Abstract:
A UV-emitting phosphor and lamp containing same are described. The phosphor is a praseodymium-activated pyrophosphate-based phosphor which may be represented by the general formula (Ca 2-x ,Sr x )P 2 O 7 :Pr where 0≦x≦2. The phosphor is excitable by vacuum ultraviolet (VUV) radiation and in particular it may be excited by Xe-excimer discharges and thereby provide a Hg-free UV-emitting lamp. The phosphor exhibits a broad emission in the UVC region in the wavelength range from about 220 nm to about 280 nm with the peak emission occurring in the wavelength range from about 230 nm to about 240 nm. The emission characteristics of the phosphor may be varied depending on the ratio of Sr/Ca.

Description:
BACKGROUND OF THE INVENTION 
     The ultraviolet spectrum generally is divided into three regions: UVA (400 nm-320 nm), UVB (320 nm-290 nm) and UVC (290 nm-200 nm). The UVA and UVB regions are important for suntan lamps and medical phototherapy applications and the UVC is important for germicidal lamp applications. 
     In recent years, there has been increasing interest in germicidal lamps because of concerns about supplying potable drinking water, especially during natural disasters. In addition, there is a concurrent interest worldwide in reducing the widespread use of mercury because of its environmental impact. These two factors taken together have led to the development of mercury-free (Hg-free) germicidal lamps. One such water disinfecting device described in U.S. Pat. No. 6,398,970 is a Xe-plasma based vacuum ultraviolet (VUV) excited lamp which is coated with phosphors emitting in the germicidal range of about 220-280 nm. 
     In addition to water purification, UVC-emitting phosphors may be used in other germicidal applications such as the purification of surfaces and air and the medical sterilization of open wounds. Other potential uses beyond germicidal applications include medical phototherapy and photo-curing of UV-sensitive polymers and resins. Also, the use of UVC-emitting phosphors in low-pressure mercury fluorescent lighting has been reported to improve light output and reduce degradation due to 185 nm radiation. See, e.g., U.S. Pat. No. 6,734,631. 
     SUMMARY OF THE INVENTION 
     The present invention is a novel UV-emitting phosphor and lamp containing same. The phosphor is a praseodymium-activated pyrophosphate-based phosphor which may be represented by the general formula (Ca 2-x ,Sr x )P 2 O 7 :Pr where 0≦x≦2. As the formula indicates, the composition of the phosphor covers the entire range of compositions from Ca 2 P 2 O 7 :Pr to Sr 2 P 2 O 7 :Pr. In between, there exists a mixture of the Sr 2 P 2 O 7 :Pr and Ca 2 P 2 O 7 :Pr phases in an apparent solid solution. 
     The phosphor of this invention is excitable by vacuum ultraviolet (VUV) radiation and in particular it may be excited by the 172 nm radiation emitted by Xe-excimer discharges. The phosphor exhibits a broad emission in the UVC region in the wavelength range from about 220 nm to about 280 nm with the peak emission occurring in the wavelength range from about 230 nm to about 240 nm. The emission characteristics of the phosphor may be varied depending on the ratio of Sr/Ca. 
     In a preferred embodiment, the phosphor is formulated to have a slight excess of the pyrophosphate anion relative to the total cation amount. Such slight deviations in stoichiometry are an idea common to many phosphors where a small excess of anionic species is used in the formulated phosphor blend and results in improved brightness for the fired phosphor material. It is also preferred to include a 1+ metal cation, preferably Na + , to provide charge balancing for the Pr 3+  activator. 
     Such formulation adjustments are known for cerium-activated calcium pyrophosphate phosphors. For example, U.S. Pat. No. 4,757,233 describes a Ce-activated calcium pyrophosphate phosphor represented by the formula Ca (2-w-x-y )(NSF) w Ce x Na y P 2 O 7  where NSF is the nonstoichiometric factor, and w ranges from 0 to 0.1, x ranges from 0.05 to 0.20, and y ranges from 0.05 to 0.20. In this case, the amount of Na +  is approximately equal to the amount of Ce 3+  in the phosphor for overall charge balance. 
     Accordingly, in a more preferred embodiment, the phosphor of this invention may be represented by the formula Ca (2-w-x-y-z) Sr x A y Pr z P 2 O 7  where: A is a 1+ metal cation, preferably Na + ; w is a nonstoichiometric factor which ranges from 0 to about 0.1 and is more preferably equal to about 0.06; x ranges from 0 to 2-w-y-z; y ranges from 0 to about 0.25 and more preferably from z−0.01 to z+0.01; and z ranges from greater than 0 to about 0.12 and more preferably from about 0.02 to about 0.08. The 1+ metal cation is included in the formulation primarily for charge balancing. It is therefore preferred that the amount of the 1+ metal cation equal the amount of the Pr activator, i.e., y=z. 
     Both Ca 2 P 2 O 7  and Sr 2 P 2 O 7  are known to have β- to α-phase transitions. These transitions occur at approximately 1140° C. and 775° C. respectively, with the α-phase being a monoclinic structure while the β-phase is tetragonal. Both phases may be activated with praseodymium to form the UV-emitting phosphor of this invention. Moreover, the phosphor may be a mixture of the α- and β-phases which each have different emission characteristics. Preferred phosphors are α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr, and α-Sr 2 P 2 O 7 :Pr. 
     For Ca 2 P 2 O 7 :Pr phosphors (x=0), a preferred formula is: Ca (2-w-y-z) A y Pr z P 2 O 7  where: A is a 1+ metal cation, preferably Na + ; w ranges from 0 to about 0.1 and is more preferably equal to about 0.06; y ranges from 0 to about 0.25 and more preferably from z−0.01 to z+0.01; and z ranges from about 0.04 to about 0.12 for β-Ca 2 P 2 O 7 :Pr and from about 0.02 to about 0.08 for α-Ca 2 P 2 O 7 :Pr. More preferably, y=z for both phases. 
     For Sr 2 P 2 O 7 :Pr phosphors (x=2), a preferred formula is: Sr (2-w-y-z) A y Pr z P 2 O 7  where: A is a 1+ metal cation, preferably Na + ; w ranges from 0 to about 0.1 and is more preferably equal to about 0.06; y ranges from 0 to about 0.25 and more preferably from z−0.01 to z+0.01; and z ranges from about 0.03 to about 0.08. The α-phase is preferred for the strontium pyrophosphate phosphors. For charge balancing, it is more preferred that y=z. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a graph of the UVC emission spectra of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr and α-Sr 2 P 2 O 7 :Pr phosphors under excitation by 172 nm radiation compared to the DIN germicidal activity curve (GAC). 
         FIG. 2  is a graph comparing the UVC emission spectra of α-Ca 2 P 2 O 7 :Pr, LaPO 4 :Pr, and YPO 4 :Pr phosphors under excitation by 172 nm radiation. 
         FIG. 3  compares the UVC emission spectra of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr and α-Sr 2 P 2 O 7 :Pr phosphors with LaPO 4 :Pr under excitation by 172 nm radiation 
         FIG. 4  shows the excitation spectra of the UVC-emitting phosphors α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr, LaPO 4 :Pr, and YPO 4 :Pr. 
         FIG. 5  shows the x-ray diffraction patterns of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr, and α-Sr 2 P 2 O 7 :Pr. 
         FIG. 6  is a graph of the UVC emission spectra of Examples 14-16 under excitation by 172 nm radiation. 
         FIG. 7  is a graph of the UVC emission spectra of Examples 44, 47 and 50 under excitation by 172 nm radiation. 
         FIG. 8  shows the change in the UVC emission of the phosphor of this invention under 172 nm excitation as the percentage of the strontium cation is increased from 0% to 50%. 
         FIG. 9  shows the change in the UVC emission of the phosphor of this invention under 172 nm excitation as the percentage of the strontium cation is increased from 50% to 100%. 
         FIG. 10  is a cross-sectional illustration of a lamp containing the phosphor of this invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims taken in conjunction with the above-described drawings. 
     Pr 3+  may substitute for Ce 3+  in many materials because they are chemically similar rare earth ions with similar radii. However, the electronic states of Pr 3+  and Ce 3+  are quite different and the optical properties of the same phosphor lattices with these two different activator ions are typically quite different. As examples, LaPO 4 :Ce and YPO 4 :Ce are good UVB- and UVA-emitting phosphors, respectively, while LaPO 4 :Pr and YPO 4 :Pr are good UVC-emitting phosphors. The same applies for the Ca 2 P 2 O 7  system. The Ce-activated phosphor described in U.S. Pat. No. 4,757,233 emits at about 330 nm when stimulated by 254 nm radiation whereas when Pr 3+  is substituted as the activator ion the emission occurs at about 230 nm in response to excitation by 172 nm radiation. 
     As described previously, Ca 2 P 2 O 7  and Sr 2 P 2 O 7  are known to have β- to α-phase transitions at approximately 1140° C. and 775° C. respectively, with the α-phase being a monoclinic structure while the β-phase is tetragonal. Previously, the α-phase was reported as an orthorhombic structure, but more recently the structure has been determined to be monoclinic with a very small deviation from the orthogonal orthorhombic lattice. 
     The Ce-activated calcium pyrophosphate disclosed in U.S. Pat. No. 4,757,233 is a β-phase material and is commonly fired at 1000° C. The same raw material blends fired at 1200° C. will form an β-phase material. The β-phase Ca 2 P 2 O 7 :Ce phosphor has a single broad emission peak centered at ˜335 nm under 254 nm radiation, which appears to be at least two separate emission peaks which overlap. The α-phase Ca 2 P 2 O 7 :Ce phosphor exhibits a less intense emission under 254 nm radiation with two distinct peaks centered at 326 nm and 344 nm. Similar behavior is observed for Ca 2 P 2 O 7 :Pr phosphors except the higher temperature α-phase phosphor has a much stronger emission intensity than the lower temperature β-phase phosphor under vacuum ultraviolet radiation. In particular, β-Ca 2 P 2 O 7 :Pr has two broad peaks centered at approximately 235 nm and 263 nm, while α-Ca 2 P 2 O 7 :Pr has four distinct emission peaks centered at approximately 231 nm, 240 nm, 258 nm, and 267 nm. The UVC emission spectra of these phosphors is shown in  FIG. 1  under 172 nm excitation. Also depicted is the DIN germicidal activity curve (GAC) for the UV inactivation of  E. Coli  bacteria. DIN 5031-10, Strahlungsphysik im optischen bereich und lichttechnik, Deutsches Insitut für Normung (1996). 
     As expected from the phase transition temperature, α-Ca 2 P 2 O 7 :Pr is formed in a reducing atmosphere at temperatures greater than about 1140° C., while β-Ca 2 P 2 O 7 :Pr is formed in a reducing atmosphere at temperatures less than about 1140° C. Similarly, α-Sr 2 P 2 O 7 :Pr is formed in reducing atmospheres between 1000° C. and 1200° C. As shown in  FIG. 1 , this phosphor also has an intense emission spectrum under VUV excitation with peaks centered at approximately 234 nm, 245 nm, and 262 nm and much weaker shoulders at approximately 222 nm and 273 nm. In contrast, β-Sr 2 P 2 O 7  is reported to form at temperatures under 775° C., but Sr 2 P 2 O 7 :Pr phosphors prepared at 750° C. exhibited only the emission spectra of α-Sr 2 P 2 O 7 :Pr. 
     The phase transition temperature of these materials is, in part, dependent upon the formulation of the reactant blend. Mixtures of the two Ca 2 P 2 O 7 :Pr phases may be prepared at temperatures ranging from 1050° C. to 1150° C. However, (Ca 2-x ,Sr x )P 2 O 7 :Pr phosphors (where x&gt;0.4) tend to be primarily α-phase even when fired at 1000° C. When x≦0.4, β-phase is detected. The x-ray diffraction patterns of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr, and α-Sr 2 P 2 O 7 :Pr are shown in  FIG. 5 . 
     The phosphors of this invention have emission spectra that are comparable to other UVC-emitting phosphors and, in particular, LaPO 4 :Pr and YPO 4 :Pr. For example, α-Ca 2 P 2 O 7 :Pr phosphors have been prepared with an integrated UVC emission intensity of up to 127% that of LaPO 4 :Pr under 172 nm excitation radiation. Similarly, α-Sr 2 P 2 O 7 :Pr phosphors have been prepared with up to 105% the UVC emission intensity of LaPO 4 :Pr and α-(Ca,Sr) 2 P 2 O 7 :Pr phosphors have attained up to 116% the emission intensity of LaPO 4 :Pr.  FIG. 2  compares the emission spectra of LaPO 4 :Pr and YPO 4 :Pr with α-Ca 2 P 2 O 7 :Pr under excitation by 172 nm radiation.  FIG. 3  compares the UVC emission spectra of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr and α-Sr 2 P 2 O 7 :Pr phosphors with LaPO 4 :Pr under 172 nm excitation.  FIG. 4  shows the excitation spectra of α-Ca 2 P 2 O 7 :Pr, β-Ca 2 P 2 O 7 :Pr, LaPO 4 :Pr and YPO 4 :Pr. To obtain the excitation spectra in  FIG. 4 , the intensities of the indicated emission wavelengths were measured as the excitation wavelength was varied from 140 nm to 220 nm. 
     EXAMPLES 1-31 
     Ca 2 P 2 O 7 :Pr Phosphors 
     Ca 2 P 2 O 7 :Pr may be prepared by thoroughly dry blending the appropriate reactants, then firing the blended materials in a reducing atmosphere, preferably for 2-4 hours at 1000° C.-1200° C. in a 5% H 2 -95% N 2  atmosphere The reactants preferably include calcium hydrogen phosphate, (CaHPO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), sodium carbonate (Na 2 CO 3 ), and praseodymium oxide (Pr 4 O 7 ). The fired cakes may be softened by soaking for 2-12 hours in de-ionized water and then wet-sieved −60 mesh and dried. Alternatively, the dry fired cakes may be broken into smaller pieces, ground and then dry sifted −60 mesh. The phosphor powder can be wet-milled to the appropriate size using a ball-milling technique with a minimal loss in brightness due to particle damage. 
     Examples 1-4 were prepared by thoroughly blending the reactants in a 500 ml plastic bottle using roll-blending and paint-shaking techniques. All reactants were assayed and the diammonium hydrogen phosphate (DAP) was ground and screened −60 mesh before use. An ˜75 g amount of each reactant blend was loaded into an alumina crucible. The crucibles were then placed in silica boats and pushed through a tube furnace at 1000° C. under a reducing 5% H 2 -95% N 2  atmosphere with a total time in the hot zone of 2 hours. The fired phosphors were cooled within the tube furnace, then removed, broken into pieces, ground, and screened −60 mesh. UVC emission spectra of the phosphors under 172 nm excitation radiation were measured using an Acton SpectraPro-2500i monochromator/spectrograph with a deuterium light source and a VM-504 vacuum monochromator. 
     Further ˜75 g amounts of the same reactant blends were fired at 1150° C. using the same method as above and processed in the same fashion. Table 1 lists the mole ratios and weights of the reactants for Examples 1-4. Table 2 provides the integrated UVC emission intensities of the phosphors between 210 nm-310 nm in response to excitation by 172 nm radiation. The integrated emission intensities are given relative to LaPO 4 :Pr and YPO 4 :Pr phosphors which were used as controls. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 1 
                 mole ratio 
                 1.90 
                 0.10 
                 0.010 
                 0.005 
               
               
                   
                 weight (g) 
                 182.87 
                 9.28 
                 0.74 
                 2.36 
               
               
                 Example 2 
                 mole ratio 
                 1.86 
                 0.14 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 179.02 
                 12.99 
                 1.48 
                 4.73 
               
               
                 Example 3 
                 mole ratio 
                 1.78 
                 0.22 
                 0.040 
                 0.020 
               
               
                   
                 weight (g) 
                 171.32 
                 20.42 
                 2.97 
                 9.46 
               
               
                 Example 4 
                 mole ratio 
                 1.70 
                 0.30 
                 0.060 
                 0.030 
               
               
                   
                 weight (g) 
                 163.62 
                 27.84 
                 4.45 
                 14.19 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity under 172 nm 
               
             
          
           
               
                   
                 moles 
                 Fired at 1000° C. 
                 Fired at 1150° C. 
               
             
          
           
               
                   
                 Pr/mole 
                 relative to 
                 relative to 
                 relative to 
                 relative to 
               
               
                   
                 phosphor 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
               
               
                   
                   
               
             
          
           
               
                 Example 1 
                 0.02 
                 87% 
                 123% 
                 112% 
                 158% 
               
               
                 Example 2 
                 0.04 
                 99% 
                 140% 
                 118% 
                 167% 
               
               
                 Example 3 
                 0.08 
                 102%  
                 144% 
                 109% 
                 154% 
               
               
                 Example 4 
                 0.12 
                 96% 
                 136% 
                  95% 
                 134% 
               
               
                   
               
             
          
         
       
     
     Examples 5-8 were prepared, fired at 1150° C., processed, and analyzed in the same fashion as Examples 1-4. Table 3 lists the reactant mole ratios and weights for Examples 5-8. Table 4 provides the activator, anion, and cation levels in addition to the integrated UVC emission intensities under 172 nm excitation between 210 nm-310 nm relative to a LaPO 4 :Pr control. In these examples, lower levels of the Pr 3+  activator were investigated and the amount of DAP was kept at 0.15 moles to better flux the phosphor formation. A preferred stoichiometry for the phosphor formulation is 1.00 moles of pyrophosphate anion (2.00 moles P) to a slight deficiency of 1.94 moles of cation (Ca 2+ +Na + +Pr 3+ ). Example 6 prepared with 0.02 moles of Pr 3+  had an excess of 0.025 moles of [P 2 O 7 ] 4−  and was significantly inferior in brightness relative to Example 1, which was also prepared with 0.02 moles of Pr 3+ , but had no excess of [P 2 O 7 ] 4−  anion. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 5 
                 mole ratio 
                 1.92 
                 0.15 
                 0.005 
                 0.0025 
               
               
                   
                 weight (g) 
                 137.27 
                 10.34 
                 0.28 
                 0.88 
               
               
                 Example 6 
                 mole ratio 
                 1.90 
                 0.15 
                 0.010 
                 0.005 
               
               
                   
                 weight (g) 
                 135.84 
                 10.34 
                 0.55 
                 1.76 
               
               
                 Example 7 
                 mole ratio 
                 1.88 
                 0.15 
                 0.015 
                 0.0075 
               
               
                   
                 weight (g) 
                 134.41 
                 10.34 
                 0.83 
                 2.63 
               
               
                 Example 8 
                 mole ratio 
                 1.86 
                 0.15 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 10.34 
                 1.10 
                 3.51 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
             
             
               
                   
                   
               
               
                   
                 UVC intensity 
               
             
          
           
               
                   
                 moles/mole of phosphor 
                 under 172 nm 
               
             
          
           
               
                   
                   
                 total 
                 total 
                 relative to 
               
               
                   
                 Pr 
                 [P 2 O 7 ] 4−   
                 (Ca 2+ + Na + + Pr 3+ ) 
                 LaPO 4 :Pr 
               
               
                   
                   
               
             
          
           
               
                 Example 5 
                 0.01 
                 1.035 
                 1.94 
                 60% 
                   
               
               
                 Example 6 
                 0.02 
                 1.025 
                 1.94 
                 82% 
               
               
                 Example 7 
                 0.03 
                 1.015 
                 1.94 
                 100% 
               
               
                 Example 8 
                 0.04 
                 1.005 
                 1.94 
                 110% 
               
               
                 Example 1 
                 0.02 
                 1.000 
                 1.94 
                 112% 
               
               
                 Example 2 
                 0.04 
                 1.000 
                 1.94 
                 118% 
               
               
                   
               
             
          
         
       
     
     Examples 9-13 were prepared in a similar fashion as the previous examples to more fully investigate the effects of the firing temperature on Ca 2 P 2 O 7 :Pr. A single large amount of the reactant blend was prepared with 0.045 moles Pr/mole phosphor. Table 5 below lists the reactant mole ratios and weights. Separate 75 g amounts of the blend were fired at temperatures ranging from 1000° C. to 1200° C. Table 6 provides the results of x-ray diffraction (XRD) phase analyses and the integrated UVC emission intensities of Ca 2 P 2 O 7 :Pr phosphors between 210 nm-310 nm, relative to LaPO 4 :Pr and YPO 4 :Pr controls, under 172 nm excitation radiation. Table 7 also provides the maximum peak wavelengths and maximum peak intensities of the Ca 2 P 2 O 7 :Pr phosphors, relative to LaPO 4 :Pr, under 172 nm excitation. 
     The XRD results show that the phosphors undergo a phase shift as the firing temperature increases: from entirely β-phase at 1000° C., to a mixture of β- and α-phases between 1050° C. to 1150° C., to entirely α-phase at 1200° C. The UVC emission data indicates that for 172 nm excitation it is preferred to have at least some of the α-phase present to yield a higher UVC emission. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Examples 9-13 
                 mole ratio 
                 1.85 
                 0.171 
                 0.0225 
                 0.0113 
               
               
                   
                 weight (g) 
                 499.70 
                 44.61 
                 4.69 
                 14.94 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
             
             
               
                   
                   
               
               
                   
                 UVC intensity under 
               
               
                   
                 172 nm radiation 
               
             
          
           
               
                   
                 Firing 
                 XRD analysis 
                 relative to 
                 relative to 
               
             
          
           
               
                   
                 temp. 
                 α-phase 
                 β-phase 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
               
               
                   
                   
               
             
          
           
               
                 Example 9 
                 1000° C. 
                 None 
                 Major 
                  96% 
                 136% 
               
               
                 Example 10 
                 1050° C. 
                 Trace 
                 Major 
                 102% 
                 144% 
               
               
                 Example 11 
                 1100° C. 
                 Minor 
                 Major 
                 110% 
                 154% 
               
               
                 Example 12 
                 1150° C. 
                 Major 
                 Major 
                 114% 
                 161% 
               
               
                 Example 13 
                 1200° C. 
                 Major 
                 None 
                 112% 
                 158% 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 7 
               
               
                   
                   
               
               
                   
                   
                   
                   
                 UVC Peak 
               
               
                   
                   
                   
                 UVC Peak 
                 Intensity under 
               
               
                   
                   
                   
                 Emission 
                 172 nm radiation 
               
               
                   
                 Firing 
                 XRD 
                 under 
                 relative 
               
               
                   
                 temp. 
                 analysis 
                 172 nm 
                 to LaPO 4 :Pr 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 9 
                 1000° C. 
                 β-phase 
                 234 nm 
                 73% 
                   
               
               
                 Example 10 
                 1050° C. 
                 β + (trace α) 
                 235 nm 
                 78% 
               
               
                 Example 11 
                 1100° C. 
                 β + (minor α) 
                 235 nm 
                 83% 
               
               
                 Example 12 
                 1150° C. 
                 β + α 
                 230 nm 
                 99% 
               
               
                 Example 13 
                 1200° C. 
                 α-phase 
                 230 nm 
                 103% 
               
               
                 LaPO4:Pr 
                 NA 
                 NA 
                 227 nm 
                 100% 
               
               
                 YPO4:Pr 
                 NA 
                 NA 
                  83 nm 
                 83% 
               
               
                   
               
             
          
         
       
     
     Examples 14-19 were prepared, fired at 1100° C. and 1200° C., processed, and analyzed in the same fashion as the previous samples. The Pr 3+  activator level was kept at 0.04 moles Pr/mole phosphor in each case, but the pyrophosphate anion, [P 2 O 7 ] 4− , and Na +  levels were varied to investigate the effect of changing the anion/cation ratio from the preferred ratio of 1.00/1.94 and to determine the effect of altering the charge balance (moles Na +  to moles Pr 3+ ). Table 8 below lists the reactant mole ratios and weights for Examples 14-19. Table 9 provides the pyrophosphate anion, Na + , and total cation levels as well as the integrated UVC emission intensities between 210 nm-310 nm, relative to a LaPO 4 :Pr control, under 172 nm excitation. 
       FIG. 6  shows the emission spectra of Examples 14-16 which were fired at 1100° C. Example 14 exhibited the emission characteristics of the high-temperature α-phase when fired at 1100° C. Example 15 exhibited characteristics of both the α-phase and low-temperature β-phase when fired at 1100° C. Examples 16-19 exhibited characteristics primarily of the β-phase when fired at 1100° C. All Examples 14-19 exhibited the spectral character of the high-temperature α-phase when fired at 1200° C. In addition, the phosphors made without Na +  for charge balancing (Examples 18 and 19) were significantly less intense than the charge-balanced phosphors. The charge-balanced phosphor with greatest UVC emission intensity (Example 14) was made with the preferred 1.00/1.94 anion/cation ratio. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 14 
                 mole ratio 
                 1.86 
                 0.14 
                 0.02 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 9.65 
                 1.10 
                 3.51 
               
               
                 Example 15 
                 mole ratio 
                 1.86 
                 0.17 
                 0.02 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 11.72 
                 1.10 
                 3.51 
               
               
                 Example 16 
                 mole ratio 
                 1.86 
                 0.11 
                 0.02 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 7.58 
                 1.10 
                 3.51 
               
               
                 Example 17 
                 mole ratio 
                 1.86 
                 0.08 
                 0.02 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 5.52 
                 1.10 
                 3.51 
               
               
                 Example 18 
                 mole ratio 
                 1.90 
                 0.10 
                 0 
                 0.010 
               
               
                   
                 weight (g) 
                 135.84 
                 6.89 
                 0 
                 3.51 
               
               
                 Example 19 
                 mole ratio 
                 1.86 
                 0.14 
                 0 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 9.65 
                 0 
                 3.51 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Spectral character of Ca 2 P 2 O 7 :Pr phosphors with constant 0.04 Pr level 
               
             
          
           
               
                   
                   
                   
                 UVC Intensity under 
               
               
                   
                   
                   
                 172 nm relative 
               
               
                   
                 moles/mole of phosphor 
                 Phase 
                 to LaPO 4 :Pr 
               
             
          
           
               
                   
                 total 
                   
                 total 
                 (fired at 
                 Fired at 
                 Fired at 
               
               
                   
                 [P 2 O 7 ] 4−   
                 Na +   
                 (Ca 2+ + Na + + Pr 3+ ) 
                 1100° C.) 
                 1100° C. 
                 1200° C. 
               
               
                   
                   
               
             
          
           
               
                 Example 14 
                 1.00 
                 0.04 
                 1.94 
                 α 
                 125%  
                 126% 
                   
               
               
                 Example 15 
                 1.015 
                 0.04 
                 1.94 
                 α + β 
                 113%  
                 113% 
               
               
                 Example 16 
                 0.985 
                 0.04 
                 1.94 
                 β 
                 87% 
                 120% 
               
               
                 Example 17 
                 0.97 
                 0.04 
                 1.94 
                 β 
                 83% 
                 110% 
               
               
                 Example 18 
                 1.00 
                 0 
                 1.94 
                 β 
                 13% 
                 53% 
               
               
                 Example 19 
                 1.00 
                 0 
                 1.90 
                 β 
                 24% 
                 79% 
               
               
                   
               
             
          
         
       
     
     Examples 20-27 were prepared, fired at 1100° C. and 1200° C., processed, and analyzed in the same fashion as the previous samples. The Pr 3+  activator level was varied in order to more fully determine the preferred activator levels for the Ca 2 P 2 O 7 :Pr phosphors. The Na +  levels were kept equivalent to the Pr 3+  levels for charge balancing purposes. Table 10 below lists the reactant mole ratios and weights for Examples 20-27. Table 11 provides the Pr activator level and the integrated UVC emission intensities between 210 nm-310 nm, relative to LaPO 4 :Pr and YPO 4 :Pr controls, under 172 nm excitation. 
     Example 20 emitted with the characteristics of the low-temperature β-phase when fired at 1100° C. Example 21 exhibited emission characteristics of both β-phase and high-temperature α-phase when fired at 1100° C. Examples 22-27 exhibited characteristics primarily of the α-phase when fired at 1100° C. All Examples 20-27 exhibited the spectral character of the high-temperature α-phase when fired at 1200° C. The most intense UVC emission was obtained with 0.05 moles Pr/mole phosphor for the phosphors formed at 1100° C. whereas for the phosphors formed at 1200° C. the most intense emission was obtained at 0.03 mole Pr/mole phosphor. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 10 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 20 
                 mole ratio 
                 1.88 
                 0.12 
                 0.015 
                 0.0075 
               
               
                   
                 weight (g) 
                 134.41 
                 8.27 
                 0.83 
                 2.63 
               
               
                 Example 21 
                 mole ratio 
                 1.86 
                 0.14 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 132.98 
                 9.65 
                 1.10 
                 3.51 
               
               
                 Example 22 
                 mole ratio 
                 1.84 
                 0.16 
                 0.025 
                 0.0125 
               
               
                   
                 weight (g) 
                 131.55 
                 11.03 
                 1.38 
                 4.39 
               
               
                 Example 23 
                 mole ratio 
                 1.82 
                 0.18 
                 0.030 
                 0.015 
               
               
                   
                 weight (g) 
                 130.12 
                 12.41 
                 1.65 
                 5.27 
               
               
                 Example 24 
                 mole ratio 
                 1.80 
                 0.20 
                 0.035 
                 0.0175 
               
               
                   
                 weight (g) 
                 128.69 
                 13.79 
                 1.93 
                 6.15 
               
               
                 Example 25 
                 mole ratio 
                 1.78 
                 0.22 
                 0.040 
                 0.020 
               
               
                   
                 weight (g) 
                 127.26 
                 15.17 
                 2.20 
                 7.03 
               
               
                 Example 26 
                 mole ratio 
                 1.76 
                 0.24 
                 0.045 
                 0.0225 
               
               
                   
                 weight (g) 
                 125.83 
                 16.55 
                 2.48 
                 7.90 
               
               
                 Example 27 
                 mole ratio 
                 1.74 
                 0.26 
                 0.050 
                 0.025 
               
               
                   
                 weight (g) 
                 124.40 
                 17.92 
                 2.76 
                 8.78 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 11 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity under 172 nm radiation 
               
             
          
           
               
                   
                 moles 
                 Fired at 1100° C. 
                 Fired at 1200° C. 
               
             
          
           
               
                   
                 Pr/mole 
                 relative. to 
                 relative to 
                 relative to 
                 relative to 
               
               
                   
                 phosphor 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
               
               
                   
                   
               
             
          
           
               
                 Example 20 
                 0.03 
                 102% 
                 144% 
                 127% 
                 179% 
               
               
                 Example 21 
                 0.04 
                 108% 
                 153% 
                 126% 
                 178% 
               
               
                 Example 22 
                 0.05 
                 126% 
                 179% 
                 124% 
                 175% 
               
               
                 Example 23 
                 0.06 
                 119% 
                 168% 
                 122% 
                 172% 
               
               
                 Example 24 
                 0.07 
                 112% 
                 159% 
                 118% 
                 165% 
               
               
                 Example 25 
                 0.08 
                 110% 
                 156% 
                 113% 
                 159% 
               
               
                 Example 26 
                 0.09 
                 110% 
                 156% 
                 106% 
                 148% 
               
               
                 Example 27 
                 0.10 
                 104% 
                 148% 
                 107% 
                 149% 
               
               
                   
               
             
          
         
       
     
     It is apparent from the results for Examples 14-27 that the reactant blend formulation affects the transition temperature between the low-temperature β- and high-temperature α-phases. The changes in formulation include Pr 3+  activator level (Pr 4 O 7 ), DAP reactant and flux level, CaHPO 4  reactant level, and the Na +  (Na 2 CO 3 ) charge balance level. However, it is not readily apparent from the data which formulation change acts as the primary factor in controlling the transition temperature. 
     Examples 28-31 were prepared, fired at 1100° C. and 1200° C., processed, and analyzed in the same fashion as the previous samples. These examples were prepared to investigate the effects of varying the amount of DAP (diammonium hydrogen phosphate) used as a reactant and flux in this phosphor system. The preferred stoichiometry of 1.0 moles of pyrophosphate anion, [P 2 O 7 ] 4− , to 1.94 moles of total cation was used along with two levels of Pr 3+  activator (0.03 and 0.04 moles/moles phosphor). CaCO 3  was used as a reactant to add Ca 2+  cation in the samples with higher DAP levels. Table 12 below lists the reactant mole ratios and weights for Examples 28-31. Table 13 provides the DAP and Pr 3+  levels, and integrated UVC emission intensities between 210 nm-310 nm, relative to LaPO 4 :Pr and YPO 4 :Pr controls, under 172 nm excitation. 
     Examples 28-31 when fired at 1100° C. emitted with primarily low-temperature β-phase character and when fired at 1200° C. emitted with primarily α-phase character under 172 nm excitation. The effect of the DAP level on brightness was negligible over the range studied and the examples with a higher Pr 3+  activator content were slightly brighter. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 12 
               
               
                   
               
               
                 Reactant 
                 CaHPO 4   
                 DAP 
                 CaCO 3   
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 28 
                 mole ratio 
                 1.88 
                 0.12 
                 0 
                 0.015 
                 0.0075 
               
               
                   
                 weight (g) 
                 142.17 
                 8.75 
                 0.00 
                 0.87 
                 2.79 
               
               
                 Example 29 
                 mole ratio 
                 1.86 
                 0.14 
                 0 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 140.66 
                 10.21 
                 0.00 
                 1.17 
                 3.72 
               
               
                 Example 30 
                 mole ratio 
                 1.82 
                 0.18 
                 0.06 
                 0.015 
                 0.0075 
               
               
                   
                 weight (g) 
                 137.63 
                 13.12 
                 3.32 
                 0.87 
                 2.79 
               
               
                 Example 31 
                 mole ratio 
                 1.82 
                 0.18 
                 0.04 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 137.63 
                 13.12 
                 2.21 
                 1.17 
                 3.72 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 13 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity 
               
               
                   
                 under 172 nm radiation 
               
             
          
           
               
                   
                   
                 relative to 
                 relative to 
               
               
                   
                   
                 LaPO 4 :Pr 
                 LaPO 4 :Pr 
               
               
                   
                 moles/mole phosphor 
                 (fired at 
                 (fired at 
               
             
          
           
               
                   
                 DAP level 
                 Pr level 
                 1100° C.) 
                 1200° C.) 
               
               
                   
                   
               
             
          
           
               
                 Example 28 
                 0.12 
                 0.03 
                  95% 
                 116% 
               
               
                 Example 29 
                 0.14 
                 0.04 
                 101% 
                 119% 
               
               
                 Example 30 
                 0.18 
                 0.03 
                  92% 
                 112% 
               
               
                 Example 31 
                 0.18 
                 0.04 
                 102% 
                 120% 
               
               
                   
               
             
          
         
       
     
     Table 14 lists the integrated UVC emission intensities between 210 nm-310 nm for the selected α-Ca 2 P 2 O 7 :Pr and β-Ca 2 P 2 O 7 :Pr phosphors (relative to LaPO 4 :Pr and YPO4:Pr controls under 172 nm excitation). Germicidal activity was calculated by multiplying the DIN germicidal activity curve ( FIG. 1 ) by the emission data for the phosphor relative to LaPO 4 :Pr. The data show that the Ca 2 P 2 O 7 :Pr phosphors in general can be expected to have a germicidal activity at least as effective as the LaPO 4 :Pr phosphor and that the α-Ca 2 P 2 O 7 :Pr phosphor can be expected to have a significantly greater germicidal activity compared to the LaPO 4 :Pr phosphor. 
     
       
         
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 14 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity 
                   
               
               
                   
                 under 172 nm radiation 
               
             
          
           
               
                   
                   
                 relative to 
                 relative to 
                 Germicidal 
               
               
                 Phosphor 
                 Example 
                 LaPO 4 :Pr 
                 YPO 4 :Pr 
                 Activity 
               
               
                   
               
             
          
           
               
                 β-Ca 2 P 2 O 7 :Pr 
                 Example 31 
                 102% 
                 144% 
                 98% 
                   
               
               
                   
                 (fired at 
               
               
                   
                 1100° C.) 
               
               
                 β-Ca 2 P 2 O 7 :Pr + 
                 Example 21 
                 108% 
                 153% 
                 105% 
               
               
                 α-Ca 2 P 2 O 7 :Pr 
                 (fired at 
               
               
                   
                 1100° C.) 
               
               
                 α-Ca 2 P 2 O 7 :Pr 
                 Example 20 
                 127% 
                 179% 
                 125% 
               
               
                   
                 (fired at 
               
               
                   
                 1200° C.) 
               
               
                 YPO 4 :Pr 
                 NA 
                  71% 
                 100% 
                 70% 
               
               
                 LaPO 4 :Pr 
                 NA 
                 100% 
                 141% 
                 100% 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 32-43 
     Sr 2 P 2 O 7 :Pr Phosphors 
     Sr 2 P 2 O 7 :Pr phosphors may be prepared similar to the Ca 2 P 2 O 7 :Pr phosphors. The reactants preferably include strontium hydrogen phosphate (SrHPO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), sodium carbonate (Na 2 CO 3 ), and praseodymium oxide (Pr 4 O 7 ). 
     Examples 32-35 were prepared and fired at 750° C., 1000° C., and 1150° C. under a reducing atmosphere to form Sr 2 P 2 O 7 :Pr phosphors. The phosphors were then processed and analyzed in the same fashion as the previous examples. These examples were designed to investigate the effects of varying the Pr 3+  activator levels and firing temperatures on this phosphor system. The preferred stoichiometry of 1.0 moles of anion [P 2 O 7 ] 4−  to 1.94 moles of total cation was used along with four levels of Pr 3+  activator (0.02, 0.04, 0.08 and 0.12 moles Pr/moles phosphor). Table 15 below lists the reactant mole ratios and weights. Table 16 provides the Pr 3+  levels, and integrated emission intensities between 180 nm-340 nm for the Sr 2 P 2 O 7 :Pr phosphors under 172 nm excitation relative to a LaPO 4 :Pr control. 
     All Examples 32-35 emitted with the high temperature α-phase character under 172 nm excitation. The activator level which gave the greatest intensity at the 1000° C. and 1150° C. firing temperatures was 0.04 moles of Pr 3+  per mole of phosphor. The 1000° C. firing temperature resulted in phosphors which were slightly more intense than those fired at 1150° C. The phosphors formed at 750° C. were significantly less intense than the phosphors formed at 1000° C. and 1150° C. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 15 
               
               
                   
               
               
                 Reactant 
                 SrHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 32 
                 mole ratio 
                 1.90 
                 0.10 
                 0.010 
                 0.005 
               
               
                   
                 weight (g) 
                 190.37 
                 7.16 
                 0.57 
                 1.82 
               
               
                 Example 33 
                 mole ratio 
                 1.86 
                 0.14 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 186.36 
                 10.02 
                 1.14 
                 3.65 
               
               
                 Example 34 
                 mole ratio 
                 1.78 
                 0.22 
                 0.040 
                 0.020 
               
               
                   
                 weight (g) 
                 178.35 
                 15.75 
                 2.29 
                 7.30 
               
               
                 Example 35 
                 mole ratio 
                 1.70 
                 0.30 
                 0.060 
                 0.030 
               
               
                   
                 weight (g) 
                 170.33 
                 21.48 
                 3.43 
                 10.95 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 16 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity under 172 nm 
               
               
                   
                 radiation relative to LaPO 4 :Pr 
               
             
          
           
               
                   
                 moles Pr/mole 
                 Fired at 
                 Fired at 
                 Fired at 
               
               
                   
                 phosphor 
                 1150° C. 
                 1000° C. 
                 750° C. 
               
               
                   
                   
               
             
          
           
               
                 Example 32 
                 0.02 
                 98% 
                 100% 
                 11% 
               
               
                 Example 33 
                 0.04 
                 100%  
                 105% 
                 22% 
               
               
                 Example 34 
                 0.08 
                 90% 
                  91% 
                 36% 
               
               
                 Example 35 
                 0.12 
                 76% 
                  79% 
                 48% 
               
               
                   
               
             
          
         
       
     
     Examples 36-43 were prepared and fired at 1050° C., 1100° C., and 1150° C. under a reducing atmosphere to form Sr 2 P 2 O 7 :Pr phosphors. The phosphors were then processed and analyzed in the same fashion as the previous samples. The preferred stoichiometry of 1.0 moles of anion [P 2 O 7 ] 4−  to 1.94 moles of total cation was used along with eight levels of Pr 3+  activator (0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 and 0.08 moles Pr/moles phosphor). Table 17 below lists the reactant mole ratios and weights used for Examples 36-43. Table 18 gives the Pr 3+  levels and integrated emission intensities between 180 nm-340 nm for the Sr 2 P 2 O 7 :Pr phosphors samples under 172 nm excitation relative to a LaPO 4 :Pr control. 
     All of the Sr 2 P 2 O 7 :Pr phosphors emitted with the high temperature α-phase character under 172 nm excitation. The emission intensities of Examples 37, 39, and 43 were found to be slightly lower than the intensities of the comparable Examples 32, 33, and 34 when fired at 1150° C. Presumably this was due to a change in the specific lot of the SrHPO 4  reactant that was used. The activator levels between 0.03 and 0.06 moles Pr/mole phosphor gave good intensities at all firing temperatures. The phosphor prepared with 0.07 moles Pr/mole of phosphor and fired at 1100° C. exhibited the highest emission intensity. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 17 
               
               
                   
               
               
                 Reactant 
                 SrHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 36 
                 mole ratio 
                 1.92 
                 0.08 
                 0.005 
                 0.0025 
               
               
                   
                 weight (g) 
                 192.38 
                 5.73 
                 0.29 
                 0.91 
               
               
                 Example 37 
                 mole ratio 
                 1.90 
                 0.10 
                 0.010 
                 0.005 
               
               
                   
                 weight (g) 
                 190.37 
                 7.16 
                 0.57 
                 1.82 
               
               
                 Example 38 
                 mole ratio 
                 1.88 
                 0.12 
                 0.015 
                 0.0075 
               
               
                   
                 weight (g) 
                 188.37 
                 8.59 
                 0.86 
                 2.74 
               
               
                 Example 39 
                 mole ratio 
                 1.86 
                 0.14 
                 0.020 
                 0.010 
               
               
                   
                 weight (g) 
                 186.36 
                 10.02 
                 1.14 
                 3.65 
               
               
                 Example 40 
                 mole ratio 
                 1.84 
                 0.16 
                 0.025 
                 0.0125 
               
               
                   
                 weight (g) 
                 184.36 
                 11.45 
                 1.43 
                 4.56 
               
               
                 Example 41 
                 mole ratio 
                 1.82 
                 0.18 
                 0.030 
                 0.015 
               
               
                   
                 weight (g) 
                 182.36 
                 12.89 
                 1.72 
                 5.47 
               
               
                 Example 42 
                 mole ratio 
                 1.80 
                 0.20 
                 0.035 
                 0.0175 
               
               
                   
                 weight (g) 
                 180.35 
                 14.32 
                 2.00 
                 6.38 
               
               
                 Example 43 
                 mole ratio 
                 1.78 
                 0.22 
                 0.040 
                 0.020 
               
               
                   
                 weight (g) 
                 178.35 
                 15.75 
                 2.29 
                 7.30 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 18 
               
             
             
               
                   
                   
               
               
                   
                 Relative UVC Intensity under 172 nm 
               
               
                   
                 radiation relative to LaPO 4 :Pr 
               
             
          
           
               
                   
                 moles Pr/mole 
                 Fired at 
                 Fired at 
                 Fired at 
               
               
                   
                 phosphor 
                 1050° C. 
                 1100° C. 
                 1150° C. 
               
               
                   
                   
               
             
          
           
               
                 Example 36 
                 0.03 
                 77% 
                 66% 
                 75% 
               
               
                 Example 37 
                 0.04 
                 88% 
                 85% 
                 87% 
               
               
                 Example 38 
                 0.05 
                 89% 
                 91% 
                 91% 
               
               
                 Example 39 
                 0.06 
                 92% 
                 96% 
                 92% 
               
               
                 Example 40 
                 0.07 
                 89% 
                 98% 
                 92% 
               
               
                 Example 41 
                 0.08 
                 89% 
                 96% 
                 90% 
               
               
                 Example 42 
                 0.09 
                 88% 
                 90% 
                 88% 
               
               
                 Example 43 
                 0.10 
                 85% 
                 89% 
                 86% 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 44-50 
     (Ca 2-x Sr x )P 2 O 7 :Pr Phosphors 
     (Ca 2-x Sr x )P 2 O 7 :Pr phosphors may be prepared similar to the Ca 2 P 2 O 7 :Pr phosphors. The reactants preferably include calcium hydrogen phosphate, (CaHPO 4 ), strontium hydrogen phosphate (SrHPO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), sodium carbonate (Na 2 CO 3 ), and praseodymium oxide (Pr 4 O 7 ). 
     Examples 44-50 were prepared and fired at 1000° C., 1100° C., and 1200° C. under a reducing atmosphere to form (Ca 2-x Sr x )P 2 O 7 :Pr phosphors. The phosphors were then processed and analyzed in the same fashion as the previous samples. The preferred stoichiometry of 1.0 moles of anion [P 2 O 7 ] 4−  to 1.94 moles of total cation was used along with a constant Pr 3+  activator level of 0.04 moles Pr/moles phosphor. Table 19 below lists the reactant mole ratios and weights used for Examples 44-50. Table 20 gives the ratio, expressed as a percentage, of the number of moles Sr to the total number of moles of Sr and Ca. Table 20 also provides the integrated emission intensities between 180 nm-340 nm for the (Ca 2-x Sr x )P 2 O 7 :Pr phosphors under 172 nm VUV excitation relative to a LaPO 4 :Pr control as well as the phase identity of the phosphors fired at 1000° C. as determined by x-ray diffraction (XRD). Table 21 lists the peak wavelengths for the most intense emission peaks of the phosphors under 172 nm excitation. 
     These phosphors were prepared to investigate the effects of varying the Sr 2+ /Ca 2+  cation ratios and firing temperatures. Since the α-Sr 2 P 2 O 7 :Pr and α-Ca 2 P 2 O 7 :Pr phosphors form with the same structure, complete solid solution behavior was expected. X-ray diffraction analysis of the phosphors corroborated this expectation. For phosphors fired at 1200° C., the emission intensities under VUV excitation increased continuously as the Ca 2+  content increased. The mixed Sr 2+ /Ca 2+  phosphors exhibited the highest emission intensities under VUV excitation when fired at 1000° C. The peak wavelengths of the most intense emission peaks under VUV excitation also increased continuously as the Ca 2+  content increased for all examples. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 19 
               
               
                   
               
               
                 Reactant 
                 SrHPO 4   
                 CaHPO 4   
                 DAP 
                 Na 2 CO 3   
                 Pr 4 O 7   
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Example 44 
                 mole ratio 
                 0 
                 1.860 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 0 
                 153.44 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 45 
                 mole ratio 
                 0.186 
                 1.674 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 20.71 
                 138.10 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 46 
                 mole ratio 
                 0.465 
                 1.395 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 51.77 
                 115.08 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 47 
                 mole ratio 
                 0.930 
                 0.930 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 103.54 
                 76.72 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 48 
                 mole ratio 
                 1.395 
                 0.465 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 155.30 
                 38.36 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 49 
                 mole ratio 
                 1.674 
                 0.186 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 186.36 
                 15.34 
                 11.14 
                 1.27 
                 4.05 
               
               
                 Example 50 
                 mole ratio 
                 1.860 
                 0 
                 0.14 
                 0.02 
                 0.01 
               
               
                   
                 weight (g) 
                 207.07 
                 0 
                 11.14 
                 1.27 
                 4.05 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
                 TABLE 20 
               
             
             
               
                   
                   
               
               
                   
                   
                 XRD 
               
               
                   
                   
                 Phase 
               
               
                   
                 Relative UVC Intensity under 
                 Analysis 
               
               
                   
                 172 nm radiation relative to 
                 of 
               
               
                   
                 LaPO 4 :Pr 
                 Phosphors 
               
             
          
           
               
                   
                   
                 Fired at 
                 Fired at 
                 Fired at 
                 Fired at 
               
               
                   
                 % Sr 
                 1000° C. 
                 1100° C. 
                 1200° C. 
                 1000° C. 
               
               
                   
                   
               
             
          
           
               
                 Example 44 
                  0% 
                 102% 
                  99% 
                 116% 
                 beta 
               
               
                 Example 45 
                 10% 
                 110% 
                 109% 
                 113% 
                 major beta 
               
               
                   
                   
                   
                   
                   
                 minor alpha 
               
               
                 Example 46 
                 25% 
                 116% 
                 110% 
                 110% 
                 major alpha 
               
               
                   
                   
                   
                   
                   
                 minor beta 
               
               
                 Example 47 
                 50% 
                 116% 
                 110% 
                 106% 
                 major alpha 
               
               
                   
                   
                   
                   
                   
                 (broad 
               
               
                   
                   
                   
                   
                   
                 peaks) 
               
               
                 Example 48 
                 75% 
                 109% 
                 106% 
                 103% 
                 major alpha 
               
               
                   
                   
                   
                   
                   
                 (broad 
               
               
                   
                   
                   
                   
                   
                 peaks) 
               
               
                 Example 49 
                 90% 
                 106% 
                 102% 
                 101% 
                 alpha 
               
               
                 Example 50 
                 100%  
                  90% 
                  94% 
                  95% 
                 alpha 
               
               
                   
               
             
          
         
       
     
     
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 21 
               
             
             
               
                   
                   
               
               
                   
                 Peak Wavelengths of Most Intense Peaks 
               
             
          
           
               
                   
                   
                 Fired at 
                 Fired at 
                 Fired at 
               
               
                   
                 % Sr 
                 1000° C. 
                 1100° C. 
                 1200° C. 
               
               
                   
                   
               
             
          
           
               
                 Example 44 
                  0% 
                 236 nm 
                 236 nm 
                 240 nm 
               
               
                   
                   
                   
                   
                 231 nm 
               
               
                 Example 45 
                 10% 
                 237.5 nm     
                 239 nm 
                 239 nm 
               
               
                   
                   
                   
                 230 nm 
                 230 nm 
               
               
                 Example 46 
                 25% 
                 238 nm 
                 238 nm 
                 238 nm 
               
               
                   
                   
                   
                 229 nm 
                 229 nm 
               
               
                 Example 47 
                 50% 
                 237 nm 
                 237 nm 
                 237.5 nm     
               
               
                 Example 48 
                 75% 
                 236 nm 
                 236 nm 
                 236 nm 
               
               
                 Example 49 
                 90% 
                 234.5 nm     
                 234.5 nm     
                 235 nm 
               
               
                 Example 50 
                 100%  
                 234 nm 
                 234 nm 
                 234 nm 
               
               
                   
               
             
          
         
       
     
       FIG. 7  shows the UVC emission spectra of Examples 44, 47, and 50 under 172 nm excitation. All three phosphors were formed by firing at 1200° C. The UVC emission of the phosphors indicates α-phase materials.  FIG. 7  also shows how the UVC emission can vary depending on the composition. Example 44 contained no Sr 2+  and Example 50 contained no Ca 2+ . Example 47 contained equal amounts of the two cations.  FIGS. 8 and 9  better demonstrate the changes in the UVC emission as the percentage of the Sr 2+  cation is increased. 
     ULTRAVIOLET-EMITTING LAMP 
       FIG. 10  illustrates a type of VUV-excited device which is generally referred to as a dielectric barrier discharge lamp. The flat rectangular-shaped device is shown in cross section. The discharge vessel  10  is constructed of a transparent material such as glass and comprises a front plate  3  and a back plate  2  which are joined by frame  5  at the periphery of the plates. The discharge vessel  10  encloses discharge chamber  15  which contains a rare gas, typically xenon, or mixture of rare gases, and is used to generate a discharge which emits vacuum ultraviolet (VUV) radiation. A preferred discharge is a Xe-excimer discharge which emits VUV radiation at about 172 nm. The back plate  2  has multiple strip electrodes  6  which may serve as anodes and cathodes during operation. At least some of the electrodes  6 ′ are covered with a dielectric barrier layer  7 . Further examples of dielectric barrier discharge lamps are described in U.S. Pat. Nos. 6,566,810, 6,246,171 and 6,469,435. 
     In a preferred embodiment, the UV-emitting lamp may be formed by coating the inner surface of the top plate  3  and back plate  2  with a phosphor layer  11  that contains the UV-emitting phosphor of this invention. The UV-emitting phosphor converts at least some of the VUV radiation from the gas discharge into longer wavelength UV radiation. More preferably, the lamp emits UVC radiation which may be used for germicidal applications. 
     While there have been shown and described what are present considered to be the preferred embodiments of the invention, it will be apparent to those skilled in the art that various changes and modifications can be made herein without departing from the scope of the invention as defined by the appended claims.