Complex oxynitride phosphor, light-emitting device using same, image display, illuminating device, phosphor-containing composition and complex oxynitride

Abstract

To provide a green phosphor with high conversion efficiency of blue of near-ultraviolet light and excellent color purity, a multinary oxynitride phosphor represented by the general formula [I] is proposed. M1 x Ba y M2 z L u O v N w   [I] In the formula [I], M1 represents Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb, M2 represents Sr, Ca, Mg and Zn, L represents metal elements belonging to the fourth group or the fourteenth group of the periodic table, and x, y, z, u, v and w are the numeric values in the following ranges: 0.00001≦x≦3 0≦y≦2.99999 2.6≦x+y+z≦3 0<u≦11 6<v≦25 0<w≦17.

1 . A multinary oxynitride phosphor represented by the general formula [I]
   M1 x Ba y M2 z L u O v N w   [I]   in the general formula [I],   M 1  represents at least one kind of an activation element selected from the group consisting of Cr, Mn, Fe, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb,   M 2  represents at least one kind of a divalent metal element selected from the group consisting of Sr, Ca, Mg and Zn,   L represents a metal element selected from the metal elements belonging to the fourth group or the fourteenth group of the periodic table, and   x, y, z, u, v and w are the numeric values in the following ranges:
   0.00001=x=3 
   0=y=2.99999 
   2.6 =x+y+z= 3 
   0<u=11 
   6<v=25 
   0 <w= 17.) 
   
   
   
       2 . A multinary oxynitride phosphor according to  claim 1 , wherein u, v and w are 5=u=7, 9≦v<15 and 0<w<4, respectively, in the general formula [I]. 
   
   
       3 . A multinary oxynitride phosphor according to  claim 1 , wherein
 the crystalline structure of said multinary oxynitride phosphor has a trigonal unit cell.   
   
   
       4 . A multinary oxynitride phosphor according to  claim 1 , wherein
 M 1  includes at least Eu or Ce.   
   
   
       5 . A multinary oxynitride phosphor according to  claim 1 , wherein
 y is the numeric value in the range of 0<y<2.99999, in the general formula [I].   
   
   
       6 . A multinary oxynitride phosphor according to  claim 1 , wherein
 said multinary oxynitride phosphor includes BSON crystal phase defined as follows:   BSON crystal phase:   a crystal phase of which diffraction peak is observed within the range (R 0 ) of the diffraction angle (2θ) of from 26.9° to 28.2°, in X-ray diffraction measurement using a CuKa as an X-ray source, wherein,   when that diffraction peak (P 0 ) is taken as the reference diffraction peak, with 5 diffraction peaks (other than the diffraction peaks existing in the angle range of from 20.9° to 22.9°) derived from the Bragg angle (θ0) of P 0  shown by P 1 , P 2 , P 3 , P 4  and P 5  respectively in increasing order of angle and with diffraction angle ranges of these diffraction peaks shown by R 1 , R 2 , R 3 , R 4  and R 5 ,   R 1 , R 2 , R 3 , R 4  and R 5  indicate the following angle ranges respectively:
     R 1 =R 1 s˜R 1 e,    
     R 2= R 2 s˜R 2 e,    
     R 3= R 3 s˜R 3 e,    
     R 4= R 4 s˜R 4 e,    
     R 5= R 5 s˜R 5 e,    
   at least one diffraction peak exists in all the ranges of R 1 , R 2 , R 3 , R 4  and R 5 , and, to the highest diffraction peak height among those of P 0 , P 1 , P 2 , P 3 , P 4  and P 5 , P 0  has an intensity of 20% or stronger in diffraction peak height ratio and at least one of P 1 , P 2 , P 3 , P 4  and P 5  has a peak intensity of 5% or stronger in diffraction peak height ratio;   in this context, when two or more diffraction peaks exist in each angle range of R 0 , R 1 , R 2 , R 3 , R 4  or R 5 , the peak having the highest peak intensity of them is taken as P 0 , P 1 , P 2 , P 3 , P 4  or P 5 , and   R 1   s , R 2   s , R 3   s , R 4   s  and R 5   s , indicating the starting angles of R 1 , R 2 , R 3 , R 4  and R 5  respectively and R 1   e , R 2   e , R 3   e , R 4   e  and R 5   e , indicating the ending angles of R 1 , R 2 , R 3 , R 4  and R 5  respectively, are the following angles:
   R1s:2×arcsin {sin(θ0)/(1.994×1.015)} 
   R1e:2×arcsin {sin(θ0)/(1.994×0.985)} 
   R2s:2×arcsin {sin(θ0)/(1.412×1.015)} 
   R2e:2×arcsin {sin(θ0)/(1.412×0.985)} 
   R3s:2×arcsin {sin(θ0)/(1.155×1.015)} 
   R3e:2×arcsin {sin(θ0)/(1.155×0.985)} 
   R4s:2×arcsin {sin(θ0)/(0.894×1.015)} 
   R4e:2×arcsin {sin(θ0)/(0.894×0.985)} 
   R5s:2×arcsin {sin(θ0)/(0.756×1.015)} 
   R5e:2×arcsin {sin(θ0)/(0.756×0.985)}. 
   
   
   
       7 . A multinary oxynitride phosphor according  claim 1 , wherein,
 in X-ray diffraction measurement using a CuKα as an X-ray source, the strongest peak intensity of the impurity phase, among the measurement results of the X-ray diffraction, is 40% or weaker to the strongest peak intensity of the P 0 , P 1 , P 2 , P 3 , P 4  and P 5 .   
   
   
       8 . A phosphor-containing composition comprising:
 said multinary oxynitride phosphor according to  claim 1  and a liquid medium.   
   
   
       9 . A light emitting device comprising:
 an excitation light source and   a phosphor emitting green fluorescence when irradiated with light from the excitation light source and having the below characteristics (1), (2) and (3);   (1) when irradiated with light having wavelength of 455 nm, the ratio of the peak intensity value of the emission at 150° C. in the emission spectrum, to the peak intensity value of the emission at 20° C. in the emission spectrum, is 55% or more;   (2) the ratio of the peak intensity value of the emission when irradiated with light having wavelength of 410 nm in the emission spectrum, to the peak intensity value of the emission when irradiated with light having wavelength of 390 nm in the emission spectrum, is 90% or more;   (3) the chromaticity coordinate of the luminescent color of the phosphor, according to JIS Z8701, meets conditions of x=0.3 and y=0.5.   
   
   
       10 . A light emitting device comprising:
 an excitation light source and   a phosphor emitting green fluorescence when irradiated with light from the excitation light source and having the below characteristics (4), (2) and (3);   (4) the crystalline structure of an oxynitride has a trigonal unit cell;   (2) the ratio of the peak intensity value of the emission when irradiated with light having wavelength of 410 nm in the emission spectrum, to the peak intensity value of the emission when irradiated with light having wavelength of 390 nm in the emission spectrum, is 90% or more;   (3) the chromaticity coordinate of the luminescent color of the phosphor, according to JIS Z8701, meets conditions of x=0.3 and y=0.5.   
   
   
       11 . A light emitting device according to  claim 9 , wherein
 the chromaticity (x,y) of the light emission after energization with current density of 238 mA/mm for 200 hrs at a temperature of 85° C. and relative humidity of 85%, to the chromaticity (x′, y′) before the energization, meets each condition of 0=|x−x′|=0.035 and 0=|y−y′|=0.035.   
   
   
       12 . A light emitting device according to  claim 10 , wherein
 the chromaticity (x,y) of the light emission after energization with current density of 238 mA/mm 2  for 200 hrs at a temperature of 85° C. and relative humidity of 85%, to the chromaticity (x′, y′) before the energization, meets each condition of 0=|x−x′|=0.035 and 0=|y−y′|=0.035.   
   
   
       13 . A light emitting device according to  claim 9 , wherein
 the emission efficiency is 30 lm/W or larger.   
   
   
       14 . A light emitting device according to  claim 10 , wherein
 the emission efficiency is 30 lm/W or larger.   
   
   
       15 . A light emitting device according to  claim 9 , wherein
 said light emitting device comprises at least one kind of said multinary oxynitride phosphor as said phosphor.   
   
   
       16 . A light emitting device according to  claim 10 , wherein
 said light emitting device comprises at least one kind of said multinary oxynitride phosphor as said phosphor.   
   
   
       17 . A light emitting device comprising: a first luminous body and a second luminous body which emits visible light when irradiated with light from said first luminous body, wherein
 said light emitting device comprises, as said second luminous body, a first phosphor including at least one kind of said multinary oxynitride phosphor according to  claim 1 .   
   
   
       18 . A light emitting device according to  claim 17 , wherein
 said light emitting device comprises, as said second luminous body, a second phosphor including at least one kind of a phosphor of which emission peak wavelength is different from that of said first phosphor.   
   
   
       19 . A light emitting device according to  claim 18 , wherein
 said light emitting device comprises, as said second phosphor, at least one kind of a phosphor having emission peak wavelength in the wavelength range of from 570 nm to 780 nm.   
   
   
       20 . A light emitting device according to  claim 17 , wherein
 said first luminous body has an emission peak in the wavelength range of from 420 nm to 500 nm.   
   
   
       21 . A light emitting device according to  claim 18 , wherein
 said first luminous body has an emission peak in the wavelength range of from 300 nm to 420 nm, and   said light emitting device comprises, as said second phosphor, at least one kind of a phosphor having emission peak in the wavelength range of from 420 nm to 490 nm and at least one kind of a phosphor having emission peak in the wavelength range of from 570 nm to 780 nm.   
   
   
       22 . A light emitting device according to  claim 18 , wherein
 said light emitting device comprises, as said second phosphor, at least one kind of a phosphor selected from the group consisting of (Ca,Sr,Ba) 2 Si 5 (N, O) 8 :Eu, (Ca, Sr, Ba)Si(N,O) 2 :Eu, (Ca,Sr,Ba)AlSi(N, O) 3 :Eu, (Ca,Sr,Ba)AlSi(N,O) 3 :Ce, (Sr, Ba) 3 SiO 5 :Eu, (Ca, Sr)S:Eu, (La, Y) 2 O 2 S:Eu and Eu complex.   
   
   
       23 . A light emitting device according to  claim 18 , wherein
 said light emitting device comprises, as said second phosphor, at least one kind of a phosphor selected from the group consisting of (Ca,Sr,Ba)MgAl 10 O 17 :Eu, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 (Cl, F) 2 :Eu and (Ba, Ca, Mg, Sr) 2 SiO 4 :Eu.   
   
   
       24 . A light emitting device according to  claim 9 , wherein
 the luminescent color is in the range which is defined, in JIS Z8701, as (Yellowish) White, (Greenish) White, (Bluish) White, (Purplish) White or White.   
   
   
       25 . A light emitting device according to  claim 10 , wherein
 the luminescent color is in the range which is defined, in JIS Z8701, as (Yellowish) White, (Greenish) White, (Bluish) White, (Purplish) White or White.   
   
   
       26 . A light emitting device according to  claim 17 , wherein
 the luminescent color is in the range which is defined, in JIS Z8701, as (Yellowish) White, (Greenish) White, (Bluish) White, (Purplish) White or White.   
   
   
       27 . An image display comprising a light emitting device according to  claim 9 . 
   
   
       28 . An image display comprising a light emitting device according to  claim 10 . 
   
   
       29 . An image display comprising a light emitting device according to  claim 17 . 
   
   
       30 . An illuminating device comprising a light emitting device according to  claim 9 . 
   
   
       31 . An illuminating device comprising a light emitting device according  claim 10 . 
   
   
       32 . An illuminating device comprising a light emitting device according to  claim 17 . 
   
   
       33 . A multinary oxynitride represented by the general formula [II]
   Ba y′ M2′ z L u′ O v′ N w′   [II]   in the general formula [II],   M 2 ′ represents at least one kind of a metal element selected from the group consisting of Sr, Ca, Mg, Zn, Cr, Mn, Fe, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu,   L represents a metal element selected from the metal elements belonging to the fourth group or the fourteenth group of the periodic table, and   y′, z′, u′, v′ and w′ are the numeric values in the following ranges:
   0=y′=3 
   2.6 =y′+z′= 3 
   5=u′=7 
   9<v′<15 
   0 <w′< 4.) 
   
   
   
       34 . A multinary oxynitride according to  claim 33 , wherein the crystalline structure of said multinary oxynitride has the trigonal unit cell. 
   
   
       35 . A multinary oxynitride according to  claim 33 , wherein
 said multinary oxynitride includes BSON crystal phase defined as follows;   BSON crystal phase:   a crystal phase of which diffraction peak is observed within the range (R 0 ) of the diffraction angle (2θ) of from 26.9° to 28.2°, in X-ray diffraction measurement using a CuKa as an X-ray source, wherein,   when that diffraction peak (P 0 ) is taken as the reference diffraction peak, with 5 diffraction peaks (other than the diffraction peaks existing in the angle range of from 20.9° to 22.9°) derived from the Bragg angle (θ0) of P 0  shown by P 1 , P 2 , P 3 , P 4  and P 5  respectively in increasing order of angle and with diffraction angle ranges of these diffraction peaks shown by R 1 , R 2 , R 3 , R 4  and R 5 ,   R 1 , R 2 , R 3 , R 4  and R 5  indicate the following angle ranges respectively:
     R 1= R 1 s˜R 1 e,    
     R 2= R 2 s˜R 2 e,    
     R 3= R 3 s˜R 3 e,    
     R 4= R 4 s˜R 4 e,    
     R 5= R 5 s˜R 5 e,    
   at least one diffraction peak exists in all the ranges of R 1 , R 2 , R 3 , R 4  and R 5 , and, to the highest diffraction peak height among those of P 0 , P 1 , P 2 , P 3 , P 4  and P 5 , P 0  has an intensity of 20% or stronger in diffraction peak height ratio and at least one of P 1 , P 2 , P 3 , P 4  and P 5  has a peak intensity of 5% or stronger in diffraction peak height ratio.   in this context, when two or more diffraction peaks exist in each angle range of R 0 , R 1 , R 2 , R 3 , R 4  or R 5 , the peak having the highest peak intensity of them is taken as P 0 , P 1 , P 2 , P 3 , P 4  or P 5 , and   R 1   s , R 2   s , R 3   s , R 4   s  and R 5   s , indicating the starting angles of R 1 , R 2 , R 3 , R 4  and R 5  respectively and R 1   e , R 2   e , R 3   e , R 4   e  and R 5   e , indicating the ending angles of R 1 , R 2 , R 3 , R 4  and R 5  respectively, are the following angles:
   R1s:2×arcsin {sin(θ0)/(1.994×1.015)} 
   R1e:2×arcsin {sin(θ0)/(1.994×0.985)} 
   R2s:2×arcsin {sin(θ0)/(1.412×1.015)} 
   R2e:2×arcsin {sin(θ0)/(1.412×0.985)} 
   R3s:2×arcsin {sin(θ0)/(1.155×1.015)} 
   R3e:2×arcsin {sin(θ0)/(1.155×0.985)} 
   R4s:2×arcsin {sin(θ0)/(0.894×1.015)} 
   R4e:2×arcsin {sin(θ0)/(0.894×0.985)} 
   R5s:2×arcsin {sin(θ0)/(0.756×1.015)} 
   R5e:2×arcsin {sin(θ0)/(0.756×0.985)}. 
   
   
   
       36 . A multinary oxynitride according to  claim 33 , wherein,
 in X-ray diffraction measurement using a CuKa as an X-ray source, the strongest peak intensity of the impurity phase, among the measurement results of the X-ray diffraction, is 40% or weaker to the strongest peak intensity of the P 0 , P 1 , P 2 , P 3 , P 4  and P 5 .