Ce,Pr-coactivated Yttrium Phosphate Phosphor and Lamp Containing Same

Abstract

The sensitivity of YPO4:Ce phosphors to 185 nm radiation may be increased by incorporating a praseodymium coactivator. The use of Ce and Pr as co-activators in a YPO4 phosphor improves the sensitivity of the phosphor to excitation by both 185 nm and 254 nm radiation and should increase total UVA and UVB output in fluorescent lamps. The co-activated phosphor has emission peaks at about 355 nm and about 335 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the emission spectra between 260 nm and 400 nm of various YPO₄:Ce,Pr phosphors under 254 nm excitation radiation.

FIG. 2 shows the emission spectra between 260 nm and 400 nm of various YPO₄:Ce,Pr phosphors under 185 nm excitation radiation.

FIG. 3 compares the excitation spectra of various YPO₄:Ce,Pr phosphors measured for an emission at 355 nm.

FIG. 4 compares the excitation spectra of various YPO₄:Ce,Pr phosphors measured for an emission at 335 nm.

FIG. 5 is a cross-sectional illustration of a fluorescent lamp having a phosphor coating containing the YPO₄:Ce,Pr phosphor.

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.

Five phosphors were prepared with a general composition of (Y_1-x-yCe_xPr_y)PO₄, where x=0.04, and y=0, 0.001, 0.002, 0.005, and 0.01. Table 1 lists the Ce, Pr and Y levels (moles of activator/mole of phosphor) of the (Y_1-x-yCe_xPr_y)PO₄ phosphor samples and weights of materials used for the phosphor synthesis. In order to make the phosphate co-precipitate, Ce(NO₃)₃.6H₂O, Y₂O₃, and Pr₄O₇ were dissolved in a dilute nitric acid solution at a temperature from about 85° C. to about 95° C. The cooled solution was then slowly added into 1.2 moles of a dilute diammonium hydrogen phosphate (DAP) solution which was kept at a temperature from about 80° C. to about 90° C. and a pH from 1.0 to 1.5 for one hour in order to form co-precipitated phosphates of Y, Ce, and Pr. After settling, the supernate was decanted and the phosphate co-precipitate was resuspended in cold water and agitated for 10 minutes. This procedure was repeated until the solution reached a pH of 2 or above. After a final decantation, the phosphate co-precipitate was placed in a drying oven at 65° C. for 12 hours and then fired for 3 hours at 750° C. in air to obtain mixed phosphates of Y, Ce, and Pr. A 160 gram amount of the fired phosphates was thoroughly mixed with 5 grams of lithium carbonate and 80 grams of boric acid. The mixture was then fired in a H₂/N₂ atmosphere in an alumina crucible at a temperature of 1200° C. for about 3 hours. The resulting phosphor was soaked in hot water for 1 hour, washed, filtered, dried, and sifted −60 mesh.

TABLE 1
Formulations of (Y1−x−yCexPry)PO4 Phosphor Samples
	(Y1−x−yCexPry)PO4	Weight of Raw Materials (g)
	x	y	1 − x − y	Ce(NO3)3.6H2O	Pr4O7	Y2O3
Sample 1	0.04	0	0.96	15.53	0	97.99
(Control)
Sample 2	0.04	0.001	0.959	15.63	0.29	97.89
Sample 3	0.04	0.002	0.958	15.63	0.58	97.79
Sample 4	0.04	0.005	0.955	15.63	1.46	97.48
Sample 5	0.04	0.01	0.95	15.63	2.92	96.97

The emission and excitation spectra of the various YPO₄:Ce,Pr phosphors were measured using an Acton SpectraPro-2500i monochromator/spectrograph equipped with a deuterium light source and a VM-504 vacuum monochromator. FIG. 1 compares the UVA and UVB emissions of the YPO₄:Ce,Pr phosphors under 254 nm excitation and FIG. 2 compares the UVA and UVB emissions under 185 nm excitation. It is readily apparent from FIG. 2 that the addition of Pr has increased the sensitivity of the YPO₄:Ce phosphor to 185 nm radiation in relation to the concentration of the Pr activator. Moreover, the co-activation nearly maintains the phosphor's response to 254 nm radiation.

A better view of the increased 185 nm sensitivity of the coactivated phosphor may be seen in FIGS. 3 and 4 which show the excitation spectra of the phosphors measured for emissions at 355 nm and 335 nm, respectively. These spectra were corrected relative to the excitation curve of a sodium salicylate standard. As expected from the response demonstrated in FIG. 2, the excitation curves for the coactivated YPO₄:Ce,Pr phosphors exhibit a steady increase in intensity in the VUV region below about 200 nm with increasing Pr concentrations.

Phosphor samples were packed into plaques and excited by either 254 nm or 185 nm radiation from a mercury discharge. The emission of each sample was measured from 260 to 400 nm and the areas under the UVA (321-400 nm) and the UVB (260-320 nm) regions calculated. Table 2 lists the integrated area of their UVA and UVB emissions under 254 nm and 185 nm radiation and overall relative brightness intensity. A calculated total brightness is provided to simulate the performance of the phosphor under excitation by a low-pressure mercury discharge. This quantity was calculated by adding 8% of the integrated emission intensity under 185 nm excitation to 92% of the integrated emission intensity under 254 nm excitation. These percentages represent the approximate relative proportions of the UV radiation emitted by a low-pressure Hg discharge.

TABLE 2
Integrated Emission Intensities of (Y1−x−yCexPry)PO4 Phosphor Samples
Between 260 nm and 400 nm
	Integrated	Integrated
	Area Under	Area Under	Calculated Total
	254 nm Radiation	185 nm Radiation	Brightness
	UVA	UVB	Sum, %	UVA	UVB	Sum, %	UVA	UVB	Sum, %
Sample 1	639.9	9.4	100	231.2	4.1	100	607.2	9.0	100
(control)
Sample 2	641.5	8.9	100.2	403.1	5.5	173.7	622.5	8.6	102.4
Sample 3	644.4	10.4	100.8	453.2	6.5	195.4	629.1	10.1	103.7
Sample 4	640.7	13.1	100.8	513.4	8.9	222.0	630.5	12.8	104.4
Sample 5	633.1	22.0	100.9	538.5	13.6	234.7	625.5	21.3	105.0

Table 2 shows that all the Ce,Pr-coactivated yttrium phosphate phosphor samples exhibited significantly higher UVA and UVB emissions than the Ce only-activated control under 185 nm excitation. The enhancement of UVA and UVB emissions under 185 nm excitation was continuously improved by increasing the concentration of Pr. FIG. 2 confirms that the phosphor emission peaks at 355 nm, 335 nm, and 310 nm became stronger under 185 nm excitation with increasing Pr concentration. Under 254 nm excitation, the UVA emission improved slightly as the Pr concentration was increased to 0.002 moles Pr/mole of phosphor and then decreased gradually as the Pr concentration was increased to 0.01 moles Pr/mole of phosphor. These results can be further explained by referring to the emission spectra shown in FIG. 1. At 0.005 and 0.01 moles Pr/mole of phosphor, the intensity of the primary 355 nm emission peak lessened slightly under 254 nm excitation. Although the secondary 335 nm emission peak remained the same, the broader 310 nm emission intensified. Due to this continuous improvement of UVB emission, all the Ce,Pr-coactivated samples displayed about the same or slightly better overall UV (UVA+UVB) emission intensity than the Ce only-activated control under 254 nm excitation. As seen in Table 2, when the Pr concentration was increased to 0.005 moles Pr/mole of phosphor, the calculated total UVA emission appeared to reach a maximum under the combined 254 nm and 185 nm excitation. However, the calculated total UVB emission continued to increase with increasing Pr concentration under the combined excitation. Thus, all of the Ce,Pr-coactivated phosphor samples had a calculated total UV brightness which was greater than the Ce only-activated control. This indicates that the Ce,Pr-coactivated phosphor of this invention should exhibit better performance in a fluorescent lamp when excited with a low-pressure mercury discharge.

FIG. 5 is a cross-sectional illustration of a fluorescent lamp having a phosphor coating containing the YPO₄:Ce,Pr phosphor of this invention. The lamp has a hermetically sealed glass envelope 17. The interior of the envelope 17 is filled with an inert gas such as argon or a mixture of argon and krypton at a low pressure, for example 1-3 torr, and a small quantity of mercury, at least enough to provide a low vapor pressure of mercury during operation. An electrical discharge is generated between electrodes 12 to excite the mercury vapor to generate ultraviolet radiation. A phosphor coating 15 is applied to the interior surface of the envelope 17 to convert at least a portion of the ultraviolet radiation emitted by the low-pressure mercury discharge into a desired wavelength range. The phosphor coating 15 contains the YPO₄:Ce,Pr phosphor which emits UVA and UVB radiation when stimulated by the ultraviolet radiation emitted by the discharge. The phosphor coating may contain other phosphors in order to adapt the spectral output of the lamp to the desired application, including, but not limited to other UV-emitting and/or visible light-emitting phosphors.

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.

Claims

1. A UV-emitting phosphor comprising yttrium phosphate activated with cerium and praseodymium.

2. The phosphor of claim 1 wherein the phosphor has emission peaks at about 355 nm and about 335 nm.

3. The phosphor of claim 1 wherein the phosphor is represented by a formula YPO4:Ce,Pr.

4. The phosphor of claim 1 wherein the phosphor is represented by a formula (Y1-x-yCexPry)PO4, where x is from about 0.01 to about 0.20, and y is from about 0.001 to about 0.05.

5. The phosphor of claim 4 wherein x is from about 0.02 to about 0.08 and y is from about 0.002 to about 0.02.

6. A lamp comprising a glass envelope having a phosphor coating on an interior surface, the phosphor coating containing a UV-emitting phosphor comprising yttrium phosphate activated with cerium and praseodymium.

7. The lamp of claim 6 wherein the envelope is hermetically sealed and contains an amount of mercury and an inert gas and generates a discharge that emits 254 nm and 185 nm radiation when operating.

8. The lamp of claim 6 wherein the UV-emitting phosphor is represented by a formula YPO4:Ce,Pr.

9. The lamp of claim 6 wherein the UV-emitting phosphor is represented by a formula (Y1-x-yCexPry)PO4, where x is from about 0.01 to about 0.20, and y is from about 0.001 to about 0.05.

10. The lamp of claim 9 wherein x is from about 0.02 to about 0.08 and y is from about 0.002 to about 0.02.

11. A method of making a yttrium phosphate phosphor activated with cerium and praseodymium, the method comprising: combining a flux with stoichiometric amounts of a phosphate source, a yttrium source, a cerium source, and a praseodymium source to form a mixture, the flux being selected from a lithium-containing compound, a boron-containing compound, or a combination thereof, and firing the mixture at a temperature and for a time sufficient to form the phosphor.

12. The method of claim 11 wherein the mixture is fired in a reducing atmosphere.

13. The method of claim 11 wherein the lithium-containing compound is lithium carbonate and the boron-containing compound is boric acid.

14. The method of claim 11 wherein the yttrium source, the cerium source and the praseodymium source are oxides of Y, Ce, Pr or compounds of Y, Ce and Pr which are capable of being converted to oxides of Y, Ce and Pr.

15. The method of claim 14 wherein the compounds are nitrates, sulfates, halides or hydroxides of Y, Ce and Pr.

16. The method of claim 11 wherein the phosphate source is selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or boron phosphate.

17. The method of claim 11 wherein the mixture is fired for about 3 hours to about 10 hours at a temperature from about 800° C. to about 1400° C.

18. The method of claim 11 wherein the mixture is formed by reacting an aqueous solution containing the yttrium, cerium and praseodymium sources with a stoichiometric amount, or slight excess, of the phosphate source in a pH-adjusted solution at a temperature from about 70° C. to about 95° C. to form a co-precipitate of mixed (Y, Ce, Pr) phosphate, firing the phosphate co-precipitate at a temperature from about 600° C. to about 800° C., and mixing with the flux.

19. The method of claim 11 wherein the mixture is formed by dissolving the yttrium, cerium and praseodymium sources in nitric acid to form a solution, adding oxalic acid or ammonia to the solution to form a coprecipitate of oxalates or hydroxides, firing the coprecipitate to form a mixed oxide coprecipitate, and mixing with the flux and the phosphate source.

20. The method of claim 19 wherein the phosphate source is selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or boron phosphate.

21. The method of claim 20 wherein the mixture is fired for about 3 hours to about 10 hours at a temperature from about 800° C. to about 1400° C.

22. The method of claim 18 wherein the mixture is fired for about 3 hours to about 10 hours at a temperature from about 800° C. to about 1400° C.