Abstract:
A rare earth ions doped luminescent silicate glass is provided having the general formula of: 45SiO 2 -aLi 2 O-bMO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :cEu 2 O 3 , wherein a is molar ratio of Li 2 O, b is molar ratio of MO and c is molar ratio of Eu 2 O 3 , wherein a+b=45, 25≦a≦35 and 0.025≦c≦0.50, and wherein MO is one or more of alkaline earth metal oxides. The luminescent glass can be prepared by simple progress, without pollution and at low cost. The resulting glass can be excited by UV LED chip and blue LED chip. Bright green light can be obtained by the sample under excitation of UV LED chip, while bright white light can be obtained under excitation of blue LED chip. The luminescent glass can be coupled with LED to obtain novel LED devices and provides potential applications in the field of semiconductor lighting.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application is a national phase entry under 35 U.S.C. §371 of International Application No. PCT/CN2013/073989 filed Apr. 10, 2013, which claims priority from Chinese Patent Application No. 201310069174.9 filed on Mar. 5, 2013. 
     FIELD OF THE INVENTION 
     The present invention relates to the field of white-light-emitting glass, and in particular, to a rare earth ions doped silicate luminescent glass and used for white-light-emitting diode (WLED), and the preparation method thereof. 
     BACKGROUND OF THE INVENTION 
     WLED is a novel solid state lighting source, which is efficient, energy saving and friendly to the environment. Therefore, it is expected to be the fourth-generation lighting source to provide “green lighting”. 
     Currently commercialized solutions for providing white light by WLED device comprise: “blue LED+yellow phosphor”, “blue LED+yellow+red phosphor” or “blue LED+green+red phosphor”. Although these phosphors provide high luminous efficiency, they have the following deficiencies: (a) poor thermal stability, which causes drift of white light; (b) easy aging of fluorescent paste formed by combination with epoxy resin. 
     Compared to phosphors, rare earth ions doped luminescent glasses provides many advantages in preparing WLED: (a) easy machining into various shapes and good plasticity; (b) good thermal conductivity and chemical stability; (c) simple processing, readily available materials and low cost; (d) ability to replace epoxy resin. Therefore, rare earth ions doped luminescent glasses provide high application value. 
     There have been many studies on luminescent glasses, but there are only a few of luminescent glasses which can actually be excited by blue LED chip (440˜480 nm). Chinese patent No. 101830638 A reported a Eu 2+  singly doped luminescent glass, which has an optimal excitation wavelength at 349 nm. Chinese patent No. 102701590 A reported a high silica luminescent glass, which has an optimal excitation wavelength extended to be 350˜390 nm. Chinese patent No. 101749642 A reported a luminescent glass excited by blue light, which has an optimal excitation wavelength extended to blue light region (about 440 nm) with the variation in the amount of B 2 O 3 . Recently, L.H.C. Andrade reported the excitation and emission spectra of 41.5Al 2 O 3 -47.4CaO-7SiO 2 -2.1MgO-2.0CeO 2  (wt. %) (Journal of Alloys and Compounds 510 (2012) 54-59), which has an optimal excitation wavelength at 405 nm. Zijun Liu reported the excitation and emission spectra of 27Al 2 O 3 -58CaO-8SiO 2 -7MgO-xEu 2 O 3  (mol %) (Appl Phys A (2012) 108:777-781), which has an optimal excitation wavelength extended to blue light region (about 440 nm). 
     In the above mentioned luminescent glasses, some of them have an excitation wavelength which can not be well matched with the emission band of blue LED chip, while the others still have low luminous efficiency. In conclusion, up to now there is no patent or other publications related to the series of luminescent glasses provided by the present invention. 
     SUMMARY OF THE INVENTION 
     The present invention focuses on the development of a novel series of luminescent glasses with high efficiency, which can be excited by blue LED chip. 
     A luminescent glass is provided by the present invention, wherein the general formula of chemical constitution of the luminescent glass is:
 
45SiO 2 - a Li 2 O- b MO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :cEu 2 O 3 ,
 
     wherein a is the molar ratio of Li 2 O, b is the molar ratio of MO, and c is the molar ratio of Eu 2 O 3 , wherein a+b=45 and 0.025≦c≦0.50, 
     and wherein MO is one or more of alkaline earth metal oxides. 
     Preferably, the molar ratio a is 25 to 35. 
     Preferably, the alkaline earth metal oxide is one or more of calcium oxide, strontium oxide and barium oxide. 
     A method for the preparation of the above mentioned luminescent glass is also provided, comprising the steps of: 
     S1: providing oxides or salts of respective elements according to the molar ratios in the general formula, followed by grinding and mixing; 
     S2: melting at high temperature under reducing atmosphere; 
     S3: pouring into a preheated mould, annealing, cooling, cutting and polishing. 
     Preferably, the salts in step S1 are carbonates or phosphates. 
     Preferably, the reducing atmosphere in step S2 is thermal-carbon, pure hydrogen or mixed gas of nitrogen and hydrogen. 
     Preferably, the high temperature in step S2 is 1450 to 1700° C. for 0.5 to 3 hours. 
     Preferably, the annealing in step S3 is carried out at 450 to 650° C. for 2 to 5 hours. 
     Compared to the luminescent glasses which have already been published by the patents and literatures, the luminescent glass provided by the present invention provides the following advantages: 
     1. The luminescent glass provided by the present invention has a broad absorption band ranging from the UV region to blue light region, which is suitable for both the excitation of UV LED chip and blue LED chip. Bright green light emission can be obtained by the combination of the present luminescent glass and UV LED chip, while bright white light emission can be obtained by the combination of the present luminescent glass and blue LED chip. 
     2. Continuous adjustability in the excitation spectra can be provided with the variation in doped amount of Eu 2 O 3 , which allows the optimal excitation wavelength adjustable within 410˜470 nm, suitable for application of UV LED and blue LED at various wavelength. 
     3. Continuous adjustability in the emission spectra can be provided with the variation in doped amount of Eu 2 O 3  and variation of MO (M=Ca, Sr, Ba), which allows the peak emission wavelength adjustable within 500˜555 nm, providing light from green to yellowish green. 
     4. Adjustability of the emission wavelength can be obtained by fixing the doped amount of Eu 2 O 3  and changing the excitation wavelength, which allows the peak emission wavelength adjustable within 500˜545 nm, providing light from green to yellowish green. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  shows the excitation spectra of glass samples with different concentrations of Eu 2 O 3  (Example 1: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.025Eu 2 O 3 ; Example 2: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3 ; Example 3: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.50Eu 2 O 3 ). 
         FIG. 2  shows the emission spectra of glass samples with different concentrations of Eu 2 O 3  (Example 1: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.025Eu 2 O 3 ; Example 2: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3 ; Example 3: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.50Eu 2 O 3 ). 
         FIG. 3  shows the emission spectra of glass sample 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3  (Example 2) at different excitation wavelengths. 
         FIG. 4  shows the emission spectra of glass samples with different MO (M=Ca, Sr, Ba) (Example 2: 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3 ; Example 6: 45SiO 2 -25Li 2 O-20CaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3 ; Example 7: 45SiO 2 -25Li 2 O-20BaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3 ). 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In the following descriptions, the present invention will be further described in combination with specific examples, which is exemplary and is not limiting the scope of the present invention. 
     Example 1 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.025Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 1. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 O 
                 SrO 
                 Al 2 O 3   
                 K 2 CO 3   
                 NH 4 H 2 PO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 1.49 
                 4.14 
                 1.01 
                 0.82 
                 0.9202 
                 0.01 
               
               
                 (g) 
                 76 
                 41 
                 48 
                 96 
                 92 
                   
                 76 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium oxide (Li 2 O), strontium oxide (SrO), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 1. The materials were fully grinded and mixed for 6 hours in a ball mill, and then transferred into a crucible and kept at 1450° C. for 3 hours under reducing atmosphere of thermal-carbon. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 450° C. for 5 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     The optimal excitation wavelength of the resulting glass is at 410 nm (shown in  FIG. 1 ), while the main emission peak is at 500 nm under excitation of light at 410 nm (shown in  FIG. 2 ). 
     Example 2 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 2. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 CO 3   
                 SrCO 3   
                 Al 2 O 3   
                 K 2 CO 3   
                 NH 4 H 2 PO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 3.69 
                 5.90 
                 1.01 
                 0.82 
                 0.9202 
                 0.03 
               
               
                 (g) 
                 76 
                 45 
                 52 
                 96 
                 92 
                   
                 52 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium carbonate (Li 2 CO 3 ), strontium carbonate (SrCO 3 ), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 2. The materials were fully grinded and mixed for 8 hours in a ball mill, and then transferred into a crucible and kept at 1500° C. for 2 hours under reducing atmosphere of nitrogen (N 2 )˜hydrogen (H 2 ) mixed gas. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 500° C. for 4 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     The optimal excitation wavelength of the resulting glass is at 430 nm (shown in  FIG. 1 ), while the main emission peak is at 520 nm under excitation of light at 430 nm (shown in  FIG. 2 ). Simultaneously, as shown in  FIG. 3 , the peak emission wavelength transferred from 505 nm to 545 nm when the sample was excited by light at different wavelengths. 
     Example 3 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-20SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.50Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 3. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 CO 3   
                 SrO 
                 Al 2 O 3   
                 K 2 CO 3   
                 (NH 4 ) 2 HPO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 3.69 
                 4.14 
                 1.01 
                 0.82 
                 1.0565 
                 0.35 
               
               
                 (g) 
                 76 
                 45 
                 48 
                 96 
                 92 
                   
                 20 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium carbonate (Li 2 CO 3 ), strontium oxide (SrO), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), diammonium phosphate ((NH 4 ) 2 HPO 4 ) and Eu 2 O 3  were accurately weighed according to table 3. The materials were fully grinded and mixed for 10 hours in a ball mill, and then transferred into a crucible and kept at 1550° C. for 1 hour under reducing atmosphere of hydrogen (H 2 ). The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 550° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     The optimal excitation wavelength of the resulting glass is at 440˜490 nm (shown in  FIG. 1 ), while the main emission peak is at 550 nm under excitation of light at 455 nm (shown in  FIG. 2 ). Bright white light can be obtained by the combination of the resulting glass and blue LED chip (450 nm). 
     It is confirmed by Examples 1, 2 and 3 that the luminescent glass provided by the present invention has a broad absorption band ranging from the UV to blue light (shown in  FIG. 1 ), which matches well with the emissions of UV LED chip and blue LED chip; and that continuous adjustability in the excitation spectra can be provided (shown in  FIG. 1 ), which allows the optimal excitation wavelength adjustable within 410˜470 nm, suitable for application of UV and blue LED at various wavelength. Continuous adjustability in the emission spectra can be provided (shown in  FIG. 2 ), which allows the peak emission wavelength adjustable within 500˜555 nm, providing light from green to yellowish green. 
     Example 4 
     Synthesis of Luminescent Glass Based on 45SiO 2 -30Li 2 O-15SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.40Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 4. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 O 
                 SrCO 3   
                 Al 2 O 3   
                 K 2 CO 3   
                 NH 4 H 2 PO 4   
                 EU 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 1.79 
                 4.42 
                 1.01 
                 0.82 
                 0.9202 
                 0.28 
               
               
                 (g) 
                 76 
                 29 
                 89 
                 96 
                 92 
                   
                 15 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium oxide (Li 2 O), strontium carbonate (SrCO 3 ), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 4. The materials were fully grinded and mixed for 8 hours in a ball mill, and then transferred into a crucible and kept at 1600° C. for 1 hour under reducing atmosphere of thermal-carbon. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 500° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     Bright white light can be obtained by the combination of the resulting glass and blue LED chip (450 nm). 
     Example 5 
     Synthesis of Luminescent Glass Based on 45SiO 2 -35Li 2 O-10SrO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.40Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 5. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 O 
                 SrO 
                 Al 2 O 3   
                 K 2 CO 3   
                 (NH 4 ) 2 HPO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 2.09 
                 2.07 
                 1.01 
                 0.82 
                 1.0565 
                 0.28 
               
               
                 (g) 
                 76 
                 17 
                 24 
                 96 
                 92 
                   
                 15 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium oxide (Li 2 O), strontium oxide (SrO), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), diammonium phosphate ((NH 4 ) 2 HPO 4 ) and Eu 2 O 3  were accurately weighed according to table 5. The materials were fully grinded and mixed for 6 hours in a ball mill, and then transferred into a crucible and kept at 1600° C. for 1 hour under reducing atmosphere of thermal-carbon. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 600° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     Bright white light can be obtained by the combination of the resulting glass and blue LED chip (450 nm). 
     Example 6 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-20CaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 6. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 CO 3   
                 CaCO 3   
                 Al 2 O 3   
                 K 2 CO 3   
                 NH 4 H 2 PO 4   
                 EU 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 3.69 
                 4.00 
                 1.01 
                 0.82 
                 0.9202 
                 0.03 
               
               
                 (g) 
                 76 
                 45 
                 3 
                 96 
                 92 
                   
                 52 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium carbonate (Li 2 CO 3 ), calcium carbonate (CaCO 3 ), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ) ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 6. The materials were fully grinded and mixed for 8 hours in a ball mill, and then transferred into a crucible and kept at 1700° C. for 0.5 hour under reducing atmosphere of nitrogen (N 2 )˜hydrogen (H 2 ) mixed gas. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 650° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     The excitation wavelength of the resulting glass is at 250˜475 nm, while the main emission peak is at 530 nm under excitation of light at 450 nm (shown in  FIG. 4 ). 
     Example 7 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-20BaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.05Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 7. 
               
             
          
           
               
                 material 
                 SiO 2   
                 Li 2 O 
                 BaCO 3    
                 Al 2 O 3   
                 K 2 CO 3   
                 NH 4 H 2 PO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 1.49 
                 7.893 
                 1.01 
                 0.82 
                 0.9202  
                 0.03 
               
               
                 (g) 
                 76 
                 41 
                 4 
                 96 
                 92 
                   
                 52 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium oxide (Li 2 O), barium carbonate (BaCO 3 ), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 7. The materials were fully grinded and mixed for 8 hours in a ball mill, and then transferred into a crucible and kept at 1550° C. for 2 hours under reducing atmosphere of thermal-carbon. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 550° C. for 4 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     The excitation wavelength of the resulting glass is at 250˜500 nm, while the main emission peak is at 550 nm under excitation of light at 450 nm (shown in  FIG. 4 ). 
     It is confirmed by Examples 2, 6 and 7 that there is a red shift in the emission wavelength with variation of Ca→Sr→Ba (as shown in  FIG. 4 ). 
     Example 8 
     Synthesis of Luminescent Glass Based on 45SiO 2 -25Li 2 O-10SrO-10CaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.10Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 8. 
               
             
          
           
               
                 mate- 
                   
                 Li 2   
                   
                   
                 Al 2   
                 K 2   
                 (NH 4 ) 2   
                 Eu 2   
               
               
                 rial 
                 SiO 2   
                 CO 3   
                 SrO 
                 CaO 
                 O 3   
                 CO 3   
                 HPO 4   
                 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 3.694 
                 2.07 
                 1.12 
                 1.01 
                 0.82 
                 1.0565 
                 0.07 
               
               
                 (g) 
                 76 
                 5 
                 24 
                 15 
                 96 
                 92 
                   
                 04 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium carbonate (Li 2 CO 3 ), strontium oxide (SrO), calcium oxide (CaO), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), diammonium phosphate ((NH 4 ) 2 HPO 4 ) and Eu 2 O 3  were accurately weighed according to table 8. The materials were fully grinded and mixed for 10 hours in a ball mill, and then transferred into a crucible and kept at 1700° C. for 0.5 hour under reducing atmosphere of thermal-carbon. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 500° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     Bright white light can be obtained by the combination of the resulting glass and blue LED chip (450 nm). 
     Example 9 
     Synthesis of Luminescent Glass Based on 45SiO 2 -30Li 2 O-5SrO-5CaO-5BaO-5Al 2 O 3 -3K 2 O-2P 2 O 5 :0.20Eu 2 O 3   
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Compositions of the rare earth ions doped silicate 
               
               
                 luminescent glass of Example 9. 
               
             
          
           
               
                 mate- 
                   
                   
                   
                   
                 Ba 
                   
                   
                 NH 4 H 2   
                   
               
               
                 rial 
                 SiO 2   
                 Li 2 CO 3   
                 SrCO 3   
                 CaCO 3   
                 CO 3   
                 Al 2 O 3   
                 K 2 CO 3   
                 PO 4   
                 Eu 2 O 3   
               
               
                   
               
             
          
           
               
                 weight 
                 5.40 
                 4.433 
                 1.47 
                 1.000 
                 1.97 
                 1.01 
                 0.82 
                 0.9202 
                 0.14 
               
               
                 (g) 
                 76 
                 5 
                 63 
                 9 
                 34 
                 96 
                 92 
                   
                 08 
               
               
                   
               
             
          
         
       
     
     Silicon dioxide (SiO 2 ), lithium carbonate (Li 2 CO 3 ), strontium carbonate (SrCO 3 ), calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ), aluminum oxide (Al 2 O 3 ), potassium carbonate (K 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) and Eu 2 O 3  were accurately weighed according to table 9. The materials were fully grinded and mixed for 10 hours in a ball mill, and then transferred into a crucible and kept at 1600° C. for 1 hour under reducing atmosphere of nitrogen (N 2 )˜hydrogen (H 2 ) mixed gas. The resulting glass liquid was poured into a preheated mould for shaping, and then annealed at 550° C. for 2 hours, and took out after naturally cooled to room temperature, after which it was cut and polished to give luminescent glass sample. 
     Bright white light can be obtained by the combination of the resulting glass and blue LED chip (450 nm).