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

Description:
BACKGROUND OF THE INVENTION  
       [0001]     1. Field of the Invention  
         [0002]     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.  
         [0003]     2. Description of the Related Art  
         [0004]     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 Pb 2+ .  
         [0005]     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.  
         [0006]     Lead has in the ground state  1 S 0  two outer electrons. The electron configuration of the ground state is d 10 s 2 , so that the lowest excited state has d 10 sp configuration. The excited sp configuration has four levels,  3 P 0 ,  3 P 1 ,  3 P 2  and  1 P 1 , which can be achieved between 165.57 nm ( 3 P 0 ) and 104.88 nm ( 1 P 1 ) in the free ion. Transitions between  1 S 0  and  2 P 1  excited level are allowed by all selection rules. While transitions between  1 S 0  and  3 P 0  are only allowed with the lowest symmetry, transitions between  1 S 0  and  3 P 1  as well as  3 P 2  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.  
         [0007]     Otherwise, luminescent materials are known having lead as a host lattice component. Molybdate phosphors containing MoO 4   2−  centers are described in Bernhardt, H. J., Phys. Stat. Sol. (a), 91, 643, 1985. PbMoO 4  shows at room temperature red emission with an emission maximum at 620 nm under photoexcitation at 360 nm.  
         [0008]     However, such emission is not caused by lead itself. In molybdates the luminescence properties are not caused by the metal ion M 2+  (M 2+ MoO 4  where M 2+ =Ca, Sr, Cd, Zn, Ba, Pb etc). Here, defect centers of MoO 4   2−  ions coupled to O 2− -ion vacancies seem to be the reason. Nevertheless, the Pb 2+ -ion influences the preferred emission properties because it stabilizes the host lattice.  
         [0009]     As a familiar example, tungstates (Ca,Pb)WO 4  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 PbWO 4  shows blue emission and under 313 nm excitation PbWO 4  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).  
         [0010]     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 3d 10 . That is the level  1 S 0 . After exciting the lowest excited configuration is 3d 9 4s. This configuration has two terms,  3 D and  1 D. The next higher configuration, 3d 9 4p, gives 6 terms  3 P°,  3 F°,  3 D°,  1 F°,  1 D° and  1 P°. The transitions between the ground state  1 S 0  and the  1 D or  3 D 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  1 D state of the 3d 9 4s configuration to the ground state.  
         [0011]     The ground state of bivalent copper has 3d 9 -configuration. That is the level  2 D 5/2 . In the bivalent copper, one of the d-electrons can be excited to the 4s or 4p orbital. The lowest exciting configuration is the 3d 8 4s with two quartet terms  4 F,  4 P and four doublet terms,  2 F,  2 D,  2 P and  2 G without emission caused by forbidden transitions. The higher exciting configuration is the 3d 8 4p-configuration with four terms  4 D°,  4 G°,  4 F°, and  4 P°, where emission can occur.  
         [0012]     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.  
         [0013]     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).  
         [0014]     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.  
         [0015]     The influence of lead and copper ions as host lattice component in oxygen dominated compounds, activated by rare earth ions such as Eu 2+ , Ce 3+  and others, has not been yet described. It should to be expected that the incorporation of lead and/or copper as a host lattice component influences the preferred luminescent-optical properties regarding improved luminescent intensity as well as desirable shifting of emission maxima, color points, and shape of emission spectra and stabilizing of the lattice.  
         [0016]     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.  
         [0017]     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.  
         [0018]     Lead ions having an ionic radius of 119 pm can substitute the alkaline earth ions Ca having an ionic radius of 100 pm and Sr having an ionic radius of 118 pm very easily. The electro negativity of lead with 1.55 is much higher than that of Ca (1.04) and Sr (0.99). The preparation of substances containing lead is complicated due to the possibility of an oxidation of these ions in reducing atmospheres. For the preparation of lead doped compounds, which need reducing atmosphere, special preparation processes are necessary.  
         [0019]     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.  
         [0020]     A similar effect shows the substitution of copper for alkaline earth ions. Here, an additional influence is effective. Due to the higher ionic potential of copper as a quotient of ionic charge and ionic radius compared to the bigger alkaline earth ions, the copper ions can attract the neighboring oxygen ions stronger than the alkaline earth ions. So the substitution of the bigger alkaline earth ions Ca, Sr and Ba by copper leads to a stronger crystal field in the surrounding of the activator ions, too. Thus, the shape of emission bands can be influenced, the shifting of the emission peak to longer wavelength is connected in a broadening of the emission curves for band emission. In addition, it should be possible to increase the intensity of emission by substitution of ions copper and lead. Generally, the shifts of emission peaks to longer as well as to shorter wavelength are desirable in the field of LED lighting. Here, it is necessary to realize a fine tuning to get a special wavelength for desired color points as well as for better brightness of optical devices. By using cations, copper and lead, such a fine tuning should be possible.  
         [0021]     It is known that some luminescent materials and phosphors are unstable in water, air humidity, water steam or polar solvents. For instance, aluminates with spinell structure or silicates with orthorhomcic as well as akermanite structures show more or less high sensitivity to water, air humidity, water steam or polar solvents due to high basicity. However, due to a higher covalency and a lower basicity, the incorporation of lead and or copper in a host lattice should improve this behavior of luminescent materials against water, air humidity and polar solvents if substituted for cations having a high basicity.  
       SUMMARY OF THE INVENTION  
       [0022]     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.  
         [0023]     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.  
         [0024]     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 up to over 90 in LED.  
         [0025]     To achieve these and other objects, as embodied and broadly described herein, luminescent materials for ultraviolet light or visible light excitation comprises lead and/or copper doped chemical compounds containing a rare earth element or other luminescent ions.  
         [0026]     The luminescent materials may be composed of one or more compounds of aluminate, silicate, antimonate, germanate/or germanate-silicate, and phosphate.  
         [0027]     The aluminate is expressed as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d Al 2 O 3   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″ o O p ). h (M″″″ x O y ) 
 
 a (M′O). b (M″ 2 O). c (M″X).4 −a−b−c (M′″O).7(Al 2 O 3 ). d (B 2 O 3 ). e (Ga 2 O 3 ). f (SiO 2 ). g (GeO 2 ). h (M″″ x O y ) and 
 
 a (M′O). b (M″O). c (Al 2 O 3 ). d (M′″ 2 O 3 ). e (M″″O 2 ). f (M′″″ x O y ) 
 
         [0028]     The silicate is expressed as follows: 
 
 a (M′O). b (M″O). c (M′″X). d (M′″O 2 ). e (M″″ 2 O 3 ). f (M′″″ o O p ). g (SiO 2 ). h (M″″″ x O y ) 
 
         [0029]     The antimonate is expressed as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d (Sb 2 O 5 ). e (M′″O). f (M″″ x O y ) 
 
         [0030]     The germanate/or germanate-silicate is expressed as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d GeO 2   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″ o O p ). h (M″″″ x O y ) 
 
         [0031]     The phosphate is expressed as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d P 2 O 5   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″O 2 ). h (M″″″ x O y ) 
 
         [0032]     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&gt;90.  
         [0033]     Furthermore, the luminescent materials may be used in LED as a single compound and/or a mixture of a plurality of single compounds for realizing white light with a color rendering up to Ia. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT  
       [0034]     Hereinafter, the present invention will be described in detail.  
       EXAMPLE 1  
       [0035]     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″ 2 O). c (M″X). d Al 2 O 3   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″ o O p ). h (M″″″ x O y ) 
        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&lt;a≦2; 0≦b≦2; 0≦c≦2; 0≦d≦8; 0&lt;e≦4; 0≦f≦3; 0≦g≦8; 0&lt;h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5. 
 
 a (M′O). b (M″ 2 O). c (M″X).4 −a−b−c (M′″O).7(Al 2 O 3 ). d (B 2 O 3 ). e (Ga 2 O 3 ). f (SiO 2 ). g (GeO 2 ). h (M″″ x O y )  (2) 
    wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be one or more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be one or more divalent elements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may be Bi, Sn, Sb, Sc, Y, La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and any combination thereof; X may be F; Cl, Br, J, and any combination thereof; 0&lt;a≦4; 0≦b≦2; 0≦c≦2; 0≦d≦1; 0≦e≦1; 0≦f≦1; 0≦g≦1; 0&lt;h≦2; 1≦x≦2; and 1≦y≦5.        
 
         [0038]     The preparation of copper as well as lead doped luminescent materials may be a basic solid state reaction. Pure starting materials without any impurities, e.g. iron, may be used. Any starting material which may transfer into oxides via a heating process may be used to form oxygen dominated phosphors.  
         [0039]     Examples of Preparation:  
         [0040]     Preparation of the luminescent material having formula (3) 
 
Cu 0.02 Sr 3.98 Al 14 O 25 :Eu  (3) 
 
         [0041]     Starting materials: CuO, SrCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof.  
         [0042]     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 3 BO 3 . The mixture may be fired in an alumina crucible in a first step at about 1,200° C. for about one hour. After milling the pre-fired materials a second firing step at about 1,450° C. in a reduced atmosphere for about 4 hours may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 494 nm.  
                                               TABLE 1                           copper doped Eu 2+ -activated aluminate compared with Eu 2+ -activated       aluminate without copper at about 400 nm excitation wavelength                Copper doped   Compound           compound   without copper           Cu 0.02 Sr 3.98 Al 14 O 25 :Eu   Sr 4 Al 14 O 25 :Eu                            Luminous density (%)   103.1   100           Wavelength (nm)   494   493                      
 
         [0043]     Preparation of the luminescent material having formula (4) 
 
Pb 0.05 Sr 3.95 Al 14 O 25 :Eu  (4) 
 
         [0044]     Starting materials: PbO, SrCO 3 , Al 2 O 3 , Eu 2 O 3 , and/or any combination thereof.  
         [0045]     The starting materials in form of very pure oxides, carbonates, or other components which may decompose thermically into oxides, may be mixed in stoichiometric proportion together with small amounts of flux, for example, H 3 BO 3 . The mixture may be fired in an alumina crucible at about 1,200° C. for about one hour in the air. After milling the pre-fired materials a second firing step at about 1,450° C. in air for about 2 hours and in a reduced atmosphere for about 2 hours may be followed. Then the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum of from about 494.5 nm.  
                                               TABLE 2                           lead doped Eu 2+ -activated aluminate compared with Eu 2+ -activated       aluminate without lead at about 400 nm excitation wavelength                Lead doped   Compound           compound   without lead           Pb 0.05 Sr 3.95 Al 14 O 25 :Eu   Sr 4 Al 14 O 25 :Eu                            Luminous density (%)   101.4   100           Wavelength (nm)   494.5   493                      
 
         [0046]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                   
               
               
                 optical properties of some copper and/or lead doped aluminates excitable by long wave ultraviolet  
               
               
                 and/or by visible light and their luminous density in % at 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                 Luminous density at 
                 Peak wave 
                   
               
               
                   
                 Possible 
                 400 nm excitation 
                 length of 
               
               
                   
                 excitation 
                 compared with 
                 lead/copper 
                 Peak wave length of 
               
               
                   
                 range 
                 copper/lead not doped 
                 doped materials 
                 materials without 
               
               
                 Composition 
                 (nm) 
                 compounds (%) 
                 (nm) 
                 lead/copper (nm) 
               
               
                   
               
             
          
           
               
                 Cu 0.5 Sr 3.5 Al 14 O 25 :Eu 
                 360-430 
                 101.2 
                 495 
                 493 
               
               
                 Cu 0.02 Sr 3.98 Al 14 O 25 :Eu 
                 360-430 
                 103.1 
                 494 
                 493 
               
               
                 Pb 0.05 Sr 3.95 Al 14 O 25 :Eu 
                 360-430 
                 101.4 
                 494.5 
                 493 
               
               
                 Cu 0.01 Sr 3.99 Al 13.995 Si 0.005 O 25 :Eu 
                 360-430 
                 103 
                 494 
                 492 
               
               
                 Cu 0.01 Sr 3.395 Ba 0.595 Al 14 O 25 :Eu, 
                 360-430 
                 100.8 
                 494 
                 493 
               
               
                 Dy 
               
               
                 Pb 0.05 Sr 3.95 Al 13.95 Ga 0.05 O 25 :Eu 
                 360-430 
                 101.5 
                 494 
                 494 
               
               
                   
               
             
          
         
       
     
       EXAMPLE 2  
       [0047]     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 (Al 2 O 3 ). d (M′″ 2 O 3 ). e (M″″O 2 ). f (M′″″ x O y )  (5) 
        wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M′″ may be B, Ga, In, and/or any combination thereof; M″″ may be Si, Ge, Ti, Zr, Hf, and/or any 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&lt;a≦1; 0≦b≦2; 0≦c≦8; 0≦d≦1; 0≦e≦1; 0&lt;f≦2; 1≦x≦2; and 1≦y≦5.        
 
         [0049]     The luminous peak and density of Example 2 are described in Table 7, which will be shown below.  
         [0050]     Example of Preparation:  
         [0051]     Preparation of the luminescent material having formula (6) 
 
Cu 0.05 Sr 0.95 Al 1.9997 Si 0.0003 O 4 :Eu  (6) 
 
         [0052]     Starting materials: CuO, SrCO 3 , Al 2 O 3 , SiO 2 , Eu 2 O 3 , and/or any combination thereof.  
         [0053]     The starting materials in the form of, for example, pure oxides and/or as carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, AlF 3 . The mixture may be fired in an alumina crucible at about 1,250° C. in a reduced atmosphere for about 3 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 521.5 nm.  
                                           TABLE 4                           copper doped Eu 2+ -activated aluminate compared with Eu 2+ -activated       aluminate without copper at about 400 nm excitation wavelength                Copper doped   Compound           compound   without copper           Cu 0.05 Sr 0.95 Al 1.9997 Si 0.0003 O 4 :Eu   SrAl 2 O 4 :Eu                        Luminous density (%)   106   100       Wavelength (nm)   521.5   519                  
 
         [0054]     Preparation of the luminescent material having formula (7) 
 
Cu 0.12 BaMg 1.88 Al 16 O 27 :Eu  (7) 
 
         [0055]     Starting materials: CuO, MgO, BaCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof.  
         [0056]     The starting materials in the form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, AlF 3 . The mixture may be fired in an alumina crucible at about 1,420° C. in a reduced atmosphere for about 2 hours. After that the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum of about 452 nm.  
                                           TABLE 5                           copper doped Eu 2+ -activated aluminate compared with copper not doped       Eu 2+ -activated aluminate at 400 nm excitation wavelength                Copper doped   Comparison           compound   without copper           Cu 0.12 BaMg 1.88 Al 16 O 27 :Eu   BaMg 2 Al 16 O 27 :Eu                        Luminous density (%)   101   100       Wavelength (nm)   452   450                  
 
         [0057]     Preparation of the luminescent material having formula (8) 
 
Pb 0.1 Sr 0.9 Al 2 O 4 :Eu  (8) 
 
         [0058]     Starting materials: PbO, SrCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof.  
         [0059]     The starting materials in form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stochiometric proportions together with small amounts of flux, for example, H 3 BO 3 . The mixture may be fired in an alumina crucible at about 1,000° C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,420° C. in the air for about 1 hour and in a reduced atmosphere for about 2 hours may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum of about 521 nm.  
                                           TABLE 6                           lead doped Eu 2+ -activated aluminate compared with Eu 2+ -activated       aluminate without lead at about 400 nm excitation wavelength                Lead doped compound   Compound without lead           Pb 0.1 Sr 0.9 Al 2 O 4 :Eu   SrAl 2 O 4 :Eu                        Luminous density (%)   102   100       Wavelength (nm)   521   519                  
 
         [0060]     Results obtained in regard to copper and/or lead doped aluminates are shown in table 7.  
                                                           TABLE 7                           optical properties of some copper and/or lead doped aluminates excitable by       long wave ultraviolet and/or by visible light and their luminous density in % at 400 nm       excitation wavelength                    Luminous density at   Peak wave               Possible   400 nm excitation   length of           excitation   compared with   lead/copper   Peak wave length of           range   copper/lead not doped   doped   materials without       Composition   (nm)   compounds (%)   materials (nm)   lead/copper (nm)                    Cu 0.05 Sr 0.95 Al 1.9997 Si 0.0003 O 4 :Eu   360-440   106   521.5   519       Cu 0.2 Mg 0.7995 Li 0.0005 Al 1.9 Ga 0.1 O 4 :Eu,   360-440   101.2   482   480       Dy       Pb 0.1 Sr 0.9 Al 2 O 4 :Eu   360-440   102   521   519       Cu 0.05 BaMg 1.95 Al 16 O 27 :Eu, Mn   360-400   100.5   451, 515   450, 515       Cu 0.12 BaMg 1.88 Al 16 O 27 :Eu   360-400   101   452   450       Cu 0.01 BaMg 0.99 Al 10 O 17 :Eu   360-400   102.5   451   449       Pb 0.1 BaMg 0.9 Al 9.5 Ga 0.5 O 17 :Eu,   360-400   100.8   448   450       Dy       Pb 0.08 Sr 0.902 Al 2 O 4 :Eu, Dy   360-440   102.4   521   519       Pb 0.2 Sr 0.8 Al 2 O 4 :Mn   360-440   100.8   658   655       Cu 0.06 Sr 0.94 Al 2 O 4 :Eu   360-440   102.3   521   519       Cu 0.05 Ba 0.94 Pb 0.06 Mg 0.95 Al 10 O 17 :Eu   360-440   100.4   451   449       Pb 0.3 Ba 0.7 Cu 0.1 Mg 1.9 Al 16 O 27 :Eu   360-400   100.8   452   450       Pb 0.3 Ba 0.7 Cu 0.1 Mg 1.9 Al 16 O 27 :Eu,   360-400   100.4   452, 515   450, 515       Mn                  
 
       EXAMPLE 3  
       [0061]     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′″ 2 O). e (M″″ 2 O 3 ). f (M′″″ o O p ). g (SiO 2 ). h (M″″″ x O y )  (9) 
        wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M′″ may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M″″ may be Al, Ga, In, and/or 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, J, and any combination thereof; 0&lt;a≦2; 0≦b≦8; 0≦c≦4; 0≦d≦2; 0≦e≦2; 0≦f≦2; 0≦g≦10; 0&lt;h≦5; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.        
 
         [0063]     The superior luminous density of Example 3 can be seen below.  
         [0064]     Example of Preparation:  
         [0065]     Preparation of the luminescent material having formula (10) 
 
Cu 0.05 Sr 1.7 Ca 0.25 SiO 4 :Eu  (10) 
 
         [0066]     Starting materials: CuO, SrCO 3 , CaCO 3 , SiO 2 , Eu 2 O 3 , and/or any combination thereof.  
         [0067]     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 4 Cl. The mixture may be fired in an alumina crucible at about 1,200° C. in an inert gas atmosphere (e.g., N 2  or noble gas) for about 2 hours. Then the material may be milled. After that, the material may be fired in an alumina crucible at about 1,200° C. in a slightly reduced atmosphere for about 2 hours. Then, the material may be milled, washed, dried, and sieved. The resulting luminescent material may have an emission maximum at about 592 nm.  
                                           TABLE 8                           copper doped Eu 2+ -activated silicate compared with Eu 2+ -activated       silicate without copper at about 400 nm excitation wavelength                    Compound           Copper doped compound   without copper           Cu 0.05 Sr 1.7 Ca 0.25 SiO 4 :Eu   Sr 1.7 Ca 0.3 SiO 4 :Eu                        Luminous density (%)   104   100       Wavelength (nm)   592   588                  
 
         [0068]     Preparation of the luminescent material having formula (11): 
 
Cu 0.2 Ba 2 Zn 0.2 Mg 0.6 Si 2 O 7 :Eu  (11) 
 
         [0069]     Starting materials: CuO, BaCO 3 , ZnO, MgO, SiO 2 , Eu 2 O 3 , and/or any combination thereof.  
         [0070]     The starting materials in the form of very pure oxides and carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH 4 Cl. In a first step the mixture may be fired in an alumina crucible at about 1,100° C. in a reduced atmosphere for about 2 hours. Then the material may be milled. After that the material may be fired in an alumina crucible at about 1,235° C. in a reduced atmosphere for about 2 hours. Then that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 467 nm.  
                                           TABLE 9                           copper doped Eu 2+ -activated silicate compared with Eu 2+ -activated       silicate without copper at 400 nm excitation wavelength                    Compound           Copper doped compound   without copper           Cu 0.2 Sr 2 Zn 0.2 Mg 0.6 Si 2 O 7 :Eu   Sr 2 Zn 2 Mg 0.6 Si 2 O 7 :Eu                    Luminous density   101.5   100       (%)       Wavelength (nm)   467   465                  
 
         [0071]     Preparation of the luminescent material having formula (12) 
 
Pb 0.1 BaO 0.95 Sr 0.95 Si 0.998 Ge 0.002 O 4 :Eu  (12) 
 
         [0072]     Starting materials: PbO, SrCO 3 , BaCO 3 , SiO 2 , GeO 2 , Eu 2 O 3 , and/or any combination thereof.  
         [0073]     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH 4 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 1,220° C. in air for 4 hours and in reducing atmosphere for 2 hours may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 527 nm.  
                                           TABLE 10                           lead doped Eu 2+ -activated silicate compared with Eu 2+ -activated       silicate without lead at about 400 nm excitation wavelength                    Compound           Lead doped compound   without lead           Pb 0.1 Ba 0.95 Sr 0.95 Si 0.998 Ge 0.002 O 4 :Eu   BaSrSiO 4 :Eu                    Luminous density   101.3   100       (%)       Wavelength (nm)   527   525                  
 
         [0074]     Preparation of the luminescent material having formula (13) 
 
Pb 0.25 Sr 3.75 Si 3 O 8 Cl 4 :Eu  (13) 
 
         [0075]     Starting materials: PbO, SrCO 3 , SrCl 2 , SiO 2 , Eu 2 O 3 , and any combination thereof.  
         [0076]     The starting materials in the form of oxides, chlorides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH 4 Cl. The mixture may be fired in an alumina crucible in a first step at about 1,100° C. for about 2 hours in the air. After milling the pre-fired materials a second firing step at about 1,220° C. in the air for about 4 hours and in a reduced atmosphere for about 1 hour may be followed. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 492 nm.  
                                           TABLE 11                           lead doped Eu 2+ -activated chlorosilicate compared with Eu 2+ -activated       chlorosilicate without lead at 400 nm excitation wavelength                Lead doped compound   Compound without lead           Pb 0.25 Sr 3.75 Si 3 O 8 Cl 4 :Eu   Sr 4 Si 3 O 8 Cl 4 :Eu                        Luminous density   100.6   100       (%)       Wavelength (nm)   492   490                  
 
         [0077]     Results obtained with respect to copper and/or lead doped silicates are shown in table 12.  
                                                           TABLE 12                           optical properties of some copper and/or lead doped rare earth activated silicates excitable by long wave       ultraviolet and/or by visible light and their luminous density in % at about 400 nm excitation wavelength                    Luminous density at                   Possible   400 nm excitation   Peak wave length   Peak wave length           excitation   compared with   of lead/copper   of materials           range   copper/lead not doped   doped materials   without       Composition   (nm)   compounds (%)   (nm)   lead/copper (nm)                    Pb 0.1 Ba 0.95 Sr 0.95 Si 0.998 Ge 0.002 O 4 :Eu   360-470   101.3   527   525       Cu 0.02 (Ba,Sr,Ca,Zn) 1.98 SiO 4 :Eu   360-500   108.2   565   560       Cu 0.05 Sr 1.7 Ca 0.25 SiO 4 :Eu   360-470   104   592   588       Cu 0.05 Li 0.002 Sr 1.5 Ba 0.448 SiO 4 :Gd,   360-470   102.5   557   555       Eu       Cu 0.2 Sr 2 Zn 0.2 Mg 0.6 Si 2 O 7 :Eu   360-450   101.5   467   465       Cu 0.02 Ba 2.8 Sr 0.2 Mg 0.98 Si 2 O 8 :Eu,   360-420   100.8   440, 660   438, 660       Mn       Pb 0.25 Sr 3.75 Si 3 O 8 Cl 4 :Eu   360-470   100.6   492   490       Cu 0.2 Ba 2.2 Sr 0.75 Pb 0.05 Zn 0.8 Si 2 O 8 :Eu   360-430   100.8   448   445       Cu 0.2 Ba 3 Mg 0.8 Si 1.99 Ge 0.01 O 8 :Eu   360-430   101   444   440       Cu 0.5 Zn 0.5 Ba 2 Ge 0.2 Si 1.8 O 7 :Eu   360-420   102.5   435   433       Cu 0.8 Mg 0.2 Ba 3 Si 2 O 8 :Eu, Mn   360-430   103   438, 670   435, 670       Pb 0.15 Ba 1.84 Zn 0.01 Si 0.99 Zr 0.01 O 4 :Eu   360-500   101   512   510       Cu 0.2 Ba 5 Ca 2.8 Si 4 O 16 :Eu   360-470   101.8   495   491                  
 
       EXAMPLE 4  
       [0078]     Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped antimonates according to the formula as follows: 
 
 a (M′O). b (M″ 2 O). c (M′X). d (Sb 2 O 5 ). e (M′″O). f (M″″ x O y )  (14) 
        wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may be Bi, Sn, Sc, Y, La, Pr, Sm, Eu, Tb, Dy, Gd, and/or any combination thereof; X may be F, Cl, Br, J, and/or any combination thereof; 0&lt;a≦2; 0≦b≦2; 0≦c≦4; 0≦d≦8; 0≦e≦8; 0≦f≦2; 1≦x≦2; and 1≦y≦5.        
 
         [0080]     Examples of Preparation:  
         [0081]     Preparation of the luminescent material having formula (15) 
 
Cu 0.2 Mg 1.7 Li 0.2 Sb 2 O 7 :Mn  (15) 
 
         [0082]     Starting materials: CuO, MgO, Li 2 O, Sb 2 O 5 , MnCO 3 , and/or any combination thereof.  
         [0083]     The starting materials in the form of oxides may be mixed in stoichiometric proportion together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 985° C. in the air for about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,200° C. in an atmosphere containing oxygen for about 8 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 626 nm.  
                                           TABLE 13                           copper doped antimonate compared with antimonate without copper at       about 400 nm excitation wavelength                    Comparison           Copper doped compound   without copper           Cu 0.2 Mg 1.7 Li 0.2 Sb 2 O 7 :Mn   Mg 2 Li 0.2 Sb 2 O 7 :Mn                        Luminous density (%)   101.8   100       Wavelength (nm)   652   650                  
 
         [0084]     Preparation of the luminescent material having formula (16) 
 
Pb 0.006 Ca 0.6 Sr 0.394 Sb 2 O 6   (16) 
 
         [0085]     Starting materials: PbO, CaCO 3 , SrCO 3 , Sb 2 O 5 , and/or any combination thereof.  
         [0086]     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 975° C. in the air for about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,175° C. in the air for about 4 hours and then in an oxygen-containing atmosphere for about 4 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 637 nm.  
                             TABLE 14                           lead doped antimonate compared with antimonate without lead at       400nm excitation wavelength                Lead doped compound   Compound without lead           Pb 0.006 Ca 0.6 Sr 0.394 Sb 2 O 6     Ca 0.6 Sr 0.4 Sb 2 O 6                 Luminous density   102   100       (%)       Wavelength (nm)   637   638                  
 
         [0087]     Results obtained in respect to copper and/or lead doped antimonates are shown in table 15.  
                                                           TABLE 15                           optical properties of some copper and/or lead doped antimonates excitable by long wave       ultraviolet and/or by visible light and their luminous density in % at about 400 nm       excitation wavelength                    Luminous density at   Peak wave                   400 nm excitation   length of   Peak wave length           Possible   compared with   lead/copper   of materials           excitation   copper/lead not doped   doped materials   without       Composition   range (nm)   compounds (%)   (nm)   lead/copper (nm)                    Pb 0.2 Mg 0.002 Ca 1.798 Sb 2 O 6 F 2 :Mn   360-400   102   645   649       Cu 0.15 Ca 1.845 Sr 0.005 Sb 1.998 Si 0.002 O 7 :Mn   360-400   101.5   660   658       Cu 0.2 Mg 1.7 Li 0.2 Sb 2 O 7 :Mn   360-400   101.8   652   650       Cu 0.2 Pb 0.01 Ca 0.79 Sb 1.98 Nb 0.02 O 6 :Mn   360-400   98.5   658   658       Cu 0.01 Ca 1.99 Sb 1.9995 V 0.0005 O 7 :Mn   360-400   100.5   660   657       Pb 0.006 Ca 0.6 Sr 0.394 Sb 2 O 6     360-400   102   637   638       Cu 0.02 Ca 0.9 Sr 0.5 Ba 0.4 Mg 0.18 Sb 2 O 7     360-400   102.5   649   645       Pb 0.198 Mg 0.004 Ca 1.798 Sb 2 O 6 F 2     360-400   101.8   628   630                  
 
       EXAMPLE 5  
       [0088]     Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped germanates and/or a germanate-silicates according to the formula as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d GeO 2   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″ o O p ). h (M″″″ x O y )  (17) 
        wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be, Mg, Ca, Sr, Ba, Zn, Cd, and/or any combination thereof; M″″ may be Sc, Y, B, Al, La, Ga, In, and/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, J, and/or any combination thereof; 0&lt;a≦2; 0≦b≦2; 0≦c≦10; 0&lt;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.        
 
         [0090]     Example of Preparation:  
         [0091]     Preparation of the luminescent material having formula (18) 
 
Pb 0.004 Ca 1.99 Zn 0.006 Ge 0.8 Si 0.2 O 4 :Mn  (18) 
 
         [0092]     Starting materials: PbO, CaCO 3 , ZnO, GeO 2 , SiO 2 , MnCO 3 , and/or any combination thereof,  
         [0093]     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH 4 Cl. In a first step the mixture may be fired in an alumina crucible at about 1,200° C. in an oxygen-containing atmosphere for about 2 hours. Then, the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,200° C. in oxygen containing atmosphere for about 2 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 655 nm.  
                                           TABLE 16                           lead doped Mn-activated germanate compared with Mn-activated germanate       without lead at about 400 nm excitation wavelength                Copper doped compound   Comparison without copper           Pb 0.004 Ca 1.99 Zn 0.006 Ge 0.8 Si 0.2 O 4 :Mn   Ca 1.99 Zn 0.01 Ge 0.8 Si 0.2 O 4 :Mn                        Luminous density (%)   101.5   100       Wavelength (nm)   655   657                  
 
         [0094]     Preparation of the luminescent material having formula (19) 
 
Cu 0.46 Sr 0.54 Ge 0.6 Si 0.4 O 3 :Mn  (19) 
 
         [0095]     Starting materials: CuO, SrCO 3 , GeO 2 , SiO 2 , MnCO 3 , and/or any combination thereof  
         [0096]     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, NH 4 Cl. In a first step the mixture may be fired in an alumina crucible at about 1,100° C. in an oxygen-containing atmosphere for about 2 hours. Then, the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,180° C. in an oxygen-containing atmosphere for about 4 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 658 nm.  
                                           TABLE 17                           copper doped Mn-activated germanate-silicate compared with Mn-       activated germanate-silicate without copper at 400 nm excitation       wavelength                    Compound           Copper doped compound   without copper           Cu 0.46 Sr 0.54 Ge 0.6 Si 0.4 O 3 :Mn   SrGe 0.6 Si 0.4 O 3 :Mn                        Luminous density (%)   103   100       Wavelength (nm)   658   655                  
 
         [0097]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 18 
               
             
             
               
                   
               
               
                   
               
               
                 optical properties of some copper and/or lead doped germanate-silicates excitable by long wave ultraviolet 
               
               
                 and/or by visible light and their luminous density in % at about 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                 Luminous density at 
                 Peak wave 
                 Peak wave 
               
               
                   
                 Possible 
                 400 nm excitation 
                 length of 
                 length of 
               
               
                   
                 excitation 
                 compared with 
                 lead/copper 
                 materials without 
               
               
                   
                 range 
                 copper/lead not doped 
                 doped 
                 lead/copper 
               
               
                 Composition 
                 (nm) 
                 compounds (%) 
                 materials (nm) 
                 (nm) 
               
               
                   
               
             
          
           
               
                 Pb 0.004 Ca 1.99  Zn 0.006 Ge 0.8 Si 0.2 O 4 :Mn 
                 360-400 
                 101.5 
                 655 
                 657 
               
               
                 Pb 0.002 Sr 0.954 Ca 1.044 Ge 0.93 Si 0.07 O 4 :Mn 
                 360-400 
                 101.5 
                 660 
                 661 
               
               
                 Cu 0.46 Sr 0.54 Ge 0.6 Si 0.4 O 3 :Mn 
                 360-400 
                 103 
                 658 
                 655 
               
               
                 Cu 0.002 Sr 0.998 Ba 0.99 Ca 0.01 Si 0.98 Ge 0.02 O 4 :Eu 
                 360-470 
                 102 
                 538 
                 533 
               
               
                 Cu 1.45 Mg 26.55 Ge 9.4 Si 0.6 O 48 :Mn 
                 360-400 
                 102 
                 660 
                 657 
               
               
                 Cu 1.2 Mg 26.8 Ge 8.9 Si 1.1 O 48 :Mn 
                 360-400 
                 103.8 
                 670 
                 656 
               
               
                 Cu 4 Mg 20 Zn 4 Ge 5 Si 2.5 O 38 F 10 :Mn 
                 360-400 
                 101.5 
                 658 
                 655 
               
               
                 Pb 0.001 Ba 0.849 Zn 0.05 Sr 1.1 Ge 0.04 Si 0.96 O 4 :Eu 
                 360-470 
                 101.8 
                 550 
                 545 
               
               
                 Cu 0.05 Mg 4.95 GeO 6 F 2 :Mn 
                 360-400 
                 100.5 
                 655 
                 653 
               
               
                 Cu 0.05 Mg 3.95 GeO 5.5 F:Mn 
                 360-400 
                 100.8 
                 657 
                 653 
               
               
                   
               
             
          
         
       
     
       EXAMPLE 6  
       [0098]     Luminescent materials for ultraviolet light or visible light excitation comprise lead and/or copper doped phosphates according to the formula as follows: 
 
 a (M′O). b (M″ 2 O). c (M″X). d P 2 O 5   .e (M′″O). f (M″″ 2 O 3 ). g (M′″″O 2 ). h (M″″″ x O y )  (20) 
        wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may be Sc, Y, B, Al, La, Ga, In, and/or any combination thereof, M′″″ may be Si, Ge, Ti, Zr, Hf; V, Nb, Ta, W, Mo, and/or any combination thereof; M″″″ may be Bi, Sn, Pr, Sm, Eu, Gd, Dy, Ce, Tb, and/or any combination thereof; X may be F, Cl, Br, J, and/or any combination thereof; 0&lt;a≦2; 0≦b≦12; 0≦c≦16; 0&lt;d≦3; 0≦e≦5; 0≦f≦3; 0≦g≦2; 0&lt;h≦2; 1≦x≦2; and 1≦y≦5.        
 
         [0100]     The luminescent materials comprising the lead and/or copper doped phosphates may be used as compounds for ultraviolet light in a light emitting device.  
         [0101]     Examples of Preparation:  
         [0102]     Preparation of the luminescent material having formula (21) 
 
Cu 0.02 Ca 4.98 (PO 4 ) 3 Cl:Eu  (21) 
 
         [0103]     Starting materials: CuO, CaCO 3 , Ca 3 (PO 4 ) 2 , CaCl 2 , Eu 2 O 3 , and/or any combination thereof,  
         [0104]     The starting materials in the form of oxides, phosphates, and/or carbonates and chlorides may be mixed in stoichiometric proportions together with small amounts of flux. The mixture may be fired in an alumina crucible at about 1,240° C. in reducing atmosphere for about 2 hours. After that the material may be milled, washed, dried and sieved. The luminescent material may have an emission maximum at about 450 nm.  
                                           TABLE 19                           copper doped Eu 2+ -activated chlorophosphate compared with Eu 2+ -       activated chlorophosphate without copper at about 400 nm excitation       wavelength                    Compound           Copper doped compound   without copper           Cu 0.02 Ca 4.98 (PO 4 ) 3 Cl:Eu   Ca 5 (PO 4 ) 3 Cl:Eu                        Luminous density (%)   101.5   100       Wavelength (nm)   450   447                  
 
         [0105]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 20 
               
             
             
               
                   
               
               
                   
               
               
                 copper and/or lead doped phosphates excitable by long wave ultraviolet and/or by visible light 
               
               
                 and their luminous density in % at about 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                 Luminous density at 400 nm 
                 Peak wave length 
                 Peak wave length 
               
               
                   
                 Possible 
                 excitation compared 
                 of lead/copper 
                 of materials 
               
               
                   
                 excitation 
                 with copper/lead not 
                 doped materials 
                 without 
               
               
                 Composition 
                 range (nm) 
                 doped compounds (%) 
                 (nm) 
                 lead/copper (nm) 
               
               
                   
               
             
          
           
               
                 Cu 0.02 Sr 4.98 (PO 4 ) 3 Cl:Eu 
                 360-410 
                 101.5 
                 450 
                 447 
               
               
                 Cu 0.2 Mg 0.8 BaP 2 O 7 :Eu, Mn 
                 360-400 
                 102 
                 638 
                 635 
               
               
                 Pb 0.5 Sr 1.5 P 1.84 B 0.16 O 6.84 :Eu 
                 360-400 
                 102 
                 425 
                 420 
               
               
                 Cu 0.5 Mg 0.5 Ba 2 (P,Si) 2 O 8 :Eu 
                 360-400 
                 101 
                 573 
                 570 
               
               
                 Cu 0.5 Sr 9.5 (P,B) 6 O 24 Cl 2 :Eu 
                 360-410 
                 102 
                 460 
                 456 
               
               
                 Cu 0.5 Ba 3 Sr 6.5 P 6 O 24 (F,Cl) 2 :Eu 
                 360-410 
                 102 
                 443 
                 442 
               
               
                 Cu 0.05 (Ca,Sr,Ba) 4.95 P 3 O 12 Cl:Eu, 
                 360-410 
                 101.5 
                 438, 641 
                 435, 640 
               
               
                 Mn 
               
               
                 Pb 0.1 Ba 2.9 P 2 O 8 :Eu 
                 360-400 
                 103 
                 421 
                 419 
               
               
                   
               
             
          
         
       
     
         [0106]     Lead and/or copper doped luminescent materials can be act as converter for light emitting devices, such as ultraviolet as well as blue emitting LEDs, back lights and painting pigments. They can convert the excitation wavelength from the ultraviolet and blue light to longer visible wavelength. For all color temperatures as well as for all color coordinates inside of the white light coordinates color mixture can be found. That is caused by the different emission colors corresponding to the RGB principle by using different kinds of luminescent materials