Title of Invention	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 band's 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.

Title of Invention

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 band's 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.

Full Text	1 WO 2006/068360 PCT/KR2005/002333 Description LUMINESCENT MATERIAL Technical Field [1] 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. Background Art [2] Lead and copper activated materials are known for short wave excitation, e.g. from a low pressure mercury lamp, such as barium disilicale activated by lead (Keith H. Butler, The Pennsylvania Stale University Press, 1980, S 175, orthosilicatc activated by lead (Keith H. Butler, The Pennsylvania State University Press, 1980, S. 181), ak- ermanites activated by lead, or Ca-metasilicatc activated by Pb2+. [3] 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. [4] Lead has in the ground state S two outer electrons. The electron configuration of the ground state is d10s2, so that the lowest excited stale has d10sp configuration. The excited sp configuration has four levels, P P , P and P , which can be achieved between 165.57 nm (3P ) and 104.88 nm (1P1 ) in the free ion. Transitions between '1S0 and P excited level arc allowed by all selection rules. While transitions between S 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. [5] Otherwise, luminescent materials arc known having lead as a host lattice component. Molybdate phosphors containing MoO4 2'-centers are described in Bcrnhardt, 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. [6] However, such emission is not caused by lead itself. In molybdates the lu- minescence properties arc not caused by the metal ion M2+ (M2+MoO4 where M2+ = Ca, Sr, Cd, Zn, Ba, Pb etc). Here, defect centers of MoO4 2- 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. [7] 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, DiBarlolo, B., Ed. Plenum Press, New York, 1980, 287). Under 250 nm excitation PbWO shows blue emission and 2 WO 2006/068360 PCT/KR2005/002333 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). [8] 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 level1 S . After exciting the lowest excited configuration is 3d94s. This configuration has two terms, 3D and lD. The next higher configuration, 3d94p, gives 6 terms 3P°, 3F°, 3D°, 1F°, 1D° and 1P0. 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 3 D or 1D state of the 3d94s configuration to the ground state. [9] The ground state of bivalent copper has 3d -configuration. That is the level D . In the bivalent copper, one of the d-clcctrons 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 P°, where emission can occur. [10] 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 ap- plications. [11] 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). [12] 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. [13] 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 3 WO 2006/068360 PCT/KR2005/002333 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. [14] 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. [15] 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. [16] 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 arc necessary. [17] 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. [18] 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 4 WO 2006/068360 PCT/KR2005/002333 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. [19] 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. Disclosure of Invention Technical Problem [20] 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. [21 ] 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. [22J 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 CR1 up to over 90 in LED. Technical Solution [23] To achieve these and other objects, as embodied and broadly described herein, 1 uminesccnt materials for ultraviolet light or visible light excitation comprises lead and/ or copper doped chemical compounds containing a rare earth clement or other lu- minescent ions. [24] The luminescent materials may be composed of one or more compounds of aluminate, silicate, antimonate, germanale/or germanate-silicate, and phosphate. 5 WO 2006/068360 PCT/KR2005/002333 [38J 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. [39] 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 la. Best Mode [40] Hereinafter, the present invention will be described in detail. [41] Example 1; [42] Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped aluminates according to the formula as follows: [43] a(M'O)-b(M"2O)-c(M"X)-dAl2 O3 •e(M""O).f(M""2 O3 )g(M"""0 Op) h(M"""x Oy ) (l) [44] 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, J, 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. [45] a(M'O)-b(M" 2O).c(M"X)4-a-b [46] -c(M'"O).7(Al2 O3 ).d(B2 O3) .e(Ga2 O3 ).f(SiO2).g(GeO2 ).h(M"" O ) (2) [47] wherein M1 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 6 WO 2006/068360 PCT/KR2005/002333 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≤l;0≤e≤l;0≤f≤l;0≤g≤l;0≤h≤2; 1 ≤ x ≤ 2; and 1 ≤ y ≤ 5. [48] The preparation of copper as well as lead doped luminescent materials may be a basic solid stale 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. [49] Examples of preparation: [50] Preparation of the luminescent material having formula (3) [51] Cu0.02 Sr3.98 Al14 O25 :Eu (3) [52] Starting materials: CuO, SrCO3 Al(OH)3, Eu2 O3 , and/or any combination thereof. [53] 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., H BO . 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 l,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. [54] Table 1: copper doped Eu 2+ -activated aluminate compared with Eu 2+-activated aluminatc without copper at about 400 nm excitation wavelength Copper doped compound Compound without copper Cu0.02 Sr3.98 Al14 O25 :Eu103.1 Sr4Al14 O25 :Eu100 Luminous density (%) Wavelength (nm) 494 493 [55] [56] Preparation of the luminescent material having formula (4) [57] Pb0.05 Sr3.95 Al14 O25 : Eu (4) [58] Starting materials: PbO, SrCO3 , Al2 O3 , Eu O3 , and/or any combination thereof. [59] 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 l,450°C in air for about 2 hours and in a reduced atmosphere for about 2 hours may be followed. Then the 7 WO 2006/068360 PCT/KR2005/002333 material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum of from about 494.5 nm. [60] Table 2: lead doped Eu 2+-activaled aluminale compared with Eu 2+-activated aluminate without lead at about 400 nm excitation wavelength [611 Lead doped compound Compound without lead Pb0.05 Sr3.95 Al14 O25 :Eu Sr4 Al14 O25 :Eu Luminous density (%) 101.4 100 Wavelength (nm) 494.5 493 [62] Table 3: optical properties of some copper and/or lead doped aluminales excitable by long wave ultraviolet and/or by visible light and their luminous density in % at 400 nm excitation wavelength [63] Composition Possible Luminous density Peak wave Peak wave excitation at 400 nm length of lead/ length of range(nm) excitation copper doped materials compared with materials (nm) without lead/ copper/lead not copper (nm) doped compounds (%) Cu0.5 Sr3.5 Al14 O25 : 360 - 430 101.2 495 493 Eu Cu0.02 Sr3.98 Al14 O25 : Eu 360 - 430 103.1 494 493 Pb0.05 Sr3.95 Al14 O25 : Eu 360 - 430 101.4 494.5 493 Cu0.01 Sr3.99 Al13.995 Si O0.005 :Eu25 360-430 103 494 492 Cu0.01 Sr3.395 Ba0.595 Al 14O25 :Eu,Dy 360 - 430 100.8 494 493 Pb0.05 Sr3.95 Al13.95 Ga 0.05O25 :Eu 360 - 430 101.5 494 494 [64] Example 2: [65] Luminescent materials for ultraviolet light or visible light excitation comprise lead 8 WO 2006/068360 PCT/KR2005/002333 and/or copper doped aluminates according to the formula as follows: [66] a(M'O) • b(M"O) • c(Al2 O3 ) • d(M'"2O3 ) • e(M""O2 ) • f (M""" xOy ) (5) [67] 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, Gc, Ti, Zr, Hf, and/or any combination thereof; M""' may be Bi, Sn, Sb, Sc, Y, La, Cc, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; 0≤a≤l;0≤b≤2;0≤c≤8;0≤d ≤ 1; 0 ≤ c ≤ 1; 0 ≤ f ≤ 2; 1 ≤ x ≤ 2; and 1 ≤ y ≤ 5. [68] The luminous peak and density of Example 2 are described in Table 7, which will be shown below. [69] Example of preparation: [70] Preparation of the luminescent material having formula (6) [71] Cu0.05 Sr0.95 Al1.9997 Si0.0003 O4 : Eu (6) [72] Starting materials: CuO, SrCO3 , Al2 O3 , SiO2 , Eu2 O3 , and/or any combination thereof. [73] The starting materials in the form of, for example, pure oxides and/or as carbonates may be mixed in stoichiomctric proportions together with small amounts of flux, for example, A1F3 . The mixture may be fired in an alumina crucible at about l,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. [74] Table 4: copper doped Eu 2+-activated aluminale compared with Eu2+-activated aluminate without copper at about 400 nm excitation wavelength [75] Copper doped compound Compound without copper Cu0.05 Sr0.95 Al1.9997 Si0.0003 O 4 : Eu SrAl2 O4 :Eu Luminous density (%) 106 100 Wavelength (nm) 521.5 519 [76] Preparation of the luminescent material having formula (7) [77] Cu0.12 BaMg1.88 Al16 O27 : Eu (7) [78] Starting materials: CuO, MgO, BaCO3 , Al(OH)3 Eu2 O3 , and/or any combination thereof. [79] The starling 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, A1F . The mixture may be fired in an alumina crucible at about 9 WO 2006/068360 PCT/KR2005/002333 l,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. [80] Table 5: copper doped Eu 2+-activatcd aluminate compared with copper not doped Eu +-activated aluminate at 400 nm excitation wavelength [81] Copper doped compound Comparison without copper Cu0.12 BaMg1.88 Al16 O27 : Eu BaMg2Al16 O27 :Eu Luminous density (%) 101 100 Wavelength (nm) 452 450 [82] Preparation of the luminescent material having formula (8) [83] Pb0.1 Sr 0.9 A12O4 : Eu (8) [84] Starting materials: PbO, SrCO , Al(OH)3, Eu2 O3 , and/or any combination thereof. [85] The starling materials in form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stochiomctric proportions together with small amounts of flux, for example , H BO . 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 l,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 he milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 521 nm. [86] Table 6: lead doped Eu2+-activated aluminate compared with Eu2+-activated aluminate without lead at about 400 nm excitation wavelength [87] Lead doped compound Compound without lead Pb0.1 Sr0.9 A12O4 :Eu SrAl2O4 :Eu Luminous density (%) 102 100 Wavelength (nm) 521 519 [88] Results obtained in regard to copper and/or lead doped aluminates are shown in table 7. [89] 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 [90] 10 WO 2006/068360 PCT/KR2005/002333 [91] Example 3: [92] Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped silicates according to the formula as follows: [93] a(M'O).b(M"O)-c(M"'X).d(M"' 2O).e(M"" 0Op).g(SiO2).h(M"""xOy) 11 WO 2006/068360 PCT/KR2005/002333 (9) [94] 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, Cc, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; X may be F, Cl, Br, J, 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. [95] The superior luminous density of Example 3 can be seen below. [96] Example of preparation: [97] Preparation of the luminescent material having formula (10) [98] Cu0.05 Sr1.7 Ca0.25 SiO4 : Eu (10) [99] Starting materials: CuO, SrCO3 CaCO3 , SiO2 , Eu2 O3 , and/or any combination thereof. [100] The starting materials in the form of pure oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH Cl. The mixture may be fired in an alumina crucible at about l,200°C in an inert gas atmosphere (e.g., N 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 l,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. [101] Table 8: copper doped Eu2+-activated silicate compared with Eu2+-activated silicate without copper at about 400 nm excitation wavelength Copper doped compound Compound without copper Cu0.05 Sr1.7 Ca0.25 SiO4 : Eu Sr1.7 Ca0.3 SiO4 : Eu Luminous density (%) 104 100 Wavelength (nm) 592 588 [102] [ 103 ] Preparation of the luminescent material having formula (11): [104] Cu0.2 Ba2 Zn0.2 Mg0.6 Si2 O7 : Eu (11) [105] Starting materials: CuO, BaCO3 , ZnO, MgO, SiO2 , Eu2 O3 , and/or any combination thereof. [106] 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, 12 WO 2006/068360 PCT/KR2005/002333 NH4 Cl. In a first step the mixture may be fired in an alumina crucible at about l,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. [107] Table 9: copper doped Eu2+-activated silicate compared with Eu2+-activatcd silicate without copper at 400 nm excitation wavelength [108] Copper doped compound Compound without copper Cu0.2 Sr2Zn0.2 Mg0.6 Si2 O7 : Eu Sr2 Zn2 Mg0.6 Si2 O7 : Eu Luminous density (%) 101.5 100 Wavelength (nm) 467 465 [109] Preparation of the luminescent material having formula (12) [110] Pb0.1 Ba0.95 Sr0.95 Si0.998 Gc0.002 O4 : Eu (12) [111] Starting materials: PbO, SrCO3 , BaCO3 SiO2 , GeO2 Eu2 O3 , and/or any combination thereof [112] The starting materials in the form of oxides and/or carbonates may be mixed in sto- ichiornetric proportions together with small amounts of flux, for example. NH Cl. 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 l,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. [113] Table 10: lead doped Eu2+-activated silicate compared with Eu2+-activated silicate without lead at about 400 nm excitation wavelength [114] Lead doped compound Compound without lead Pb0.1 Ba0.95 Sr0.95 Si0.998 Gc0.002 O4 :Eu BaSrSiO4 : Eu Luminous density (%) 101.3 100 Wavelength (nm) 527 525 [115] Preparation of the luminescent material having formula (13) [116] Pb0.25 Sr3.75 Si3O8Cl4 : Eu (13) 13 WO 2006/068360 PCT/KR2005/002333 [117] Starling materials : PbO, SrCO , SrCl SiO , Eu O , and any combination thereof. [118] 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 l,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. [119] Table 11: lead doped Eu2+-activated chlorosilicate compared with Eu2+-activated chlorosilicate without lead at 400 nm excitation wavelength [120] Lead doped compound Compound without lead Pb0.25 Sr3.75 Si3O8Cl4 : Eu Sr4 Si3O8Cl4 :Eu Luminous density (%) 100.6 100 Wavelength (nm) 492 490 [121] Results obtained with respect to copper and/or lead doped silicates arc shown in table 12. [ 122] 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 [123] 14 WO 2006/068360 PCT/KR2005/002333 [124] Example 4: [125] Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped antimonates according to the formula as follows: [126] a(M'O) • b(M"2 O) • c(M"X) • d(Sb2 O5 ) • e(M'"0) • f(M"" xOy ) (14) [127] 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"1 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, J, and/or any combination thereof; 0≤a≤2;0≤b≤2;0≤c≤4;0≤d≤8;0≤e≤8;0≤f≤2;l ≤ x ≤ 2; and 1 ≤ y ≤ 5. [128] Examples of preparation: [ 129] Preparation of the luminescent material having formula (15) [130] Cu0.2 Mg1.7 Li0.2 Sb2O7 : Mn (15) [131] Starting materials: CuO, MgO, Li2 O, Sb2O5 , MnCO3 , and/or any combination thereof. [132] The starting materials in the form of oxides may be mixed in stoichiometric 15 WO 2006/068360 PCT/KR2005/002333 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 l,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. [133] Table 13: copper doped antimonate compared with antimonatc without copper at about 400 nm excitation wavelength [134] Copper doped compound Comparison without copper Cu0.2 Mg1.7 Li0.2 Sb2O7 :Mn Mg2Li0.2 Sb2O7 :Mn Luminous density (%) 101.8 100 Wavelength (nm) 652 650 [135] Preparation of the luminescent material having formula (16) [136] Pb0.006 Ca0.6 Sr0.394 Sb2 O6 (16) [137] Starting materials: PbO, CaCO3 , SrCO3 Sb2 O5 , and/or any combination thereof. [138] The starling materials in the form of oxides and/or carbonates may be mixed in sto- ichiometric 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. [139] Table 14: lead doped antimonate compared with antimonate without lead at 400 nm excitation wavelength [140] Lead doped compound Compound without lead Pb0.006 Ca0.6 Sr0.394 Sb2 O6 Ca0.6 Sr0.4 Sb2O6 Luminous density (%) 102 100 Wavelength (nm) 637 638 [141] Results obtained in respect to copper and/or lead doped antimonates are shown in table 15. [142] Table 15: optical properties of some copper and/or lead doped antimonates 16 WO 2006/068360 PCT/KR2005/002333 excitable by long wave ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength [143] [144] Example 5: [145] 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: [146] a(M'O).b(M"2 O).c(M"X)-dGcO2 •c(M""O)-f(M"""2 O3 ).g(M""" 0Op )-h(M"""xOy (17) [147] 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 20 WO 2006/068360 PCT/KR2005/002333 Copper doped compound Compound without copper Cu0.02 Ca4.98 (PO4 )3 Cl: Eu Ca5 (PO4 )3 Cl: Eu Luminous density (%) 101.5 100 Wavelength (nm) 450 447 [175] 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 [176] [177] 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 21 WO 2006/068360 PCT/KR2005/002333 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 22 WO 2006/068360 PCT/KR2005/002333 Claims [1] 1. A luminescent material for ultraviolet light or visible light excitation, comprising: lead and/or copper doped chemical compounds containing a rare earth element and/or other luminescent ions. [2] 2. The luminescent material according to claim 1, wherein the compounds include lead and/or copper doped aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonatcs, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof. [3] 3. The luminescent material according to claim 1, wherein the compounds include a compound having formula (1) a(M'O)-b(M"2 O)-c(M"X)-dAl2 O3 .c(M"'O)-f(M"" 2O3 )-g(M""" 0Op ).h(M"""" xOy ) (1) wherein M' is Pb, Cu, or any combination thereof; M' is one or more monovalent elements, Li, Na, K, Rb, Cs, Au, Ag or any combination thereof; M'" is one or more divalent elements, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn or any combination thereof; M"""" is one or mure divalent elements, Sc, B, Ga, In, and/or any combination thereof; M'"" is Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or any combination thereof; M""" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof; X is F, Cl, Br, J, or any combination thereof; 0 0 ≤ b ≤ 2; 0 ≤ c ≤ 2; 0≤d≤8; 0 ≤ c ≤ 4; 0≤f≤3; 0≤g≤8; 0≤h≤2; l≤o≤2; 1≤P≤5; 1 ≤ x ≤ 2; and 23 WO 2006/068360 PCT/KR2005/002333 1 ≤ y ≤ 5. [4] 4. The luminescent material according to claim 1, wherein the compounds include a compound having formula (2) a(M'O) b(M" 2O).c(M"X)4-a-b -c(M'"O)-7(Al2O3)-d(B2O 3)-e(Ga203)-f(Si02)-g(Ge0 2)-h(M"" xOy ) (2) wherein M' is Pb, Cu, or any combination thereof; M" is one or more monovalent elements, Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M'" is one or more divalent elements, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M"" is 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 is F, Cl, Br, J, and any combination thereof; 0 ≤ a ≤ 4; 0 ≤ b 2 0≤c ≤2; 0≤d≤ 1; 0≤c≤ 1; 0≤f≤ 1; 0≤g≤l; 0≤h≤2; 1 ≤ x ≤ 2; and 1 ≤ y ≤ 5. [5] 5. The luminescent material according to claim 1, wherein the compounds include a compound having formula (5) a(M'O) • b(M"O) • C(A12O3) • d(M"'2 O3 ) • e(M""O2) • f (M"""xOy ) (5) wherein M' is Pb, Cu, or any combination thereof; M" is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof; M'" is B, Ga, In, or any combination thereof; M"" is Si, Ge, Ti, Zr, Hf, or any combination thereof; M'"" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof; 0≤a≤ 1; 0 ≤ b ≤ 2; 0≤c≤8; 0≤d≤l; 24 WO 2006/068360 PCT/KR2005/002333 0≤e ≤ 1; 0≤f≤2; 1 ≤ x ≤ 2; and 1 ≤y≤5. [6] 6. The luminescent material according to claim 1, wherein the compounds include a compound having formula (9) a(M'O).b(M"O)c(M"'X).d(M"' O)c(M""2O3 )-f(M"""0Op).g(SiO2 )• h(M""" xOy ) (9) wherein M' is Pb, Cu, or any combination thereof; M" is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof; M'" is Li, Na, K, Rb, Cs, Au, Ag, or any combination thereof; M"" is Al, Ga, In, or any combination thereof; M'"" is Ge, V, Nb, Ta, W, Mo, Ti, Zr, Hf, or any combination thereof; M""" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof; X is F, Cl, Br, J, 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. [7] 7. The luminescent material according to claim 1, wherein the compounds include a compound having formula (14) a(M'O) • b(M"2 O) • c(M"X) • d(Sb2 O5 ) • e(M'"O) • f(M""xOy ) (14) wherein M' is Pb, Cu, or any combination thereof; 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, Cl, Br, J, or any combination thereof; 25 WO 2006/068360 PCT/KR2005/002333 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. [8] 8. The luminescent material according to claim 1, wherein the compounds include a compound having formula (17) a(M'O)-b(M"2 O)-c(M"X)-dGcO2 e(M""O)-f(M""2 O3).g(M""' 0Op )-h(M""" xOy (17) wherein M' is Pb, Cu, or any combination thereof; 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, Cl, Br, J, 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; l≤o≤2; 1≤P≤5; 1 ≤ x ≤ 2; and 1 ≤y ≤ 5. [9] 9. The luminescent material according to claim 1, wherein the compounds include a compound having formula (20) a(M'O)-b(M" 2O).c(M"X)-dP205-c(M"'0)-f(M"" 203)g( M"""O2)-h(M xOy ) (20) wherein M' is Pb, Cu, or any combination thereof, 26 WO 2006/068360 PCT/KR2005/002333 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. Al, 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, Cl, Br, J, or any combination thereof, 0≤a≤2; 0≤b≤12; 0≤c≤ 16; 0≤d≤3; 0≤c≤5; 0≤f≤3; 0≤g≤2; 0 ≤ h ≤ 2; 1 ≤x ≤ 2; and l [10] 10. The luminescent material according to any one of claims 1 to 9, wherein said compound converts primary long-wave ultraviolet in the range of 300-400nm and/or blue radiation in the range of 380-500nm 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. [11] 11. The luminescent material according to any one of claims 1 to 9, wherein the luminescent material is 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. 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 band's 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.

Full Text

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WO 2006/068360 PCT/KR2005/002333
Description
LUMINESCENT MATERIAL
Technical Field
[1] 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.
Background Art
[2] Lead and copper activated materials are known for short wave excitation, e.g. from
a low pressure mercury lamp, such as barium disilicale activated by lead (Keith H.
Butler, The Pennsylvania Stale University Press, 1980, S 175, orthosilicatc activated
by lead (Keith H. Butler, The Pennsylvania State University Press, 1980, S. 181), ak-
ermanites activated by lead, or Ca-metasilicatc activated by Pb2+.
[3] 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.
[4] Lead has in the ground state S two outer electrons. The electron configuration of
the ground state is d10s2, so that the lowest excited stale has d10sp configuration. The
excited sp configuration has four levels, P P , P and P , which can be achieved
between 165.57 nm (3P ) and 104.88 nm (1P1 ) in the free ion. Transitions between '1S0
and P excited level arc allowed by all selection rules. While transitions between S
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.
[5] Otherwise, luminescent materials arc known having lead as a host lattice
component. Molybdate phosphors containing MoO4 2'-centers are described in
Bcrnhardt, 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.
[6] However, such emission is not caused by lead itself. In molybdates the lu-
minescence properties arc not caused by the metal ion M2+ (M2+MoO4 where M2+ = Ca,
Sr, Cd, Zn, Ba, Pb etc). Here, defect centers of MoO4 2- 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.
[7] 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, DiBarlolo, B., Ed. Plenum Press,
New York, 1980, 287). Under 250 nm excitation PbWO shows blue emission and

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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).
[8] 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 level1
S . After exciting the lowest excited configuration is 3d94s. This configuration has two
terms, 3D and lD. The next higher configuration, 3d94p, gives 6 terms 3P°, 3F°, 3D°, 1F°,
1D° and 1P0. 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 3
D or 1D state of the 3d94s configuration to the ground state.
[9] The ground state of bivalent copper has 3d -configuration. That is the level D . In
the bivalent copper, one of the d-clcctrons 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 P°, where emission can occur.
[10] 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 ap-
plications.
[11] 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).
[12] 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.
[13] 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

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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.
[14] 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.
[15] 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.
[16] 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 arc necessary.
[17] 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.
[18] 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

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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.
[19] 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.
Disclosure of Invention
Technical Problem
[20] 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.
[21 ] 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.
[22J 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 CR1 up to over 90 in LED.
Technical Solution
[23] To achieve these and other objects, as embodied and broadly described herein, 1
uminesccnt materials for ultraviolet light or visible light excitation comprises lead and/
or copper doped chemical compounds containing a rare earth clement or other lu-
minescent ions.
[24] The luminescent materials may be composed of one or more compounds of
aluminate, silicate, antimonate, germanale/or germanate-silicate, and phosphate.
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[38J 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.
[39] 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 la.
Best Mode
[40] Hereinafter, the present invention will be described in detail.
[41] Example 1;
[42] Luminescent materials for ultraviolet light or visible light excitation comprise lead
and/or copper doped aluminates according to the formula as follows:
[43] a(M'O)-b(M"2O)-c(M"X)-dAl2 O3 •e(M""O).f(M""2 O3 )g(M"""0 Op) h(M"""x Oy )
(l)
[44] 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, J, 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.
[45] a(M'O)-b(M" 2O).c(M"X)4-a-b
[46] -c(M'"O).7(Al2 O3 ).d(B2 O3) .e(Ga2 O3 ).f(SiO2).g(GeO2 ).h(M"" O ) (2)
[47] wherein M1 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

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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≤l;0≤e≤l;0≤f≤l;0≤g≤l;0≤h≤2; 1 ≤ x ≤ 2; and 1 ≤ y ≤ 5.
[48] The preparation of copper as well as lead doped luminescent materials may be a
basic solid stale 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.
[49] Examples of preparation:
[50] Preparation of the luminescent material having formula (3)
[51] Cu0.02 Sr3.98 Al14 O25 :Eu (3)

[52] Starting materials: CuO, SrCO3 Al(OH)3, Eu2 O3 , and/or any combination thereof.
[53] 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., H BO .
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
l,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.
[54] Table 1: copper doped Eu 2+ -activated aluminate compared with Eu 2+-activated
aluminatc without copper at about 400 nm excitation wavelength
Copper doped compound Compound without copper
Cu0.02 Sr3.98 Al14 O25 :Eu103.1 Sr4Al14 O25 :Eu100
Luminous density (%)
Wavelength (nm) 494 493
[55]
[56] Preparation of the luminescent material having formula (4)
[57] Pb0.05 Sr3.95 Al14 O25 : Eu (4)
[58] Starting materials: PbO, SrCO3 , Al2 O3 , Eu O3 , and/or any combination thereof.
[59] 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 l,450°C in air for about 2
hours and in a reduced atmosphere for about 2 hours may be followed. Then the

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material may be milled, washed, dried, and sieved. The resulting luminescent material
may have an emission maximum of from about 494.5 nm.
[60] Table 2: lead doped Eu 2+-activaled aluminale compared with Eu 2+-activated
aluminate without lead at about 400 nm excitation wavelength
[611

Lead doped compound Compound without lead
Pb0.05 Sr3.95 Al14 O25 :Eu Sr4 Al14 O25 :Eu
Luminous density (%) 101.4 100
Wavelength (nm) 494.5 493
[62] Table 3: optical properties of some copper and/or lead doped aluminales excitable
by long wave ultraviolet and/or by visible light and their luminous density in % at 400
nm excitation wavelength
[63]

Composition Possible Luminous density Peak wave Peak wave
excitation at 400 nm length of lead/ length of
range(nm) excitation copper doped materials
compared with materials (nm) without lead/
copper/lead not copper (nm)
doped compounds
(%)
Cu0.5 Sr3.5 Al14 O25 : 360 - 430 101.2 495 493
Eu
Cu0.02 Sr3.98 Al14 O25 : Eu 360 - 430 103.1 494 493
Pb0.05 Sr3.95 Al14 O25 : Eu 360 - 430 101.4 494.5 493
Cu0.01 Sr3.99 Al13.995 Si O0.005 :Eu25 360-430 103 494 492
Cu0.01 Sr3.395 Ba0.595 Al 14O25 :Eu,Dy 360 - 430 100.8 494 493
Pb0.05 Sr3.95 Al13.95 Ga 0.05O25 :Eu 360 - 430 101.5 494 494
[64] Example 2:
[65] Luminescent materials for ultraviolet light or visible light excitation comprise lead

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and/or copper doped aluminates according to the formula as follows:
[66] a(M'O) • b(M"O) • c(Al2 O3 ) • d(M'"2O3 ) • e(M""O2 ) • f (M""" xOy ) (5)
[67] 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, Gc, Ti, Zr, Hf, and/or any combination
thereof; M""' may be Bi, Sn, Sb, Sc, Y, La, Cc, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,
Er, Tm, Yb, Lu, and/or any combination thereof; 0≤a≤l;0≤b≤2;0≤c≤8;0≤d
≤ 1; 0 ≤ c ≤ 1; 0 ≤ f ≤ 2; 1 ≤ x ≤ 2; and 1 ≤ y ≤ 5.
[68] The luminous peak and density of Example 2 are described in Table 7, which will
be shown below.
[69] Example of preparation:
[70] Preparation of the luminescent material having formula (6)
[71] Cu0.05 Sr0.95 Al1.9997 Si0.0003 O4 : Eu (6)
[72] Starting materials: CuO, SrCO3 , Al2 O3 , SiO2 , Eu2 O3 , and/or any combination
thereof.
[73] The starting materials in the form of, for example, pure oxides and/or as carbonates
may be mixed in stoichiomctric proportions together with small amounts of flux, for
example, A1F3 . The mixture may be fired in an alumina crucible at about l,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.
[74] Table 4: copper doped Eu 2+-activated aluminale compared with Eu2+-activated
aluminate without copper at about 400 nm excitation wavelength
[75]

Copper doped compound Compound without copper
Cu0.05 Sr0.95 Al1.9997 Si0.0003 O 4 : Eu SrAl2 O4 :Eu
Luminous density (%) 106 100
Wavelength (nm) 521.5 519
[76] Preparation of the luminescent material having formula (7)
[77] Cu0.12 BaMg1.88 Al16 O27 : Eu (7)
[78] Starting materials: CuO, MgO, BaCO3 , Al(OH)3 Eu2 O3 , and/or any combination
thereof.
[79] The starling 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, A1F . The mixture may be fired in an alumina crucible at about

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l,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.
[80] Table 5: copper doped Eu 2+-activatcd aluminate compared with copper not doped
Eu +-activated aluminate at 400 nm excitation wavelength
[81]

Copper doped compound Comparison without copper
Cu0.12 BaMg1.88 Al16 O27 : Eu BaMg2Al16 O27 :Eu
Luminous density (%) 101 100
Wavelength (nm) 452 450
[82] Preparation of the luminescent material having formula (8)
[83] Pb0.1 Sr 0.9 A12O4 : Eu (8)
[84] Starting materials: PbO, SrCO , Al(OH)3, Eu2 O3 , and/or any combination thereof.
[85] The starling materials in form of, for example, pure oxides, hydroxides, and/or
carbonates may be mixed in stochiomctric proportions together with small amounts of
flux, for example , H BO . 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 l,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 he milled, washed, dried
and sieved. The resulting luminescent material may have an emission maximum of
about 521 nm.
[86] Table 6: lead doped Eu2+-activated aluminate compared with Eu2+-activated
aluminate without lead at about 400 nm excitation wavelength
[87]

Lead doped compound Compound without lead
Pb0.1 Sr0.9 A12O4 :Eu SrAl2O4 :Eu
Luminous density (%) 102 100
Wavelength (nm) 521 519
[88] Results obtained in regard to copper and/or lead doped aluminates are shown in
table 7.
[89] 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
[90]

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[91] Example 3:
[92] Luminescent materials for ultraviolet light or visible light excitation comprise lead
and/or copper doped silicates according to the formula as follows:
[93] a(M'O).b(M"O)-c(M"'X).d(M"' 2O).e(M"" 0Op).g(SiO2).h(M"""xOy)

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(9)
[94] 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, Cc, Pr, Nd, Pm, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; X may be F, Cl, Br, J,
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.
[95] The superior luminous density of Example 3 can be seen below.
[96] Example of preparation:
[97] Preparation of the luminescent material having formula (10)
[98] Cu0.05 Sr1.7 Ca0.25 SiO4 : Eu (10)
[99] Starting materials: CuO, SrCO3 CaCO3 , SiO2 , Eu2 O3 , and/or any combination
thereof.
[100] The starting materials in the form of pure oxides and/or carbonates may be mixed
in stoichiometric proportions together with small amounts of flux, for example, NH Cl.
The mixture may be fired in an alumina crucible at about l,200°C in an inert gas
atmosphere (e.g., N 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 l,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.
[101] Table 8: copper doped Eu2+-activated silicate compared with Eu2+-activated silicate
without copper at about 400 nm excitation wavelength
Copper doped compound Compound without copper
Cu0.05 Sr1.7 Ca0.25 SiO4 : Eu Sr1.7 Ca0.3 SiO4 : Eu
Luminous density (%) 104 100
Wavelength (nm) 592 588
[102]
[ 103 ] Preparation of the luminescent material having formula (11):
[104] Cu0.2 Ba2 Zn0.2 Mg0.6 Si2 O7 : Eu (11)
[105] Starting materials: CuO, BaCO3 , ZnO, MgO, SiO2 , Eu2 O3 , and/or any combination
thereof.
[106] 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,

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NH4 Cl. In a first step the mixture may be fired in an alumina crucible at about l,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.
[107] Table 9: copper doped Eu2+-activated silicate compared with Eu2+-activatcd silicate
without copper at 400 nm excitation wavelength
[108]

Copper doped compound Compound without copper
Cu0.2 Sr2Zn0.2 Mg0.6 Si2 O7 : Eu Sr2 Zn2 Mg0.6 Si2 O7 : Eu
Luminous density (%) 101.5 100
Wavelength (nm) 467 465
[109] Preparation of the luminescent material having formula (12)
[110] Pb0.1 Ba0.95 Sr0.95 Si0.998 Gc0.002 O4 : Eu (12)
[111] Starting materials: PbO, SrCO3 , BaCO3 SiO2 , GeO2 Eu2 O3 , and/or any combination
thereof
[112] The starting materials in the form of oxides and/or carbonates may be mixed in sto-
ichiornetric proportions together with small amounts of flux, for example. NH Cl. 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 l,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.
[113] Table 10: lead doped Eu2+-activated silicate compared with Eu2+-activated silicate
without lead at about 400 nm excitation wavelength
[114]

Lead doped compound Compound without lead
Pb0.1 Ba0.95 Sr0.95 Si0.998 Gc0.002 O4 :Eu BaSrSiO4 : Eu
Luminous density (%) 101.3 100
Wavelength (nm) 527 525
[115] Preparation of the luminescent material having formula (13)
[116] Pb0.25 Sr3.75 Si3O8Cl4 : Eu (13)

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[117] Starling materials : PbO, SrCO , SrCl SiO , Eu O , and any combination thereof.
[118] 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 l,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.
[119] Table 11: lead doped Eu2+-activated chlorosilicate compared with Eu2+-activated
chlorosilicate without lead at 400 nm excitation wavelength
[120]

Lead doped compound Compound without lead
Pb0.25 Sr3.75 Si3O8Cl4 : Eu Sr4 Si3O8Cl4 :Eu
Luminous density (%) 100.6 100
Wavelength (nm) 492 490
[121] Results obtained with respect to copper and/or lead doped silicates arc shown in
table 12.
[ 122] 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
[123]

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[124] Example 4:
[125] Luminescent materials for ultraviolet light or visible light excitation comprise lead
and/or copper doped antimonates according to the formula as follows:
[126] a(M'O) • b(M"2 O) • c(M"X) • d(Sb2 O5 ) • e(M'"0) • f(M"" xOy ) (14)
[127] 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"1 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, J, and/or any
combination thereof; 0≤a≤2;0≤b≤2;0≤c≤4;0≤d≤8;0≤e≤8;0≤f≤2;l
≤ x ≤ 2; and 1 ≤ y ≤ 5.
[128] Examples of preparation:
[ 129] Preparation of the luminescent material having formula (15)
[130] Cu0.2 Mg1.7 Li0.2 Sb2O7 : Mn (15)
[131] Starting materials: CuO, MgO, Li2 O, Sb2O5 , MnCO3 , and/or any combination
thereof.
[132] The starting materials in the form of oxides may be mixed in stoichiometric

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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 l,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.
[133] Table 13: copper doped antimonate compared with antimonatc without copper at
about 400 nm excitation wavelength
[134]

Copper doped compound Comparison without copper
Cu0.2 Mg1.7 Li0.2 Sb2O7 :Mn Mg2Li0.2 Sb2O7 :Mn
Luminous density (%) 101.8 100
Wavelength (nm) 652 650
[135] Preparation of the luminescent material having formula (16)
[136] Pb0.006 Ca0.6 Sr0.394 Sb2 O6 (16)
[137] Starting materials: PbO, CaCO3 , SrCO3 Sb2 O5 , and/or any combination thereof.
[138] The starling materials in the form of oxides and/or carbonates may be mixed in sto-
ichiometric 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.
[139] Table 14: lead doped antimonate compared with antimonate without lead at 400 nm
excitation wavelength
[140]

Lead doped compound Compound without lead
Pb0.006 Ca0.6 Sr0.394 Sb2 O6 Ca0.6 Sr0.4 Sb2O6
Luminous density (%) 102 100
Wavelength (nm) 637 638
[141] Results obtained in respect to copper and/or lead doped antimonates are shown in
table 15.
[142] Table 15: optical properties of some copper and/or lead doped antimonates

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excitable by long wave ultraviolet and/or by visible light and their luminous density in
% at about 400 nm excitation wavelength
[143]

[144] Example 5:
[145] 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:
[146] a(M'O).b(M"2 O).c(M"X)-dGcO2 •c(M""O)-f(M"""2 O3 ).g(M""" 0Op )-h(M"""xOy
(17)
[147] 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

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Copper doped compound Compound without copper
Cu0.02 Ca4.98 (PO4 )3 Cl: Eu Ca5 (PO4 )3 Cl: Eu
Luminous density (%) 101.5 100
Wavelength (nm) 450 447
[175] 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
[176]

[177] 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

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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

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Claims
[1] 1. A luminescent material for ultraviolet light or visible light excitation,
comprising:
lead and/or copper doped chemical compounds containing a rare earth element
and/or other luminescent ions.
[2] 2. The luminescent material according to claim 1, wherein the compounds
include lead and/or copper doped aluminate type compounds, lead and/or copper
doped silicates, lead and/or copper doped antimonatcs, lead and/or copper doped
germanates, lead and/or copper doped germanate-silicates, lead and/or copper
doped phosphates, or any combination thereof.
[3] 3. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (1)
a(M'O)-b(M"2 O)-c(M"X)-dAl2 O3 .c(M"'O)-f(M"" 2O3 )-g(M""" 0Op ).h(M"""" xOy )
(1)
wherein
M' is Pb, Cu, or any combination thereof;
M' is one or more monovalent elements, Li, Na, K, Rb, Cs, Au, Ag or any
combination thereof;
M'" is one or more divalent elements, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn or any
combination thereof;
M"""" is one or mure divalent elements, Sc, B, Ga, In, and/or any combination
thereof;
M'"" is Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or any combination thereof;
M""" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu, or any combination thereof;
X is F, Cl, Br, J, or any combination thereof;
0 0 ≤ b ≤ 2;
0 ≤ c ≤ 2;
0≤d≤8;
0 ≤ c ≤ 4;
0≤f≤3;
0≤g≤8;
0≤h≤2;
l≤o≤2;
1≤P≤5;
1 ≤ x ≤ 2; and

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1 ≤ y ≤ 5.
[4] 4. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (2)
a(M'O) b(M" 2O).c(M"X)4-a-b
-c(M'"O)-7(Al2O3)-d(B2O 3)-e(Ga203)-f(Si02)-g(Ge0 2)-h(M"" xOy ) (2)
wherein
M' is Pb, Cu, or any combination thereof;
M" is one or more monovalent elements, Li, Na, K, Rb, Cs, Au, Ag, and/or any
combination thereof;
M'" is one or more divalent elements, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or
any combination thereof;
M"" is 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 is F, Cl, Br, J, and any combination thereof;
0 ≤ a ≤ 4;
0 ≤ b 2
0≤c ≤2;
0≤d≤ 1;
0≤c≤ 1;
0≤f≤ 1;
0≤g≤l;
0≤h≤2;
1 ≤ x ≤ 2; and
1 ≤ y ≤ 5.
[5] 5. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (5)
a(M'O) • b(M"O) • C(A12O3) • d(M"'2 O3 ) • e(M""O2) • f (M"""xOy ) (5)
wherein
M' is Pb, Cu, or any combination thereof;
M" is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof;
M'" is B, Ga, In, or any combination thereof;
M"" is Si, Ge, Ti, Zr, Hf, or any combination thereof;
M'"" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Yb, Lu, or any combination thereof;
0≤a≤ 1;
0 ≤ b ≤ 2;
0≤c≤8;
0≤d≤l;

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0≤e ≤ 1;
0≤f≤2;
1 ≤ x ≤ 2; and
1 ≤y≤5.
[6] 6. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (9)
a(M'O).b(M"O)c(M"'X).d(M"' O)c(M""2O3 )-f(M"""0Op).g(SiO2 )• h(M""" xOy )
(9)
wherein
M' is Pb, Cu, or any combination thereof;
M" is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof;
M'" is Li, Na, K, Rb, Cs, Au, Ag, or any combination thereof;
M"" is Al, Ga, In, or any combination thereof;
M'"" is Ge, V, Nb, Ta, W, Mo, Ti, Zr, Hf, or any combination thereof;
M""" is Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu, or any combination thereof;
X is F, Cl, Br, J, 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.
[7] 7. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (14)
a(M'O) • b(M"2 O) • c(M"X) • d(Sb2 O5 ) • e(M'"O) • f(M""xOy ) (14)
wherein
M' is Pb, Cu, or any combination thereof;
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, Cl, Br, J, or any combination thereof;

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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.
[8] 8. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (17)
a(M'O)-b(M"2 O)-c(M"X)-dGcO2 e(M""O)-f(M""2 O3).g(M""' 0Op )-h(M""" xOy
(17)
wherein
M' is Pb, Cu, or any combination thereof;
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, Cl, Br, J, 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;
l≤o≤2;
1≤P≤5;
1 ≤ x ≤ 2; and
1 ≤y ≤ 5.
[9] 9. The luminescent material according to claim 1, wherein the compounds
include a compound having formula (20)
a(M'O)-b(M" 2O).c(M"X)-dP205-c(M"'0)-f(M"" 203)g( M"""O2)-h(M xOy )
(20)
wherein
M' is Pb, Cu, or any combination thereof,

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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. Al, 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, Cl, Br, J, or any combination thereof,
0≤a≤2;
0≤b≤12;
0≤c≤ 16;
0≤d≤3;
0≤c≤5;
0≤f≤3;
0≤g≤2;
0 ≤ h ≤ 2;
1 ≤x ≤ 2; and
l [10] 10. The luminescent material according to any one of claims 1 to 9, wherein said
compound converts primary long-wave ultraviolet in the range of 300-400nm
and/or blue radiation in the range of 380-500nm 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.
[11] 11. The luminescent material according to any one of claims 1 to 9, wherein the
luminescent material is 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.

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 band's 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.

Documents:

02467-kolnp-2007-abstract.pdf

02467-kolnp-2007-assignment.pdf

02467-kolnp-2007-claims.pdf

02467-kolnp-2007-correspondence others 1.1.pdf

02467-kolnp-2007-correspondence others-1.2.pdf

02467-kolnp-2007-correspondence others.pdf

02467-kolnp-2007-description complete.pdf

02467-kolnp-2007-form 1.pdf

02467-kolnp-2007-form 18.pdf

02467-kolnp-2007-form 3-1.1.pdf

02467-kolnp-2007-form 3.pdf

02467-kolnp-2007-form 5.pdf

02467-kolnp-2007-gpa.pdf

02467-kolnp-2007-international publication.pdf

02467-kolnp-2007-international search report.pdf

02467-kolnp-2007-pct request form.pdf

2467-KOLNP-2007-(06-12-2013)-CORRESPONDENCE.pdf

2467-KOLNP-2007-(06-12-2013)-FORM-3.pdf

2467-KOLNP-2007-(10-12-2013)-CORRESPONDENCE.pdf

2467-KOLNP-2007-ABSTRACT.pdf

2467-KOLNP-2007-AMENDED CLAIMS.pdf

2467-KOLNP-2007-CANCELLED PAGES.pdf

2467-kolnp-2007-correspondence 1.1.pdf

2467-kolnp-2007-correspondence 1.2.pdf

2467-KOLNP-2007-DESCRIPTION (COMPLETE).pdf

2467-KOLNP-2007-FORM 1.pdf

2467-KOLNP-2007-FORM 2.pdf

2467-KOLNP-2007-PCT PRIORITY DOCUMENT NOTIFICATION.pdf

2467-KOLNP-2007-PETITION UNDER RULE 137.pdf

2467-KOLNP-2007-REPLY TO EXAMINATION REPORT-1.1.pdf

2467-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

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Patent Number

263347

Indian Patent Application Number

2467/KOLNP/2007

PG Journal Number

43/2014

Publication Date

24-Oct-2014

Grant Date

21-Oct-2014

Date of Filing

03-Jul-2007

Name of Patentee

ROTH, GUNDULA

Applicant Address

DORFSTRASSE 13 A, 17498, LEVENHAGEN

Inventors:

#	Inventor's Name	Inventor's Address
1	ROTH, GUNDULA	DORFSTRASSE 13A, 17498, LEVENHAGEN
2	LEE, CHUNG HOON	28-2, SOHA-DONG, GWANGMYEONG-SI, GYEONGGI-DO, 423-821
3	TEWS, WALTER	FLEISCHMANNSTRASSE 1C, 17489, GREIFSWALD

PCT International Classification Number

C09K 11/77

PCT International Application Number

PCT/KR2005/002333

PCT International Filing date

2005-07-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	04106880.0	2004-12-22	EUROPEAN UNION