CN103249803B - 发光陶瓷转换器及包含它的led - Google Patents

发光陶瓷转换器及包含它的led Download PDF

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CN103249803B
CN103249803B CN201180054192.9A CN201180054192A CN103249803B CN 103249803 B CN103249803 B CN 103249803B CN 201180054192 A CN201180054192 A CN 201180054192A CN 103249803 B CN103249803 B CN 103249803B
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luminophore
transmodulator
light
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led
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CN103249803A (zh
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J·F·克尔索
W·P·拉帕托维奇
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Osram Sylvania Inc
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Abstract

本文描述了发光陶瓷转换器,其包括含有发光物质的平的单片陶瓷材料,其中所述发光物质的浓度在所述转换器的外围区域低于在所述转换器的中央区域。

Description

发光陶瓷转换器及包含它的LED
技术领域
本发明涉及发光装置,更具体地涉及发光二极管(LED)。还更具体涉及将LED发射的光转换成波长不同的光的结构。特别地,本发明涉及制备发白光的LED。
背景技术
众所周知,使用磷光体将LED发射的蓝光转换成更长波长以便影响LED组件发射光的整体颜色。参见,例如,美国专利6,613,247和6,653,765号。通常将这样的LED称为磷光体转换LED(pc-LED)。pc-LED的一个非常重要的应用是产生白光,其中通过嵌入在封装LED的环氧树脂中的磷光体将由LED发射的蓝光的一部分转换成黄光。余下未转换的蓝光和转换后的黄光的结合效果是产生从pc-LED的整体白光输出。可以添加额外的磷光体来产生具有较高显色指数(CRI)的较温暖的白色。用于发白光的pc-LED的优选磷光体是发黄光的,铈激活的钇铝石榴石磷光体,其可以由式Y3Al5O12:Ce3+(YAG:Ce)表示。钇铝石榴石(YAG)基质中的Ce3+发光物质在可见光谱的蓝色区域(420-490nm)中有吸收,并在约570nm的黄色区域中重新发射出所吸收的能量。
然而,在pc-LED中使用磷光体粉末并不是没有问题的。特别是,可能很难在LED源上获得均匀的磷光体层从而导致LED之间不可接受的颜色变化。此外,嵌入在环氧树脂中的磷光体粒子散射从LED发射的蓝光,这会降低效率。
在pc-LED中实现类似结果的另一种手段是使用固体烧结陶瓷转换器代替磷光体粉末。这种固体单片转换器相对于磷光体粉末具有至少两个明显的优势。首先,发光陶瓷转换器可以制备成限定形状和均匀厚度在制造时提供更好的一致性和颜色控制。第二,它们可制成半透明的,这样可以减少散射损失并提高提取效率。在美国专利7,554,258号,美国专利申请公开2007/0126017号和国际专利申请公开WO 2006/087660号中描述了这类发光陶瓷转换器的例子。
类似于上述pc-LED中使用的磷光体粉末,在白色pc-LED中所述陶瓷转换器用于将来自蓝色LED的光转换成黄光,以产生整体白光。通常情况下,发光陶瓷转换器是约1毫米见方且厚度小于200微米的薄平板。该转换器固定到LED管芯(die)的表面,使得转换器紧靠发光表面。如同上述磷光体转换LED,所述转换器优选包含铈激活的钇铝石榴石Y3Al5O12:Ce3+或由其组成。也可将一些钆掺入到YAG结构中以使发射光的颜色更朝向红色稍微偏移。
使用发光陶瓷转换器的pc-LED的一个目标应用是汽车的前大灯,在此投射在道路上的光束的颜色均匀性是一个重要的考虑因素。为了实现这一点,pc-LED组件输出光的颜色在视角改变时必须保持相对恒定。这对于使用高度半透明或透明陶瓷转换器的pc-LED是成问题的,因为蓝色光线在转换器内必须经过的距离变得越长视角偏离表面法线越多。其结果是,以相对于表面法线为0°的角度发射的光将比以相对于表面法线大于0°的角度发射的光更蓝。
一种减少角度颜色偏移差异的解决方案是通过在陶瓷转换器中引入散射位点使得对所有光线产生更长的路径长度。这可以通过如国际专利申请公开WO2007/107917A2号中描述的在陶瓷材料中遗留孔隙来实现。然而,如同使用磷光体粉末一样,过多的散射可能导致不可接受的提取效率损失。此外,散射的效率由陶瓷中孔的数量和尺寸决定。如果数量过大,光将大部分通过内部散射吸收且总LED光输出减少。如果孔径分布不是在一个狭窄的最佳区域内,则光输出也会减少。特别是,已报道800纳米尺寸的孔的效力最佳,效力在500nm以下快速下降而在1000nm以上稳定下降。因为陶瓷加工的热力学和动力学特点,在发光陶瓷转换器中实现最佳的孔径分布是困难的。
发明内容
本发明的一个目的是避免上面列举的现有技术中的至少一些缺点。
本发明的另一个目的是改善pc-LED的性能。
本发明的又一目的是提供应用于汽车前大灯的改进的LED。
在本发明的一个方面中,通过提供包括含有发光物质的平的单片陶瓷材料的发光陶瓷转换器实现了这些目的,其中转换器外围区域中的发光物质的浓度低于转换器中央区域中的发光物质的浓度。在优选的实施方案中,该陶瓷材料配对有发蓝光的LED以提供发白光的装置。
在本发明的另一方面,提供了制备发光陶瓷转换器的方法,它包括以下步骤:形成含有大致均匀浓度的发光物质的陶瓷材料;以及以一定方式处理所述陶瓷材料,该处理方式能减少在陶瓷材料外围区域中的所述发光物质的浓度并完成所述发光陶瓷转换器。
附图简述
图1是利用具有发光陶瓷转换器的LED的发光装置的示意性图示。
图2是具有发光陶瓷转换器的LED在0°和60°视角的发射光谱的谱图。
图3是根据本发明的发光陶瓷转换器的俯视图。
图4是对于常规转换器和根据本发明的转换器1931 CIE x色坐标随视角的变化的比较。
图5a是处理前的发光陶瓷转换器的示意图。
图5b是处理后发光陶瓷转换器的示意图。
发明详述
为了更好地理解本发明,连同它的其它的和进一步的目的,优点和性能,参考以下的公开内容和所附权利要求并结合上述附图。
为了本申请的目的,应当理解,当元件或层被称为“在…上”,“连接到”或“偶连到”另一元件或层时,它可以直接连接到或偶连到所述另一元件或层或在它之上,或者可以存在中间元件或中间层。与此相反,当元件被称为“直接在…之上”,“直接连接到”或“直接偶连到”另一元件或层时,不存在中间元件或中间层。相同的附图标记始终指代相同的元件。术语“和/或”包括相关联的所列项目中一个或多个的任意组合及所有组合。
虽然术语“第一”,“第二”,“第三”等可用于描述各种元件,部件,区域,层和/或部分,但是这些元件,组件,区域,层和/或部分不被这些术语所限制,因为它们仅用于区分一个元件,组件,区域,层或部分与另一个元件,组件,区域,层或部分。因此,第一元件,组件,区域,层或部分可以被称为第二元件,组件,区域,层或部分,而不脱离本发明的范围和教导。
为了便于说明,可能使用空间相对术语,如“在…下面”,“在…下方”,“上面”,“下面”,“在…上方”等来描述附图中所示的一个元件或特征相对于另外一个或多个元件或特征的关系。这些空间相对术语意在涵盖所述装置在使用或操作中除附图所示方位之外的不同方位。例如,如果将附图中的装置翻转,则描述为在其它元件或特征“下方”或“下面”的元件则将定向为在其它元件或特征“上方”。因此,示例性术语“在…下方”可以涵盖上方和下方两个方位。所述装置可以有其它取向(旋转90度或者处于其它方位),并对本文中所用的空间相对描述信息作相应的解释。
本文使用的术语仅用于描述特定实施方案的目的,而不是意在限制本发明。例如,如本文所用,单数形式的“a(一个)”、“an(一种)”和“the(该)”意在也涵盖复数形式,除非上下文清楚地另有指示。还应当理解,术语“包括”和/或“包含”在本说明书中使用时,明确指出存在所述的特征、整数、步骤、操作、元件和/或组件,但并不排除存在或添加一个或多个其它特征、整数、步骤、操作、元件、组件和/或它们的组合。
现在参照更详细的附图,图1中显示了pc-LED装置10,该装置使用高度半透明或透明的陶瓷转换器板6,其包含主体材料和发光物质(如YAG:Ce)或由它们组成,随着视角增大pc-LED装置10经历颜色偏移。从发蓝光的LED8的表面7上的位点发射出的光穿过发光陶瓷转换器板6,在此期间一部分蓝光转换成黄光。最终从转换器板6表面发射出的光的颜色取决于通过转换器的未转换的蓝光量相对于在转换器内转换为黄光的蓝光量的比率。该比率进而又取决于蓝色光线必须从转换器中穿过的路径长度。
更具体地,发光陶瓷转换器中的吸收量(以及随后以更长波长重新发射)遵循比尔-朗伯定律:
I/Io=10-εct
其中Io和I分别为入射光和透射光的强度,ε为吸光物质的摩尔吸光系数,c为吸光物质的浓度,而t是穿过所述材料的路径长度。由于转换为黄光的量指数级地依赖于浓度和路径长度,对于恒定的浓度c,穿过陶瓷转换器的路径长度越长,吸收并转换成黄光的蓝光更多。例如,如图1所示,与以较大视角α(如60°)行进穿过陶瓷转换器板6的光线4相比,沿LED表面的法线方向行进的光线2具有较短的穿过陶瓷转换器板6的路径长度。其结果是,沿光线2方向从转换器板6发射出的光将为更蓝的颜色,而由于在转换器内的路径长度更长沿光线4方向发射出的光将更黄。
图2演示了在60°视角处,在455纳米蓝光LED上的YAG:Ce转换器板6的光谱如何变化。(光谱已对550nm作了标准化)。在60°视角蓝光455nm峰相比集中在550nm附近的黄光发射相对强度更低,使得光线在这个角度显得不那么蓝,即比沿陶瓷转换器板6表面的法线看时更黄。理想情况下,希望在0°和60°具有几乎相同的光谱,或者换句话说,在所有的视角蓝光455nm峰相对于550nm处的黄光发射的比率应尽可能接近。
再次参照比尔-朗伯定律,能够操纵来改变入射光相对于透射光的比率的三个因素是:路径长度(厚度),浓度和摩尔吸光系数。摩尔吸光系数随吸收物质而变化,并因此对于特定发光陶瓷而言是固定的。而且,虽然操纵陶瓷转换器板的厚度以纠正角度颜色偏移也许是可能的,但是预计实现起来很可能是困难的或昂贵的,因为陶瓷转换器板的厚度通常小于200微米。相反,已经发现,可以在陶瓷转换器板中建立具有降低的吸防发光物质浓度的外围区域,且该特性可以基本上消除角度颜色偏移。陶瓷转换器板6可以初始烧结成在整个部件中具有均匀浓度的吸收/发光物质(如Ce3+)给整个部件赋予均匀的黄色外观。随后在特定气氛中对该部件进行热处理,该气氛使Ce3+氧化成Ce4+或使得Ce3+从陶瓷扩散出来并蒸发,导致该陶瓷具有在中央较高和边缘处较低的Ce3+浓度梯度。这样,中央部分保持黄色而边缘显示白色。图5a和5b示意地图示了这种情况,其中发光物质30显示为在图5a中基本上均匀地分布,但在图5b中具有较低的外围浓度。可选择地,可以在特定气氛中以温度周期烧结陶瓷,该气氛同时烧结所述陶瓷和提供浓度梯度。在实现浓度梯度的又一可选择的实施方案中,将YAG前体烧结以形成片材,然后将少量的Ce或CeO2放置在片材的中央并将该片材加热以使Ce扩散到YAG中。扩散会导致浓度梯度。
参考图3,其中示出了根据本发明的一个方面的发光陶瓷转换器板26的实施方案。该转换器板26是平的单片发光陶瓷材料。发光陶瓷材料包含发光物质30(参见图5a和图5b),其能够将LED发射的第一波长的光转换成第二波长的光。转换器板26优选为长方形形状,并且可以具有凹口20,使得能够引线结合到LED管芯的顶表面。发光陶瓷转换器板26通常期望的形状为约1mm×1mm的正方形,厚度为70到150微米。
陶瓷转换器板26具有以虚线18为界的中央区域16,和位于虚线18和转换器板26的边缘14之间的外围区域12。在优选的实施方案中,如图3所示,外围区域12包围着中央区域16,并具有宽度W,对于1mm2面积的转换器板它可以是约100微米。当然,外围区域的大小取决于板的整体尺寸,当板面积增加时将会增加。如上所述,在外围区域发光物质30的浓度较低,如在5b中图示意性所示。在优选的实施方案中,在外围区域中存在浓度梯度,其中当从中央区域16移动到边缘14时发光物质的浓度降低。在外围区域中发光物质的较低浓度减少了在较大视角处被转换为更长波长的蓝光量,从而降低了颜色随视角的偏移。
在更优选的实施方案中,发光陶瓷转换器板26具有组成(Y1-xCex)3Al5O12,其中x为0.0015至0.0075。YAG:Ce陶瓷在转换器外围区域中的颜色变化标志着发光物质Ce3+浓度的降低。当从转换器的中央区域向边缘移动时,在中央区域中观察到的YAG:Ce陶瓷的正常黄体色在外围区域中变成白色。不管这种发光Ce3+物质的减少是由氧化态到不发光态(如Ce4+)的转变引起还是由外围区域中YAG颗粒内的铈量减少引起,都没有区别。在任一情况下,其效果仍然是外围区域中发光Ce3+物质的浓度降低。
实施例
根据本发明的一个方面的发光陶瓷转换器板由Y2O3(45.52g),Al2O3(35.66g),Gd2O3(7.60g)和CeO2(0.2168g)的氧化物混合物制成,该混合物与水;氢氧化铵;粘合剂如WB4101;消泡剂如DF002;聚合物分散剂如DS001;和增塑剂如PL005结合。所有这些材料均可以从Polymer Innovations,Inc.,Vista,CA92081获得。采用~0.8毫米的刀片间隙设置浇注条带,并从该条带上冲压出1.35毫米×1.35毫米的部件。使用如下的时间-温度周期在空气中预烧结该部件:在4小时内从25℃至400℃;在4小时内从400℃至1150℃;在1150℃保持2个小时;以及在3个小时内冷却。然后将该部件放置在钼板上,并在干燥的8%N2/H2气氛中在1745℃下进行最终烧结,停留时间约一小时。炉子是开放式的隧道炉,它不能提供炉内气氛与室内空气的完全分离。所得发光转换器具有中央黄色区域和具有适度蚀刻外观的白色外围区域。
在替代实施方案中,可以如上所述但不添加铈来制造不发光的转换器板。随后,将一定量的Ce或CeO2铺展在不发光主体的顶部形成预转换器,并且将该预转换器在特定气氛和温度下加热,该气氛和温度足以使Ce或CeO2扩散到所述不发光主体内并使Ce转化成发光Ce3+
图4比较了对于常规YAG:Ce转换器(比较例)和根据本发明的陶瓷转换器(本发明实施例)1931 CIE x色坐标随视角的变化。(常规YAG:Ce转换器在转换器的整个表面上具有大致均匀的黄色。)图4显示了当视角从0°增加到70°时常规转换器在CIE x坐标上的大变化,而根据本发明一个方面的发光陶瓷转换器在CIE x色坐标上几乎没有变化。CIE y色坐标的变化与CIE x色坐标成正比(即蓝光LED的x-y颜色与转换后的黄光光谱的x-y颜色之间线性相关)。
虽然已经示出和描述了目前被认为是本发明的优选实施方案,对本领域技术人员而言显而易见地,可以在不脱离由所附权利要求限定的本发明范围的情况下对本发明作出各种改变和变更。

Claims (7)

1.发光陶瓷转换器,包括:包含发光物质的平的单片陶瓷材料,其中所述发光物质的浓度在所述转换器的相对更靠近其边缘的外围区域低于在所述转换器的中央区域,其中所述陶瓷材料是钇铝石榴石且所述发光物质是Ce3+,并且所述转换器具有基本上均匀的铈浓度,且所述外围区域中的至少一部分铈是Ce4+
2.根据权利要求1所述的发光陶瓷转换器,其中所述外围区域具有小于约100微米的宽度,并且围绕所述转换器的中央区域。
3.根据权利要求1所述的发光陶瓷转换器,其中所述转换器具有大致矩形的形状。
4.制备发光陶瓷转换器的方法,包括以下步骤:
形成包含基本上均匀浓度的发光物质的陶瓷材料,其中所述陶瓷材料是钇铝石榴石且所述发光物质是Ce3+;以及
以一定方式处理所述陶瓷材料,该方式能够降低所述发光物质在所述陶瓷材料的相对更靠近其边缘的外围区域中的浓度并完成所述发光陶瓷转换器,其中所述处理包括将所述发光物质的价态由Ce3+改变为Ce4+
5.发光装置,包括:
发蓝光的LED;和
覆盖所述发蓝光的LED的发光陶瓷转换器板,所述转换器板包括含有发光物质的平的单片陶瓷材料,其中所述发光物质的浓度在所述转换器的相对更靠近其边缘的外围区域低于在所述转换器的中央区域,其中所述陶瓷材料是钇铝石榴石且所述发光物质是Ce3+,并且所述转换器具有基本上均匀的铈浓度,且所述外围区域中的至少一部分铈是Ce4+
6.根据权利要求5所述的发光装置,其中所述外围区域具有小于约100微米的宽度,并且围绕所述转换器的中央区域。
7.根据权利要求5所述的发光装置,其中所述转换器具有大致矩形的形状。
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