CN101828273A - 发光装置、使用该发光装置的车辆用灯具及前照灯 - Google Patents
发光装置、使用该发光装置的车辆用灯具及前照灯 Download PDFInfo
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- CN101828273A CN101828273A CN200880111856A CN200880111856A CN101828273A CN 101828273 A CN101828273 A CN 101828273A CN 200880111856 A CN200880111856 A CN 200880111856A CN 200880111856 A CN200880111856 A CN 200880111856A CN 101828273 A CN101828273 A CN 101828273A
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Abstract
一种发光装置,由发射激发光的光源、和吸收该激发光后发射光的荧光体组合而成。作为荧光体,使用以用通式(Caα,Euβ)(Si,Al)12(O,N)16表示的α型塞隆为主要成分的、比表面积为0.1~0.35m2/g的荧光体,其中,1.5<α+β<2.2,0<β<0.2,O/N≤0.04。该发光装置,即使在温度高的环境下使用,随温度变化的颜色变化也少,并有效发光,特别适用于前照灯等的车辆用灯具中。
Description
技术领域
本发明涉及一种由半导体发光元件(LED:Light-EmittingDiode)和新型荧光体组合而成的发光装置及使用该发光装置的照明装置,特别涉及一种发光色为琥珀色的车辆用灯具及前照灯。
背景技术
迄今为止,作为发出琥珀色光的车辆用灯具例如方向指示器,一直使用内部装有着色为琥珀色的灯泡的照明装置。作为克服灯泡的缺点即巨大的消耗功率和小型化的限制的技术方案,提出一种利用LED的技术方案,并进行了实用化。
作为琥珀色的LED,已知在约580~610nm具有发光光谱的AlGaInP半导体和GaAsP半导体。但是,这些LED存在周围温度变高时发光强度大大降低的问题。因此,在后组合灯等的、周围温度较高的用途中,为了满足所需的光通量,需要准备大量琥珀色LED,导致高成本化和基于确保设置场所的灯具设计的限制。另外,被组装到前照灯中的转向信号灯,由于距离发动机较近且周围温度特别高,因此如果使用上述琥珀色LED则不能够确保所需的光通量。
与此相对,还提出了一种关于组合蓝色LED和可利用LED的发光来发射长波长光的荧光体而实现琥珀色的灯具的技术方案(专利文献1)。专利文献1中,记载了作为与蓝色LED组合使用的长波长用荧光体使用(Ca,Sr)2Si5N8:Eu的技术方案。
但是,该荧光体,由于半值宽度较大约为100nm,且可见度低的长波长成分较多,因此存在效率低的问题。另外,由于具有余辉特性,因此如果用于以闪亮的方式使用这一用途中,存在非发光时的余辉使可见性降低的问题。另外,如果使用专利文献1中记载的琥珀色的灯具,则需要用于阻断LED的发光的滤光片。
专利文献1:日本特开2005-123165号公报
发明内容
发明要解决的问题
本发明要解决的问题在于,提供一种即使在温度高的环境下使用时随温度变化的颜色变化也少、并有效发光的发光装置。另外,本发明要解决的问题在于,提供一种利用上述发光装置、可见性优良的车辆用灯具。
用于解决问题的方案
本发明通过在由LED和荧光体组合而成的发光装置中使用新型荧光体解决了上述问题。
即,本发明的发光装置,其特征在于,由发射激发光的LED、和吸收该激发光后发射光的荧光体组合而成,作为荧光体,使用以用通式(Caα,Euβ)(Si,Al)12(O,N)16(其中,1.5<α+β<2.2,且0<β<0.2,O/N≤0.04)表示的α型塞隆(Sialon)为主要成分的荧光体。特别是,其特征在于,使用了以α型塞隆为主要成分的荧光体,所述α型塞隆的比表面积为0.1~0.35m2/g。
该发光装置所发射的光的色度,在色度坐标(CIE1931)上为x≥0.545,y≥0.39,y≤x-0.12。
另外,本发明的车辆用灯具,是一种使用上述发光装置的车辆用灯具。
附图说明
图1是表示本发明的发光装置的一实施方式的附图;
图2是表示本发明的车辆用灯具的一实施方式的附图;
图3是表示使用了本发明的发光装置的前照灯的一实施方式的附图;
图4是表示实施例的发光装置的发射光谱的附图;
图5是表示实施例的发光装置的光通量的温度依赖性的附图;
图6是表示实施例的发光装置的色度的温度依赖性的附图。
附图标记说明
1 树脂
2 蓝色LED
3 灯罩
4、5 电极
6 导线
21 发光元件
23 反射镜
24 外透镜
具体实施方式
以下,说明本发明的发光装置及车辆用灯具的实施方式。
首先,详述构成本发明的发光装置的荧光体。
本发明的发光装置所使用的α型塞隆,是一种用通式Mz(Si,Al)12(O,N)16表示的、作为元素M使用Ca、在其一部分中导入了成为发光中心的Eu的Eu赋活Ca-α-塞隆荧光体。一般而言,Eu赋活Ca-α-塞隆荧光体,被紫外~蓝色的宽范围波长区域的光激发而呈现黄色~橙色的可见光。本发明中使用的塞隆荧光体,是一种通过降低塞隆晶体内的氧含有率并提高Ca(包括Eu)的固溶浓度、可实现橙色~红色的长波长发光的荧光体。具体而言,通过波长范围420~480nm的激发,呈现琥珀色的发光。
上述α型塞隆荧光体,例如,可以使用下述方法制造,将由(a)氮化硅、(b)氮化铝、(c)含Ca化合物、(d)含Eu化合物、(e)α型塞隆构成的原料混合粉末在氮气氛围中、1650~1850℃下加热处理,由此得到α型塞隆,仅通过分级处理,得到平均粒径为15~25μm的粉末。该方法的特征在于,在原料混合粉末中含有α型塞隆(e),并仅通过分级处理得到平均粒径为15~25μm的粉末。使用该方法得到的荧光体,比表面积小,发光效率优良,且发光色的温度依赖性低,即使在高温的环境中颜色变化也少。
荧光体中的Ca和Eu的合计摩尔比(α+β)为大于1.5且小于2.2。如果(α+β)为1.5以下,则难以得到峰波长为595nm以上的荧光。另外,如果(α+β)超过2.2,则容易生成给荧光特性带来不良影响的第二相。另外,Eu的固溶量(β值)小于0.2。如果β值为0.2以上,则荧光峰波长发生位移,难以得到琥珀色,另外,发光效率降低。
氧与氮之比O/N比为0.04以下。如果O/N大于0.04,则不仅难以得到峰波长为595nm以上的荧光,而且Ca及Eu的固溶极限量降低,难以实现(α+β)大于1.5。
上述荧光体,以粉末(粒子)的形态而得到,可以使用粒子的比表面积优选为0.1~0.35m2/g、更优选为0.1~0.3m2/g的粒子。如果粒子的比表面积大于0.35m2/g,则初级粒子未充分发达,或者在荧光体粒子表面存在凹凸,其结果不能得到60%以上高发光效率。另外,如果粒子的比表面积小于0.1m2/g,则粒子的粒径变得过大,有时发生组装发光装置时所使用的分配器用喷嘴堵塞等的问题。
另外,本发明中,比表面积,是根据BET法测定、并通过BET多点分析求得的数值。
本发明的发光装置,除作为荧光体使用上述α型塞隆荧光体以外,与公知的发光装置同样,对于结构和类型没有特别限制。
作为第一实施方式,图1中示出一种适用本发明的典型的发光装置。该发光装置的结构如下,将阳极/阴极两极用的电极4、5设置在由玻璃纤维、环氧树脂等的绝缘体构成的灯罩3上,用环氧树脂等的粘合剂将LED2固定在灯罩3上。用导线6将LED2的阳极/阴极各电极与相应的引出电极4、5电连接。在灯罩3上,在大致中央的地方形成凹部,在该凹部内填充橙色荧光体和树脂1,构成发光元件。
作为蓝色LED2,可以使用峰波长在420~480nm范围的公知的蓝色LED。具体而言,可列举出GaN系化合物半导体、InGaN系化合物半导体、ZnO系化合物半导体、ZnSe系化合物半导体等。
作为用作填充凹部的密封材料的树脂,只要是直到比LED2的发光峰波长短的短波长区域都透明的、可混合荧光体的材料即可。具体可以列举:热固化树脂、光固化性树脂和低熔点玻璃等。特别优选环氧树脂、有机硅树脂、具有环氧基的聚二甲基硅氧烷衍生物、氧杂环丁烷树脂、丙烯酸类树脂、环烯烃树脂等热固化树脂。这些树脂,可以使用一种或者混合使用两种以上。
本发明的发光装置所发射的光的色度,优选:在色度坐标(CIE1931)上为x≥0.545,y≥0.39,y≤x-0.12。这样的色度,能够通过组合峰波长为420~480nm的范围的蓝色LED和上述α型塞隆荧光体来实现。但是,在未超出该色度范围的范围内,也可以含有上述琥珀色荧光体以外的荧光体。
作为其它的荧光体,可以使用下述的一般已知的荧光体的一种或者混合使用两种以上,即铕赋活的M2SiO4(M=Mg、Ca、Sr、Ba)、铕赋活的M2Si5N8(M=Mg、Ca、Sr、B a)、铕赋活的M3SiO5(M=Mg、Ca、Sr、Ba)、铕赋活的MAlSiN3(M=Mg、Ca、Sr、Ba)、铈赋活的A3B5O12(A=Y、Gd、Lu、Tb;B=Al、Ga)等。另外,根据需要,为了辅助激发光及波长已被变换的光的反射,可以使硫酸钡、氧化镁、二氧化硅等的散射剂混合存在于各波长变换用材料中。
荧光体,可以适量混合在上述树脂中使用。在树脂中混合的情况下的混合量,没有特别限制,一般约为树脂的1~50重量%,优选5~20重量%。另外,也可以使荧光体分散于灯罩3中。
关于灯罩3、蓝色LED2及电极4、5,只要是蓝色LED2固定在灯罩3上、且阳极/阴极用的各引出电极与LED2的阳极/阴极电极对应地电连接即可,除图1所示的方式外,还可以使用各种其它的方式。虽然未给出图示,但是可以采用下述方式等。例如,用Au-Sn等的共晶材料、Au焊点(bump)、具有各向异性的导电性薄片、以Ag糊为代表的导电性树脂等,将LED2的阳极/阴极电极和相应的各引出电极电连接,并固定在灯罩3上的方式;用上述材料仅将LED2的任一个电极与相应的引出电极电连接,并固定在灯罩3上,用导线将另一个电极和相应的引出电极电连接的方式等。另外,灯罩3,也可以为了提高LED2的散热性而由金属等的导电性材料构成,并兼做一个电极的引出电极5。
在形成在灯罩3上的凹部的内侧,还可以通过涂布、电镀或蒸镀等形成高反射率材料。凹部的形状,优选为准圆锥台形,也可以为准四角锥台形。凹部的侧壁,优选为倾斜式,根据用途,也可以大致垂直。
本发明的发光装置,作为因蓝色LED的激发而发光的荧光体,使用特定的Eu赋活Ca-α型塞隆荧光体,由此,即使在高温的环境下颜色变化也少,并且发光效率优良。本发明的发光装置,通过使用发光峰波长为420~480nm的LED和上述α型塞隆荧光体,能够使其发射光谱中500nm以下的区域的面积达到发射光谱总面积的5%以下。另外,发光装置的发射光谱中主峰的半值宽度为100nm以下。由此,即使没有用于阻断波长为500nm以下的光的滤光片等,也可以实现在色度坐标(CIE1931)上为x≥0.545,y≥0.39,y≤x-0.12的色度。
另外,关于色度的变化,可以实现:在环境温度为-20℃~85℃的范围,色度的变化量在色度坐标(CIE1931)上为Δx≤0.03,Δy≤0.03。
以下,说明本发明的车辆用灯具及组装有该车辆用灯具的前照灯。
图2是示出本发明的车辆用灯具的一例的附图。该灯具,具有发光元件21、支撑发光元件21的支撑部22、具有准圆弧状的形状的反射镜23、与反射镜23相向地配置的外透镜24。发光元件21,是具有与如图1所示的发光装置同样结构的发光元件21,为了使来自外侧的光不直接照射到发光元件21上,以填充有荧光体的发光元件21的上表面朝向与连接发光元件21和外透镜24的直线大致垂直的方向的方式,将发光元件21固定在支撑部22上。发光元件21与未图示的电源部连接。反射镜23,是将发光元件21所发射的光向外透镜24侧反射的反射镜,至少其与发光元件21相向的表面由金属或白色的材料构成。例如,在该反射镜的表面,通过蒸镀、涂布等,形成有铝等的金属膜或白色颜料的膜。另外,虽然未给出图示,但是根据需要,有时在外透镜与发光元件之间配置用于调整颜色的滤光片。
使用上述结构,在发光元件21的非发光时,从外部不会看到滤光片和外透镜的颜色。在发光时,被反射镜23反射的光通过外透镜24向外部照射。因此,在开灯时和非开灯时,颜色(美观性)完全不同,可见性良好。
本发明的车辆用灯具,可以适用于例如车载式转向信号灯、后组合灯、车内照明灯、里程表灯、开关类照明灯等各种车辆用灯具中。图3中示出适用了本发明的前照灯的一例。图3(a)是其主视图,图3(b)是A-A’剖视图。该前照灯,由远光灯31、近光灯32、33、位置灯34、转向信号灯35等数种灯具构成。本发明的发光装置,虽然可以适用于这些灯具中任一种,但是特别适用于琥珀色的颜色范围在各国均已规格化的车载式转向信号灯中。用于车载式转向信号灯的琥珀色的颜色范围,在日本,在JIS D5500中,作为橙色范围,规定:0.429≥y≥0.398,z≤0.007(其中,z=1-x-y,x、y、z均为色度坐标);在欧洲,根据ECE标准,规定:y≥0.39,y≥0.79-0.67x,y≤x-0.12;在美国,在SAE J578c、J578d中,规定:y=0.39,y=0.79-0.67x,y≤x-0.12。
本发明的车辆用灯具使用的发光元件21,可以实现在色度坐标(CIE1931)上为x≥0.545、y≥0.39、y≤x-0.12的色度范围,因此可以提供满足上述规格的车载式转向信号灯。
另外,本发明的车辆用灯具,作为光源的发光装置(发光元件21)本身在车载式转向信号灯的色度规格范围内,因此即使不使用滤光片也可以制造转向信号灯。由于不使用滤光片,因此可以减少发光损失,并提高效率。
实施例
以下,说明本发明的实施例。
1.α型塞隆的制造
将氮化硅粉末61.2质量%、氮化铝粉末22.1质量%、氮化钙粉末9.5质量%、氟化钙粉末5.0质量%、氧化铕粉末2.2质量%,用研钵混合,填充于氮化硼制坩埚中,使用具有石墨加热器的电炉,在大气压氮气中,在1750℃下,进行16小时的加热处理。通过加热处理得到的粉末,使用粉末X射线衍射法测定的结果,确认为α型塞隆。
将通过加热处理得到的粉末(α型塞隆)15质量%、氮化硅粉末53质量%、氮化铝粉末19.1质量%、氮化钙粉末11质量%、氧化铕粉末1.9质量%混合,填充于氮化硼制坩埚,使用具有石墨加热器的电炉,在氮气氛围中,在1750℃下,进行16小时的加热处理。分级筛分所得的试样,将通过45μm的筛的粉末作为发光装置制作用的荧光体。
关于该荧光体,用粉末X射线衍射法测定其晶相,结果确认:存在的晶相仅为α型塞隆。使用荧光分光光度计测定荧光光谱,得到下述结果,峰波长为600nm,半值宽度为85nm,比表面积为0.24m2/g。
将荧光体组成式(Caα,Euβ)(Si,Al)12(O,N)16中的α+β、O/N比,如表1所示地进行变换,使用与上述同样的制造方法制作多种荧光体(实施例1~3,比较例1~5)。其中,在比较例1的荧光体中,作为原料粉末,按化学计量比混合除α型塞隆以外的原料粉末来使用。
[表1]
2.荧光体的发光特性的测定
关于实施例1~3和比较例1~5的荧光体,测定了用455nm的激发光激发的情况的荧光特性。荧光体的发光特性,如下所述地测定,作为激发光源使用由氙灯光源分光的波长为455nm的蓝色光,并使用大冢电子株式会社制造的MCPD7000多通道光谱仪测定使用了积分球的总光通量发射光谱。色度,如下所述地测定,根据发射光谱的465~780nm的波长区域的数据,使用基于JIS Z8724的方法,算出在JIS Z8701中所规定的XYZ表色系中的色度坐标CIEx和CIEy。根据大久保等的方法(照明学会志,第83卷第2号,平成11年,87~93页“NBS标准荧光体的量子效率的测定”)算出量子效率。其结果示于表1。
与实施例1的比表面积为0.24m2/g相对,在作为用于制造荧光体的原料未使用α型塞隆的比较例1中,比表面积较大,为0.42m2/g。根据该实施例1与比较例1的比较,判明:如果比表面积大于0.35m2/g,则不能够得到60%以上高发光效率。
关于Ca和Eu的含量(α+β),根据实施例2(α+β=1.71)与比较例2(α+β=1)、比较例3(α+β=2.5)的比较,判明:如果α+β为1.5以下,则难以得到峰波长为595nm以上的荧光,如果旨在制造超过2.2的α型塞隆,则容易生成给荧光特性带来不良影响的第二相。
另外,关于Eu的固溶量(β值),根据实施例3(β=0.04)与比较例4(β=0.25)的比较,判明:即使α+β相同,如果Eu的固溶量(β值)为0.2以上,则荧光峰波长也发生位移,发光效率降低。
另外,根据实施例2(O/N=0.02)与比较例5(O/N比=0.06)的比较,判明:关于峰波长和发光效率中任一项,氧与氮的比优选为0.04以下。
3.发光装置的制作
相对于热固性有机硅树脂100重量份配合20重量份的实施例1的荧光体,均匀搅拌后,使用注入机注入到固定有电极5及蓝色LED(氮化镓系化合物半导体LED,发光峰的波长约为460nm)的灯罩3中。然后,150℃下,加热1~4小时,将树脂固化而固定化,制作如图1所示的发光装置。
对该发光装置的蓝色LED流通350mA的电流,使用积分球测定总光通量,并且测定25℃的周围温度中的发射光谱。将发射光谱示于图4中。其结果如下,总光通量为29lm,峰波长为603nm,发射光谱的半值宽度为86nm。另外,500nm以下的积分值,相对于总积分值为0.33%。发光时的色度坐标为x、y=0.5798、0.4169,确认了该数值在用于车载式转向信号灯的琥珀色的范围内。
4.温度特性的评价
关于在3中所制作的发光装置及现有的AlGaInP半导体LED,在控制周围温度的状态下,通电而流通350mA的电流,使用积分球,测定总光通量及色度。将其结果示于图5及图6。图5中,作为光通量的强度,示出了相对于周围温度为25℃时的光通量的相对强度。图6中,用虚线围成的区域表示ECE方向指示器色度区域。点划线表示CIE 1971 Spectrum Locus(单色光轨迹)。
根据图5也可判明:AlGaInP半导体LED,在高温区域光通量降低,与此相对,本发明的发光装置,即使在高温区域,光通量的降低也较少。
另外,如图6所示,AlGaInP半导体LED,对周围的温度变化的色度变化较大,偏离方向指示器的色度区域,与此相对,本发明的发光装置,即使周围环境的温度为100℃,色度变化也较少。
根据这些结果,可以确认:本发明的发光装置,即使在高温的使用环境中,也可以稳定保持光通量,并且色度变化较少。
产业上的可利用性
根据本发明,可以提供即使在高温下也可稳定保持光通量、且色度变化较少的琥珀色的发光装置。该发光装置可以适用于车辆用灯具、一般的琥珀色光源,并且特别适用于周围温度较高的车辆用灯具中。
Claims (13)
1.一种发光装置,其特征在于,由发射激发光的光源、和吸收该激发光后发射光的荧光体组合而成,
作为荧光体,使用以用通式(Caα,Euβ)(Si,Al)12(O,N)16表示的α型塞隆为主要成分的荧光体,其中,1.5<α+β<2.2,0<β<0.2,O/N≤0.04。
2.一种发光装置,其特征在于,由发射激发光的光源、和吸收该激发光后发射光的荧光体组合而成,
作为荧光体,使用以用通式(Caα,Euβ)(Si,Al)12(O,N)16表示的α型塞隆为主要成分的、比表面积为0.1~0.35m2/g的荧光体,其中,1.5<α+β<2.2,0<β<0.2,O/N≤0.04。
3.根据权利要求1或2所述的发光装置,其特征在于,
发光装置所发射的光的色度在色度坐标(CIE 1931)上为x≥0.545,y≥0.39,y≤x-0.12。
4.根据权利要求1~3中任一项所述的发光装置,其特征在于,
光源所发射的激发光的发光峰波长为420~480nm。
5.根据权利要求1~4中任一项所述的发光装置,其特征在于,
发光装置的发射光谱中500nm以下的区域的面积为发射光谱总面积的5%以下。
6.根据权利要求1~5中任一项所述的发光装置,其特征在于,
发光装置的发射光谱中主峰的半值宽度为100nm以下。
7.一种发光装置,其特征在于,由发射激发光的光源、和吸收该激发光后发射光的荧光体组合而成,
在环境温度为-20℃~85℃的范围下,总光通量的变化量在±30%以内,所发射的颜色的色度在色度坐标(CIE1931)上为x≥0.545,y≥0.39,y≤x-0.12。
8.根据权利要求7所述的发光装置,其特征在于,
在环境温度为-20℃~85℃的范围下,色度的变化量在色度坐标(CIE 1931)上为Δx≤0.03,Δy≤0.03。
9.一种车辆用灯具,其使用权利要求1~8中任一项所述的发光装置。
10.一种车辆用灯具,其特征在于,具有发光元件、接受并反射来自所述发光元件发射的光的反射镜和用于向外部照射被反射镜反射的光的透镜,
作为发光元件,使用权利要求1~8中任一项所述的发光装置。
11.根据权利要求10所述的车辆用灯具,其特征在于,
不使用滤色镜测定的发射光谱中500nm以下的区域的面积为发射光谱总面积的5%以下。
12.根据权利要求10所述的车辆用灯具,其特征在于,
发光元件的主发光方向与灯具的主发光方向大致垂直。
13.一种前照灯,其组装有权利要求9~12中任一项所述的灯具。
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