CN103080270A - β型赛隆、β型赛隆的制备方法和发光装置 - Google Patents
β型赛隆、β型赛隆的制备方法和发光装置 Download PDFInfo
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Abstract
一种β型赛隆的制备方法,其具有如下工序:将氧化铝或氧化硅中的至少一种、氮化硅、氮化铝和铕化合物进行混合的混合工序;以大于1950℃且小于等于2200℃、10小时以上的条件对混合工序后的混合物进行烧成的烧成工序;和烧成工序后在1300℃以上至1600℃以下、分压为10kPa以下的除氮气以外的惰性气体气氛中进行热处理的热处理工序。
Description
技术领域
本发明涉及β型赛隆、β型赛隆的制备方法和发光装置。
背景技术
使Eu2+固溶于β型赛隆的晶体结构内而得到的荧光体能够被紫外光至蓝色光激发而呈现520nm~550nm的绿色发光。固溶有Eu2+的β型赛隆也被称为Eu固溶β型赛隆。该荧光体可以被用作白色发光二极管(称为白色LED(LightEmitting Diode))等发光装置的绿色发光成分。即使在固溶有Eu2+的荧光体中,Eu固溶β型赛隆的发光光谱也非常清晰,其是一种特别适合于要求由蓝、绿、红三原色光所构成的窄带发光的液晶显示面板的背光光源的绿色发光成分的荧光体(参见专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2005-255895公报
非专利文献
非专利文献1:大久保和明等,NBS标准荧光体的量子效率的测定,照明学会杂志,第83卷第2号,pp.87-93,平成11年
发明内容
随着实用化的进展,希望能改善Eu固溶β型赛隆的发光效率。
本发明的第一目的在于,提供一种能实现高发光效率的Eu固溶β型赛隆及其制备方法,第二目的在于提供一种能够高效率地进行发光的发光装置。
实现第一目的的本发明的β型赛隆是用通式:Si6-ZAlZOZN8-Z(0<Z≤0.42)表示、并固溶有Eu的β型赛隆,β型赛隆的一次粒子的50%面积平均直径为5μm以上。
本发明的β型赛隆的一次粒子的50%面积平均直径优选为7μm以上。而且,β型赛隆的二次粒子的分布的中值粒径(以下称为D50粒径)优选为30μm以下。
可以通过如下的烧成工序得到本发明的β型赛隆,所述烧成工序是将氧化铝或氧化硅中的至少一种、氮化硅、氮化铝和铕化合物进行混合后的β型赛隆的原料,在大于1950℃且小于等于2200℃、10小时以上的条件下进行烧成。烧成的压力条件优选为0.5MPa以上至10MPa以下。
实现上述第二目的的本发明的发光装置包括:发光光源和波长转换部件,波长转换部件包括:吸收由发光光源发出的近紫外光至蓝色光而产生荧光的荧光体,荧光体是用通式:Si6-ZAlZOZN8-Z(0<Z≤0.42)表示、且固溶有Eu的β型赛隆,β型赛隆的一次粒子的50%面积平均直径为5μm以上。
发光装置中的发光光源优选是发出波长为350nm~500nm的光的LED芯片。
荧光体优选为,进一步含有固溶有Eu的α型赛隆。
固溶有Eu的α型赛隆优选为Ca-α型赛隆。
通过本发明的β型赛隆和β型赛隆的制备方法,可以提供一种能实现高发光效率的Eu固溶β型赛隆。
本发明的发光装置由于使用了能实现高发光效率的β型赛隆,所以可以提供高亮度的发光装置。
附图说明
图1是表示用于EBSD法的测定装置的结构示意图。
图2是表示本发明的发光装置的结构的截面示意图。
图3是表示实施例1的β型赛隆的扫描电子显微镜图像(SEM(ScanningElectron Microscope)图像)的图。
图4表示图3所示的β型赛隆通过EBSD法得到的EBSD图像,图4(A)是EBSD图像,图4(B)是图4(A)的说明图。
图5是表示实施例1的β型赛隆的SEM图像的图。
图6表示图5所示的β型赛隆的EBSD图像,图6(A)是EBSD图像,图6(B)是图6(A)的说明图。
具体实施方式
以下,利用附图详细说明本发明的实施方式。
(β型赛隆)
本发明的实施方式所涉及的β型赛隆是用通式:Si6-ZAlZOZN8-Z:Eu(0<Z≤0.42)表示,并由固溶有Eu2+的β型赛隆构成的荧光体。以下,将Eu2+固溶β型赛隆称为β型赛隆。
在通式Si6-ZAlZOZN8-Z:Eu中,设定Z大于0且小于等于0.42是为了发挥高发光强度。
β型赛隆是在烧成工序中的加热处理时将多个粒子牢固地形成为一体的物质,将多个粒子的每一个粒子称为一次粒子,并将多个粒子牢固地形成为一体的物质称为二次粒子。
本发明人等获得了以下的见解,即一次粒子的50%面积平均直径对β型赛隆的发光强度有贡献,并且发现,为了使β型赛隆的发光强度提高,只要一次粒子的50%面积平均直径为5μm以上即可,优选为7μm以上。
针对一次粒子的50%面积平均直径进行说明。
在β型赛隆的各一次粒子、即单晶粒子中,按截面面积从小到大的顺序,存在有面积为CA1、CA2、CA3、…、CAi、…、CAk的粒子。将该一次粒子的集合的总面积(CA1+CA2+CA3+…+CAi+…+CAk)设定为100%,从而求出累积曲线,由累积曲线为50%的点的一次粒子的面积计算出一次粒径,将该一次粒径作为50%面积平均直径。
对于一次粒子的50%面积平均直径的测定方法进行说明。
可以利用电子背散射衍射法(Electron backscatter diffraction,也称为EBSD法)测定一次粒子的50%面积平均直径。
图1是表示用于EBSD法的测定装置的结构示意图。
如图1所示,用于EBSD法的装置1是在扫描电子显微镜2上附加电子背散射衍射法测定装置3而构成的。扫描电子显微镜2由镜筒部2A、用于载置试样4的台部2B、台控制部2C、电子射线扫描部2D、控制用计算机2E等构成。电子背散射衍射法测定装置3由荧光屏7、照相机8和软件等构成,所述荧光屏7用于检测电子射线5被照射到试样4后而产生的向后方散射的电子6;所述照相机8对该荧光屏7的荧光图像进行拍摄;所述软件未图示,用于获取电子背散射衍射图像的数据并进行解析。
针对基于EBSD法的测定方法进行说明。
对β型赛隆照射电子射线,使其产生与晶体结构和晶面对应的电子散射,对该电子散射的图案的形状进行解析。具体地说,识别各个荧光体的粒子的晶体取向,对各晶体取向的粒径进行图像解析,由下式(1)计算出一次粒子的50%面积平均直径。
一次粒子的50%面积平均直径=2×(S/π)1/2 (1)
在式中,S为各一次粒子的面积累积曲线为50%的点的一次粒子的面积。
如果一次粒子的50%面积平均直径小,则存在于晶界的杂质有增加的趋势,而且结晶性有降低的趋势。因此,发光效率有降低的趋势。一次粒子的50%面积平均直径优选为5μm以上,更优选为7μm以上。可以通过原料粉的组成、以及烧成工序中的加热处理时的温度和处理时间的调节等,对一次粒子的50%面积平均直径进行控制。一次粒子的50%面积平均直径的上限,根据后述的二次粒子的大小的上限而自行决定。
即,为了提高β型赛隆的发光强度,优选将β型赛隆的一次粒子的50%面积平均直径设定为5μm以上,优选为7μm以上,并且将β型赛隆的二次粒子的D50粒径设定为30μm以下。
β型赛隆的二次粒子的D50粒径优选为30μm以下,特别优选为25μm以下。
如果β型赛隆的二次粒子的D50粒径大,则在应用于白色LED等发光装置时,具有在树脂中的分散状态差,并且亮度降低和产生色偏差的趋势。相反,如果β型赛隆的二次粒子的D50粒径小,则具有荧光体自身的发光效率降低的趋势、或者具有因光散射导致发光装置的亮度降低的趋势。
D50粒径的下限虽然也受到一次粒子的大小的影响,但是可以通过粉碎、分级、或粉碎与分级的组合,来调整β型赛隆的二次粒子的D50粒径。
由于本发明的β型赛隆能够在紫外线至可见光的宽波长区域被激发,并且高效率地发出主波长为520nm以上至550nm以下范围内的绿色光,所以,作为绿色发光的荧光体是优异的。因此,本发明的β型赛隆通过单独使用或者该β型赛隆与其他荧光体组合,能够适用于以各种发光元件、特别是紫外LED芯片或蓝色LED芯片为光源的白色LED中。
(β型赛隆的制备方法)
本发明的β型赛隆的制备方法具有烧成工序和热处理工序,烧成工序是在大于1950℃且小于等于2200℃的环境下将原料放置10小时以上,热处理工序是用于使烧成工序后的β型赛隆的主晶中的被外部激发光激发的电子(捕获激发电子的电子陷阱)的数量减少的工序。优选在热处理工序后,包括用于提高品质的酸处理工序、将比重轻的悬浮物去除的去除工序。
针对β型赛隆的烧成工序进行说明。
将包含作为β型赛隆构成元素的Si、Al、N、O、Eu的原料进行混合,并将得到的混合组合物作为原料混合物。作为原料混合物,例如包含氮化硅(Si3N4)、氮化铝(AlN)、氧化硅(SiO2)和/或氧化铝(Al2O3)、以及选自Eu的金属、氧化物、碳酸盐、氮化物或氮氧化物中的Eu化合物。
将原料混合物的粉末填充到与原料接触的面由氮化硼构成的坩锅等容器中,通过在氮气等气氛中加热,促进固溶反应,由此得到β型赛隆。对于向容器中填充原料混合物粉末,从抑制固溶反应中的粒子间的烧结的观点考虑,优选堆积密度为0.8g/cm3以下。
烧成工序中的烧成条件为,在大于1950℃且小于等于2200℃的条件下烧成10小时以上。通过设定为这样的范围,从而可得到一次粒子的50%面积平均直径为5μm以上的β型赛隆,由此,可以制备具有更高的发光强度的β型赛隆。
为了调整一次粒子的50%面积平均直径,对烧成工序的烧成温度和烧成时间做了特别规定。烧成工序中的压力条件优选为0.5MPa以上至10MPa以下。
即使在烧成工序后,也可以通过在氮气气氛下于2200℃以上至2500℃以下对烧成工序后的β型赛隆进行热处理,来控制一次粒子的50%面积平均直径的大小。氮气的压力例如可以设定为70MPa以上至200MPa以下。为了置于这样的温度和压力环境下,优选使用热等静压(Hot Isostatic Press)炉。
优选将通过本发明所涉及的制备方法而得到的β型赛隆设定成平均粒径D50为30μm以下。作为将β型赛隆设定为所述平均粒径和上述50%面积平均直径的具体处理,有利用破碎机、球磨机、振动球磨机、喷射式粉碎机等粉碎机对烧成后的β型赛隆进行的粉碎处理、以及粉碎处理后的筛分。
筛分时的分级的尺寸变更通过适当选择筛的网眼(40μm、45μm等)即可。
烧成工序后的热处理工序是在分压为10kPa以下的除氮气以外的惰性气体气氛中于1300℃以上至1600℃以下的温度,对烧成工序后的β型赛隆热处理2小时以上至10小时以下的工序。作为惰性气体有氩气、氦气。通过该热处理工序,能够使β型赛隆的主晶中的被外部激发光激发的电子(捕获激发电子的电子陷阱)的数量减少。
热处理工序后,通过酸处理,能够将β型赛隆以外的材料溶解,并且溶解除去通过热处理工序发生分解而新生成的Si。由此,能够减少β型赛隆的杂质。
(发光装置)
对本发明第二实施方式所涉及的使用β型赛隆的发光装置进行详细说明。
图2是表示本发明第二实施方式所涉及的、使用β型赛隆的发光装置10的结构的截面示意图。
本发明的发光装置10由作为发光光源12的LED芯片、搭载发光光源12的第一引线框13、第二引线框14、用于覆盖发光光源12和第一引线框13和第二引线框14的波长转换部件15、将发光光源12和第二引线框14电连接的接合线16、以及覆盖这些部件的合成树脂制的盖(cap)19而形成。波长转换部件15由荧光体18和密封树脂17构成,所述密封树脂17中分散并混合有荧光体18。
在第一引线框13的上部13a形成有用于搭载作为发光光源12的发光二极管芯片的凹部13b。凹部13b具有孔径从其底面朝向上方而缓慢扩大的大致漏斗形状,并且凹部13b的内面形成反射面。将发光二极管芯片12的下面侧的电极芯片焊接(die bonding)在该反射面的底面上。在LED芯片12的上面所形成的另一电极,通过接合线16与第二引线框14的表面进行连接。
作为发光光源12,可以使用各种LED芯片,特别优选为,能发出近紫外光至蓝色光的波长350nm~500nm的光的LED芯片。
作为在发光装置1的波长转换部件5中所使用的荧光体18,有β型赛隆、α型赛隆、CaAlSiN3、YAG的单体或混合体,作为固溶在这些荧光体中的元素,有铕(Eu)、铈(Ce)、锶(Sr)、钙(Ca)。通过组合发光光源2与波长转换部件5,能够发出具有高发光强度的光。
由β型赛隆构成的荧光体18优选为用通式:Si6-ZAlZOZN8-Z(0<Z≤0.42)表示的β型赛隆。β型赛隆的一次粒子的50%面积平均直径为5μm以上。一次粒子的50%面积平均直径更优选为7μm以上。而且,二次粒子的D50粒径优选为30μm以下。
为了调节发光装置10的光波长,可以在由β型赛隆构成的荧光体18中进一步含有Eu固溶α型赛隆,或者含有CaAlSiN3。
在单独使用本发明的β赛隆的发光装置10的情况下,发光光源12具有如下发光特性,即通过照射作为激发源的、特别是含有波长350nm以上至500nm以下的近紫外光或可见光,在波长520nm以上至550nm以下的范围内具有峰的绿色发光特性。因此,通过使用作为发光光源12的近紫外LED芯片或蓝色LED芯片和本发明的β赛隆,并且通过进一步组合波长为600nm以上至700nm以下的红色发光荧光体、蓝色发光荧光体、黄色发光荧光体或橙色发光荧光体的单体或混合体,由此能够发出白色光。
本发明的发光装置10由于β型赛隆18的发光强度高,一次粒子的50%面积平均直径大,所以具有高发光强度。
实施例
以下,参照表1详细说明本发明所涉及的实施例。
[表1]
实施例1
(β型赛隆的烧成)
作为原料混合物,将95.5质量%的α型氮化硅粉末(电气化学工业株式会社制造,NP-400等级,氧含量为0.96质量%,β相含量为14.8质量%)、3.1质量%的氮化铝粉末(Tokuyama公司制造,F等级,氧含量为0.9质量%)、0.6质量%的氧化铝粉末(大明化学公司制造,TM-DAR等级)、0.8质量%的氧化铕粉末(信越化学工业公司制造,RU等级)进行混合,以使该原料混合物烧成后的β型赛隆的Z值为0.25。在计算用于将Z值设定为0.25的配合比时,不考虑氧化铕的氧量。
使用摇摆式混合机(爱知电机公司制造,RM-10),对原料混合物干式混合60分钟后,全量通过网眼为150μm的不锈钢制筛,得到用于荧光体烧成的原料混合物粉末。
将原料混合物粉末90g填充在内部容积为0.4升的带盖的圆筒型氮化硼制容器(电气化学工业株式会社制造,N-1等级)中。将该原料混合物粉末连同容器一起在碳加热器的电炉中,于0.9MPa的加压氮气气氛中,在2000℃进行10小时的加热处理。对加热处理后的烧成物进行轻度碎解后,通过网眼为45μm的筛,得到烧成混合粉末。
使用Cu的Kα射线,对烧成混合粉末进行粉末X射线衍射测定(称为XRD(X-ray Diffraction)测定),并进行晶相的鉴定和β型赛隆的晶格常数测定。其结果为,具有作为第一晶相的β型赛隆和作为第二晶相的在2θ=33~38°附近的多个微小衍射线。第二晶相中最高的衍射线强度相对于β型赛隆的(101)面的衍射线强度为1%以下。
将烧成混合粉末20g填充在直径6cm×高度4cm的带盖的圆筒型氮化硼制容器(电气化学工业株式会社制造,N-1等级)中,在碳加热器的电炉中,在大气压的氩气气氛中,于1450℃进行8小时的加热处理。加热处理得到的粉末不会随着烧结而发生收缩,其性状基本与加热前相同,并全部通过了网眼为45μm的筛。XRD测定的结果是检测出微量的Si。
接下来,将加热处理得到的粉末在50%氢氟酸和70%硝酸的1:1混酸中进行处理。由粉末和混酸形成的悬浮液在处理中从类似茶色的绿色变为鲜艳的绿色。其后,通过对悬浮液进行水洗和干燥,得到β型赛隆。
(通过ESBD求出的50%面积平均直径)
使用EBSD法测定实施例1的β型赛隆的一次粒子的50%面积平均直径。使用在扫描电子显微镜2(日本电子公司制造的FE-SEM、JSM-7001F型)上附加了电子背散射衍射法测定装置3(EDAX-TSL公司制造,OIM装置)而得到的装置进行EBSD法测定。
以如下方式计算ESBD的50%面积平均直径:对实施例1的β型赛隆照射电子射线,使其产生与晶体结构和晶面对应的散射,通过软件(EDAX-TSL公司制造的OIM、Ver5.2)解析该散射图案的形状,从而识别出各荧光体粒子的晶体取向,进而通过图像解析,由上述(1)式求出各晶体取向的粒径,并计算出一次粒子的50%面积平均直径。
以下表示用EBSD法求出的晶体取向的测定条件。
加速电压:15kV
工作距离:15mm
试样倾斜角度:70°
测定区域:80μm×200μm
步长(step size):0.2μm
测定时间:50毫秒/步
数据点数:约400,000点
(图像解析)
在图像解析时,由图3所示的实施例1的β型赛隆的扫描电子显微镜图像(SEM图像,电子的加速电压为15kV,倍率为500倍),来制作图4(A)的EBSD图像,并由图4(A)的EBSD图像制作图4(B)的图,从而进行图像解析。
在图4(B)中,斜线以外的地方为一次粒子,各轮廓内部所示的线表示取向不同的一次粒子的边界。一次粒子的数量越多,统计的解析精度越高。只要一次粒子的数量为3000个以上,就可以得到解析所需的足够的数据。如表1所示,通过该图像解析求出的实施例1的β型赛隆的ESBD的50%面积平均直径为5.4μm。
(D50)
通过激光衍射散射法测定实施例1的β型赛隆的粒度分布,并求出D50。实施例1的β型赛隆的D50为21.8μm。
(发光峰强度)
对于实施例1的β型赛隆的荧光所产生的发光峰强度,可使用荧光分光光度计(Hitachi High-Technologies公司制造,F4500),测定荧光光谱。对以455nm的蓝色光作为激发光时的荧光光谱的峰值波长的高度进行测定。由该测定值,求出相对于在同一条件下使用YAG:Ce荧光体(化成Opto公司制造,P46-Y3)进行测定的峰值波长高度的相对值。激发光使用分光后的氙气灯光源。实施例1的β型赛隆的发光峰强度为207%。
(CIE色度)
利用瞬时多重测光系统(大塚电子公司制造,MCPD-7000),对使用积分球将对应于455nm激发的荧光会聚而得到的全光束测定发光光谱,由此求出荧光光谱的CIE(国际照明委员会:Commission Internationale de l'Eclairage)色度(参见非专利文献1)。实施例1的β型赛隆的CIE色度为X=0.361、Y=0.618。
实施例2
将原料混合物粉末的组成设定为氮化硅95.4质量%、氮化铝2.3质量%、氧化铝粉末1.6质量%、氧化铕0.8质量%,以使烧成后的Eu固溶β型赛隆的Z值为0.25。除了这些条件以外,与实施例1同样地制作β型赛隆。
实施例2的β型赛隆的一次粒子的50%面积平均直径为6.0μm,其D50为23.5μm。发光峰强度为213%,CIE色度为X=0.359、Y=0.620。
实施例3
将原料混合物粉末的组成设定为氮化硅95.4质量%、氮化铝2.8质量%、氧化铝粉末1.0质量%、氧化铕0.8质量%,以使烧成后的Eu固溶β型赛隆的Z值为0.25。除了这些条件以外,与实施例1同样地制作β型赛隆。
实施例3的β型赛隆的一次粒子的50%面积平均直径为8.0μm,其D50为25.1μm。关于实施例3的β型赛隆,发光峰强度为221%,CIE色度为X=0.362、Y=0.619。
图5表示实施例3的β型赛隆的SEM图像(扫描电子显微镜图像;电子的加速电压为15kV,倍率为500倍),图6(A)表示由SEM图像制作的EBSD图像,图6(B)表示由EBSD图像制作的图。与图4(B)相同,图6(B)中斜线以外的地方为一次粒子,各轮廓内部所示的线表示取向不同的一次粒子的边界。
实施例4
实施例4是利用超音速气流粉碎机(Nippon Pneumatic Mfg.Co.,Ltd.制造、PJM-80型)对实施例2的β型赛隆进行粉碎,除此以外与实施例2同样地制作β型赛隆。实施例4的制备方法是在实施例2的制备工序中进一步增加了粉碎分级工序。
实施例4的β型赛隆的一次粒子的50%面积平均直径为7.2μm,其D50为14.5μm。实施例4的β型赛隆的发光峰强度为224%,CIE色度为X=0.363、Y=0.616。
(比较例1)
比较例1是将实施例1的烧成容器的体积设定为0.085升,并将加热处理工序的条件设定为1800℃、4小时,除此以外以与实施例1相同的条件制作β型赛隆。
比较例1的β型赛隆的一次粒子的50%面积平均直径为1.2μm,D50为14.3μm。比较例1的β型赛隆的发光峰强度为86%,CIE色度为X=0.363、Y=0.611。
(比较例2)
比较例2是将实施例1的烧成时的温度设定为1950℃,除此以外以与实施例1相同的条件进行制作。
比较例2的β型赛隆的一次粒子的50%面积平均直径为2.5μm,D50为23.2μm。比较例2的β型赛隆的发光峰强度为190%,CIE色度为X=0.353、Y=0.625。
由实施例1~4和比较例1、2可知,如果烧成温度不大于1950℃、烧成时间不在10小时以上,则β型赛隆的一次粒子的50%面积平均直径不会达到5μm以上,且发光峰强度低。
即,实施例1~4的β型赛隆的二次粒子的D50粒径与比较例2相同程度或者比比较例2更小,而一次粒子的50%面积平均直径为比较例2的2倍以上。换言之,本发明的β型赛隆是粒径大的一次粒子结合而成。因此,一次粒子彼此的接触界面量少。
如果一次粒子彼此的接触界面量增多,则由于对发光峰强度造成不良影响,因而优选接触界面量少。
本发明发现了不会增大β型赛隆的二次粒子的粒径、而能够仅使一次粒子的50%面积平均直径为5μm以上的烧成条件。
本发明人等进一步发现了一次粒子彼此的接触界面量不仅对发光峰强度造成影响,而且对其他荧光体的不同颜色的吸收也造成影响。本发明的β型赛隆通过与其他荧光体组合,能够发挥使发光装置的发光强度提高的效果。对于该效果,用实施例5进行说明。
实施例5
参照图2,对使用了β型赛隆的发光装置的实施例5进行详细说明。
本发明的实施例5所涉及的发光装置10的结构与图2相同。荧光体18是实施例4的β型赛隆、与具有组成为Ca0.66Eu0.04Si9.9Al2.1O0.7N15.3的Ca-α型赛隆:Eu荧光体的混合体。Ca-α型赛隆:Eu荧光体的发光峰波长为585nm,该荧光体在450nm激发下的发光效率为60%。
以如下方式将荧光体18混合到密封树脂17中。
预先将荧光体18分别用硅烷偶联剂(信越SILICONE公司制造、KBE402)进行硅烷偶联处理,将进行硅烷偶联处理后的荧光体18混炼到作为密封树脂17的环氧树脂(Sanyu Rec公司制造、NLD-SL-2101)中,从而完成了混合。
作为发光光源12,使用发光波长为450nm的蓝色LED芯片。
(比较例3)
比较例3的发光装置是在实施例5的发光装置10中,将用作荧光体18的实施例4的β型赛隆变更为比较例1的β型赛隆,除此以外与实施例5进行同样制作。
使实施例5的发光装置10和比较例3的发光装置在同一条件下发光,利用亮度计,测定同一条件下的中心照度和CIE色度(CIE1931)。在用色度坐标(x、y)为(0.31、0.32)的白色发光装置来比较中心照度时,实施例5的亮度为比较例3的1.49倍。
本发明并不限于上述实施方式,在权利要求书记载的发明范围内可进行各种变形,当然这些变形也包含在本发明的范围内。例如,通过对β型赛隆荧光体18进一步改变发出黄色或红色的荧光体的发光波长、配合比,能够将发光装置10的颜色变更为白色光以外的颜色,例如暖色。
产业上的可利用性
本发明所涉及的β型赛隆适合用作LED的荧光体。
另外,本发明所涉及的发光装置可以适用于照明装置、液晶面板的背光源、图像显示用投影仪的光源等。
符号说明
1:用于EBSD法的装置
2:扫描电子显微镜
2A:镜筒部
2B:台部
2C:台控制部
2D:电子射线扫描部
2E:控制用计算机
3:电子背散射衍射法测定装置
4:试样
5:电子射线
6:背散射后的电子
7:荧光屏
8:照相机
10:发光装置
12:发光光源(LED芯片)
13:第一引线框
13a:上部
13b:凹部
14:第二引线框
15:波长转换部件
16:接合线
17:密封树脂
18:荧光体(β型赛隆)
19:盖
Claims (9)
1.一种β型赛隆的制备方法,其中,具有如下工序:
混合工序,将氧化铝或氧化硅中的至少一种、氮化硅、氮化铝和铕化合物进行混合;
烧成工序,以大于1950℃且小于等于2200℃、10小时以上的条件对混合工序后的混合物进行烧成;
热处理工序,在烧成工序后于1300℃以上至1600℃以下、分压为10kPa以下的除氮气以外的惰性气体气氛中进行热处理。
2.如权利要求1所述的β型赛隆的制备方法,其中,
所述烧成工序是以2000℃以上至2200℃以下、10小时以上的条件进行烧成的工序。
3.一种β型赛隆,其是用通式:Si6-ZAlZOZN8-Z表示并固溶有Eu的β型赛隆,其中,0<Z≤0.42,
β型赛隆的一次粒子的50%面积平均直径为5μm以上。
4.如权利要求3所述的β型赛隆,其中,
所述β型赛隆的一次粒子的50%面积平均直径为7μm以上。
5.如权利要求3或4所述的β型赛隆,其中,
所述β型赛隆的二次粒子的D50粒径为30μm以下。
6.一种发光装置,其包括发光光源和波长转换部件,其中,
波长转换部件包括:吸收由发光光源发出的近紫外光至蓝色光而产生荧光的荧光体,
荧光体为权利要求3~5中任一项所述的荧光体。
7.如权利要求6所述的发光装置,其中,
所述发光光源是发出波长为350nm~500nm的光的LED芯片。
8.一种发光装置,其中,
在权利要求7所述的发光装置中所用的荧光体是具有权利要求3所述的荧光体和固溶有Eu的α型赛隆的荧光体。
9.如权利要求8所述的发光装置,其中,
固溶有Eu的α型赛隆为Ca-α型赛隆。
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JP5558787B2 (ja) * | 2009-11-13 | 2014-07-23 | 電気化学工業株式会社 | β型サイアロンの製造方法 |
JP5697387B2 (ja) * | 2010-09-15 | 2015-04-08 | 電気化学工業株式会社 | β型サイアロンの製造法 |
JP5886069B2 (ja) * | 2012-02-09 | 2016-03-16 | デンカ株式会社 | 蛍光体及び発光装置 |
JP5916410B2 (ja) * | 2012-02-09 | 2016-05-11 | デンカ株式会社 | 蛍光体及び発光装置 |
CN103811637B (zh) * | 2012-11-05 | 2018-01-30 | 晶元光电股份有限公司 | 波长转换材料及其应用 |
CN104871326B (zh) * | 2013-01-23 | 2017-08-08 | 夏普株式会社 | 发光装置 |
JP6020756B1 (ja) * | 2015-05-29 | 2016-11-02 | 日亜化学工業株式会社 | βサイアロン蛍光体の製造方法 |
JPWO2021033646A1 (zh) | 2019-08-20 | 2021-02-25 | ||
JPWO2021033645A1 (zh) | 2019-08-20 | 2021-02-25 | ||
JP7278924B2 (ja) * | 2019-10-30 | 2023-05-22 | デンカ株式会社 | β型サイアロン蛍光体および発光装置 |
JP2022120801A (ja) * | 2021-02-05 | 2022-08-18 | 住友化学株式会社 | 蛍光体の製造方法及び蛍光体 |
JP2022120802A (ja) * | 2021-02-05 | 2022-08-18 | 住友化学株式会社 | 蛍光体及び蛍光体の製造方法 |
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TWI820100B (zh) * | 2018-03-29 | 2023-11-01 | 日商電化股份有限公司 | β型賽隆螢光體及發光裝置 |
CN113166644A (zh) * | 2018-11-19 | 2021-07-23 | 电化株式会社 | β型赛隆荧光体和发光装置 |
CN113166644B (zh) * | 2018-11-19 | 2023-08-18 | 电化株式会社 | β型赛隆荧光体和发光装置 |
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EP2597130A1 (en) | 2013-05-29 |
TW201207086A (en) | 2012-02-16 |
WO2012011444A1 (ja) | 2012-01-26 |
US20120313507A1 (en) | 2012-12-13 |
KR20120094083A (ko) | 2012-08-23 |
TWI450946B (zh) | 2014-09-01 |
JPWO2012011444A1 (ja) | 2013-09-09 |
EP2597130A4 (en) | 2015-04-22 |
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