CN102790164B - 发光装置 - Google Patents

发光装置 Download PDF

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CN102790164B
CN102790164B CN201210286813.2A CN201210286813A CN102790164B CN 102790164 B CN102790164 B CN 102790164B CN 201210286813 A CN201210286813 A CN 201210286813A CN 102790164 B CN102790164 B CN 102790164B
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增田昌嗣
寺岛贤二
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GE Phosphors Technology LLC
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Abstract

本发明提供一种发光装置(1),其具有发出一次光的发光元件(2)与波长转化部(3),所述波长转化部(3)吸收由发光元件(2)发出的一部分一次光,发出具有比一次光的波长长的波长的二次光,所述波长转化部(3)含有绿色系发光荧光体(4)及红色发光荧光体(5),所述绿色系发光荧光体(4)包括选自下述荧光体中的至少一种:实质上以EuaSibAlcOdNe表示的2价铕激活氧氮化物荧光体以及实质上以2(Ba1‑f‑gMIfEug)O·SiO2表示的2价铕激活硅酸盐荧光体,所述红色系发光荧光体(5)包括选自实质上以MII2(MIII1‑hMnh)F6及/或MIV(MIII1‑hMnh)F6表示4价锰激活氟化4价金属盐荧光体中的至少1种,所述发光装置具有优异的色再现性(NTSC比)。

Description

发光装置
本申请是200980107694.6(国际申请号:PCT/JP2009/052051)的分案申请,原申请的申请日为2009年2月6日,原申请的发明名称为发光装置
技术领域
本发明涉及具有发出一次光的发光元件和波长转化部的发光装置,所述波长转化部吸收由发光元件发出的一部分一次光,并发出具有比一次光的波长更长的波长的二次光。
背景技术
组合了半导体发光元件与荧光体得到的发光装置作为期待低耗电、小型化、高辉度以及广范围的色再现性的次世代发光装置而受到关注,正在积极地进行研究、开发。由发光元件发出的一次光通常使用从长波长的紫外线至蓝色的范围、即380~480nm的光。另外,也提出了使用适合该用途的各种荧光体的波长转化部。
进而,近年,小型液晶显示器(以下为LCD(Liquid Crystal Display))用背光的开发竞争越来越激烈。该领域中,提出了各种方案,但并没有找到同时满足明度和色再现性(NTSC比)的方式。
现在,作为白色的发光装置,主要使用蓝色发光的发光元件(峰波长:450nm左右)与被该蓝色激发并显示黄色发光的被3价铈激活的(Y、Gd)3(Al,Ga)5O12荧光体或被2价的铕激活的(Sr,Ba,Ca)2SiO4荧光体的组合。但是,上述发光装置中,色再现性(NTSC比)为65%左右(CIE1931)。另一方面,近年,在小型LCD中,也要求色再现性更良好的LED。上述背景中,当务之急是改善小型LCD用背光的色再现性(NTSC比)。
作为着眼于LCD的色再现性(NTSC比)的文献,例如有日本专利特开2003-121838号公报(专利文献1)。专利文献1中,记载了下述内容:作为背光光源,在505~535nm的范围具有光谱峰,以及作为用于该光源的绿荧光体的激活剂,含有铕、钨、锡、锑、锰的任一种,进而,作为绿荧光体,实施例中记载有使用MgGa2O4:Mn、Zn2SiO4:Mn。但是,发光元件的峰波长在430~480nm的范围时,含有铕、钨、锡、锑、锰的任一种的荧光体并不全部适用。即,记载于专利文献1的实施例的MgGa2O4:Mn、Zn2SiO4:Mn在430~480nm的范围的激发光下,其发光效率显著降低。
另外,例如日本专利特开2004-287323号公报(专利文献2)中记载,作为背光,除红发光LED芯片、绿发光LED芯片与蓝发光LED芯片组成一组的RGB-LED之外,有3波长型荧光管、紫外光LED+RGB荧光体、有机EL光源等。但是,专利文献2并没有关于以蓝色光为激发源的RG荧光体的具体记载。
另一方面,关于4价的锰激活氟金属盐荧光体,记载在例如US20060169998A1(专利文献3)中。但是,专利文献3中,与高效率的绿色荧光体组合,并未提及其色再现性(NTSC比)。
专利文献1:日本专利特开2003-121838号公报
专利文献2:日本专利特开2004-287323号公报
专利文献3:US20060169998A1
发明内容
本发明是为了解决上述课题而得到的,其目的在于,通过使用利用由发光元件发出的430~480nm的范围的光进行高效率发光的特定的荧光体,提供色再现性(NTSC比)优异的发光装置。
本发明的发光装置具有发出一次光的发光元件和波长转化部,所述波长转化部吸收由发光元件发出的一部分一次光,并发出具有比一次光的波长更长的波长的二次光,所述波长转化部含有绿色系发光荧光体及红色发光荧光体,上述绿色系发光荧光体包括选自实质上以通式(A):EuaSibAlcOdNe表示的作为β型SiAlON的2价铕激活氧氮化物荧光体;以及实质上以通式(B):2(Ba1-f-gMIfEug)O·SiO2表示的2价铕激活硅酸盐荧光体中的至少一种,
(上述通式(A)中,0.005≤a≤0.4、b+c=12、d+e=16。)
(上述通式(B)中,MI表示选自Mg、Ca及Sr中的至少1种碱土类金属元素,0<f≤0.55,0.03≤g≤0.10。);
所述红色系发光荧光体包括选自实质上以通式(C):MII2(MIII1-hMnh)F6表示的4价锰激活氟化4价金属盐荧光体;以及实质上以通式(D):MIV(MIII1-hMnh)F6表示的4价锰激活氟化4价金属盐荧光体中的至少一种,
(上述通式(C)中,MII表示选自Li、Na、K、Rb及Cs中的至少1种碱金属元素,MIII表示选自Ge、Si、Sn、Ti及Zr中的至少1种4价金属元素,0.001≤h≤0.1。)
(上述通式(D)中,MIV表示选自Mg、Ca、Sr、Ba及Zn中的至少一种碱土类金属元素,MIII表示选自Ge、Si、Sn、Ti及Zr中的至少1种4价金属元素,0.001≤h≤0.1。)
此处,优选MII为K,MIII为Ti。
另外,本发明的发光装置中,优选0.005≤h≤0.05。
另外,本发明的发光装置中,MI优选为Sr。
本发明的发光装置中的发光元件优选为发出峰波长为430~480nm的一次光的氮化镓系半导体。
根据本发明,提供在波长转化部有效地吸收来自发光元件的发光,发出高效率的白色光,并且可以得到色再现性(NTSC比)显著良好的白色光的发光装置。
附图说明
[图1]是示意地表示本发明优选的一例的发光装置1的截面图。
[图2]是表示能用于本发明的发光装置的作为β型SiAlON的2价铕激活氧氮化物绿色系发光荧光体的具体一例的发光光谱分布的图。
[图3]是表示能用于本发明的发光装置的2价铕激活硅酸盐荧光体的具体一例的发光光谱分布的图。
[图4]是表示能用于本发明的发光装置的4价锰激活氟化4价金属盐荧光体的具体一例的发光光谱分布的图。
[图5]是表示本发明的优选一例的发光装置的发光光谱分布的图。
[图6]是表示组装本发明的优选一例的发光装置作为背光光源得到的LCD的色再现性的色度图。
[图7]是表示使用黄色系发光荧光体的现有发光装置的发光光谱分布的图。
[图8]是表示组装使用黄色系发光荧光体的现有的发光装置作为背光光源得到的LCD的色再现性的色度图。
符号说明
1发光装置、2发光元件、3波长转化部、4绿色系发光荧光体、5红色系发光荧光体、6密封剂。
具体实施方式
图1是示意地表示本发明的优选一例的发光装置1的截面图。本发明的发光装置1如图1所示,基本上具有发出一次光的发光元件2和波长转化部3,所述波长转化部3吸收由发光元件2发出的一部分一次光,并发出具有比一次光的波长更长的波长的二次光,波长转化部3含有绿色系发光荧光体4及红色系发光荧光体5。图1表示实现波长转化部3的例子,发光元件2、绿色系发光荧光体4及红色系发光荧光体5被密封于密封剂6中,能吸收由发光元件2发出的一部分一次光,并发出具有一次光的波长以上的长度的波长的二次光。本发明的发光装置1中的波长转化部3的特征在于,含有选自以下的(A)作为β型SiAlON的2价铕激活氧氮化物荧光体及(B)2价铕激活硅酸盐荧光体中的至少1种作为绿色系发光荧光体4,含有选自以下的2种(C)、(D)4价的锰激活氟化4价金属盐荧光体中的至少1种作为红色系发光荧光体。
(A)作为β型SiAlON的2价铕激活氧氮化物绿色系发光荧光体
该2价的铕激活氧氮化物绿色系发光荧光体实质上以通式(A):EuaSibAlcOdNe表示(以下,将该2价的铕激活氧氮化物绿色系发光荧光体称为“第1滤色系发光荧光体”。)。通式(A)中,Eu表示铕,Si表示硅,Al表示铝,O表示氧,N表示氮。通式(A)中,表示Eu的组成比(浓度)的a的值为0.005≤a≤0.4。原因在于a的值小于0.005时,得不到充分的明度,另外a的值超过0.4时,由于浓度消光等而明度大幅降低。需要说明的是,从粉体特性的稳定性、母体的均质性来看,上述式中的a值优选为0.01≤a≤0.2。另外,通式(A)中,表示Si的组成比(浓度)的b及表示Al的组成比(浓度)的c是满足b+c=12的数,表示O的组成比(浓度)的d及表示N的组成比(浓度)的e是满足d+e=16的数。
作为该第1的绿色系发光荧光体,具体而言,可以举出Eu0.05Si11.50Al0.50O0.05N15.95、Eu0.10Si11.00Al1.00O0.10N15.90、Eu0.30Si9.80Al2.20O0.30N15.70、Eu0.15Si10.00Al2.00O0.20N15.80、Eu0.01Si11.60Al0.40O0.01N15.99、Eu0.005Si11.70Al0.30O0.03N15.97等,但并不限定于此。
(B)2价的铕激活硅酸盐荧光体
该2价的铕激活硅酸盐荧光体实质上以通式(B):2(Ba1-f-gMIfEug)O·SiO2表示(以下,将该2价的铕激活硅酸盐荧光体称为“第2绿色系发光荧光体”。)。通式(B)中,Ba表示钡,Eu表示铕,O表示氧,Si表示硅。通式(B)中,MI表示选自Mg、Ca及Sr中的至少1种碱土类金属元素,为了得到高效率的母体,MI优选为Sr。通式(B)中,表示MI的组成比(浓度)的f值为0<f≤0.55,通过将f的值设定在该范围内,可以得到510~540nm的范围的绿色系发光。F的值超过0.55时,得到带有黄色的绿色系发光,色纯度变差。进而,从效率、色纯度的观点来看,f的值优选在0.15≤f≤0.45的范围内。另外,通式(B)中,表示Eu的组成比(浓度)的g值为0.03≤g≤0.10。原因在于g值小于0.03时,得不到充分的明度,另外,g值超过0.10时,由于浓度消光等而明度大幅降低。需要说明的是,从明度及粉体特性的稳定性来看,优选g值在0.04≤g≤0.08的范围内。
作为该第2绿色系发光荧光体,具体地可以举出2(Ba0.70Sr0.26Eu0.04)·SiO2、2(Ba0.57Sr0.38Eu0.05)O·SiO2、2(Ba0.53Sr0.43Eu0.04)O·SiO2、2(Ba0.82Sr0.15Eu0.03)O·SiO2、2(Ba0.46Sr0.49Eu0.05)O·SiO2、2(Ba0.59Sr0.35Eu0.06)O·SiO2、2(Ba0.52Sr0.40Eu0.08)O·SiO2、2(Ba0.85Sr0.10Eu0.05)O·SiO2、2(Ba0.47Sr0.50Eu0.03)O·SiO2、2(Ba0.54Sr0.36Eu0.10)O·SiO2、2(Ba0.69Sr0.25Ca0.02Eu0.04)O·SiO2、2(Ba0.56Sr0.38Mg0.01Eu0.05)O·SiO2、2(Ba0.81Sr0.13Mg0.01Ca0.01Eu0.04)O·SiO2等,但当然不限定于此。
(C)4价的锰激活氟化4价金属盐荧光体
该4价的锰激活氟化4价金属盐荧光体实质上以通式(C):MII2(MIII1-hMnh)F6表示(以下,将该4价的锰激活氟化4价金属盐荧光体称为“第1红色系发光荧光体”。)。需要说明的是,通式(C)中,Mn表示锰,F表示氟。通式(C)中,MII表示选自Na、K、Rb及Cs中的至少1种碱金属元素,从明度及粉体特性的稳定性来看,MII优选为K。另外,通式(C)中,MIII表示选自Ge、Si、Sn、Ti及Zr中的至少1种4价金属元素,从明度及粉体特性的稳定性来看,优选MIII为Ti。另外,通式(C)中,表示Mn的组成比(浓度)的h的值为0.001≤h≤0.1。原因在于h的值小于0.001时,有得不到充分的明度的情况,另外,h值超过0.1时,因浓度消光等而具有明度大幅降低的不良情况。从明度及粉体特性的稳定性来看,优选h的值为0.005≤h≤0.5。
作为该第1红色系发光荧光体,具体而言,可以举出K2(Ti0.99Mn0.01)F6、K2(Ti0.9Mn0.1)F6、K2(Ti0.999Mn0.001)F6、Na2(Zr0.98Mn0.02)F6、Cs2(Si0.95Mn0.05)F6、Cs2(Sn0.98Mn0.02)F6、K2(Ti0.88Zr0.10Mn0.02)F6、Na2(Ti0.75Sn0.20Mn0.05)F6、Cs2(Ge0.999Mn0.001)F6、(K0.80Na0.20)2(Ti0.69Ge0.30Mn0.01)F6等,当然并不限定于此。
(D)4价的锰激活氟化4价金属盐荧光体
该4价的锰激活氟化4价金属盐荧光体实质上以通式(D):MIV(MIII1-hMnh)F6表示(以下将该4价的锰激活氟化4价金属盐荧光体称为“第2红色系发光荧光体”。)。需要说明的是,通式(D)中,Mn表示锰,F表示氟。通式(D)中,MIII与上述通式(C)中的MIII相同,表示选自Ge、Si、Sn、Ti及Zr中的至少一种1种4价金属元素,基于相同的理由,优选MIII为Ti。另外,通式(D)中,MIV表示选自Mg、Ca、Sr、Ba及Zn中的至少1种碱土类金属元素,从明度及粉体特性的稳定性考虑,优选MIV为Ca。另外,通式(D)中,表示Mn的组成比(浓度)的h值与上述通式(C)中的h相同,为0.001≤h≤0.1,基于相同的理由,优选0.005≤h≤0.5。
作为该第2红色系发光荧光体,具体而言,可以举出Zn(Ti0.98Mn0.02)F6、Ba(Zr0.995Mn0.005)F6、Ca(Ti0.995Mn0.005)F6、Sr(Zr0.98Mn0.02)F6等,当然并不限定于此。
本发明的发光装置中的波长转化部中,含有选自上述(A)作为β型SiAlON的2价铕激活氧氮化物荧光体(第1绿色系发光荧光体)及(B)2价铕激活硅酸盐荧光体(第2绿色系发光荧光体)中的至少一种作为绿色系发光荧光体,含有选自上述2种(C)4价锰激活氟化4价金属盐荧光体(第1红色系发光荧光体)及(D)4价锰激活氟化4价金属盐荧光体(第2红色系发光荧光体)中的至少1种作为红色系发光荧光体。需要说明的是,图2表示能用于本发明的发光装置的作为β型SiAlON的2价铕激活氧氮化物绿色系发光荧光体的具体的一例(具体的组成:Eu0.05Si11.50Al0.50O0.05N15.95)的发光光谱分布,图3表示能用于本发明的发光装置的2价铕激活硅酸盐荧光体的具体的一例(具体的组成:2(Ba0.70Sr0.26Eu0.04)O·SiO2)的发光光谱分布,图4表示能用于本发明的发光装置的4价锰激活氟化4价金属盐荧光体的具体的一例(具体的组成:K2(Ti0.99Mn0.01)F6)的发光光谱分布。图2~图4所示的发光光谱均是在激发波长450nm下使用荧光分光光度计测定的结果,纵轴为强度(任意单位),横轴为波长(nm)。
本发明的发光装置中,绿色系发光荧光体与红色系发光荧光体的混合比率没有特别限定,但相对于红色系发光荧光体,优选以重量比在5~70%的范围内的混合比率混合绿色系发光荧光体,较优选在15~45%的范围内的混合比率混合。
此处,图5是表示本发明的优选一例的发光装置(在下述实施例1中制作的发光装置)的发光光谱分布的图,图5中,纵轴为强度(任意单位),横轴为波长(nm)。另外,图6是表示组装本发明的优选一例的发光装置(下述实施例1中制作的发光装置)为背光光源得到的LCD的色再现性的色度图(CIE1931)。相对于此,图7是表示使用黄色系发光荧光体的现有的发光装置(下述的比较例1中制作的发光装置)的发光光谱分布的图,图8是表示组装该发光装置作为背光光源得到的LCD的色再现性的色度图(CIE1931)。需要说明的是,图5及图7所示的发光装置的发光光谱分布是使用MCPD-2000(大塚电子(株)制)测定的结果,另外,图6及图8所示的色再现性是使用Bm5((株)拓普康(トプコン)制)测定的结果。由图5~图8可知,根据本发明的发光装置,能提供与现有的发光装置不同,在波长转化部有效地吸收来自发光元件的发光,发出高效率的白色光,同时可以得到色再现性(NTSC比)显著良好的白色光的发光装置。需要说明的是,所谓NTSC比,NTSC(National Television System Committee)规定的红、绿、蓝各色的XYZ表色系色度图中的色度座标(x、y)分别为红(0.670,0.330)、绿(0.210,0.710)、蓝(0.140,0.080),表示相对于连结该红、绿、蓝各自的色度座标得到的三角形的面积的比率。
作为用于上述本发明的发光装置的发光元件,没有特别限定,但可以优选使用发出峰波长为430~480nm(较优选440~480nm)的蓝色区域的一次光的氮化镓(GaN)系半导体作为发光元件。使用峰波长小于430nm的发光元件时,蓝色光成分的作用减小,演色性变差,有可能不实用,另外,使用峰波长超过480nm的发光元件时,白色下的明度降低,有可能不实用。
本发明的发光装置只要具有上述特征,对其他构成就没有特别限定。作为密封剂6,可以使用作为具有透光性的树脂材料的环氧树脂、硅酮树脂、尿素树脂等,但并不限定于此。另外,波长转化部3中除上述荧光体及密封剂以外,当然可以在无损本发明效果的范围含有适当的SiO2、TiO2、ZrO2、Al2O3、Y2O3等添加剂。
需要说明的是,用于本发明的发光装置的上述绿色系发光荧光体、红色系发光荧光体均为公知的物质,能用现有公知的适当的方法制造,或者能作为产品购得。
以下,举出实施例及比较例更详细地说明本发明,但本发明并不限定于此。
<实施例1>
如以下所述地制作图1所示例的发光装置1。作为发光元件2,使用450nm处具有峰波长的氮化镓(GaN)系半导体,波长转化部3使用Eu0.05Si11.50Al0.50O0.05N15.95(β型SiAlON)作为绿色系发光荧光体,使用K2(Ti0.99Mn0.01)F6作为红色系发光萤光体。将以30∶70的比例(重量比)混合上述绿色系发光荧光体与红色系发光萤光体得到的物质分散在规定的树脂中(树脂与荧光体的比率为1.00∶0.25),制作波长转化部。如上所述地制作实施例1的发光装置。
<比较例1>
除将(Y0.40Gd0.45Ce0.15)3Al5O12表示的黄色系发光荧光体用于波长转化部以外,与实施例1相同地操作,制作发光装置。
针对实施例1、比较例1分别得到的发光装置,评价明度、Tc-duv及色再现性(NTSC比)。明度如下求得:在顺电流(IF)为20mA的条件下开灯,将来自发光装置的白色光转化为光电流。另外,关于Tc-duv,在顺电流(IF)为20mA的条件下开灯,用大塚电子(株)制MCPD-2000测定来自发光装置的白色光,求出其值。另外,色再现性(NTSC比)如下求得:组装制作的发光装置作为市售的LCD电视显示器的背光光源,用(株)拓普康制Bm5测定其值。结果示于表1。
[表1]
明度(相对值) Tc-duv 色再现性(NTSC比)
实施例1 96.5% 8700K+0.002 88.3%
比较例1 100.0% 8700K+0.002 70.1%
由表1可知,本发明的发光装置与现有产品相比,色再现性(NTSC比)大幅提高,具有作为中、小型LCD用背光理想的特性。
<实施例2>
除使用440nm处具有峰波长的氮化镓(GaN)系半导体作为发光元件2,使用2(Ba0.70Sr0.26Eu0.04)O·SiO2作为绿色系发光荧光体,使用K2(Ti0.996Mn0.005)F6作为红色系发光荧光体以外,与实施例1相同地制作发光装置。
<比较例2>
除在波长转化部使用(Y0.40Gd0.50Ce0.10)3Al5O12表示的黄色系发光荧光体之外,与实施例2相同地制作发光装置。
针对实施例2、比较例2分别得到的发光装置,与上述实施例1、比较例1的装置的情况相同地评价明度、Tc-duv及色再现性(NTSC比)。结果示于表2。
[表2]
明度(相对值) Tc-duv 色再现性(NTSC比)
实施例2 96.1% 7900K+0.002 88.1%
比较例2 100.0% 7900K+0.002 69.8%
由表2可知,本发明的发光装置与现有产品相比,色再现性(NTSC比)大幅提高,具有作为中、小型LCD用背光理想的特性。
<实施例3~8、比较例3~8>
除分别使用下述表3所示的发光元件的峰波长及荧光体的组合之外,与实施例1相同地制作实施例3~8及比较例3~8的发光装置,与上述相同地评价明度、Tc-duv及色再现性(NTSC比)。结果也一同示于表3。
[表3]
由表3也可知,本发明的发光装置与现有产品相比,色再现性(NTSC比)大幅提高,具有作为中、小型LCD用背光理想的特性。

Claims (3)

1.一种液晶显示器,其具备作为背光源的发光装置,该发光装置的色温Tc至少包含6800K、7900K、8700K、8800K、9000K、或9500K中的任一色温,
所述发光装置发出白色的光,具有发出一次光的发光元件和波长转化部,所述波长转化部吸收由发光元件发出的一部分一次光,并发出具有比一次光的波长更长的波长的二次光,所述波长转化部含有绿色系发光荧光体及红色发光荧光体,
发光元件是发出峰波长为430~480nm的一次光的氮化镓系半导体,
上述绿色系发光荧光体包括选自以通式(A):EuaSibA1cOdNe表示的作为β型SiAlON的2价铕激活氧氮化物荧光体;以及以通式(B):2(Ba1-f-gMIfEug)O·SiO2表示的2价铕激活硅酸盐荧光体中的至少一种,
上述通式(A)中,0.005≦a≦0.4、b+c=12、d+e=16,
上述通式(B)中,MI表示选自Mg、Ca及Sr中的至少1种碱土类金属元素,0<f≦0.55,0.03≦g≦0.10,
所述红色系发光荧光体包括以通式(C):MII2(MIII1-hMnh)F6表示的4价锰激活氟化4价金属盐荧光体,
上述通式(C)中,MII表示选自Li、Na、K、Rb及Cs中的至少1种碱金属元素,MIII表示选自Ge、Si、Sn、Ti及Zr中的至少1种4价金属元素,0.001≦h≦0.1,
相对于红色系发光荧光体,以重量比计在15~45%的范围内的混合比率,混合绿色系发光荧光体。
2.如权利要求1所述的液晶显示器,其中,在波长转化部含有选自SiO2、TiO2、ZrO2、Al2O3、Y2O3中的至少一种添加剂。
3.如权利要求1所述的液晶显示器,其中,0.005≦h≦0.05。
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