Abstract:
A light emitting device can be characterized as including a light emitting diode configured to emit light and a phosphor configured to change a wavelength of the light. The phosphor substantially covers at least a portion of the light emitting diode. The phosphor includes a compound having a host material. Divalent copper ions and oxygen are components of the host material.

Description:
RELATED APPLICATIONS 
     This application is a continuation of application Ser. No. 11/024,702, filed on Dec. 30, 2004, now pending. This application also claims priority of Korean Patent Application No. 2004-042396, filed on Jun. 10, 2004, the contents of which are incorporated herein by reference in their entirety. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to light emitting devices and more particularly to light emitting devices including at least one light-emitting diode and phosphor, the phosphor including lead and/or copper doped chemical compounds and converting the wavelength of light. 
     BACKGROUND OF THE INVENTION 
     Light emitting devices (LEDs), which used to be used for electronic devices, are now used for automobiles and illumination products. Since light emitting devices have superior electrical and mechanical characteristics, demands for light emitting devices have been increased. In connection to this, interests in white LEDs are increasing as an alternative to fluorescent lamps and incandescent lamps. 
     In LED technology, solution for realization of white light is proposed variously. Normally, realization of white LED technology is to put the phosphor on the light-emitting diode, and mix the primary emission from the light emitting diode and the secondary emission from the phosphor, which converts the wavelength. For example, as shown in WO 98/05078 and WO 98/12757, use a blue light emitting diode, which is capable of emitting a peak wavelength at 450-490 nm, and YAG group material, which absorbs light from the blue light emitting diode and emits yellowish light (mostly), which may have different wavelength from that of the absorbed light 
     However, in such a usual white LED, color temperature range is narrow which is between about 6,000-8,000K, and CRI (Color Rendering Index) is about 60 to 75. Therefore, it is hard to produce the white LED with color coordination and color temperature that are similar to those of the visible light. It is one of the reasons why only white light color with a cold feeling could be realized. Moreover, phosphors which are used for white LEDs are usually unstable in the water, vapor or polar solvent, and this unstableness may cause changes in the emitting characteristics of white LED. 
     A light emitting device can be characterized as including a light emitting diode configured to emit light and a phosphor configured to change a wavelength of the light. The phosphor includes a compound having a host material. Divalent copper ions and oxygen are components of the host material. 
    
    
     
       DESCRIPTION OF THE DRAWINGS 
       Further aspects of the invention may be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which: 
         FIG. 1  shows a side cross-sectional view of an illustrative embodiment of a portion of a chip-type package light emitting device consistent with this invention; 
         FIG. 2  shows a side cross-sectional view of an illustrative embodiment of a portion of a top-type package light emitting device consistent with this invention; 
         FIG. 3  shows a side cross-sectional view of an illustrative embodiment of a portion of a lamp-type package light emitting device consistent with this invention; 
         FIG. 4  shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power consistent with this invention; 
         FIG. 5  shows a side cross-sectional view of another illustrative embodiment of a portion of a light emitting device for high power consistent with this invention; 
         FIG. 6  shows emitting spectrum of a light emitting device with luminescent material consistent with this invention; and 
         FIG. 7  shows emitting spectrum of the light emitting device with luminescent material according to another embodiment of the invention. 
     
    
    
     DETAILED DESCRIPTION 
     Refer to the attached drawing, the wavelength conversion light emitting device is going to be explained in detail, and the light emitting device and the phosphor are separately explained for easiness of explanation as below. 
     (Light Emitting Device) 
       FIG. 1  shows a side cross-sectional view of an illustrative embodiment of a portion of a chip-type package light emitting device consistent with this invention. The chip-type package light emitting device may comprise at least one light emitting diode and a phosphorescent substance. Electrodes  5  may be formed on both sides of substrate  1 . Light emitting diode  6  emitting light may be mounted on one of the electrodes  5 . Light emitting diode  6  may be mounted on electrode  5  through electrically conductive paste  9 . An electrode of light emitting diode  6  may be connected to electrode pattern  5  via an electrically conductive wire  2 . 
     Light emitting diodes may emit light with a wide range of wavelengths, for example, from ultraviolet light to visible light. In one embodiment consistent with this invention, a UV light emitting diode and/or blue light emitting diode may be use. 
     Phosphor, i.e., a phosphorescent substance,  3  may be placed on the top and side faces of the light emitting diode  6 . The phosphor in consistent with this invention may include lead and/or copper doped aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof. Phosphor  3  converts the wavelength of the light from the light emitting diode  6  to another wavelength or other wavelengths. In one embodiment consistent with this invention, the light is in a visible light range after the conversion. Phosphor  3  may be applied to light emitting diode  6  after mixing phosphor  3  with a hardening resin. The hardening resin including phosphor  3  may also be applied to the bottom of light emitting diode  6  after mixing phosphor  3  with electrically conductive paste  9 . 
     The light emitting diode  6  mounted on substrate  1  may be sealed with one or more sealing materials  10 . Phosphor  3  may be placed on the top and side faces of light emitting diode  6 . Phosphor  3  can also be distributed in the hardened sealing material during the production. Such a manufacturing method is described in U.S. Pat. No. 6,482,664, which is hereby incorporated by reference in its entirety. 
     Phosphor  3  may comprise lead and/or copper doped chemical compound(s). Phosphor  3  may include one or more single chemical compounds. The single compound may have an emission peak of, for example, from about 440 nm to about 500 nm, from about 500 nm to about 590 nm, or from about 580 nm to 700 nm. Phosphor  3  may include one or more single phosphors, which may have an emission peak as exemplified above. 
     In regard to light emitting device  40 , light emitting diode  6  may emit primary light when light emitting diode  6  receives power from a power supply. The primary light then may stimulate phosphor(s)  3 , and phosphor(s)  3  may convert the primary light to a light with longer wavelength(s) (a secondary light). The primary light from the light emitting diode  6  and the secondary light from the phosphors  3  are diffused and mixed together so that a predetermined color of light in visible spectrum may be emitted from light emitting diode  6 . In one embodiment consistent with this invention, more than one light emitting diodes that have different emission peaks can be mounted together. Moreover, if the mixture ratio of phosphors is adjusted properly, specific color of light, color temperature, and CRI can be provided. 
     As described above, if the light emitting diode  6  and the compound included in phosphor  3  are properly controlled then desired color temperature or specific color coordination can be provided, especially, wide range of color temperature, for example, from about 2,000K to about 8,000K or about 10,000K and/or color rendering index of greater than about 90. Therefore, the light emitting devices consistent with this invention may be used for electronic devices such as home appliances, stereos, telecommunication devices, and for interior/exterior custom displays. The light emitting devices consistent with this invention may also be used for automobiles and illumination products because they provide similar color temperatures and CRI to those of the visible light. 
       FIG. 2  shows a side cross-sectional view of an illustrative embodiment of a portion of a top-type package light emitting device consistent with this invention. A top-type package light emitting device consistent with this invention may have a similar structure as that of the chip type package light emitting device  40  of  FIG. 1 . The top-type package device may have reflector  31  which may reflect the light from the light emitting diode  6  to the desire direction. 
     In top-type package light emitting device  50 , more than one light emitting diodes can be mounted. Each of such light emitting diodes may have a different peak wavelength from that of others. Phosphor  3  may comprise a plurality of single compounds with different emission peak. The proportion of each of such plurality of compounds may be regulated. Such a phosphor may be applied to the light emitting diode and/or uniformly distributed in the hardening material of the reflector  31 . As explained more fully below, the phosphor in consistent with this invention may include lead and/or copper doped aluminate type compounds, lead and/or copper doped silicates, lead and/or copper doped antimonates, lead and/or copper doped germanates, lead and/or copper doped germanate-silicates, lead and/or copper doped phosphates, or any combination thereof. 
     In one embodiment consistent with this invention, the light emitting device of the  FIG. 1  or  FIG. 2  can include a metal substrate, which may have good heat conductivity. Such a light emitting device may easily dissipate the heat from the light emitting diode. Therefore, light emitting devices for high power may be manufactured. If a heat sink is provided beneath the metal substrate, the heat from the light emitting diode may be dissipated more effectively. 
       FIG. 3  shows a side cross-sectional view of an illustrative embodiment of a portion of a lamp-type package light emitting device consistent with this invention. Lamp type light emitting device  60  may have a pair of leads  51 ,  52 , and a diode holder  53  may be formed at the end of one lead. Diode holder  53  may have a shape of cup, and one or more light emitting diodes  6  may provided in the diode holder  53 . When a number of light emitting diodes are provided in the diode holder  53 , each of them may have a different peak wavelength from that of others. An electrode of light emitting diode  6  may be connected to lead  52  by, for example, electrically conductive wire  2 . 
     Regular volume of phosphor  3 , which may be mixed in the epoxy resin, may be provided in diode holder  53 . As explained more fully below, phosphor  3  may include lead and/or copper doped components. 
     Moreover, the diode holder may include the light emitting diode  6  and the phosphor  3  may be sealed with hardening material such as epoxy resin or silicon resin. 
     In one embodiment consistent with this invention, the lamp type package light emitting device may have more than one pair of electrode pair leads. 
       FIG. 4  shows a side cross-sectional view of an illustrative embodiment of a portion of a light emitting device for high power consistent with this invention. Heat sink  71  may be provided inside of housing  73  of the light emitting device for high power  70 , and it may be partially exposed to outside. A pair of lead frame  74  may protrude from housing  73 . 
     One or more light emitting diodes may be mounted one lead frame  74 , and an electrode of the light emitting diode  6  and another lead frame  74  may be connected via electrically conductive wire. Electrically conductive plate  9  may be provided between light emitting diode  6  and lead frame  74 . The phosphor  3  may be placed on top and side faces of light emitting diode  6 . 
       FIG. 5  shows a side cross-sectional view of another illustrative embodiment of a portion of a light emitting device for high power consistent with this invention. 
     Light emitting device for high power  80  may have housing  63 , which may contain light emitting diodes  6 ,  7 , phosphor  3  arranged on the top and side faces of light emitting diodes  6 ,  7 , one or more heat sinks  61 ,  62 , and one or more lead frames  64 . The lead frames  64  may receive power from a power supplier and may protrude from housing  63 . 
     In the light emitting devices for high power  70 ,  80  in the  FIGS. 4 and 5 , the phosphor  3  can be added to the paste, which may be provided between heat sink and light emitting devices. A lens may be combined with housing  63 ,  73 . 
     In a light emitting device for high power consistent with this invention, one or more light emitting diodes can be used selectively and the phosphor can be regulated depending on the light emitting diode. As explained more fully below, the phosphor may include lead and/or copper doped components. 
     A light emitting device for high power consistent with this invention may have a radiator (not shown) and/or heat sink(s). Air or a fan may be used to cool the radiator. 
     The light emitting devices consistent with this invention is not limited to the structures described above, and the structures can be modified depending on the characteristics of light emitting diodes, phosphor, wavelength of light, and also applications. Moreover, new part can be added to the structures. 
     An exemplary phosphor consistent with this invention is as follows. 
     (Phosphor) 
     Phosphor in consistence with this invention may include lead and/or copper doped chemical compounds. The phosphor may be excited by UV and/or visible light, for example, blue light. The compound may include Aluminate, Silicate, Antimonate, Germanate, Germanate-silicate, or Phosphate type compounds. 
     Aluminate type compounds may comprise compounds having formula (1), (2), and/or (5)
 
 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 )  (1)
 
     wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be one or more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be one or more divalent elements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may be one or more trivalent elements, for example, Sc, B, Ga, In, and/or any combination thereof; M′″″ may be Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, and/or any combination thereof; M″″″ may be Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or any combination thereof; X may be F, Cl, Br, 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. 
     The preparation of copper as well as lead doped luminescent materials may be a basic solid state reaction. Pure starting materials without any impurities, e.g. iron, may be used. Any starting material which may transfer into oxides via a heating process may be used to form oxygen dominated phosphors. 
     Examples of Preparation: 
     Preparation of the luminescent material having formula (3)
 
Cu 0.02 Sr 3.98 Al 14 O 25 :Eu  (3)
 
     Starting materials: CuO, SrCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in the form of oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, e.g., 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 
               
             
          
           
               
                   
                   
                 Compound 
               
               
                   
                 Copper doped 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 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (4)
 
Pb 0.5 Sr 3.95 Al 14 O 25 :Eu  (4)
 
     Starting materials: PbO, SrCO 3 , Al 2 O 3 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in form of very pure oxides, carbonates, or other components which may decompose thermically into oxides, may be mixed in stoichiometric proportion together with small amounts of flux, for example, 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 
               
               
                   
               
             
          
         
       
     
                                                                 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                       400 nm excitation   Peak wave               compared with   length of   Peak wave length           Possible   copper/lead not   lead/copper   of materials           excitation   doped compounds   doped   without       Composition   range (nm)   (%)   materials (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                      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&lt;c≦8; 0≦d≦1; 0≦e≦1; 0&lt;f≦2; 1≦x≦2; and and 1≦y≦5. 
     Example of Preparation: 
     Preparation of the luminescent material having formula (6)
 
Cu 0.05 Sr 0.95 Al 1.9997 Si 0.0003 O 4 :Eu  (6)
 
     Starting materials: CuO, SrCO 3 , Al 2 O 3 , SiO 2 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in the form of, for example, pure oxides and/or as carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
             
          
           
               
                   
                   
                 Compound 
               
               
                   
                 Copper doped 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 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (7)
 
Cu 0.12 BaMg 1.88 Al 16 O 27 :Eu  (7)
 
     Starting materials: CuO, MgO, BaCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in the form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
             
          
           
               
                   
                   
                 Comparison 
               
               
                   
                 Copper doped 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 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (8)
 
Pb 0.1 Sr 0.9 Al 2 O 4 :Eu  (8)
 
     Starting materials: PbO, SrCO 3 , Al(OH) 3 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in form of, for example, pure oxides, hydroxides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
               
                   
               
             
          
         
       
     
     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 
                   
               
               
                   
                   
                 400 nm excitation 
                 length of 
               
               
                   
                 Possible 
                 compared with 
                 lead/copper 
               
               
                   
                 excitation 
                 copper/lead not 
                 doped 
                 Peak wave length 
               
               
                   
                 range 
                 doped compounds 
                 materials 
                 of materials without 
               
               
                 Composition 
                 (nm) 
                 (%) 
                 (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, 
                 360-400 
                 100.5 
                 451, 515 
                 450, 515 
               
               
                 Mn 
               
               
                 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 
               
               
                   
               
             
          
         
       
     
     A lead and/or copper doped silicates having formula (9)
 
 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&lt;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. 
     Example of Preparation: 
     Preparation of the luminescent material having formula (10)
 
Cu 0.05 Sr 1.7 Ca 0.25 SiO 4 :Eu  (10)
 
     Starting materials: CuO, SrCO 3 , CaCO 3 , SiO 2 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in the form of pure oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
               
                   
               
             
          
         
       
     
     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)
 
     Starting materials: CuO, BaCO 3 , ZnO, MgO, SiO 2 , Eu 2 O 3 , and/or any combination thereof. 
     The starting materials in the form of very pure oxides and carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
               
                 silicatewithout 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 
                 101.5 
                 100 
               
               
                 density (%) 
               
               
                 Wavelength (nm) 
                 467 
                 465 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (12)
 
Pb 0.1 Ba 0.95 Sr 0.95 Si 0.998 Ge 0.002 O 4 :Eu  (12)
 
     Starting materials: PbO, SrCO 3 , BaCO 3 , SiO 2 , GeO 2 , Eu 2 O 3 , and/or any combination thereof 
     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
                 101.3 
                 100 
               
               
                 density (%) 
               
               
                 Wavelength (nm) 
                 527 
                 525 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (13)
 
Pb 0.25 Sr 3.75 Si 3 O 8 Cl 4 :Eu  (13)
 
     Starting materials: PbO, SrCO 3 , SrCl 2 , SiO 2 , Eu 2 O 3 , and any combination thereof. 
     The starting materials in the form of oxides, chlorides, and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
             
          
           
               
                   
                   
                 Compound 
               
               
                   
                 Lead doped 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 
               
               
                   
               
             
          
         
       
     
     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 
               
             
          
           
               
                   
                   
                   
                   
                 Peak wave 
               
               
                   
                   
                 Luminous density at 
                 Peak wave 
                 length of 
               
               
                   
                 Possible 
                 400 nm excitation 
                 length of 
                 materials 
               
               
                   
                 excitation 
                 compared with 
                 lead/copper 
                 without 
               
               
                   
                 range 
                 copper/lead not doped 
                 doped materials 
                 lead/copper 
               
               
                 Composition 
                 (nm) 
                 compounds (%) 
                 (nm) 
                 (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, 
                 360-430 
                 103 
                 438, 670 
                 435, 670 
               
               
                 Mn 
               
               
                 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 
               
               
                   
               
             
          
         
       
     
     With lead and/or copper doped antimonates having formula (14)
 
 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&lt;d≦8; 0≦e≦8; 0≦f≦2; 1≦x≦2; and 1≦y≦5. 
     Examples of Preparation: 
     Preparation of the luminescent material having formula (15)
 
Cu 0.2 Mg 1.7 Li 0.2 Sb 2 O 7 :Mn  (15)
 
     Starting materials: CuO, MgO, Li 2 O, Sb 2 O 5 , MnCO 3 , and/or any combination thereof. 
     The starting materials in the form of oxides may be mixed in stoichiometric proportion together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 985° C. in the air for about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,200° C. in an atmosphere containing oxygen for about 8 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 626 nm. 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 copper doped antimonate compared with antimonate without copper at 
               
               
                 about 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                 Comparison 
               
               
                   
                 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 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (16)
 
Pb 0.006 Ca 0.6 Sr 0.394 Sb 2 O 6   (16)
 
     Starting materials: PbO, CaCO 3 , SrCO 3 , Sb 2 O 5 , and/or any combination thereof 
     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux. In a first step the mixture may be fired in an alumina crucible at about 975° C. in the air for about 2 hours. After pre-firing the material may be milled again. In a second step the mixture may be fired in an alumina crucible at about 1,175° C. in the air for about 4 hours and then in an oxygen-containing atmosphere for about 4 hours. After that the material may be milled, washed, dried and sieved. The resulting luminescent material may have an emission maximum at about 637 nm. 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 14 
               
             
             
               
                   
               
               
                 lead doped antimonate compared with antimonate without lead at 
               
               
                 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                 Compound 
               
               
                   
                 Lead doped compound 
                 without lead 
               
               
                   
                 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 
               
               
                   
               
             
          
         
       
     
     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 
                 Peak wave 
                 length of 
               
               
                   
                 Possible 
                 compared with 
                 length of 
                 materials 
               
               
                   
                 excitation 
                 copper/lead not 
                 lead/copper 
                 without 
               
               
                   
                 range 
                 doped compounds 
                 doped 
                 lead/copper 
               
               
                 Composition 
                 (nm) 
                 (%) 
                 materials (nm) 
                 (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 
               
               
                   
               
             
          
         
       
     
     Lead and/or copper doped germanates and/or a germanate-silicates having formula (17)
 
 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. 
     Example of Preparation: 
     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)
 
     Starting materials: PbO, CaCO 3 , ZnO, GeO 2 , SiO 2 , MnCO 3 , and/or any combination thereof, 
     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
               
                   
               
             
          
         
       
     
     Preparation of the luminescent material having formula (19)
 
Cu 0.46 Sr 0.54 Ge 0.6 Si 0.4 O 3 :Mn  (19)
 
     Starting materials: CuO, SrCO 3 , GeO 2 , SiO 2 , MnCO 3 , and/or any combination thereof 
     The starting materials in the form of oxides and/or carbonates may be mixed in stoichiometric proportions together with small amounts of flux, for example, 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 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 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 
               
               
                   
                   
                 400 nm excitation 
                 length of 
                 length of 
               
               
                   
                 Possible 
                 compared with 
                 lead/copper 
                 materials 
               
               
                   
                 excitation 
                 copper/lead not 
                 doped 
                 without 
               
               
                   
                 range 
                 doped compounds 
                 materials 
                 lead/copper 
               
               
                 Composition 
                 (nm) 
                 (%) 
                 (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 
               
               
                   
               
             
          
         
       
     
     Lead and/or copper doped phosphates having formula (20)
 
 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. 
     Examples of Preparation: 
     Preparation of the luminescent material having formula (21)
 
Cu 0.02 Ca 4.98 (PO 4 ) 3 Cl:Eu  (21)
 
     Starting materials: CuO, CaCO 3 , Ca 3 (PO 4 ) 2 , CaCl 2 , Eu 2 O 3 , and/or any combination thereof, 
     The starting materials in the form of oxides, phosphates, and/or carbonates and chlorides may be mixed in stoichiometric proportions together with small amounts of flux. The mixture may be fired in an alumina crucible at about 1,240° C. in reducing atmosphere for about 2 hours. After that the material may be milled, washed, dried and sieved. The luminescent material may have an emission maximum at about 450 nm. 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 19 
               
             
             
               
                   
               
               
                 copper doped Eu 2+ -activated chlorophosphate compared  
               
               
                 with Eu 2+ -activated chlorophosphate without copper at about  
               
               
                 400 nm excitation wavelength 
               
             
          
           
               
                   
                 Copper doped compound 
                 Compound without copper 
               
               
                   
                 Cu 0.02 Ca 4.98 (PO 4 ) 3 Cl:Eu 
                 Ca 5 (PO 4 ) 3 Cl:Eu 
               
               
                   
                   
               
             
          
           
               
                 Luminous 
                 101.5 
                 100 
               
               
                 density (%) 
               
               
                 Wavelength (nm) 
                 450 
                 447 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 20 
               
             
             
               
                   
               
               
                 copper and/or lead doped phosphates excitable by long wave ultraviolet and/or 
               
               
                 by visible light and their luminous density in % at about 400 nm excitation wavelength 
               
             
          
           
               
                   
                   
                   
                   
                 Peak wave 
               
               
                   
                   
                 Luminous density at 
                 Peak wave 
                 length of 
               
               
                   
                   
                 400 nm excitation 
                 length of 
                 materials 
               
               
                   
                 Possible 
                 compared with 
                 lead/copper 
                 without 
               
               
                   
                 excitation 
                 copper/lead not doped 
                 doped materials 
                 lead/copper 
               
               
                 Composition 
                 range (nm) 
                 compounds (%) 
                 (nm) 
                 (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, 
                 360-400 
                 102 
                 638 
                 635 
               
               
                 Mn 
               
               
                 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 
               
               
                   
               
             
          
         
       
     
     Meanwhile, the phosphor of the light emitting device consistent with this invention can comprise aluminate, silicate, antimonate, germanate, phosphate type chemical compound, and any combination thereof. 
       FIG. 6  is a one of the embodiment&#39;s emission spectrum according to the invention, which the phosphor is used for the light emitting device. The embodiment may have a light emitting diode with 405 nm wavelength and the phosphor, which is mixture of the selected multiple chemical compounds in proper ratio. The phosphor may be composed of Cu 0.05 BaMg 1.95 Al 16 O 27 :Eu which may have peak wavelength at about 451 nm, Cu 0.03 Sr 1.5 Ca 0.47 SiO 4 :Eu which may have peak wavelength at 586 nm, Pb 0.006 Ca 0.6 Sr 0.394 Sb 2 O 6 :Mn 4+  which may have peak wavelength at about 637 nm, Pb 0.15 Ba 1.84 Zn 0.01  Si 0.99 Zr 0.01 O 4 :Eu which may have peak wavelength at around 512 nm, and Cu 0.2 Sr 3.8 Al 14 O 25 :Eu which may have peak wavelength at about 494 nm. 
     In such an embodiment, part of the initial about 405 nm wavelength emission light from the light emitting diode is absorbed by the phosphor, and it is converted to longer 2 nd  wavelength. The 1 st  and 2 nd  light is mixed together and the desire emission is produced. As the shown  FIG. 6 , the light emitting device convert the 1 st  UV light of 405 nm wavelength to wide spectral range of visible light, that is, white light, and at this time the color temperature is about 3,000K and CRI is about 90 to about 95. 
       FIG. 7  is another embodiment&#39;s emission spectrum according to the invention, which the phosphor is applied for the light emitting device. The embodiment may have a light emitting diode with about 455 nm wavelength and the phosphor, which is mixture of the selected multiple chemical compounds in proper ratio. 
     The phosphor is composed of Cu 0.05 Sr 1.7 Ca 0.25 SiO 4 :Eu which may have peak wavelength at about 592 nm, Pb 0.1 Ba 0.95 Sr 0.95 Si 0.998 Ge 0.002 O 4 :Eu which may have peak wavelength at about 527 nm, and Cu 0.05 Li 0.002 Sr 1.5 Ba 0.448 SiO 4 :Gd, Eu which may have peak wavelength at about 557 nm. 
     In such an embodiment, part of the initial about 455 nm wavelength emission light from the light emitting diode is absorbed by the phosphor, and it is converted to longer 2 nd  wavelength. The 1 st  and 2 nd  light is mixed together and the desire emission is produced. As the shown  FIG. 7 , the light emitting device convert the 1 st  blue light of about 455 nm wavelength to wide spectral range of visible light, that is, white light, and at this time the color temperature is about 4,000K to about 6,500K and CRI is about 86 to about 93. 
     The phosphor of the light emitting device according to the invention can be applied by single chemical compound or mixture of plurality of single chemical compound besides the embodiments in relation to  FIG. 6  and  FIG. 7 , which are explained above. 
     According to the description above, light emitting device with wide range of color temperature about 2,000K or about 8,000K or about 10,000K and superior color rendering index more than about 90 can be realized by using the lead and/or copper doped chemical compounds containing rare earth elements. 
     In such a wavelength conversion light emitting device is capable of applying on mobile phone, note book and electronic devices such as home appliance, stereo, telecommunication products, but also for custom display&#39;s key pad and back light application. Moreover, it can be applied for automobile, medical instrument and illumination products. 
     According to the invention, it is also able to provide a wavelength conversion light emitting device with stability against water, humidity, vapor as well as other polar solvents. 
     In the foregoing described embodiments, various features are grouped together in a single embodiment for purposes of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description of Embodiments, with each claim standing on its own as a separate preferred embodiment of the invention.