materials for ultraviolet light or visible light excitation comprise lead- and/or copper-containing aluminates exemplarily characterized 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, 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.
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 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.
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.
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.
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.
Results obtained in regard to copper and/or lead doped aluminates are shown in table 7.
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 copper-containing silicates exemplarily described herein may, in some embodiments, contain SiO4 and be characterized as having an Olivine 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.
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.
Preparation of the luminescent material having formula (II):
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.
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.
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.
Results obtained with respect to copper- and/or lead-containing silicates are shown in table 12.
Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper-containing 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.
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.
Results obtained in respect to copper- and/or lead-containing antimonates are shown in table 15.
Luminescent materials for ultraviolet light or visible light excitation comprise lead- and/or copper-containing germanates and/or a germanate-silicates exemplarily characterized according to the formula as follows:
a(M′O)b(M″2O)c(M″X)dGeO2e(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.
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.
Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper-containing phosphates exemplarily characterized according to the formula as follows:
a(M′O)b(M″2O)c(M″X)dP2O5e(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-containing 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, 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.
Lead- and/or copper-containing luminescent materials exemplarily described above 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. According to some embodiments, one or more of the lead- and/or copper-containing luminescent materials exemplarily described above may be used or mixed to produce a luminescent material with a color temperature ranging from about 2,000K to about 8,0000K 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). Thus, for all color temperatures as well as for all color coordinates inside of the white light coordinates, an appropriate luminescent material or mixture thereof can be found.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2004-0042397 | Jun 2004 | KR | national |
The present application is a continuation of U.S. patent application Ser. No. 13/099,879, filed on May 3, 2011, now U.S. Pat. No. 8,070,984, which is a continuation of U.S. patent application Ser. No. 11/948,813, filed on Nov. 30, 2007, now U.S. Pat. No. 8,070,984, which is a continuation-in-part of U.S. patent application Ser. No. 11/024,722, filed on Dec. 30, 2004, now U.S. Pat. No. 8,070,983, and claims priority from and the benefit of Korean Patent Application No. 10-2004-0042397, filed on Jun. 10, 2004, which is hereby incorporated by reference for all purposes as if fully set forth herein.
| 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 | Aug 1971 | A |
| 3644212 | McAllister et al. | Feb 1972 | A |
| 3893939 | De Kalb 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 |
| 4810416 | Hase | Mar 1989 | 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 et al. | Feb 2004 | B1 |
| 6842664 | Harada et al. | Jan 2005 | B2 |
| 6982045 | Menkara et al. | Jan 2006 | B2 |
| 6982048 | Atwater et al. | 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 |
| 7204607 | Yano | Apr 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 |
| 8137589 | Lee et al. | Mar 2012 | B2 |
| 8173042 | Lee et al. | May 2012 | B2 |
| 8252203 | Roth et al. | Aug 2012 | B2 |
| 8318044 | Lee et al. | Nov 2012 | B2 |
| 8440106 | Lee et al. | May 2013 | B2 |
| 8501040 | Lee et al. | Aug 2013 | 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 et al. | 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 |
| 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 |
| 0765925 | Apr 1997 | EP |
| 0862794 | Sep 1998 | EP |
| 0896994 | 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 1974 | 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 |
| 2001-308393 | 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 |
| 2004-071726 | 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 |
| 2001-115157 | Dec 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 |
| 10-2001-0032450 | Apr 2001 | KR |
| 10-2001-0050839 | Jun 2001 | KR |
| 10-2001-0101910 | Nov 2001 | KR |
| 10-2002-0000835 | Jan 2002 | KR |
| 10-2002-0053975 | Jul 2002 | KR |
| 10-0392363 | Jul 2002 | KR |
| 10-2002-0079513 | Oct 2002 | KR |
| 10-2003-0063211 | 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 |
| 10-2006-0034056 | Apr 2006 | KR |
| 10-0626272 | Sep 2006 | KR |
| 10-2006-0134728 | Dec 2006 | KR |
| 10-2007-0016900 | Feb 2007 | KR |
| 10-2007-0050833 | May 2007 | KR |
| 10-2007-0086483 | Aug 2007 | KR |
| 10-2008-0046789 | May 2008 | KR |
| 10-2008-0075181 | Jul 2008 | KR |
| I328885 | Mar 1999 | TW |
| 546854 | Aug 2003 | TW |
| 96-32457 | 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 |
| 0033390 | Jun 2000 | WO |
| 01-41215 | Jun 2001 | WO |
| 02-054502 | Jul 2002 | WO |
| 02-054503 | 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 |
| 2005-068584 | Jul 2005 | WO |
| 2005-112137 | Nov 2005 | WO |
| 2005109532 | Nov 2005 | WO |
| 2006-043682 | Apr 2006 | WO |
| 2006-068359 | Jun 2006 | WO |
| 2006-081803 | Aug 2006 | WO |
| 2006109659 | Oct 2006 | WO |
| 2007-035026 | Mar 2007 | WO |
| 2007-055538 | May 2007 | WO |
| 2007055538 | May 2007 | WO |
| 2007-069869 | Jun 2007 | WO |
| 2007-114614 | Nov 2007 | WO |
| 2009028818 | Mar 2009 | WO |
| Entry |
|---|
| Feldmann C., “Inorganic Luminescent Materials: 100 Years of Research and Application”, Adv. Funct. Matter, 2003, pp. 511-516. |
| G. Blasse, B.C. Grabmeier, “Luminescent Materials”, Springer, 1994, 87-90. |
| B. Cordero, V. Gómez, A. E. Platero-Prats, M. Revés, J. Echeverria, E Cremades, F. Barragán, and S. Alvarez, “Covalent radii revisted”, Dalton Trans., (2008), pp. 2832-2838. |
| R.J. Angel et al., “Structure and twinning of single-crystal MgSiO3 garnet synthisized at 17 GPa and 1800 ° C”, American Minerologist, 74 (1989) pp. 509-512. |
| G.L. Miessler, D.A. Tarr, “Inorganic Chemistry”, (2004) pp. 117-118, 3rd ed., Pearson / Prentice Hall, New Jersey, US. |
| P.A. Cox, “Transition Metal Oxides”, Oxford University Press, 1995, p. 105. |
| Garcia Solé, L.E. Bausá, D. Jaque, “An Introduction to the Optical Spectroscopy of Inorganic Solids”, Wiley, 2005, pp. 163-164. |
| G. Blasse, B.C. Grabmeier, “Luminescent Materials”, Springer, 1994, p. 25. |
| S. Shionoya, W.M. Yen, “Phospher Handbook” CRC press, 1999, ch. 3.3, pp. 183-184. |
| Garcia Solé, L.E. Bausá, D. Jaque, “An Introduction to the Optical Spectroscopy of Inorganic Solids”, Wiley, 2005, pp. 132-133. |
| S. Shionoya, W.M. Yen, “Phosphor Handbook” CRC press, 1999, ch. 3.3, pp. 179-182. |
| G. Blasse, “Characteristic Luminescence”, Philips Technical Review, vol. 31, 1970, pp. 304-332. |
| G. Blasse, B.C. Grabmeier, “Luminescent Materials”, Springer, 1994, pp. 40-47. |
| R. Chen, “Developments in Luminescence and Display Materials Over the Last 100 Years as Reflected in Electrochemical Society Publications” the Electrochemical Society, pp. 69-78, 2002. |
| Indian Office Action of Indian Application No. 2468/KOLNP/2007 issued on Jan. 28, 2011, corresponding to U.S. Appl. No. 12/098,263. |
| Non-Final Office Action of U.S Appl. No. 12/854,001 issued on Apr. 6, 2011. |
| Chinese Office Action of Chinese Patent Application No. 200880105091.8 issued on Apr. 1, 2011. |
| Chinese Office Action of Chinese Patent Application No. 201010198537.5 issued on Mar. 18, 2011. |
| Chinese Office Action of Chinese Patent Application No. 201010185274.4 issued on Mar. 2, 2011. |
| Austrian Office Action for AT Application No. 9514/2005 issued on Jun. 1, 2011. |
| Austrian Office Action for AT Application No. 1545/2010-1 issued on May 31, 2011. |
| Final Office Action of U.S. Appl. No. 12/731,811 issued on Jul. 29, 2011. |
| Non-Final Office Action dated Apr. 2, 2012 issued for U.S. Appl. No. 13/279,878. |
| Notice of Allowance dated Apr. 11, 2012 issued for U.S. Appl. No. 12/093,441. |
| Final Office Action dated Apr. 18, 2012 issued for U.S. Appl. No. 12/491,457. |
| Final Office Action dated Apr. 26, 2012 issued for U.S. Appl. No. 12/491,780. |
| International Search Report dated Jul. 12, 2007 for PCT Application No. PCT/KR2007/001587. |
| International Search Report dated Mar. 21, 2007 for PCT Application No. PCT/KR2006/005500. |
| International Search Report dated Feb. 20, 2007 for PCT Application No. PCT/KR2006/004716. |
| International Search Report dated Oct. 24, 2005 for PCT Application No. PCT/KR2005/002332. |
| International Search Report dated Oct. 13, 2005 for PCT Application No. PCT/KR2005/002333. |
| International Search Report dated Aug. 12, 2005 for PCT Application No. PCT/KR2005/001288. |
| International Search Report dated Aug. 12, 2005 for PCT Application No. PCT/KR2005/001287. |
| International Search Report dated Feb. 27, 2009 for PCT Application No. PCT/KR2008/004734. |
| International Search Report dated Feb. 11, 2009 for PCT Application No. PCT/KR2008/004733. |
| Joung Kyu Park, et al., “Silicate Phosphors for White LEDs Identified Through Combinatorial Chemistry”, Electrochemical and Solid-State Letters, vol. 10(2), pp. J15-J18, (2007), XP-00251106706-11-12). |
| Joung Kyu Park, et al., “Luminescence Characteristics of Yellow Emitting Ba3SiO5:EU2+ Phosphor”, Journal of Materials Science 40 (2005), pp. 2069-2071, XP-002511068. |
| Search Report dated Feb. 2, 2009 for EP Application No. EP08014684. |
| S.D. Jee, et al., “Photoluminescence properties of Eu2+ -activated Sr3SiO5 Phosphors,” J. Mater Sci. 41 (2006), pp. 3139-3141. |
| G. Blasse, et al., “Fluorescence of Europium2+-activated silicates,” Philips Res. Repts 23 (1968), pp. 189-199. |
| G. Roth, et al. “Advanced Silicate Phosphors for improved white LED”, Global Phosphor Summit Seoul/Korea, Mar. 5-7, 2007. |
| Non-Final Office Action dated Apr. 24, 2012 issued for U.S. Appl. No. 12/854,001. |
| H.G. Kang, et al., “Embodiment and Luminescence Properties of Sr3SiO5:Eu(yellow-orange phosphor) by co-doping lanthanide”, Solid State Phenomena, vol. 124-126 (2007) pp. 511-514. |
| T.L. Barry, “Fluorescence of Eu2+ Activated Phases in Binary Alkaline Earth Orthosilicate Systems”, J. Electrochem Soc., Nov. 1968, pp. 1181-1184. |
| Notice of Allowance dated Dec. 1, 2008 issued in U.S. Appl. No. 11/024,702. |
| Chinese Office Action corresponding to Patent App No. 2005800150173 dated Dec. 28, 2007. |
| Final OA dated Oct. 22, 2007 issued in U.S. Appl. No. 11/024,722. |
| Office Action dated Dec. 28, 2007 corresponding to China App No. 200580016844.4. |
| X. W. Sun et al., “Pulsed Laser Deposition of Silicate Phosphor Thin Films”, Appl. Phys. A 69, 1999, 5 pp. |
| W.L. Wanmaker et al. “Luminescence of Phosphors Based on the Host Lattice ABGe2O6 (A, B=Ca, Sr, Ba)” Journal of Solid State Chemistry 3, (1971), pp. 194-196. |
| Declaration under CFR 1.132 for related U.S. Appl. No. 11/024,722 dated Aug. 24, 2007. |
| Non-Final OA mailed May 23, 2007 for U.S. Appl. 11/024,722 entitled “Luminescent Material”. |
| Ageeth A. Bol et al., “Luminescence of ZnS:Cu2+”, Journal of Luminescence, No. 99, 2002, pp. 325-334. |
| J.F. Suyver et al., “Luminescence of nanocrystalline ZnSe:Cu”, Applied Physics Letters, vol. 79, No. 25, Dec. 17, 2001, pp. 4222-4224. |
| Ping Yang et al., “Photoluminescence of Cu+-doped and Cu2+-doped ZnS nanocrystallites”, Journal of Physics and Chemistry of Solids, No. 63, 2002, pp. 638-643. |
| S. Shionoya et al., (Eds.), “Principal phosphor materials and their optical properties” in Phosphor Handbook, CRC Press, 1999, pp. 231-255. |
| A. Scacco et al., “Optical Spectra of Cu2+ Ions in LiF Crystals”, Radiation Effects and Defects in Solids, vol. 134, 1995, pp. 333-336. |
| Lujcan Dubicki et al., “The First d-d Fluorescence of a Six-Coordinate Copper (II) Ion”, J. Am. Chem. Soc. 1989, No. 111, pp. 3452, 3454. |
| A.B.P. Lever, “Inorganic Electronic Spectroscopy”, 2nd ed., Elsevier, 1984, pp. 355 and 557-559. |
| A.G. Shenstone, “The Third Spectrum of Copper (Cu III)”, Journal of Research of the National Bureau of Standards—A. Physics and Chemistry, vol. 79A, No. 3, May-Jun. 1975, pp. 497-521. |
| First Office Action of the PRC to Chinese Patent App No. 20051002304.2 dated Feb. 15, 2008. |
| Yang, “Up- Conversion Fluorescence in Er3 + Yb3 + Co- Doped Oxy—Fluoride Compound Materials Based on GeO2”, Natural Science Journal of Xiangtan University, vol. 23, No. 2, 2001, pp. 37-41. |
| Bernhardt, Investigations of the Orange Luminescence of PbMo04 Crystals, Phys. Stat. Sol (a), 91, 643, 1985, pp. 643-647. |
| Butler, “Fluorescent Lamp Phosphors”, The Pennsylvania State University Press, 1980, pp. 175-176. |
| Butler, “Fluorescent Lamp Phosphors”, The Pennsylvania State University Press, 1980, pp. 181-182. |
| Wanmaker, et al., Luminescence of Copper-Activated Orthophosphates of the Type ABPO (A=Ca, Sr, or Ba and B=Li, Na or K), Journal of the Electrochemical Society, vol. 109, No. 2 pp. 109-113, Feb. 1962. |
| Butler, “Fluorescent Lamp Phosphors”, The Pennsylvania State University Press, 1980, pp. 281-284. |
| “Phosphors for Mercury Lamps” https:/www.lamptech.co.uk/Docuemnts/M14%20Phosphors.htm 2003 (2 pages). |
| Blasse, “Radiationless Processes in Luminescent Materials”, Radiationless Processes, 1980, pp. 287-289, 293. |
| Shinonoya, “Phosphor Handbook”, edited under the auspice of Phosphor Research Society, CRC Press, 1999, pp. 204-205. |
| Shinonoya, “Phosphor Handbook”, edited under the auspice of Phosphor Research Society, CRC Press, 1999, p. 238-239, 241. |
| Wanmaker, “Luminescence of Copper-Activated Calcium and Strontium Orthophosphates”, Journal of the ElectroChemical Society, pp. 1027-1031, Vol. 109, No. 2; 1962. |
| van Gool, “Philips Res. Rept. Suppl.” 3, 1, 1961, pp. 1-9, 30-51, 84-85. |
| Declaration Under Rule 37 CFR 1.132 of Ulrich Kynast dated Sep. 6, 2008. |
| Preliminary Notice of First Office Action with Search Report issued on May 15, 2013 in Taiwanese Patent Application No. 095147024. |
| International Search Report for PCT/KR2010/003302 issued on Jan. 3, 2011, corresponding to U.S. Appl. No. 12/767,253. |
| Final Office Action dated Dec. 8, 2010 in U.S. Appl. No. 11/948,813. |
| Final Office Action dated Dec. 23, 2010 in U.S. Appl. No. 11/569,060. |
| Non Final Office Action dated Dec. 29, 2010 in U.S. Appl. No. 12/731,811. |
| Final Office Action dated Dec. 7, 2010 in U.S. Appl. No. 11/948,845. |
| Non Final Office Action dated Nov. 26, 2010 in U.S. Appl. No. 12/440,001. |
| Non Final Office Action dated Nov. 24, 2010 in U.S. Appl. No. 12/093,441. |
| Final Office Action dated Nov. 30, 2010 in U.S. Appl. No. 11/024,722. |
| Notice of Allowance dated Aug. 18, 2010 in U.S. Appl. No. 12/098,263. |
| Final Office Action dated May 11, 2010 in U.S. Appl. No. 12/098,263. |
| Non Final Office Action dated Mar. 17, 2010 in U.S. Appl. No. 11/024,722. |
| Non Final Office Action dated Aug. 17, 2010 in U.S. Appl. No. 11/948,845. |
| EP Search Report dated Sep. 1, 2010 in EP Appl No. 08015119 correpsonding to U.S. Appl. No. 12/440,001. |
| EP Search Report dated Oct. 6, 2010 in Ep Appl No. 07745750.5—corresponding to U.S. Appl. No. 12/295,438. |
| Non Final Office Action dated Jun. 16, 2010 in U.S. Appl. No. 12/097,741. |
| Final Office Action dated Nov. 12, 2010 in U.S. Appl. No. 12/097,741. |
| Non-Final Office Action dated Aug. 10, 2010 in U.S. Appl. No. 11/024,722. |
| Final Office Action dated Jun. 21, 2010 in U.S. Appl. No. 11/569,060. |
| Tomas L. Barry “Equilibria and Eu2+ luminescence of subsolidus phases bounded by Ba3MgSi2O8, Sr3MgSi2O8 and Ca3MgSi2O8” pp. 733-738 vol. 115, No. 7 J. Electrochem Soc.: Solid State Sceince Jul. 1968. |
| Non-final office action dated Nov. 29, 2006 issued in U.S. Appl. No. 11/024,722, filed Dec. 30, 2004. |
| CN Office Action dated Feb. 5, 2010 in CN Appl. No. 2005100023042. |
| European Search Report of Oct. 26, 2010 in EP 10 17 7817, corresponding to U.S. Appl. No. 11/024,722. |
| Non-Final Office Action dated Aug. 18, 2010 in U.S. Appl. No. 11/948,813. |
| Non-Final Office Action dated Aug. 10, 2010 in U.S. Appl. No. 12/731,811. |
| IP Australia Office Action dated Jul. 2, 2010 for AU Patent Appl. No. 2005-319965, corresponding to U.S. Appl. No. 12/098,263. |
| TW Office Action of Sep. 10, 2010 in TW Patent Appl. No. 098123458. |
| European Search Report of Sep. 23, 2010 in European Patent Appl. No. 10 16 4970. |
| Non-final office action dated May 29, 2009 issued in U.S. Appl. No. 11/024,722, filed Dec. 30, 2004. |
| Notice of Allowance dated May 4, 2009 issued in U.S. Appl. No. 11/024,702. |
| Non-final office action dated Nov. 29, 2007 issued in U.S. Appl. No. 11/024,702, filed Dec. 30, 2004. |
| Non-final office action dated Aug. 12, 2009 issued in U.S. Appl. No. 11/569,060, filed Jun. 22, 2007. |
| Non-final office action dated Jan. 13, 2010 issued in U.S. Appl. No. 11/569,060, filed Jun. 22, 2007. |
| Non-final office action dated Nov. 17, 2009 issued in U.S. Appl. No. 12/097,741, filed Oct. 9, 2008. |
| Bogner et al., DE 102 33 050 A1, May 5, 2004, Machine Traslation. |
| Final office action dated Feb. 7, 2007 issued in U.S. Appl. No. 11/024,702, filed Dec. 30, 2004. |
| Non-final office action dated Jun. 22, 2006 issued in U.S. Appl. No. 11/024,702, filed Dec. 30, 2004. |
| Notice of Allowance of U.S. Appl. No. 11/948,813 issued on Aug. 22, 2011. |
| Final office action dated Oct. 28, 2009 issued in U.S. Appl. No. 11/024,722, filed Dec. 30, 2004. |
| Non-final office action dated May 23, 2007 issued in U.S. Appl. No. 11/024,722, filed Dec. 30, 2004. |
| Non-final office action dated Nov. 14, 2008 issued in U.S. Appl. No. 11/024,722, filed Dec. 30, 2004. |
| Non-final office action dated Nov. 2, 2009 issued in U.S. Appl. No. 12/098,263. |
| Ralchenko, Yu., Kramida, A.E., Reader, J. and NIST ASD Team (2008). NIST Atomic Spectra Database (version 3.1.5), [Online]. Available: http://physics.nist.gov/asd3 [Feb. 27, 2009]. National Institute of Standards and Technology, Gaithersburg, MD. |
| N. S. Akhmetov, “Inorganic Chemistry”, Moscow “Vysshaya Shkola”, 1975; (partial translation; translated pp. 332-333, 372-373, 384-385, 427, 432, 436, 445, 471, 476, 486, 491, 496-497, 501, 546-549). |
| Markovsky L, Ya. et al., Phosphors (Moscow-Leningrad, KHIMIYA Publishers, 1966, p. 7 (partial translation). |
| Search Report dated Apr. 11, 2006 for EP Application No. EP04106880.0. |
| Search Report dated Nov. 5, 2008 for EP Application No. EP06812549.1. |
| Search Report dated Aug. 21, 2007 for EP Application No. EP04106882.6. |
| Non-Final Office Action issued on Sep. 13, 2013 in U.S. Appl. No. 13/665,744. |
| Non-Final Office Action of U.S. Appl. No. 12/491,457 mailed on Nov. 17, 2011. |
| Non-Final Office Action of U.S. Appl. No. 12/491,780 dated on Dec. 7, 2011. |
| Non-Final Office Action of U.S Appl. No. 13/004,554 issued on Mar. 15, 2011. |
| Notice of Allowance of U.S Appl. No. 11/024,722 issued on Mar. 10, 2011. |
| Notice of Allowance of U.S. Appl. No. 13/004,554 mailed on Dec. 13, 2011. |
| Notice of Allowance of U.S. Appl. No. 11/948,845 issued on Mar. 23, 2011. |
| Non-Final Office Action of U.S. Appl. No. 12/098,263 issued on Mar. 30, 2011. |
| Non-Final Office Action of U.S. Appl. No. 12/295,438 dated on Jan. 12, 2012. |
| Chinese Office Action of CN Patent Application No. 201010185246.2 dated Dec. 27, 2011 corresponding to U.S. Appl. No. 13/004,554. |
| S. Shinoya et al. (Eds.), “Principal phosphor materials and their optical properties” in Phosphor Handbook, CRC Press, 1999, p. 826. |
| Notice of Allowance of U.S. Appl. No. 12/098,263 issued on Oct. 11, 2011. |
| Final Office Action of U.S. Appl. No. 12/854,001 issued on Oct. 11, 2011. |
| Number | Date | Country | |
|---|---|---|---|
| 20120286207 A1 | Nov 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13099879 | May 2011 | US |
| Child | 13555882 | US | |
| Parent | 11948813 | Nov 2007 | US |
| Child | 13099879 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11024722 | Dec 2004 | US |
| Child | 11948813 | US |
