CN101668829B - 赛隆荧光体 - Google Patents

赛隆荧光体 Download PDF

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CN101668829B
CN101668829B CN2008800100784A CN200880010078A CN101668829B CN 101668829 B CN101668829 B CN 101668829B CN 2008800100784 A CN2008800100784 A CN 2008800100784A CN 200880010078 A CN200880010078 A CN 200880010078A CN 101668829 B CN101668829 B CN 101668829B
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sialon phosphor
luminous
sialon
wavelength
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CN101668829A (zh
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佐久间健
广崎尚登
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Fujikura Ltd
National Institute for Materials Science
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Abstract

本发明提供一种赛隆荧光体，其特征在于，具有由通式(1)所示的组成，至少主相具有α-型赛隆结晶结构，且0.25≤p≤0.65。Lup(Si，Al)12(O，N)16:Euq (1)。

Description

赛隆荧光体
技术领域
本发明涉及一种一直以来明亮且在长波长侧发光并能够适合在白色发光二极管灯等中使用的赛隆(SiALON)荧光体及使用其的发光器件。
本申请基于2007年3月22日向日本申请的特愿2007-074657号主张优先权，并在此援用其内容。
背景技术
在照明领域等中，对固体照明，特别是对使用了半导体发光二极管的白色照明充满了期待，投入大量精力的研究开发正持续进行着。白色发光二极管灯均实现与白炽灯泡同等或其以上的发光效率，但在进一步改善的过程中，认为在不久的将来会作为节能照明设备得到广泛普及。另外，不含水银等环境负担高的物质也是白色发光二极管灯的一大优点。白色发光二极管灯，由于元件的尺寸小，所以大多组装到液晶显示装置的背光源、手机等中使用。在该白色发光二极管灯中使用的白色发光二极管，具备：发出蓝色光等短波长光的发光二极管元件、和通过吸收该光的一部分或全部被激发而发出更长波长的黄色等的荧光的荧光物质。即，白色光通过混合由作为发光源的蓝色光发光二极管所发出的蓝色光和荧光体所发出的黄色光而得到。
关于照明用途的发光器件，根据其用途而要求各种比色温度的白色发光器件，为了适应该要求，需要与以往公知的荧光体相比实现了更宽色度范围的荧光体、和该色度的调节技术。
例如，在特开2002-363554号公报(对应专利：日本专利第3668770号公报)(专利文献1)中，公开了一种荧光体，将通式设为MexSi12-(m +n)Al(m+n)OnN16-n时，Me为Ca、Mg、Y或除了La和Ce之外的镧系金属、和将其一部分置换的成为发光中心的属于镧系金属的Ce、Pr、Eu、Tb、Yb、Er及作为其共激活剂的Dy。另外，关于该荧光体，公开了当金属Me为2价时，0.6＜m＜3.0、且0≤n＜1.5的组成范围，在金属Me为3价时，0.9＜m＜4.5、且0≤n＜1.5的组成范围。此外，公开了通过使Eu2+离子的激活量发生变化而使发光峰值波长在560nm～590nm的范围内连续变化。在特开2003-124527号公报(专利文献2)中公开的荧光体，经Eu2+激活，作为金属以Ca为主体，由此实现发光主波长自546nm至583nm的范围。在WO2006/006582(专利文献3)中，我们公开了一种荧光体，经Eu2+激活，作为金属以Ca为主体，由此发光主波长为577.7～583.1nm的范围。但是，当前要求可以用蓝色激发且与这些已公开的荧光体相比能以更长的波长发光的荧光体。
为了解决该问题，例如，在“R-J.Xie et al.，“Eu2+-dopedCa-α-SiAlON：A yellow phosphor for white light-emittingdiodes，″Applied Physics Letters，Vol.84，Number 26，pp.5404-5406(2004)”(非专利文献1)中，Xie等公开了在CIE1931色度图上的色度坐标(x，y)为(0.491，0.497)至(0.560，0.436)的荧光体。其主波长在578nm～588nm的范围。但是，Xie等公开的荧光体，其原料需要使用昂贵的稀土类氮化物，因此寻求一种廉价地实现长波长发光荧光体的技术。
为了将其解决，我们在WO2006/025261(专利文献4)中公开了(Ca，Y)-α-SiAlON:Eu新荧光体。这些荧光体实现了发光主波长为580.2～590.7nm。但是，在这些荧光体中，从Ca向Y的置换量增加，发光强度随着发光波长的长波长化而急剧降低的问题。
发明内容
因此，本发明的目的在于，提供一种可以无需使用昂贵的氮化物原料而廉价制造、且与以往的荧光体相比具有长波长的发光色度和亮度、进而在长波长侧不会发生急剧的发光强度的降低的赛隆荧光体。
另外，本发明的目的还在于，提供一种使用了该赛隆荧光体的发光器件。
本发明人等为了实现上述目的进行了潜心研究，结果注意到了Lu-α-SiAlON:Eu荧光体。迄今为止提示Lu-α-SiAlON:Eu荧光体是可以合成的，但至今尚未公开最佳的组成范围、其光学特性等技术的详细内容。本发明人等合成该新的荧光体，并对其特性进行了研究，结果发现，发光主波长与以往的荧光体相比位于长波长侧，发光峰值强度较强，即便发光主波长发生长波长化其发光峰值强度也几乎不会降低，从而完成了本发明。
本发明的赛隆荧光体，其特征在于，具有由通式(1)所示的组成，主相具有α-型赛隆结晶结构，且0.25≤p≤0.65。
Lup(Si，Al)12(O，N)16:Euq          (1)
关于上述赛隆荧光体，可以是0.03≤q≤0.08。
另外，上述本发明的赛隆荧光体，可以是通式(1)由通式(2)示出的赛隆荧光体。
LupSi12-(m+n)Al(m+n)OnN16-n:Euq           (2)
(其中，将p+q设为k时，m为3×k所示的数值，n为(3×k)/2所示的数值)。
另外，关于上述赛隆荧光体，可以是0.25≤p≤0.35。
关于上述赛隆荧光体，可以是0.30≤p≤0.65。
另外，本发明提供一种发光器件，其特征在于，具备：上述赛隆荧光体、和半导体蓝色发光二极管元件。
本发明的赛隆荧光体，被紫外光或蓝色光激发，发出黄色～橙色的荧光。本发明的赛隆荧光体具有如下所述的出色特性，即可以无需使用昂贵的氮化物原料而廉价制造，与以往的荧光体相比具有长波长的发光色度和亮度，进而不会在长波长侧发生急剧的发光强度的降低。因此，该赛隆荧光体可以用于使用了蓝色半导体发光元件的白色发光二极管灯等。
附图说明
图1是表示本发明的实施例涉及的试样的X射线衍射图形的图。
图2表示试样#4的激发光谱和发光光谱。发光强度是将各自的峰值设为1而标准化。激发光谱用细线表示，发光光谱用粗线表示。
图3表示试样#5的激发光谱和发光光谱。发光强度是将各自的峰值设为1而标准化。激发光谱用细线表示，发光光谱用粗线表示。
图4表示试样#6的激发光谱和发光光谱。发光强度是将各自的峰值设为1而标准化。激发光谱用细线表示，发光光谱用粗线表示。
图5表示试样#10的激发光谱和发光光谱。发光强度是将各自的峰值设为1而标准化。激发光谱用细线表示，发光光谱用粗线表示。
图6是表示试样#4～#10及在WO2006/025261中公开的(Ca，Y)-α-SiAlON:Eu荧光体的、发光主波长和发光峰值强度的关系的图。
图7是表示本发明的发光器件的一个实施方式的立体图。
图8是表示本发明的发光器件的一个实施方式的截面图。
具体实施方式
本发明的赛隆荧光体，是经铕(Eu)激活且固溶有镥(Lu)的荧光体，具体而言具有通式(1)所示的组成、结构，更具体而言具有通式(2)所示的组成、结构。
Lup(Si，Al)12(O，N)16:Euq            (1)
LupSi12-(m+n)Al(m+n)OnN16-n:Euq      (2)
上述通式(1)、(2)使用原子比示出。在通式(1)、(2)中，p、q表示在将硅(Si)和Al的总量以原子比计设为12、将O和N的总量设为16时的Lu、Eu的量。p优选为0.25以上、0.65以下。q优选为0.03以上、0.08以下。
接着，对固溶元素的比例进行说明。α-型赛隆具有α-型氮化硅的Si-N键的一部分被Al-N键或Al-O键置换的结构，由于金属元素在晶格间进行侵入型固溶而稳定化。成为发光中心的Eu未单独在α-型赛隆中固溶。需要说明的是，在将成为3价阳离子的元素的量设为k时，Lu为3价，Eu也通常使用Eu2O3作为原料，所以为3价，因此k＝p+q。此时，m＝3k、n＝3k/2。其中，在煅烧后的成果物中Eu被还原成2价，所以m及n的值有可能会随之发生些许变化。
用以下的方法制造使q为0.05、p为0.10～1.25的组成的赛隆荧光体。作为起始原料，使用氮化硅(Si3N4)、氮化铝(AlN)、氧化铕(Eu2O3)、氧化镥(Lu2O3)。按照前述组成设计而算出的各原料的质量比如表1所示。这些原料可以廉价获得。
表1
               表1 赛隆荧光体的组成
根据该比例，以每批为30g的方式对该原料粉末进行秤量、混合。混合时使用正己烷，通过湿式行星球磨机混合2小时。用旋转式蒸发器使混合粉末干燥，在干燥的粉末状态下使用研钵将其充分揉开，使用以JIS Z 8801为基准的标准网眼125μm的不锈钢制试验用筛网，造粒成合适的粒径，在氮化硼的带盖容器中收纳。烧结温度为1700℃，氮气气氛下加压到0.9MPa，保持2小时。烧结后，在从装置取出的阶段，将一个成块的原料放置在研钵上稍微施力，就散成粉末状，由此制造粉末荧光体试样(赛隆荧光体)。
需要说明的是，本发明的赛隆荧光体并不限于该制造方法，可以通过与上述不同的原料、混合、过筛、烧结条件等进行制造。过筛可以根据试样的粉碎容易程度选择试验用筛网的标准网眼。关于荧光粉末体的粒径，当成为亚微米到1μm左右的微小粒径时，白色光发光二极管的发光强度显著降低。为了实现白色光发光二极管灯发光效率的升高，通过安装设计的改善来提高光的取出效率的研究是不可或缺的，在α-型赛隆荧光体粉末中，优选将能成为米氏散射原因的粒径2μm以下的粒子除去或使其比例降低至10％以下。在进行烧结时，氮气气氛下的气体加压烧结是合适的。为了防止烧结中的氧化、分解，优选不仅为氮气气氛，而且还要加压。为了更为确实可靠地进行烧结，特别优选为2个大气压以上。烧结时间优选为1～24小时。烧结温度优选为1650～1750℃，特别优选1700℃左右。关于在原料粉末的混合中使用的溶剂，如果使用乙醇等具有羟基的溶剂，则AlN容易分解，所以优选使用正己烷等不具有羟基的溶剂。
对于如此合成的12种粉末荧光体试样，使用荧光分光光度计实施激发光谱及发光光谱的测定。在进行光谱的测定时，使用的是用若丹明B法及使用制造商提供的标准光源进行了光谱修正的日本分光制的荧光分光光度计FP-6500。关于发光光谱，假设基于蓝色LED元件的激发，将荧光分光光度计的激发峰值波长设为450nm而进行测定。关于激发光谱，将荧光分光光度计的发光监控波长设定为根据发光光谱测定结果所得的发光峰值波长而进行测定。在表2中，示出发光峰值波长、发光主波长、CIE1931色度图中的色度坐标(x，y)、发光峰值强度的值。需要说明的是，发光峰值强度用当市售的(Y，Gd)3Al5O12:Ce3+荧光体在460nm激发时的发光光谱的发光峰值强度为100％时的相对值来表示。
表2
          表2 赛隆荧光体的光学特性测定结果
Figure G2008800100784D00071
发光峰值波长可以长波长化至608.4nm(试样#11(p＝0.95))。发光主波长可以达到579.6～589.6nm的范围，除了试样#12之外，组成式的数值p增大，即随着Lu量的增多，发光主波长向长波长移位。当限于根据粉末X射线衍射图形测定结果判断为α-型赛隆单相的0.25≤p≤0.65的试样#4～#10时，发光主波长范围为583.8～588.0nm。另外，对于该0.25≤p≤0.65的试样#4～#10，发光峰值强度较强，为59％以上。进而，对于0.25≤p≤0.35的试样#4～#6，发光峰值强度均为65％以上(68％)，发光峰值强度特别强。这是使用价格低于以往的荧光体的原料并使长波长侧的发光成为可能的荧光体，通过用蓝色发光二极管元件进行激发，可以将从来没有过的低比色温度的白色发光器件实用化。
进而，对于全部12种试样，测定粉末X射线衍射图形。图1示出其测定结果和JCPDS-ICDD的PDF-2数据库的X射线数据卡片No.33-0261的钙α-型赛隆的峰值位置。
关于试样#1、#2、#3、#11、#12，可知被看成是第2相的生成，不是α-型赛隆单相，而是具有以α-型赛隆为主相的结晶结构。对于#4～#10，即为0.25≤p≤0.65时，可知具有α-型赛隆单相的结晶结构。
在图2、图3、图4、图5中，分别示出试样#4、#5、#6、#10的激发光谱和发光光谱。发光强度是将各自的峰值强度设为1而标准化并示出。可知均可以通过紫外光～蓝色光有效激发，具有足够宽的光谱带宽，适合作为白色LED用荧光体。
图6示出我们在专利文献4中公开的(Ca，Y)-α-SiAlON:Eu荧光体、和本申请发明的Lu-α-SiAlON:Eu荧光体的、发光主波长和发光峰值强度的关系。(Ca，Y)-α-SiAlON:Eu荧光体，发光峰值强度随着发光主波长的长波长化而急剧降低，但在本申请发明的Lu-α-SiAlON:Eu荧光体中，几乎不降低。特别是在发光主波长为585nm以上的范围时，与(Ca，Y)-α-SiAlON:Eu荧光体相比，Lu-α-SiAlON:Eu荧光体的发光峰值强度更强。这与0.30≤p≤0.65的试样#5～#10相当。需要说明的是，在本实验中，q＝0.05，但优选q为0.03～0.08。
图7是表示使用了本发明的赛隆荧光体的本发明的发光器件1的一个实施方式的立体图，图8是该发光器件1的截面图。发光器件1是上部成为具有透镜功能的球面的大致圆筒形状，换言之，具有类似于炮弹的形状，由导线2及3、蓝色发光二极管元件(半导体蓝色发光二极管元件)5、导电性膏9、金制的键合线(bonding wire)10、赛隆荧光体11、第一树脂12、第二树脂14构成。蓝色发光二极管元件5由上部电极6、碳化硅(SiC)基板7、氮化铟镓(InGaN)发光层8、及下部电极13构成。另外，在导线2的上端部设置有凹部4，蓝色发光二极管元件5的下部电极13通过导电性膏9跟凹部4的底面电连接，上部电极6通过键合线10跟导线3电连接。
第一树脂12是环氧树脂等具有透光性的树脂，另外，分散有荧光体11。该第一树脂12被填充到凹部4内，密封蓝色发光二极管元件5。上述的荧光体11吸收从蓝色发光二极管元件5发出的蓝色光的一部分，发出与其不同波长的光(黄色光)。第二树脂14是环氧树脂等具有透光性的树脂，密封导线2及3的上部、键合线10、第一树脂12。具有以上构成的发光器件1，通过从蓝色发光二极管元件5发出的蓝色光和从荧光体11发出的黄色光的混色而发出白色光。
本发明的赛隆荧光体，可以无需使用昂贵的氮化物原料而廉价地制造。本发明的赛隆荧光体，作为与以往相比能在长波长侧发光的赛隆荧光体，可以用于白色发光二极管灯等发光器件。

Claims (6)

1.一种赛隆荧光体，其特征在于，
具有由通式(2)所示的组成，至少主相具有α-型赛隆结晶结构，且0.25≤p≤0.65，0.03≤q≤0.08，
LupSi12-(m+n)Al(m+n)OnN16-n:Euq(2)，
式中，将p+q设为k时，m为3×k所示的数值，n为(3×k)/2所示的数值。
2.根据权利要求1所述的赛隆荧光体，其中，
0.25≤p≤0.35。
3.根据权利要求1所述的赛隆荧光体，其中，
0.30≤p≤0.65。
4.一种发光器件，其特征在于，具备：
权利要求1所述的赛隆荧光体、和半导体蓝色发光二极管元件。
5.一种发光器件，其特征在于，具备：
权利要求2所述的赛隆荧光体、和半导体蓝色发光二极管元件。
6.一种发光器件，其特征在于，具备：
权利要求3所述的赛隆荧光体、和半导体蓝色发光二极管元件。
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