# Patent

## Title
Phosphor, its preparation method and light emitting devices using the same

## Abstract

A phosphor can be excited by UV, purple or blue light LED, its preparation method, and light emitting devices incorporating the same. The phosphor contains rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. Its General formula of is aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm; M is at least one metal element selected from a group consisting of Ca, Sr and Ba; M′ is at least one metal element selected from Al and Ga; A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba; X is at least one element selected from F and Cl; R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn; 0.01≦a≦2, 0.35≦b≦4, 0.01≦c≦1, 0.01≦d≦0.3, 0.01≦f≦3, 0.6≦e≦2.4. The phosphor has broad emitting range, high efficiency, better uniformity and stability. A light emitting device is obtained by incorporating the phosphor into a UV, purple or blue light emitting device.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation application filed under 35 U.S.C. §111(a), claiming the benefit under 35 U.S.C. §120 and §365(c) of a PCT International Application Number PCT/CN2007/000852, filed Mar. 16, 2007, it being further noted that foreign priority benefit is based upon Chinese Patent Application 200610065812.X, filed Mar. 24, 2006 in the State Intellectual Property Office of P.R. China, the disclosures of which are thereby incorporated by reference.


FIELDS OF THE INVENTION
The present invention relates to a phosphor that can be excited by ultraviolet, purple or blue LEDs, the preparation method thereof, and light emitting devices using the same.
BACKGROUND OF THE INVENTION
Light emitting diodes (“LEDs”) have attracted much attention due to many advantages, such as small volume, low power consumption, long lifetime, fast-response, environmental friendliness, and high reliability etc. They are used widely in indicating lamps, decorating lamps, signal lamps etc. It can be looked forward to the coming future that LEDs will access into general lighting field with the faster and advanced developments.
Generally, there are two ways to generate white LED: one way is to combine the red, green and blue LEDs to get white light; the other way is to excite phosphors with LED to obtain white light. According to the difference in phosphors, the latter approach includes three routes: matching yellow phosphor with blue LED, matching green and red phosphors with blue LED, or matching red, green and blue phosphors with purple or UV LEDs.
As for current LED techniques, white LEDs are preferred to be generated by incorporating blue LED with YAG (yttrium aluminum garnet) yellow phosphor. In the Chinese patent CN97196762, this phosphor is reported in details. However, due to the characteristics of the phosphor, the luminous efficiency of white LEDs using this YAG phosphor is not yet adequate at present, and it is not applicable in general lighting field by taking into account the energy-saving. Therefore, the studies on novel phosphors with good luminescence performance are focused by many researchers from all over the world.
A silicate-borate phosphor represented by the formula (Y,La)1-x-y-zCexGdyTbz(Mg,Zn,Gd)1-pMnpB5-q-s(Al,Ga)qXsO10 has been reported in the German patent DE19730005. Phosphors comprising silicon, disclosed in British patents GB1334838, GB1326868 and GB1379949, with emission main peaks at 370-430 nm, are employed as cathode ray exciting phosphors. An alkaline-earth silicate phosphor that can be excited by blue light to generate yellow light, with similar performance as that of the YAG phosphor, has been developed by Barry (J. Electrochem. Soc., 1968, 115: 1181-1184), and has been described in white LED in U.S. Patent Publication US20040051111.
SUMMARY OF THE INVENTION
One aspect of the present invention is to provide a phosphor that possesses desirable chemical stability, high luminous efficiency and can be excited efficiently by ultraviolet, purple or blue LED's.
Another aspect of the present invention is to provide a preparation method for the phosphor mentioned above.
Still another aspect of the present invention is to provide a light emitting device that incorporates the above mentioned phosphor.
A phosphor according to one aspect of the invention contains, for example, rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. Rare earth refers to “rare earth elements” or “rare earth metals,” and hereinafter, the expression “rare earth” will be used. The rare earth is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm, as well as at least one metal element selected from a group consisting of Ce, Eu and Tb. The alkaline-earth metal is at least one metal element selected from a group consisting of Mg, Ca, Sr and Ba. The halogen is at least one element selected from F and Cl. The phosphor according to one aspect of the present invention possesses high conversion efficiency, and can be used to produce white LED with high luminous efficiency.
As one embodiment, the phosphor can be represented by the general formula of

aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2;
0.35≦b≦4;
0.01≦c≦1;
0.01≦d≦0.3;
0.01≦f≦3; and
0.6≦e≦2.4.
The phosphor according to the present invention has excellent luminescent properties such as wide exciting wavelength scope, efficient emitting transition and chemical stability, and can be excited by ultraviolet, purple or blue LED. New light emitting devices can be obtained by incorporating the phosphor into the LED.
A preparation method for the phosphor mentioned above includes the following:
(1) According to the general formula:

aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2;
0.35≦b≦4;
0.01≦c≦1;
0.01≦d≦0.3;
0.01≦f≦3; and
0.6≦e≦2.4;
weighing elementary substance or compounds or salts of Ln, M, M′, halide of A, and compounds or salts of R and Si as raw materials based on the stoichiometric ratio;
adding at the same time, excess quantity of SiO2 and/or AXe as flux into the above raw materials, then mixing and grinding together to form a mixture.
(2) baking the mixture at high temperature under reducing atmosphere to form a baked product.
(3) Carrying out a post-treatment to the baked product to obtain the phosphor of the present invention.
According to (1) above, the compounds of Ln, M, M′, A, R and Si are selected from oxide, hydroxide etc.; the salts are selected from the corresponding carbonate, nitrate, organic salt etc.
According to (1) above, the amount of the flux is 0.001-20 wt % by weight of the total phosphor.
According to (1) above, the starting materials can be mixed and grinded in alcohol, acetone or water.
According to (2) above, the operation of baking can be carried out once, twice or more.
According to (2) above, the temperature of baking is at 500 ̃1600° C.
According to (2) above, each baking operation should last for 0.5 ̃15 h.
According to (3) above, the post-treatment includes grinding, air flow crushing, washing, sifting, drying and grading, etc.
According to (3) above, the washing step in the post-treatment can be done by using acid solution, alkali solution or water.
According to (3) above, the grading step in the post-treatment can be carried out with at least one method selected from a group consisting of sedimentation method, sieving method, hydraulic classification and air flow grading.
It is easily found that the above preparation method of the present phosphor is advantageous for being very simple, involving no pollution and having low cost. Also, this phosphor can be excited by UV, purple or blue light to emit broadband visible light with wavelengths peaking at 500-600 nm and having full width at half maximum (“FWHM”) beyond 30 nm. That is to say, the phosphor of the present invention can match UV, purple or blue LED, and can be implanted directly or along with other phosphors into LEDs to produce white or color light emitting devices.
In accordance with an aspect of the present invention, a light emitting device can be produced by combining the present phosphor with at least a kind of LED, such as UV, purple or blue LED. The phosphor contains rare earth, silicon, alkaline-earth metal, halogen, and oxygen, as well as aluminum or gallium. The rare earth is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm as well as at least one metal element selected from a group consisting of Ce, Eu and Tb The alkaline-earth metal is at least one metal element selected from a group consisting of Mg, Ca, Sr and Ba. The halogen is at least one element selected from F and Cl.
The phosphor can be represented by the general formula of

aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2,
0.35≦b≦4,
0.01≦c≦1,
0.01≦d≦0.3,
0.01≦f≦3, and
0.6≦e≦2.4.
The above-described phosphor of the present invention has excellent luminescent properties and stability with novel composition.
The preparation method for the phosphor is simple, involving no pollution and having lower cost.
A light emitting device is obtained by incorporating the phosphor into an LED, which has long lifetime and high luminous efficiency.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the excitation spectrum of Example 1;
FIG. 2 shows the emission spectrum of the Example 1.



DESCRIPTION OF THE EXAMPLES
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that the same are intended only as illustrative and in nowise limitative. The scope of protection of this invention will be further embodied in the claims.
Example 1
In this example, the formula of the phosphor is verified as 1.47Y2O3.BaO.2.48Al2O3.1.03SiO2.0.03BaF2:0.03Ce,0.01Eu. Raw materials Y2O3(4N), BaO(4N), Al2O3(4N), CeO2(4N), Eu2O3(4N), SiO2(4N), BaF2(AR), are weighed with appropriate stoichiometric ratio. SiO2 and BaF2 act as both reactant and flux. The amount of flux is 18 wt % by weight of above raw materials, and the weight ratio of the flux, SiO2 and BaF2, is 1:1. Mixing and grinding these materials, and then baking them at 1450° C. for 3 hours under reducing atmosphere. After crushing, washing, sifting, drying and sieving, the phosphor can be obtained. As shown in FIG. 1, the phosphor can be excited by 350-480 nm and emit 544 nm yellow light.
Example 2
In this example, the formula of the phosphor is verified as 1.47Y2O3.BaO.2.47Al2O3.1.03SiO2.0.06BaF2:0.04Ce,0.03Eu. Raw materials Y2O3(4N), BaO(4N), Al2O3(4N), CeO2(4N), Eu2O3(4N), SiO2(4N), BaF2(AR), are weighed with appropriate stoichiometric ratio. SiO2 and BaF2 act as both reactant and flux. The amount of flux is 10 wt % by weight of above raw materials, wherein the weight ratio of SiO2 and BaF2 is 1:1. The preparation method is similar as that of Example 1 but with different roasting times, temperature and period and taking crushing and sifting during the intermission of two-stage baking, namely, first, baking at 1400° C. for 2 hours in reducing atmosphere, then crushing, sieving and baking at 1550° C. for 2 hours in reducing atmosphere. After crushing, washing, sieving and drying, the phosphor can be obtained. The relative emission intensity is shown in Table 1.
Examples 3-72
In these examples, the formulae of the phosphors are listed in Table 1. In EXAMPLES 3-72, raw materials: oxides of Ln, M and M′, halide of A (AXe), oxides of R, and oxides of Si (SiO2), are weighed in accordance with the stoichiometric ratio of the formula of each embodiment. The oxides of Si and the halide of A may act as both reactant and flux. The amount of flux is 10 wt % by weight of above raw materials, wherein the weight ratio of the flux, oxides of Si and halide of A, is 1:1. The preparation step is similar as that of EXAMPLE 2, namely, first, baking at 1400° C. for 2 hours in reducing atmosphere, then crushing, sieving and baking at 1550° C. for 2 hours in reducing atmosphere. After crushing, washing, sieving and drying, the phosphor can be obtained. The relative emission intensity is showed in Table 1.







TABLE 1







The formulae and emission intensity of EXAMPLES 1-72









Relative Intensity (%)












Excited by
Excited by


EXAMPLES
Formula
330 nm
460 nm













1
1.47Y2O3•BaO•2.48Al2O3•1.03SiO2•0.03BaF2:0.03Ce, 0.01Eu
100
100


2
1.47Y2O3•BaO•2.47Al2O3•1.03SiO2•0.06BaF2:0.04Ce, 0.03Eu
105
106


3
Y2O3•0.48Sm2O3•BaO•2.45Al2O3•1.09SiO2•0.06BaF2:0.03Ce, 0.04Eu
96
97


4
La2O3•0.22Gd2O3•0.25Sm2O3•BaO•2.44Al2O3•1.12SiO2•0.06BaF2:0.06Ce, 0.01Eu, 0.001Tb
94
94


5
2.0Y2O3•BaO•1.0Al2O3•0.05Ga2O3•2.5SiO2•0.36BaF2:0.07Ce, 0.03Eu, 0.001Tb
90
91


6
1.91Y2O3•BaO•2.0Al2O3•1.06SiO2•0.1LiF:0.09Ce, 0.02Eu, 0.001Tb
104
106


7
1.34Pr2O3•BaO•2.5Al2O3•1.09SiO2•0.16LiCl:0.01Ce, 0.08Eu, 0.002Tb
108
110


8
0.818Y2O3•BaO•3.0Al2O3•1.12SiO2•0.2NaF:0.1Ce, 0.04Eu, 0.003Tb
106
105


9
0.297Y2O3•BaO•3.5Al2O3•1.15SiO2•0.2NaCl:0.12Ce, 0.02Eu, 0.004Tb
103
104


10
0.01Y2O3•BaO•4.0Al2O3•0.01SiO2•0.918KF:0.02Ce, 0.1Eu, 0.001Tb
112
115


11
1.473Nd2O3•BaO•2.79Al2O3•0.05SiO2•0.37KCl:0.02Ce, 0.11Eu, 0.002Tb
91
92


12
1.471Y2O3•BaO•2.81Al2O3•0.1SiO2•0.28MgF2:0.1Ce, 0.12Eu, 0.003Mn
90
89


13
1.472Y2O3•BaO•2.61Al2O3•0.5SiO2•0.28MgCl2:0.13Ce, 0.01Eu, 0.001Mn
82
84


14
1.482Y2O3•BaO•2.215Al2O3•1.0SiO2•0.57CaF2:0.01Ce, 0.12Eu, 0.004Mn
94
95


15
1.133Ho2O3•BaO•2.2Al2O3•2.0SiO2•0.3CaCl2:0.1Ce, 0.02Eu, 0.001Tb
97
96


16
0.8Y2O3•BaO•0.42Al2O3•3.0SiO2•0.16SrF2:0.01Ce, 0.1Eu, 0.003Tb
89
92


17
1.47Y2O3•BaO•2.42Al2O3•SiO2•0.16SrCl2:0.1Ce, 0.04Eu
88
89


18
Yb2O3•0.47Gd2O3•BaO•2.24Al2O3•1.36SiO2•0.16LiF:0.13Ce, 0.01Eu
92
93


19
Y2O3•0.44Gd2O3•BaO•2.25Al2O3•1.39SiO2•0.16LiCl:0.08Ce, 0.09Eu
91
93


20
Y2O3•0.44Gd2O3•BaO•2.21Al2O3•1.42SiO2•0.16NaF:0.09Ce, 0.02Eu
94
95


21
Y2O3•0.41Gd2O3•BaO•2.195Al2O3•1.45SiO2•0.16NaCl:0.15Ce, 0.13Eu
88
89


22
Y2O3•0.41Gd2O3•BaO•2.18Al2O3•1.48SiO2•0.16KF:0.01Ce, 0.01Eu
91
92


23
Y2O3•0.38Gd2O3•CaO•2.42Al2O3•1.48SiO2•0.16KCl:0.03Ce, 0.03Eu
86
87


24
Y2O3•0.38Gd2O3•CaO•2.165Al2O3•1.51SiO2•0.16MgF2:0.08Ce, 0.002Tb
94
95


25
Y2O3•0.35Sc2O3•CaO•2.15Al2O3•1.54SiO2•0.16MgCl2:0.02Ce, 0.005Tb
89
91


26
Y2O3•0.35Gd2O3•CaO•2.3Al2O3•1.12SiO2•0.16CaF2:0.04Ce, 0.001Tb
102
101


27
Y2O3•0.32Gd2O3•CaO•2.135Al2O3•1.57SiO2•0.16CaCl2:0.07Ce, 0.08Eu
92
93


28
Y2O3•0.32La2O3•CaO•2.12Al2O3•1.6SiO2•0.16SrF2:0.02Ce, 0.12Eu
89
90


29
Y2O3•0.29Gd2O3•CaO•2.105Al2O3•1.63SiO2•0.16SrCl2:0.14Ce, 0.02Eu
87
88


30
Y2O3•0.29Pr2O3•CaO•2.09Al2O3•1.66SiO2•0.16BaCl2:0.02Ce, 0.02Eu
93
94


31
Y2O3•0.26Sm2O3•CaO•2.125Al2O3•1.74SiO2•0.01LiF:0.06Ce, 0.06Eu
100
101


32
Y2O3•0.26Sm2O3•CaO•2.11Al2O3•1.75SiO2•0.03LiCl:0.09Ce, 0.08Eu
98
100


33
Y2O3•0.23Sm2O3•CaO•2.095Al2O3•1.75SiO2•0.06NaF:0.06Ce, 0.07Eu
102
103


34
Y2O3•0.23Sm2O3•CaO•2.08Al2O3•1.74SiO2•0.1NaCl:0.05Ce, 0.08Eu
96
97


35
Y2O3•0.2Sm2O3•CaO•2.065Al2O3•1.67SiO2•0.2KF:0.16Ce, 0.13Eu
97
98


36
Y2O3•0.2Sm2O3•CaO•2.05Al2O3•1.6SiO2•0.3KCl:0.15Ce, 0.13Eu
101
102


37
Y2O3•0.47Sm2O3•CaO•2.23Al2O3•0.9SiO2•0.4MgF2:0.13Ce, 0.1Eu
96
97


38
Y2O3•0.47Nd2O3•CaO•2.035Al2O3•1.43SiO2•0.5MgCl2:0.04Ce, 0.04Eu
96
95


39
Y2O3•0.47Sm2O3•CaO•2.02Al2O3•1.36SiO2•0.6CaF2:0.02Ce, 0.03Eu
91
92


40
Y2O3•0.47Sm2O3•CaO•2.005Al2O3•1.29SiO2•0.7CaCl2:0.12Ce, 0.03Eu
86
87


41
Y2O3•0.47Sm2O3•CaO•1.99Al2O3•1.22SiO2•0.8SrF2:0.13Ce, 0.04Eu
88
89


42
Y2O3•0.47Sm2O3•CaO•2.46Al2O3•0.18SiO2•0.9SrCl2:0.14Ce, 0.05Eu
85
86


43
Y2O3•0.47Ho2O3•CaO•2.45Al2O3•0.1SiO2•1.0BaCl2:0.06Ce, 0.06Eu
96
97


44
1.47Y2O3•CaO•2.39Al2O3•0.05Ga2O3•1.08SiO2•0.1LiF:0.08Ce, 0.05Eu
99
100


45
0.01Y2O3•CaO•3.84Al2O3•0.05Ga2O3•1.00SiO2•0.2LiCl:0.11Ce, 0.02Eu
103
102


46
0.05Yb2O3•CaO•3.36Al2O3•0.05Ga2O3•1.3SiO2•0.3NaF:0.1Ce, 0.05Eu
108
107


47
0.1Y2O3•CaO•3.74Al2O3•0.05Ga2O3•0.82SiO2•0.4NaCl:0.1Ce, 0.03Eu
93
94


48
0.5Y2O3•CaO•3.33Al2O3•0.05Ga2O3•0.74SiO2•0.5KF:0.09Ce, 0.02Eu
90
91


49
1.0Y2O3•CaO•2.82Al2O3•0.05Ga2O3•0.66SiO20.6KCl:0.08Ce
85
86


50
2.0Y2O3•CaO•1.81Al2O3•0.05Ga2O3•0.55SiO2•0.7MgF2:0.1Eu
96
97


51
0.01Sc2O3•SrO•3.79Al2O3•0.05Ga2O3•0.44SiO2•0.8MgCl2:0.007Ce, 0.01Eu
100
100


52
0.05Y2O3•SrO•3.74Al2O3•0.05Ga2O3•0.36SiO2•0.9CaF2:0.06Ce, 0.04Eu
93
92


53
0.1Y2O3•SrO•3.68Al2O3•0.05Ga2O3•0.28SiO2•1.0CaCl2:0.06Ce, 0.03Eu
96
97


54
0.5Y2O3•SrO•3.27Al2O3•0.05Ga2O3•1.2SiO2•0.1SrF2:0.07Ce, 0.04Eu
94
94


55
1.0La2O3•SrO•2.76Al2O3•0.05Ga2O3•1.12SiO2•0.2SrCl2:0.09Ce, 0.03Eu
90
91


56
2.0Y2O3•SrO•1.75Al2O3•0.05Ga2O3•1.04SiO2•0.3BaCl2:0.1Ce, 0.1Eu
105
106


57
0.47Pr2O3•0.5Gd2O3•0.5Sm2O3•SrO•2.3Al2O3•1.34SiO2•0.06BaF2:0.1Ce, 0.11Eu
90
90


58
0.47Y2O3•Gd2O3•SrO•2.29Al2O3•1.36SiO2•0.06BaF2:0.07Ce, 0.02Eu
89
88


59
0.47Y2O3•Gd2O3•SrO•2.23Al2O3•1.38SiO20.12LiF:0.12Ce, 0.02Eu
87
86


60
0.47Nd2O3•Gd2O3•SrO•2.22Al2O3•1.4SiO2•0.12LiCl:0.02Ce, 0.11Eu
86
87


61
0.44Y2O3•Gd2O3•SrO•2.21Al2O3•1.42SiO2•0.12NaF:0.02Ce, 0.02Eu
87
85


62
0.44Y2O3•Gd2O3•SrO•2.2Al2O3•1.44SiO2•0.12NaCl:0.08Ce, 0.08Eu
85
84


63
0.41Y2O3•Gd2O3•SrO•2.19Al2O3•1.43SiO2•0.12KF:0.07Ce, 0.01Eu
83
84


64
0.41Y2O3•Gd2O3•SrO•2.42Al2O3•1.18SiO2•0.12KCl:0.01Ce, 0.03Eu
83
83


65
0.38Y2O3•Gd2O3•SrO•2.19Al2O3•1.46SiO2•0.06MgF2:0.08Ce, 0.10Eu
89
91


66
0.38Y2O3•Gd2O3•SrO•2.18Al2O3•1.48SiO2•0.06MgCl2:0.1Ce, 0.1Eu, 0.1Tb
88
87


67
0.35Y2O3•Gd2O3•SrO•1.46Al2O3•1.96SiO2•0.06CaF2:0.16Ce
105
104


68
0.35Pr2O3•Gd2O3•SrO•2.17Al2O3•1.5SiO2•0.06CaCl2:0.12Ce, 0.12Eu
81
84


69
0.32Y2O3•Gd2O3•SrO•2.12Al2O3•1.6SiO2•0.06SrF2:0.12Ce, 0.10Eu
82
83


70
0.32Y2O3•Gd2O3•SrO•2.07Al2O3•1.7SiO2•0.06SrCl2:0.08Ce, 0.12Eu
78
79


71
0.29Y2O3•Gd2O3•SrO•2.02Al2O3•1.8SiO2•0.06BaF2:0.06Ce, 0.10Eu
80
78


72
0.29Nd2O3•Gd2O3•SrO•1.97Al2O3•1.9SiO2•0.06BaCl2:0.08Ce, 0.10Eu
86
84









Example 73
White light emitting device can be obtained by incorporating the phosphor of EXAMPLE 1 into a blue light LED. The phosphor powder of EXAMPLE 1 is firstly slurried, and then coated on a GaInN LED chip. After welding circuit and packaging, a white light emitting device is produced.
INDUSTRIAL APPLICABILITY
The above-described phosphor has broad emitting range, high efficiency, better uniformity and stability. The production method is simple, no pollution and a lower cost. A light emitting device can be obtained by incorporating this phosphor into a UV, purple or blue light emitting device.

## Claims

1. A phosphor represented by a general formula of:


aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein

Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2;
0.35≦b≦4;
0.01≦c≦1,
0.01≦d≦0.3;
0.01≦f≦3; and
0.6≦e≦2.4, wherein the phosphor is a member selected from the group consisting of:
1.47Y2O3.BaO.2.48Al2O3.1.03SiO2.0.03BaF2:0.03Ce,0.01Eu
1.47Y2O3.BaO.2.47Al2O3.1.03SiO2.0.06BaF2:0.04Ce,0.03Eu
Y2O3.0.48Sm2O3.BaO.2.45Al2O3.1.09SiO2.0.06BaF2:0.03Ce,0.04Eu
La2O3.0.22Gd2O3.0.25Sm2O3.BaO.2.44Al2O3.1.12SiO2.0.06BaF2:0.06Ce,0.01Eu,0.001Tb
2.0Y2O3.BaO.1.0Al2O3.0.05Ga2O3.2.5SiO2.0.36BaF2:0.07Ce,0.03Eu,0.001Tb
1.91Y2O3.BaO.2.01Al2O3.1.06SiO2.0.1LiF:0.09Ce,0.02Eu,0.001Tb
1.34Pr2O3.BaO.2.5Al2O3.1.09SiO2.0.16LiCl:0.01Ce,0.08Eu,0.002Tb
0.818Y2O3.BaO.3.0Al2O3.1.12SiO2.0.2NaF:0.1Ce,0.04Eu,0.003Tb
0.297Y2O3.BaO.3.5Al2O3.1.15SiO2.0.2NaCl:0.12Ce,0.02Eu,0.004Tb
0.01Y2O3.BaO.4.0Al2O3.0.01SiO2.0.918KF:0.02Ce,0.1Eu,0.001Tb
1.473Nd2O3.BaO.2.79Al2O3.0.05SiO2.0.37KCl:0.02Ce,0.11Eu,0.002Tb
1.471Y2O3.BaO.2.81Al2O3.0.1SiO2.0.28MgF2:0.1Ce,0.12Eu,0.003Mn
1.472Y2O3.BaO.2.61Al2O3.0.5SiO2.0.28MgCl2:0.13Ce,0.01Eu,0.001 Mn
1.482Y2O3.BaO.2.215Al2O3.1.0SiO2.0.57CaF2:0.01Ce,0.12Eu,0.004Mn
1.133Ho2O3.BaO.2.2Al2O3.2.0SiO2.0.3CaCl2:0.1Ce,0.02Eu,0.001Tb
0.8Y2O3.BaO.0.42Al2O3.3.0SiO2.0.16SrF2:0.01Ce,0.1Eu,0.003Tb
1.47Y2O3.BaO.2.42Al2O3SiO2.0.16SrCl2:0.1Ce,0.04Eu
Yb2O3.0.47Gd2O3.BaO.2.24Al2O3.1.36SiO2.0.16LiF:0.13Ce,0.01Eu
Y2O3.0.44Gd2O3.BaO.2.25Al2O3.1.39SiO2.0.16LiCl:0.08Ce,0.09Eu
Y2O3.0.44Gd2O3.BaO.2.21Al2O3.1.42SiO2.0.16NaF:0.09Ce,0.02Eu
Y2O3.0.41Gd2O3.BaO.2.195Al2O3.1.45SiO2.0.16NaCl:0.15Ce,0.13Eu
Y2O3.0.41Gd2O3.BaO.2.18Al2O3.1.48SiO2.0.16KF:0.01Ce,0.01Eu
Y2O3.0.38Gd2O3.CaO.2.42Al2O3.1.48SiO2.0.16KCl:0.03Ce,0.03Eu
Y2O3.0.38Gd2O3.CaO.2.165Al2O3.1.51SiO2.0.16MgF2:0.08Ce,0.002Tb
Y2O3.0.35Sc2O3.CaO.2.15Al2O3.1.54SiO2.0.16MgCl2:0.02Ce,0.005Tb
Y2O3.0.35Gd2O3.CaO.2.3Al2O3.1.12SiO2.0.16CaF2:0.04Ce,0.001Tb
Y2O3.0.32Gd2O3.CaO.2.135Al2O3.1.57SiO2.0.16CaCl2:0.07Ce,0.08Eu
Y2O3.0.32La2O3.CaO.2.12Al2O3.1.6SiO2.0.16SrF2:0.02Ce,0.12Eu
Y2O3.0.29Gd2O3CaO.2.105Al2O3.1.63SiO2.0.16SrCl2:0.14Ce,0.02Eu
Y2O3.0.29Pr2O3CaO.2.09Al2O3.1.66SiO2.0.16BaCl2:0.02Ce,0.02Eu
Y2O3.0.26Sm2O3.CaO.2.125Al2O3.1.74SiO2.0.01LiF:0.06Ce,0.06Eu
Y2O3.0.26Sm2O3.CaO.2.11Al2O3.1.75SiO2.0.03LiCl:0.09Ce,0.08Eu
Y2O3.0.23Sm2O3.CaO.2.095Al2O3.1.75SiO2.0.06NaF:0.06Ce,0.07Eu
Y2O3.0.23Sm2O3.CaO.2.08Al2O3.1.74SiO2.0.1NaCl:0.05Ce,0.08Eu
Y2O3.0.2Sm2O3.CaO.2.065Al2O3.1.67SiO2.0.2KF:0.16Ce,0.13Eu
Y2O3.0.2Sm2O3.CaO.2.05Al2O3.1.6SiO2.0.3KCl:0.15Ce,0.13Eu
Y2O3.0.47Sm2O3.CaO.2.23Al2O3.0.9SiO2.0.4MgF2:0.13Ce,0.1Eu
Y2O3.0.47Nd2O3.CaO.2.035Al2O3.1.43SiO2.0.5MgCl2:0.04Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.02Al2O3.1.36SiO2.0.6CaF2:0.02Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.2.005Al2O3.1.29SiO2.0.7CaCl2:0.12Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.1.99Al2O3.1.22SiO2.0.8SrF2:0.13Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.46Al2O3.0.18SiO2.0.9SrCl2:0.14Ce,0.05Eu
Y2O3.0.47Ho2O3.CaO.2.45Al2O3.0.1SiO2.1.0BaCl2:0.06Ce,0.06Eu
1.47Y2O3.CaO.2.39Al2O3.0.05Ga2O3.1.08SiO2.0.1LiF:0.08Ce,0.05Eu
0.01Y2O3CaO.3.84Al2O3.0.05Ga2O3.1.00SiO2.0.2LiCl:0.11Ce,0.02Eu
0.05Yb2O3CaO.3.36Al2O3.0.05Ga2O3.1.3SiO2.0.3NaF:0.1Ce,0.05Eu
0.1Y2O3CaO.3.74Al2O3.0.05Ga2O3.0.82SiO2.0.4NaCl:0.1Ce,0.03Eu
0.5Y2O3CaO.3.33Al2O3.0.05Ga2O3.0.74SiO2.0.5KF:0.09Ce,0.02Eu
1.0Y2O3CaO.2.82Al2O3.0.05Ga2O3.0.66SiO2.0.6KCl:0.08Ce
2.0Y2O3CaO.1.81Al2O3.0.05Ga2O3.0.55SiO2.0.7MgF2:0.1Eu
0.01Sc2O3.SrO.3.79Al2O3.0.05Ga2O3.0.44SiO2.0.8MgCl2:0.007Ce,0.01Eu
0.05Y2O3.SrO.3.74Al2O3.0.05Ga2O3.0.36SiO2.0.9CaF2:0.06Ce,0.04Eu
0.1Y2O3.SrO.3.68Al2O3.0.05Ga2O3.0.28SiO2.1.0CaCl2:0.06Ce,0.03Eu
0.5Y2O3.SrO.3.27Al2O3.0.05Ga2O3.1.2SiO2.0.1SrF2:0.007Ce,0.04Eu
1.0La2O3.SrO.2.76Al2O3.0.05Ga2O3.1.12SiO2.0.2SrCl2:0.09Ce,0.03Eu
2.0Y2O3.SrO.1.75Al2O3.0.05Ga2O3.1.04SiO2.0.3BaCl2:0.1Ce,0.1Eu
0.47Pr2O3.0.5Gd2O3.0.5Sm2O3.SrO.2.3Al2O3.1.34SiO2.0.06BaF2:0.1Ce,0.11Eu
0.47Y2O3Gd2O3.SrO.2.29Al2O3.1.36SiO2.0.06BaF2:0.07Ce,0.02Eu
0.47Y2O3Gd2O3.SrO.2.23Al2O3.1.38SiO2.0.12LiF:0.12Ce,0.02Eu
0.47Nd2O3Gd2O3.SrO.2.22Al2O3.1.4SiO2.0.12LiCl:0.02Ce,0.11Eu
0.44Y2O3Gd2O3.SrO.2.21Al2O3.1.42SiO2.0.12NaF:0.02Ce,0.02Eu
0.44Y2O3Gd2O3.SrO.2.2Al2O3.1.44SiO2.0.12NaCl:0.08Ce,0.08Eu
0.41Y2O3Gd2O3.SrO.2.19Al2O3.1.43SiO2.0.12KF:0.07Ce,0.01Eu
0.41Y2O3Gd2O3.SrO.2.42Al2O3.1.18SiO2.0.12KCl:0.01Ce,0.03Eu
0.38Y2O3.Gd2O3.SrO.2.19Al2O3.1.46SiO2.0.06MgF2:0.08Ce,0.10Eu
0.38Y2O3.Gd2O3.SrO.2.18Al2O3.1.48SiO2.0.06MgCl2:0.1Ce,0.1Eu,0.1Tb
0.35Y2O3.Gd2O3.SrO.1.46Al2O3.1.96SiO2.0.06CaF2:0.16Ce
0.35Pr2O3.Gd2O3.SrO.2.17Al2O3.1.5SiO2.0.06CaCl2:0.12Ce,0.12Eu
0.32Y2O3.Gd2O3.SrO.2.12Al2O3.1.6SiO2.0.06SrF2:0.12Ce,0.10Eu
0.32Y2O3.Gd2O3.SrO.2.07Al2O3.1.7SiO2.0.06SrCl2:0.08Ce,0.12Eu
0.29Y2O3.Gd2O3.SrO.2.02Al2O3.1.8SiO2.0.06BaF2:0.06Ce,0.10Eu and
0.29Nd2O3.Gd2O3.SrO.1.97Al2O3.1.9SiO2.0.06BaCl2:0.08Ce,0.10Eu.

2. A method of producing a phosphor, comprising:
weighing elementary substance or compounds or salts of Ln, M, M′, halide of A, and compounds or salts of R and Si as raw materials with weights that are based on the stoichiometric ratio, and adding an excess quantity of SiO2 and/or AXe as flux into the raw materials, then mixing and grinding to form a mixture;
baking the mixture at high temperature under reducing atmosphere; and
carrying out a post-treatment of the baked product to obtain the phosphor, wherein the phosphor is represented by a general formula of:


aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein


Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr, and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2;
0.35≦b≦4;
0.01≦c≦1;
0.01≦d≦0.3;
0.01≦f≦3; and
0.65≦e≦2.4, wherein the phosphor is a member from the group consisting of:
1.47Y2O3.BaO.2.48Al2O3.1.03SiO2.0.03BaF2:0.03Ce,0.01Eu
1.47Y2O3.BaO.2.47Al2O3.1.03SiO2.0.06BaF2:0.04Ce,0.03Eu
Y2O3.0.48Sm2O3.BaO.2.45Al2O3.1.09SiO2.0.06BaF2:0.03Ce,0.04Eu
La2O3.0.22Gd2O3.0.25Sm2O3.BaO.2.44Al2O3.1.12SiO2.0.06BaF2:0.06Ce,0.01Eu,0.001Tb
2.0Y2O3.BaO.1.0Al2O3.0.05Ga2O3.2.5SiO2.0.36BaF2:0.07Ce,0.03Eu,0.001Tb
1.91Y2O3.BaO.2.01Al2O3.1.06SiO2.0.1LiF:0.09Ce,0.02Eu,0.001Tb
1.34Pr2O3.BaO.2.5Al2O3.1.09SiO2.0.16LiCl:0.01Ce,0.08Eu,0.002Tb
0.818Y2O3.BaO.3.0Al2O3.1.12SiO2.0.2NaF:0.1Ce,0.04Eu,0.003Tb
0.297Y2O3.BaO.3.5Al2O3.1.15SiO2.0.2NaCl:0.12Ce,0.02Eu,0.004Tb
0.01Y2O3.BaO.4.0Al2O3.0.01SiO2.0.918KF:0.02Ce,0.1Eu,0.001Tb
1.473Nd2O3.BaO.2.79Al2O3.0.05SiO2.0.37KCl:0.02Ce,0.11Eu,0.002Tb
1.471Y2O3.BaO.2.81Al2O3.0.1SiO2.0.28MgF2:0.1Ce,0.12Eu,0.003Mn
1.472Y2O3.BaO.2.61Al2O3.0.5SiO2.0.28MgCl2:0.13Ce,0.01Eu,0.001 Mn
1.482Y2O3.BaO.2.215Al2O3.1.0SiO2.0.57CaF2:0.01Ce,0.12Eu,0.004Mn
1.133Ho2O3.BaO.2.2Al2O3.2.0SiO2.0.3CaCl2:0.1Ce,0.02Eu,0.001Tb
0.8Y2O3.BaO.0.42Al2O3.3.0SiO2.0.16SrF2:0.01Ce,0.1Eu,0.003Tb
1.47Y2O3.BaO.2.42Al2O3SiO2.0.16SrCl2:0.1Ce,0.04Eu
Yb2O3.0.47Gd2O3.BaO.2.24Al2O3.1.36SiO2.0.16LiF:0.13Ce,0.01Eu
Y2O3.0.44Gd2O3.BaO.2.25Al2O3.1.39SiO2.0.16LiCl:0.08Ce,0.09Eu
Y2O3.0.44Gd2O3.BaO.2.21Al2O3.1.42SiO2.0.16NaF:0.09Ce,0.02Eu
Y2O3.0.41Gd2O3.BaO.2.195Al2O3.1.45SiO2.0.16NaCl:0.15Ce,0.13Eu
Y2O3.0.41Gd2O3.BaO.2.18Al2O3.1.48SiO2.0.16KF:0.01Ce,0.01Eu
Y2O3.0.38Gd2O3.CaO.2.42Al2O3.1.48SiO2.0.16KCl:0.03Ce,0.03Eu
Y2O3.0.38Gd2O3.CaO.2.165Al2O3.1.51SiO2.0.16MgF2:0.08Ce,0.002Tb
Y2O3.0.35Sc2O3.CaO.2.15Al2O3.1.54SiO2.0.16MgCl2:0.02Ce,0.005Tb
Y2O3.0.35Gd2O3.CaO.2.3Al2O3.1.12SiO2.0.16CaF2:0.04Ce,0.001Tb
Y2O3.0.32Gd2O3.CaO.2.135Al2O3.1.57SiO2.0.16CaCl2:0.07Ce,0.08Eu
Y2O3.0.32La2O3.CaO.2.12Al2O3.1.6SiO2.0.16SrF2:0.02Ce,0.12Eu
Y2O3.0.29Gd2O3CaO.2.105Al2O3.1.63SiO2.0.16SrCl2:0.14Ce,0.02Eu
Y2O3.0.29Pr2O3CaO.2.09Al2O3.1.66SiO2.0.16BaCl2:0.02Ce,0.02Eu
Y2O3.0.26Sm2O3.CaO.2.125Al2O3.1.74SiO2.0.01LiF:0.06Ce,0.06Eu
Y2O3.0.26Sm2O3.CaO.2.11Al2O3.1.75SiO2.0.03LiCl:0.09Ce,0.08Eu
Y2O3.0.23Sm2O3.CaO.2.095Al2O3.1.75SiO2.0.06NaF:0.06Ce,0.07Eu
Y2O3.0.23Sm2O3.CaO.2.08Al2O3.1.74SiO2.0.1NaCl:0.05Ce,0.08Eu
Y2O3.0.2Sm2O3.CaO.2.065Al2O3.1.67SiO2.0.2KF:0.16Ce,0.13Eu
Y2O3.0.2Sm2O3.CaO.2.05Al2O3.1.6SiO2.0.3KCl:0.15Ce,0.13Eu
Y2O3.0.47Sm2O3.CaO.2.23Al2O3.0.9SiO2.0.4MgF2:0.13Ce,0.1Eu
Y2O3.0.47Nd2O3.CaO.2.035Al2O3.1.43SiO2.0.5MgCl2:0.04Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.02Al2O3.1.36SiO2.0.6CaF2:0.02Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.2.005Al2O3.1.29SiO2.0.7CaCl2:0.12Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.1.99Al2O3.1.22SiO2.0.8SrF2:0.13Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.46Al2O3.0.18SiO2.0.9SrCl2:0.14Ce,0.05Eu
Y2O3.0.47Ho2O3.CaO.2.45Al2O3.0.1SiO2.1.0BaCl2:0.06Ce,0.06Eu
1.47Y2O3.CaO.2.39Al2O3.0.05Ga2O3.1.08SiO2.0.1LiF:0.08Ce,0.05Eu
0.01Y2O3CaO.3.84Al2O3.0.05Ga2O3.1.00SiO2.0.2LiCl:0.11Ce,0.02Eu
0.05Yb2O3CaO.3.36Al2O3.0.05Ga2O3.1.3SiO2.0.3NaF:0.1Ce,0.05Eu
0.1Y2O3CaO.3.74Al2O3.0.05Ga2O3.0.82SiO2.0.4NaCl:0.1Ce,0.03Eu
0.5Y2O3CaO.3.33Al2O3.0.05Ga2O3.0.74SiO2.0.5KF:0.09Ce,0.02Eu
1.0Y2O3CaO.2.82Al2O3.0.05Ga2O3.0.66SiO2.0.6KCl:0.08Ce
2.0Y2O3CaO.1.81Al2O3.0.05Ga2O3.0.55SiO2.0.7MgF2:0.1Eu
0.01Sc2O3.SrO.3.79Al2O3.0.05Ga2O3.0.44SiO2.0.8MgCl2:0.007Ce,0.01Eu
0.05Y2O3.SrO.3.74Al2O3.0.05Ga2O3.0.36SiO2.0.9CaF2:0.06Ce,0.04Eu
0.1Y2O3.SrO.3.68Al2O3.0.05Ga2O3.0.28SiO2.1.0CaCl2:0.06Ce,0.03Eu
0.5Y2O3.SrO.3.27Al2O3.0.05Ga2O3.1.2SiO2.0.1SrF2:0.007Ce,0.04Eu
1.0La2O3.SrO.2.76Al2O3.0.05Ga2O3.1.12SiO2.0.2SrCl2:0.09Ce,0.03Eu
2.0Y2O3.SrO.1.75Al2O3.0.05Ga2O3.1.04SiO2.0.3BaCl2:0.1Ce,0.1Eu
0.47Pr2O3.0.5Gd2O3.0.5Sm2O3.SrO.2.3Al2O3.1.34SiO2.0.06BaF2:0.1Ce,0.11Eu
0.47Y2O3Gd2O3.SrO.2.29Al2O3.1.36SiO2.0.06BaF2:0.07Ce,0.02Eu
0.47Y2O3Gd2O3.SrO.2.23Al2O3.1.38SiO2.0.12LiF:0.12Ce,0.02Eu
0.47Nd2O3Gd2O3.SrO.2.22Al2O3.1.4SiO2.0.12LiCl:0.02Ce,0.11Eu
0.44Y2O3Gd2O3.SrO.2.21Al2O3.1.42SiO2.0.12NaF:0.02Ce,0.02Eu
0.44Y2O3Gd2O3.SrO.2.2Al2O3.1.44SiO2.0.12NaCl:0.08Ce,0.08Eu
0.41Y2O3Gd2O3.SrO.2.19Al2O3.1.43SiO2.0.12KF:0.07Ce,0.01Eu
0.41Y2O3Gd2O3.SrO.2.42Al2O3.1.18SiO2.0.12KCl:0.01Ce,0.03Eu
0.38Y2O3.Gd2O3.SrO.2.19Al2O3.1.46SiO2.0.06MgF2:0.08Ce,0.10Eu
0.38Y2O3.Gd2O3.SrO.2.18Al2O3.1.48SiO2.0.06MgCl2:0.1Ce,0.1Eu,0.1Tb
0.35Y2O3.Gd2O3.SrO.1.46Al2O3.1.96SiO2.0.06CaF2:0.16Ce
0.35Pr2O3.Gd2O3.SrO.2.17Al2O3.1.5SiO2.0.06CaCl2:0.12Ce,0.12Eu
0.32Y2O3.Gd2O3.SrO.2.12Al2O3.1.6SiO2.0.06SrF2:0.12Ce,0.10Eu
0.32Y2O3.Gd2O3.SrO.2.07Al2O3.1.7SiO2.0.06SrCl2:0.08Ce,0.12Eu
0.29Y2O3.Gd2O3.SrO.2.02Al2O3.1.8SiO2.0.06BaF2:0.06Ce,0.10Eu and
0.29Nd2O3.Gd2O3.SrO.1.97Al2O3.1.9SiO2.0.06BaCl2:0.08Ce,0.10Eu.

3. The method according to claim 2, wherein the compounds of Ln, M, M′, A, R and Si are selected from the group consisting of corresponding oxide, hydroxide, carbonate, nitrate, and organic salt.

4. The method according to claim 2, wherein the amount of flux is in a range between 0.001% to 20% by weight of the total phosphor.

5. The method according to claim 2, wherein baking is carried out at least two times.

6. The method according to claim 5, wherein the temperature of baking is at a range between 500° C. to 1600° C.

7. The method according to claim 4 or 6, wherein each baking operation should last from 0.5 h to 15 h.

8. The method according to claim 2, wherein the post-treatment includes grinding, air flow crushing, washing, sifting, drying and grading.

9. The method according to claim 8, wherein the washing step in the post-treatment can be carried out using acid solution, alkali solution or water.

10. The method according to claim 8, wherein the grading step in the post-treatment is carried out with at least one method selected from a group consisting of sedimentation method, sieving method, hydraulic classification and air flow grading.

11. A light emitting device comprising:
a phosphor; and
a semiconductor light emitting element capable of emitting a light in the range from ultraviolet light to visible light, wherein
the phosphor is represented by a general formula of:


aLn2O3.MO.bM′2O3.fSiO2.cAXe:dR, wherein


Ln is at least one metal element selected from a group consisting of Sc, Y, La, Pr, Nd, Gd, Ho, Yb and Sm;
M is at least one metal element selected from a group consisting of Ca, Sr and Ba;
M′ is at least one metal element selected from Al and Ga;
A is at least one metal element selected from a group consisting of Li, Na, K, Mg, Ca, Sr and Ba;
X is at least one element selected from F and Cl;
R is at least one metal element selected from a group consisting of Ce, Eu, Tb and Mn;
0.01≦a≦2;
0.35≦b≦4;
0.01≦c≦1;
0.01≦d≦0.3;
0.01≦f≦3; and
0.6≦e≦2.4 wherein the phosphor is a member selected from the group consisting of:
1.47Y2O3.BaO.2.48Al2O3.1.03SiO2.0.03BaF2:0.03Ce,0.01Eu
1.47Y2O3.BaO.2.47Al2O3.1.03SiO2.0.06BaF2:0.04Ce,0.03Eu
Y2O3.0.48Sm2O3.BaO.2.45Al2O3.1.09SiO2.0.06BaF2:0.03Ce,0.04Eu
La2O3.0.22Gd2O3.0.25Sm2O3.BaO.2.44Al2O3.1.12SiO2.0.06BaF2:0.06Ce,0.01Eu,0.001Tb
2.0Y2O3.BaO.1.0Al2O3.0.05Ga2O3.2.5SiO2.0.36BaF2:0.07Ce,0.03Eu,0.001Tb
1.91Y2O3.BaO.2.01Al2O3.1.06SiO2.0.1LiF:0.09Ce,0.02Eu,0.001Tb
1.34Pr2O3.BaO.2.5Al2O3.1.09SiO2.0.16LiCl:0.01Ce,0.08Eu,0.002Tb
0.818Y2O3.BaO.3.0Al2O3.1.12SiO2.0.2NaF:0.1Ce,0.04Eu,0.003Tb
0.297Y2O3.BaO.3.5Al2O3.1.15SiO2.0.2NaCl:0.12Ce,0.02Eu,0.004Tb
0.01Y2O3.BaO.4.0Al2O3.0.01SiO2.0.918KF:0.02Ce,0.1Eu,0.001Tb
1.473Nd2O3.BaO.2.79Al2O3.0.05SiO2.0.37KCl:0.02Ce,0.11Eu,0.002Tb
1.471Y2O3.BaO.2.81Al2O3.0.1SiO2.0.28MgF2:0.1Ce,0.12Eu,0.003Mn
1.472Y2O3.BaO.2.61Al2O3.0.5SiO2.0.28MgCl2:0.13Ce,0.01Eu,0.001 Mn
1.482Y2O3.BaO.2.215Al2O3.1.0SiO2.0.57CaF2:0.01Ce,0.12Eu,0.004Mn
1.133Ho2O3.BaO.2.2Al2O3.2.0SiO2.0.3CaCl2:0.1Ce,0.02Eu,0.001Tb
0.8Y2O3.BaO.0.42Al2O3.3.0SiO2.0.16SrF2:0.01Ce,0.1Eu,0.003Tb
1.47Y2O3.BaO.2.42Al2O3SiO2.0.16SrCl2:0.1Ce,0.04Eu
Yb2O3.0.47Gd2O3.BaO.2.24Al2O3.1.36SiO2.0.16LiF:0.13Ce,0.01Eu
Y2O3.0.44Gd2O3.BaO.2.25Al2O3.1.39SiO2.0.16LiCl:0.08Ce,0.09Eu
Y2O3.0.44Gd2O3.BaO.2.21Al2O3.1.42SiO2.0.16NaF:0.09Ce,0.02Eu
Y2O3.0.41Gd2O3.BaO.2.195Al2O3.1.45SiO2.0.16NaCl:0.15Ce,0.13Eu
Y2O3.0.41Gd2O3.BaO.2.18Al2O3.1.48SiO2.0.16KF:0.01Ce,0.01Eu
Y2O3.0.38Gd2O3.CaO.2.42Al2O3.1.48SiO2.0.16KCl:0.03Ce,0.03Eu
Y2O3.0.38Gd2O3.CaO.2.165Al2O3.1.51SiO2.0.16MgF2:0.08Ce,0.002Tb
Y2O3.0.35Sc2O3.CaO.2.15Al2O3.1.54SiO2.0.16MgCl2:0.02Ce,0.005Tb
Y2O3.0.35Gd2O3.CaO.2.3Al2O3.1.12SiO2.0.16CaF2:0.04Ce,0.001Tb
Y2O3.0.32Gd2O3.CaO.2.135Al2O3.1.57SiO2.0.16CaCl2:0.07Ce,0.08Eu
Y2O3.0.32La2O3.CaO.2.12Al2O3.1.6SiO2.0.16SrF2:0.02Ce,0.12Eu
Y2O3.0.29Gd2O3CaO.2.105Al2O3.1.63SiO2.0.16SrCl2:0.14Ce,0.02Eu
Y2O3.0.29Pr2O3CaO.2.09Al2O3.1.66SiO2.0.16BaCl2:0.02Ce,0.02Eu
Y2O3.0.26Sm2O3.CaO.2.125Al2O3.1.74SiO2.0.01LiF:0.06Ce,0.06Eu
Y2O3.0.26Sm2O3.CaO.2.11Al2O3.1.75SiO2.0.03LiCl:0.09Ce,0.08Eu
Y2O3.0.23Sm2O3.CaO.2.095Al2O3.1.75SiO2.0.06NaF:0.06Ce,0.07Eu
Y2O3.0.23Sm2O3.CaO.2.08Al2O3.1.74SiO2.0.1NaCl:0.05Ce,0.08Eu
Y2O3.0.2Sm2O3.CaO.2.065Al2O3.1.67SiO2.0.2KF:0.16Ce,0.13Eu
Y2O3.0.2Sm2O3.CaO.2.05Al2O3.1.6SiO2.0.3KCl:0.15Ce,0.13Eu
Y2O3.0.47Sm2O3.CaO.2.23Al2O3.0.9SiO2.0.4MgF2:0.13Ce,0.1Eu
Y2O3.0.47Nd2O3.CaO.2.035Al2O3.1.43SiO2.0.5MgCl2:0.04Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.02Al2O3.1.36SiO2.0.6CaF2:0.02Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.2.005Al2O3.1.29SiO2.0.7CaCl2:0.12Ce,0.03Eu
Y2O3.0.47Sm2O3.CaO.1.99Al2O3.1.22SiO2.0.8SrF2:0.13Ce,0.04Eu
Y2O3.0.47Sm2O3.CaO.2.46Al2O3.0.18SiO2.0.9SrCl2:0.14Ce,0.05Eu
Y2O3.0.47Ho2O3.CaO.2.45Al2O3.0.1SiO2.1.0BaCl2:0.06Ce,0.06Eu
1.47Y2O3.CaO.2.39Al2O3.0.05Ga2O3.1.08SiO2.0.1LiF:0.08Ce,0.05Eu
0.01Y2O3CaO.3.84Al2O3.0.05Ga2O3.1.00SiO2.0.2LiCl:0.11Ce,0.02Eu
0.05Yb2O3CaO.3.36Al2O3.0.05Ga2O3.1.3SiO2.0.3NaF:0.1Ce,0.05Eu
0.1Y2O3CaO.3.74Al2O3.0.05Ga2O3.0.82SiO2.0.4NaCl:0.1Ce,0.03Eu
0.5Y2O3CaO.3.33Al2O3.0.05Ga2O3.0.74SiO2.0.5KF:0.09Ce,0.02Eu
1.0Y2O3CaO.2.82Al2O3.0.05Ga2O3.0.66SiO2.0.6KCl:0.08Ce
2.0Y2O3CaO.1.81Al2O3.0.05Ga2O3.0.55SiO2.0.7MgF2:0.1Eu
0.01Sc2O3.SrO.3.79Al2O3.0.05Ga2O3.0.44SiO2.0.8MgCl2:0.007Ce,0.01Eu
0.05Y2O3.SrO.3.74Al2O3.0.05Ga2O3.0.36SiO2.0.9CaF2:0.06Ce,0.04Eu
0.1Y2O3.SrO.3.68Al2O3.0.05Ga2O3.0.28SiO2.1.0CaCl2:0.06Ce,0.03Eu
0.5Y2O3.SrO.3.27Al2O3.0.05Ga2O3.1.2SiO2.0.1SrF2:0.007Ce,0.04Eu
1.0La2O3.SrO.2.76Al2O3.0.05Ga2O3.1.12SiO2.0.2SrCl2:0.09Ce,0.03Eu
2.0Y2O3.SrO.1.75Al2O3.0.05Ga2O3.1.04SiO2.0.3BaCl2:0.1Ce,0.1Eu
0.47Pr2O3.0.5Gd2O3.0.5Sm2O3.SrO.2.3Al2O3.1.34SiO2.0.06BaF2:0.1Ce,0.11Eu
0.47Y2O3Gd2O3.SrO.2.29Al2O3.1.36SiO2.0.06BaF2:0.07Ce,0.02Eu
0.47Y2O3Gd2O3.SrO.2.23Al2O3.1.38SiO2.0.12LiF:0.12Ce,0.02Eu
0.47Nd2O3Gd2O3.SrO.2.22Al2O3.1.4SiO2.0.12LiCl:0.02Ce,0.11Eu
0.44Y2O3Gd2O3.SrO.2.21Al2O3.1.42SiO2.0.12NaF:0.02Ce,0.02Eu
0.44Y2O3Gd2O3.SrO.2.2Al2O3.1.44SiO2.0.12NaCl:0.08Ce,0.08Eu
0.41Y2O3Gd2O3.SrO.2.19Al2O3.1.43SiO2.0.12KF:0.07Ce,0.01Eu
0.41Y2O3Gd2O3.SrO.2.42Al2O3.1.18SiO2.0.12KCl:0.01Ce,0.03Eu
0.38Y2O3.Gd2O3.SrO.2.19Al2O3.1.46SiO2.0.06MgF2:0.08Ce,0.10Eu
0.38Y2O3.Gd2O3.SrO.2.18Al2O3.1.48SiO2.0.06MgCl2:0.1Ce,0.1Eu,0.1Tb
0.35Y2O3.Gd2O3.SrO.1.46Al2O3.1.96SiO2.0.06CaF2:0.16Ce
0.35Pr2O3.Gd2O3.SrO.2.17Al2O3.1.5SiO2.0.06CaCl2:0.12Ce,0.12Eu
0.32Y2O3.Gd2O3.SrO.2.12Al2O3.1.6SiO2.0.06SrF2:0.12Ce,0.10Eu
0.32Y2O3.Gd2O3.SrO.2.07Al2O3.1.7SiO2.0.06SrCl2:0.08Ce,0.12Eu
0.29Y2O3.Gd2O3.SrO.2.02Al2O3.1.8SiO2.0.06BaF2:0.06Ce,0.10Eu and
0.29Nd2O3.Gd2O3.SrO.1.97Al2O3.1.9SiO2.0.06BaCl2:0.08Ce,0.10Eu.