CN107801399A - 磷光体陶瓷 - Google Patents
磷光体陶瓷 Download PDFInfo
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- CN107801399A CN107801399A CN201680036689.0A CN201680036689A CN107801399A CN 107801399 A CN107801399 A CN 107801399A CN 201680036689 A CN201680036689 A CN 201680036689A CN 107801399 A CN107801399 A CN 107801399A
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Abstract
本发明涉及包括多个发光转换材料的磷光体陶瓷,其中发光转换材料用作其他材料的基体材料。
Description
技术领域
本发明涉及发光装置领域,更具体地涉及其中使用陶瓷的发光装置领域。
背景技术
最近,在发光装置中使用陶瓷用于光子下转换已经引起专家的兴趣增加,因为即使在较高的温度下它们也通常是稳定的,并且与例如有机硅材料相反,它们没有由于高温下老化而褐变并且因此劣化的风险。而且,与粉末聚合物复合材料相比,陶瓷具有较高的热导率,使得因此改进的热管理导致较少的热淬火。
正如通常用于发光装置的情况,同样在陶瓷系统的情况下,对于进一步的优化和改进有不断的需求。因此,目的是提供一种改进的发光装置和/或用于这种装置的材料。
发明内容
该目的是根据本发明的权利要求1的发光装置来实现。因此,提供了包括至少两种发光材料的磷光体陶瓷,其中:
-其中一种材料具有比其它材料的熔点低≥200℃的熔点;以及
-这种材料被用作基体材料。
令人惊讶地发现,发光装置的性能可以在许多应用中显著地改善。特别地,根据本发明的装置在大多数实施例和具体实施方式中提供以下优点中的一个或多个:
简化的、成本优化的生产工艺,在相对低的温度下生产;
单面板中的全陶瓷暖白色(CCT<4000K)解决方案;
相对于获得的光谱(CRI,CCT,CIE1931中的色点,红色比例(R9))的最终产品的适应性;
嵌入基体中的磷光体未被烧结(嵌入的磷光体的功能没有改变,例如效率或发射光谱);
陶瓷对各种生产工艺/使用各种成型工艺的可变的加工性的适应性;
面板厚度的独立选择;
不管实现的光谱如何(特别是在Eu3+的存在下),为了优化激发路径的面板厚度的适应性。
根据本发明的术语“磷光体”特别地指的是或包括在合适的激发下,优选地在蓝色、紫色、UV-A或UV-B的范围(即特别地是280nm至490nm)中发射光,特别地是在400nm至2500nm的波长范围内(可见和红外光谱)的光的材料。
根据本发明的术语“磷光体陶瓷”特别地指的是基本上由发光材料组成的陶瓷。
根据本发明的术语“本质上”指的是和/或包括≥95%(体积%/体积%)的比例,更优选地≥98%(体积%/体积%),并且最优选地≥99%(体积%/体积%)。
根据本发明的另一个实施例,磷光体陶瓷特别地包括,并且因此优选地包括基体材料,还包括非发光材料,优选地使得使用在一种情况下掺杂的并且在另一种情况下非掺杂的材料。这在本发明的许多实施例中已经证明是有利的,因为以这种方式可以限制掺杂剂材料的比例,或者可以优化掺杂水平。在某些情况下,为了优化陶瓷工艺和性能,可能期望调节掺杂剂水平以实现不同材料之间的一定的重量比。
根据本发明的术语“陶瓷”特别地指的是和/或包括致密结晶或多晶材料,其包括受控量的孔或者是无孔的。
根据本发明的术语“多晶材料”特别地指的是和/或包括具有大于主要组分的90%的体积密度的材料,该主要组分由大于80%的单个晶畴组成,其中每个晶畴具有0.1μm至20μm的直径和不同的结晶取向。单个晶畴可以经由非晶相或玻璃态材料或通过附加的晶相稀释或者彼此键合。
根据本发明的优选实施例,结晶材料具有理论密度的≥90%至≤100%的密度。这已经发现这对于本发明的许多应用是有利的。
根据本发明的术语“基体材料”特别地指的是或包括用作嵌入材料或支持将一个或多个嵌入材料固定在其限定的位置处的材料,和/或其中嵌入一种或多种无机发光材料的无机、陶瓷/多晶和发光材料。基体材料可以,并且这里代表本发明的优选实施例,通过热处理被压缩,使得实现嵌入的发光材料的牢固包含。
根据本发明,基体材料具有比其它发光材料的熔点低≥200℃的熔点。如果存在多于一种的磷光体,这特别地意味着基体材料具有比具有更高熔点的发光材料的熔点低≥200℃的熔点。
根据本发明的优选实施例,基体材料具有比其它发光材料的熔点低≥400℃的熔点,更优选地≥600℃的熔点,并且最优选地≥800℃的熔点。
根据本发明的优选实施例,基体材料是发红光的。由于许多原因,一方面是因为相应的低熔点材料是可获得的,并且另一方面是由于发射的能量位置(即红色辐射的能量最小的事实),这已经证明在大多数应用中是有利的。
根据本发明的优选实施例,不是基体材料的其中一种发光材料是发绿光或发黄光的。这已经发现在本发明的大多数应用中是有利的。
根据本发明的优选实施例,不是基体材料的其中一种发光材料是发蓝光的。这已经发现在本发明的大多数应用中是有利的。
根据本发明的优选实施例,磷光体陶瓷包括至少三种发光材料,其中优选地其中一种是发红光的,一种是发绿光的并且一种是发蓝光的。然而,本发明不限于此,备选地,例如,可以提供另外的发光材料,这些发光材料也可以是发红光、发绿光或发蓝光的或者在其他光谱范围(例如,黄光、NIR或UV)中发射。
根据本发明的另一个优选实施例,磷光体陶瓷包括发红光的基体材料和发绿光和/或发黄光的其他材料。已经发现这个实施例在从发蓝光的主要束源(例如蓝色LED)开始时是特别地有利的。
根据本发明的术语“发红光的”特别地指的是和/或包括在合适的激发下具有在600nm和650nm之间的至少一个发射带的材料。
根据本发明的优选实施例,发红光的材料包括选自以下的材料:
ALn1-x-yEuxM2O8:REy
(Ln1-x-yEux)2MO6:RE2y
(Ln1-x-yEux)2M2O9:RE2y
(Ln1-x-yEux)2M3O12:RE2y
(Ln1-x-yEux)2M4O15:RE2y
(Ln1-x-yEux)6MO12:RE6y
(AE1-2x-yEuxAx+y)3MO6:RE3y
A3AE2(Ln1-x-yEux)3(MO4)8:REy
或其混合物,
其中,对于每个结构独立地,A是碱金属,即选自锂、钠、钾、铷、铯或其混合物,AE是碱土金属,即选自铍、镁、钙、锶、钡或其混合物,Ln是选自钪、钇、镧、钆和镥或其混合物的稀土金属,M是钼、钨或其混合物,RE是选自铽、镝、镨、钕或其混合物的稀土金属,其中0<x≤1并且0≤y≤0.05。
根据本发明的优选实施例,发红光的材料包括选自以下的材料:
Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A3AE2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A(Tb1-x-yEuxLny)(Mo1-zWz)2O8,
(Tb1-x-yEuxLny)2(Mo1-zWz)O6,
(Tb1-x-yEuxLny)2(Mo1-zWz)2O9,
(Tb1-x-yEuxLny)2(Mo1-zWz)4O15,
(Tb1-x-yEuxLny)2SiO5,
(Tb1-x-yEuxLny)2Si2O7,
A(Tb1-x-yEuxLny)SiO4,
Ba2(Tb1-x-yEuxLny)2Si4O13,
AE2(Tb1-x-yEuxLny)2Si4O13,
Sr3(Tb1-x-yEuxLny)2Si6O18,
AE3(Tb1-x-yEuxLny)2Si6O18,
(Tb1-x-yEuxLny)2GeO5,
(Tb1-x-yEuxLny)2Ge2O7,
A(Tb1-x-yEuxLny)GeO4,
Ba2(Tb1-x-yEuxLny)2Ge4O13,
AE2(Tb1-x-yEuxLny)2Ge4O13,
Sr3(Tb1-x-yEuxLny)2Ge6O18
AE3(Tb1-x-yEuxLny)2Ge6O18
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)O5,
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)2O7,
A(Tb1-x-yEuxLny)(Ge1-a-bZraHfb)O4,
Ba2(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)4O13,
Sr3(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)6O18
(Tb1-x-yEuxLny)2(Mo1-zWz)3O12
其中(对于每个结构独立地):
Ln=La,Gd,Lu,Y或其混合物,
A=Li,Na,K,Rb,Cs或其混合物,优选地为Li,
AE=Sr,Ca,Br或其混合物,优选地为Ba和/或Sr,
x>0且<1并且y≥0且<1,其中1-x-y>0并且a,b≥0且<0.2并且z≥0且≤1,
或这些材料的混合物。优选地,该材料本质上由其组成。
特别优选地,材料是Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,A(Tb1-x-yEuxLny)(Mo1-zWz)2O8,(Tb1-x-yEuxLny)2(Mo1-zWz)O6,(Tb1-x-yEuxLny)2(Mo1-zWz)2O9,(Tb1-x-yEuxLny)2(Mo1-zWz)4O15,(Tb1-x-yEuxLny)2(Mo1-zWz)3O12或其混合物,其中A,Ln,x和y如上所述被指定。优选地,该材料本质上由其组成。
根据本发明的优选实施例,非基体材料包括具有石榴石结构的材料。这已经发现对于本发明内的一些应用是有利的。优选地,这种材料分布和/或分散在基体材料中。
术语“石榴石结构”特别地指的是和/或包括立方材料,特别地是通用结构A3B2[XO4]3,其中A代表二价,B代表三价,并且X代表四价阳离子;和/或是通用结构A3B2[RO4]3,其中A,B,R是三价阳离子,并且其中B和R可以相同;或者是这些结构的混合物。
根据本发明,术语“发绿光的”特别地指的是和/或包括在合适的激发下至少具有在500nm和550nm之间的发射的材料。用于发绿光的材料的以下结构是特别优选地:BaMgAl10O17:Eu2+,Mn2+,(Sr1-xCax)Si2N2O2:Eu2+,(Sr1-xBax)2SiO4:Eu2+,(Sr1-xBax)3SiO5:Eu2+,(Sr1-xBax)Ga2S4:Eu2+,(Lu1-xYx)3(Al1-yGay)5O12:Ce3+,(Lu1-xYx)3(Al1-yScy)5O12:Ce3+,BaSi2O2N2:Eu2+或这些材料的混合物。
根据本发明,术语“发蓝光的”特别地指的是和/或包括在合适的激发下至少具有在420nm和500nm之间的发射的材料。以下结构是特别优选地:(Ba1-xSrx)MgAl10O17:Eu2+,(Ba1-xSrx)Mg3Al14O25:Eu2+,(Sr,Ca,Mg)2Si2O6:Eu2+,CaAl2O4:Eu2+,(Ba1-xSrx)Al2Si2O8:Eu2+,(Ba1-xSrx)6BP5O20:Eu2+,(Ca1-x-ySrxBay)5(PO4)3(F1-aCly):Eu2+,(Y,Gd)(Nb1-xTax)O4,(Ba,Sr,Ca)2MgSi2O7:Eu2+,(Ba1-xSrx)ZrSi3O9:Eu2+或这些材料的混合物。
根据本发明,术语“发黄光的”特别地指的是和/或包括在合适的激发下至少具有在550nm和590nm之间的发射的材料。以下结构是特别优选地:Ba2Si5N8:Eu2+,(Ca1-xSrx)Si2N2O2:Eu2+,(Y1-xGdx)3(Al1-yGay)5O12:Ce3+,(Y1-xTbx)3(Al1-yGay)5O12:Ce3+,SrLi2SiO4:Eu2+,(Ca1-xSrx)2SiO4:Eu2+,(Ca1-xSrx)3SiO5:Eu2+或这些材料的混合物。可以理解的是,如本领域中惯用的那样,在指定为发绿光和发黄光的材料中存在一些重叠。
根据本发明的优选实施例,基体材料具有熔点为≤1300℃。这已经证明是有利的,因为以这种方式在大多数应用中可以确保磷光体陶瓷的良好的可加工性和可制造性。优选地,基体材料具有熔点为≤1100℃,更优选地≤1000℃,并且最优选地≤900℃。
根据本发明的优选实施例,磷光体陶瓷中基体材料的体积分数(以在成品磷光体陶瓷中的体积%/体积%计)是在≥20%和≤99%之间,优选地≥40%和≤95%之间,并且最优选地≥60%和≤90%之间。这已经证明在本发明的许多应用中是有利的。
优选地,“非基体”材料每个独立地具有≤20μm的粒径分布D90。这已经证明对许多应用是有利的。
优选地,“非基体”材料每个独立地具有≤10μm的粒径分布D50。同样,这经常被证明是有利的。
这里,粒径分布可以通过体视学方法来确定,例如关于通过显微镜获得的显示抛光和蚀刻样品结构的图像的线性截距方法。
根据本发明的优选实施例,磷光体陶瓷包括多于一种的不是基体材料的发光材料,并且在磷光体陶瓷内存在一个或多个区段或区域,在这些区段或区域本质上仅存在这些“非基体”发光材料的选择的材料。根据本发明的优选实施例的这些区段或区域可以通过磷光体陶瓷内的随机的(即均匀的)的浓度或浓度梯度,或者备选地,根据本发明的优选实施例,通过热层压工艺(热结合)将不同成分的两种磷光体陶瓷结合来实现。
这里,根据本发明的优选实施例的这些选择的材料是发射相同颜色的材料,即发绿光,发蓝光和/或发黄光的材料。
这个实施例已经证明是有利的,因为在大多数应用中的磷光体陶瓷的色点可以随后简单地改变,例如通过研磨区段或区域。
这里,根据本发明的优选实施例的材料的选择性移除可以通过离子束制备或激光加工来进行,或者根据本发明的另一个实施例,通过具有精确的或非精确的切割边缘的机械加工或精细研磨工艺来进行。
而且,根据本发明的另一个优选实施例,通过研磨和抛光工艺来执行后处理。以这种方式在本发明的许多应用中可以提高表面质量并且可以确保重现性。
备选地,复合陶瓷(即基体材料和至少一种非基体材料)的色点可以通过在陶瓷合成过程中仔细称量和混合单个组分来控制,并且通过在感兴趣的泵浦波长下的外部激发来测量。这种颜色信息可以用于将复合陶瓷与优选的发光装置匹配,其颜色也可以独立地测量。以这种方式,可以高精度地控制目标色点(通常是白色),并且可以缩小制造过程内色点的分布,这对终端用户以及从屈服点来看是期望的。
根据本发明的优选实施例,磷光体陶瓷包括至少两种发光材料,其中:
-其中一种材料用作基体材料,并且包括选自以下的材料:
ALn1-x-yEuxM2O8:REy
(Ln1-x-yEux)2MO6:RE2y
(Ln1-x-yEux)2M2O9:RE2y
(Ln1-x-yEux)2M3O12:RE2y
(Ln1-x-yEux)2M4O15:RE2y
(Ln1-x-yEux)6MO12:RE6y
(AE1-2x-yEuxAx+y)3MO6:RE3y
A3AE2(Ln1-x-yEux)3(MoO4)8:REy
Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A3AE2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
其中,对于每个结构独立地,A是碱金属,即选自锂、钠、钾、铷、铯或其混合物,AE是碱土金属,即选自铍、镁、钙、锶、钡或其混合物,Ln是选自钪、钇、镧、钆和镥或其混合物的稀土金属,M是钼、钨或其混合物,RE是选自铽、镝、镨、钕或其混合物的稀土金属,其中0<x≤1并且0≤y≤0.05;
Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A3AE2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A(Tb1-x-yEuxLny)(Mo1-zWz)2O8,
(Tb1-x-yEuxLny)2(Mo1-zWz)O6,
(Tb1-x-yEuxLny)2(Mo1-zWz)2O9,
(Tb1-x-yEuxLny)2(Mo1-zWz)4O15,
(Tb1-x-yEuxLny)2SiO5,
(Tb1-x-yEuxLny)2Si2O7,
A(Tb1-x-yEuxLny)SiO4,
Ba2(Tb1-x-yEuxLny)2Si4O13,
AE2(Tb1-x-yEuxLny)2Si4O13,
Sr3(Tb1-x-yEuxLny)2Si6O18,
AE3(Tb1-x-yEuxLny)2Si6O18,
(Tb1-x-yEuxLny)2GeO5,
(Tb1-x-yEuxLny)2Ge2O7,
A(Tb1-x-yEuxLny)GeO4,
Ba2(Tb1-x-yEuxLny)2Ge4O13,
AE2(Tb1-x-yEuxLny)2Ge4O13,
Sr3(Tb1-x-yEuxLny)2Ge6O18
AE3(Tb1-x-yEuxLny)2Ge6O18
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)O5,
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)2O7,
A(Tb1-x-yEuxLny)(Ge1-a-bZraHfb)O4,
Ba2(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)4O13,
Sr3(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)6O18
(Tb1-x-yEuxLny)2(Mo1-zWz)3O12
其中(对于每个结构独立地):
Ln=La,Gd,Lu,Y或其混合物,
A=Li,Na,K,Rb,Cs或其混合物,优选地为Li,
AE=Sr,Ca,Ba或其混合物,优选地为Ba和/或Sr,
x>0且<1并且y≥0且<1,其中1-x-y>0并且a,b≥0且<0.2并且z≥0且≤1,
或其混合物。
-以及至少一种另外的材料,包括具有石榴石结构的材料。
已经令人惊奇地发现,发光装置的性能在许多应用中可以显著地提高,特别是因为对于大多数这些应用,已经令人惊奇地发现,这些材料在制造过程中不会彼此反应或仅轻微的反应。
优选地,具有石榴石结构的材料分布和/或分散在基体材料中。
本发明还涉及一种用于制造根据本发明的磷光体陶瓷的方法,包括以下步骤:
a)提供起始材料,该起始材料包括以粉末形式的至少一种发光基体材料和至少一种另外的发光材料;
b)可选地进行成型,特别是通过轴向和/或冷等静压和/或流延成型或槽膜工艺和/或热塑工艺(注塑、热浇铸(低压或中压注塑)、挤出);
c)将起始材料烧结和/或热压成陶瓷;
d)可选地通过热等静压再压缩烧结的陶瓷;以及
e)可选地对所述烧结的陶瓷进行再加工,特别是通过离子束制备工艺,或者通过具有精确的或非精确的切割边缘的机械加工或精细研磨工艺。
这个方法已经证明是有用的,因为以这种方式在大多数应用中可以容易地生产合适的磷光体陶瓷。
优选地进行步骤b),使得压缩过程在≥20MPa和≤45MPa之间的压力下进行。
优选地进行步骤d),使得再压缩过程在≥120MPa和≤180MPa之间的压力下进行,优选地在≥140MPa和≤160MPa的压力下进行。
如果“非基体”发光材料的不均匀分布是期望的,则可以进行相应的磷光体陶瓷的生产,使得首先制备两种前体陶瓷,在其每一个中仅使用基体材料和选择的其它发光材料。这些可以例如通过热结合、层压和/或粘合而彼此结合。
根据本发明的装置可以用于各种具体的拓扑结构或应用中,包括但不限于以下:
1、“直接沉积的磷光体陶瓷”:
磷光体陶瓷作为薄板直接施加到LED骰子上,有时使用中间结合材料,例如有机硅、溶胶-凝胶或者玻璃。
2、“远程磷光体”系统:
“远程磷光体”系统特别地意味着其中磷光体(发光体,磷光体)布置在远离发射较窄波长范围的发光光源的装置,通常嵌入或连接到聚合物、玻璃或陶瓷基体上。因此,远程磷光体系统与其中将磷光体直接施加到光源上或光源处(例如其中将磷光体直接施加到发光骰子上的LED光源)的系统根本不同。通常,在两个基本结构之间做出区分,从中可以得出许多变体:
a)“透射应用中的远程磷光体”:将磷光体基体放置在其中设置LED的反射室上。光仅可以穿过磷光体基体(透射)逸出。
b)“再发射应用中的远程磷光体”:将磷光体基体施加到反射载体上或在背侧涂覆有反射材料。LED光源设置在发射方向上或稍微侧向于发射方向,并且照射到磷光体基体上。转换的光在光源的方向上或辐射的方向上被再发射,已经穿过磷光体基体的光通过背侧反射层被引导再次穿过在发射方向上的磷光体基体。因此,光仅可以在再发射的方向上逸出。
根据本发明的优选实施例,在发明的发光系统内,陶瓷磷光体可以光学耦合到LED芯片。
这种LED芯片可以是基于III-V族氮化物材料系统的芯片。例如,LED芯片可以包括在n型和p型GaN层之间的GaInN基有源区,该n型和p型GaN层通过诸如金属有机化学气相沉积(MOCVD)或分子束外延(MBE)等已知方法被沉积在合适的衬底上(例如,蓝宝石、碳化硅、硅、Ga2O3,或GaN本身)。从LED有源区到陶瓷磷光体的光学耦合可以经由衬底(在透明衬底和倒装芯片安装结构的情况下)或外延层(在衬底向下安装的情况下,或者如果衬底已经被移除如同薄膜倒装芯片LED结构的情况那样)来进行。陶瓷磷光体可以典型地通过诸如有机硅粘合剂的透明粘合剂物理地附接到LED芯片。
备选地,陶瓷磷光体可以远离LED芯片安装。光学材料被光学地提供以帮助引导和/或混合来自LED芯片并且由陶瓷磷光体发射的初级光。例如,可以施加光学反射有机硅材料以围绕LED芯片和陶瓷磷光体的旁边,使得基本上全部光发射穿过陶瓷磷光体的上表面。这具有增加亮度以及均质化颜色均匀性的益处。
LED芯片可以安装在诸如陶瓷封装或引线框架基封装的封装中,以提供机械稳定性和/或处理能力以及散热装置。另外,封装可以提供用于围绕包括陶瓷磷光体的LED芯片的透镜的应用的阶段。这种透镜可以由透明有机硅制成,并且以圆顶的形式成形,这有助于从陶瓷磷光体的光输出耦合。
电流经由封装内的电极供应到LED芯片,电极电连接到施加到LED芯片内的n型和p型层的欧姆接触材料。这种电流的一部分被转换成LED有源区内的光产生。取决于LED有源区的详细的设计,可以调谐初级光发射波长范围。例如,对于GalnN,这个范围可维持的可以从UV-A到整个可见光谱。特别地,可以以期望的方式选择初级发射波长以与陶瓷磷光体相互作用,例如以提供具有某种颜色再现性的发射光的特定色度。
如上所述的包括LED芯片和陶瓷磷光体的一个或多个封装的LED可以用作照明系统的一部分。这种照明系统可以是照明模块、灯或灯具。照明模块可以包括多个封装的LED并且包括用于光调节(光学)以及热管理(被动或主动散热装置)的附加的装置。可选地,模块还可以包括电驱动装置,用于从主电源或电池电源向一个或多个LED供应目标电流和电压电平。灯通常以标准壳体形式形成,并且除了一个或多个LED之外,典型的还包括电驱动装置以通过标准插座接口耦合到主电源。类似的,灯具具有壳体,并且除了一个或多个LED之外,典型的还包括电驱动装置以耦合到主电源。另外,传感和/或通信电子器件可以被包括到照明系统中。
根据本发明的发光装置和/或陶瓷磷光体可以用于各种系统和/或应用中,其中包括以下一项或多项:
-办公室照明系统
-家庭应用系统
-商店照明系统
-家庭照明系统
-重点照明系统
-点照明系统
-剧院照明系统,
-光纤应用系统,
-投影系统,
-自照明显示系统,
-像素化显示系统,
-分段显示系统,
-警告符号系统,
-医疗照明应用系统,
-指示器符号系统,以及
-装饰照明系统
-便携式系统
-汽车应用
-温室照明系统
根据本发明上述的和要求保护的并且在示例性实施例中描述的要使用的装置,在尺寸、形状、材料选择和技术概念方面不受任何特定的例外,使得应用领域中众所周知的选择标准可以不受限制地应用。
附图说明
本发明的主题的进一步细节、特征和优点可以从从属权利要求以及从附图的以下描述中获得,在其中,作为示例,示出了根据本发明的装置的几个实施例,以及关于以下示例,这些示例被认为是纯粹的说明而不是限制。在附图中:
图1示出了根据本发明的发光装置的第一个实施例;
图2示出了根据本发明的装置的第一个磷光体陶瓷的非常示意性的横截面;
图3示出了根据本发明的装置的第二个磷光体陶瓷的非常示意性的横截面;
图4示出了根据本发明的装置的第三个磷光体陶瓷的非常示意性的横截面;
图5示出了根据示例I的陶瓷的发射光谱;
图6示出了根据示例II的陶瓷的发射光谱;
图7示出了根据示例III的陶瓷的发射光谱;
图8示出了示例III的陶瓷以及两种单个物质的XRD光谱;
图9示出了根据示例IV的陶瓷的发射光谱;
图10示出了根据示例V的陶瓷的发射光谱;
图11示出了根据示例VI的陶瓷的发射光谱;以及
图12示出了示例VI的陶瓷以及两种单个物质的XRD光谱。
具体实施方式
图1示出了根据本发明的发光装置在“远程磷光体”应用方面的第一个实施例。然而,这不是限制性的,并且对于本领域技术人员来说显而易见的是,也可以设想其他实施例。根据图1,装置1包括UVA或发蓝光的半导体装置20,其例如是氮化镓基LED。备选地,半导体装置20可以是激光器或者可以基于其他LED技术,通过实现较高的电流来实现每平方毫米较高的辐射功率。
半导体装置20设置在反射壳体30中,在反射壳体30上方形成陶瓷磷光体10。
图2示出了根据本发明的装置的第一个磷光体陶瓷10的非常示意性的横截面。从图1中可以看出,陶瓷10包括基体材料11,在基体材料11中,附加的发光材料12以小晶粒或颗粒的形式分散。
图3示出了另一个发光陶瓷,在其中存在由虚线指示的两个区域。在图中的上部区域中仅设置“非基体”发光材料12,在下部区域中设置另外的材料13。这种磷光体陶瓷优选地被生产,使得首先制备两种预陶瓷,其中在一种情况下只有材料12与基体材料11一起被处理,并且在另一种情况下只有材料13与基体材料11一起被处理。随后两种陶瓷结合在一起并且形成最终的磷光体陶瓷。
图4示出了根据本发明的装置的第三个磷光体陶瓷的非常示意性的横截面。从图3中可以看出,陶瓷10包括第一基体材料11和非发光的第二基体材料14,其中两种另外的发光材料12和13均以小晶粒或颗粒的形式分散。这里,材料11和14优选地由相同的基本材料制成,其中材料11被掺杂并且材料14未被掺杂。
这种布置具有优点在于,基体材料的发射可以具体地限制在磷光体陶瓷内的特定区域,并且此外可以节省掺杂材料。
在下文中,通过示例来解释本发明,这些示例被认为纯粹是说明性的而不是限制性的。
示例I:
根据示例I的陶瓷包括90体积%的Li3Ba2La1.8Eu1.2(MoO4)8和10体积%的Lu3Al5O12:Ce(0.65%),并且如下制备:
Li3Ba2La1.8Eu1.2(MoO4)8的合成
在研钵中用丙酮作为助磨剂将0.7894g(4.000mmol)BaCO3,2.3030g(16.000mmol)MoO3,0.2217g(3.000mmol)Li2CO3,0.4223g(1.200mmol)Eu2O3和0.5865g(1.800mmol)La2O3研磨。将获得的粉末干燥,转移到瓷坩埚并且在800℃在空气中煅烧12小时。将因此获得的滤饼研磨并且通过36μm的筛子进行筛分。熔点大约为960度。
Lu3Al5O12:Ce(0.65%)的合成
在研钵中用丙酮作为助磨剂将2.9651g(7.451mmol)Lu2O3,0.0168g(0.098mmol)CeO2和1.2745g(12.500mmol)Al2O3研磨。将获得的粉末干燥,转移到瓷坩埚并且在1750℃在CO气氛下加热12小时。熔点大约为2040℃至2080℃。
陶瓷的制造
将90体积%的Li3Ba2La1.8Eu1.2(MoO4)8和10体积%的Lu3Al5O12:Ce(0.65%)的混合物在研磨机中彻底研磨。将因此获得的粗磷光体粉末与有机二醇粘合剂混合,压制成丸粒,并通过300MPa下的冷等静压压制。将因此获得的陶瓷生坯置于钨箔上,并且在上述还原气氛中在1700℃下加热。冷却至室温后,将陶瓷锯成晶片。量子产率为67%,并且色点位于x=0.510和y=0.458。
图5示出了在465nm的激发下陶瓷的发射光谱。
示例II:
根据示例II的陶瓷包括85体积%的Li3Ba2La1.8Eu1.2(MoO4)8和15体积%的Lu3Al5O12:Ce(0.65%)。它类似于示例I的陶瓷制备。量子产率为68%,并且色点位于x=0.473和y=0.488。
图6示出了在465nm的激发下陶瓷的发射光谱。
示例III:
根据示例III的陶瓷包括80体积%的Li3Ba2La1.8Eu1.2(MoO4)8和20体积%的Lu3Al5O12:Ce(0.65%)。它类似于示例I的陶瓷制备。量子产率为74%,并且色点位于x=0.455和y=0.504。
图7示出了在465nm的激发下陶瓷的发射光谱。
图8(从上到下)示出了陶瓷的XRD光谱以及Li3Ba2La1.8Eu1.2(MoO4)8和Lu3Al5O12:Ce(0.65%)的粉末光谱。从图中可以清楚地看出,在陶瓷光谱中没有出现另外的明显的峰,即在陶瓷的制造过程中两种物质之间几乎没有发生反应。
示例IV:
根据示例IV的陶瓷包括90体积%的Li3Ba2La1.8Eu1.2(MoO4)8和10体积%的Y3Al5O12:Ce(2.5%)。它类似于示例I的陶瓷制备。量子效率为42%,并且色点为x=0.500和y=0.483,Y3Al5O12:Ce的熔点为约1940℃至1980℃。
图9示出了在465nm的激发下陶瓷的发射光谱。
示例V:
根据示例V的陶瓷包括85体积%的Li3Ba2La1.8Eu1.2(MoO4)8和15体积%的Y3Al5O12:Ce(2.5%)。它类似于示例I的陶瓷制备。量子产率为51%,并且色点位于x=0.483和y=0.500。
图10示出了在465nm的激发下陶瓷的发射光谱。
示例VI:
根据示例VI的陶瓷包括80体积%的Li3Ba2La1.8Eu1.2(MoO4)8和20体积%的Y3Al5O12:Ce(2.5%)。它类似于示例I的陶瓷制备。量子产率为69%,并且色点为0.477和y=0.507。
图11示出了在465nm的激发下陶瓷的发射光谱。
图12(从上到下)示出了陶瓷的XRD光谱以及Li3Ba2La1.8Eu1.2(MoO4)8和Y3Al5O12:Ce(2.5%)的粉末光谱。从图中可以清楚地看出,在陶瓷光谱中没有出现另外的明显的峰,即在陶瓷的制造过程中两种物质之间几乎没有发生反应。
上述实施例的成分和特征的单个组合是示例性的,包括在该出版物中的教导与包括在所引用的文献中的其他教导的交换和代替也被明确考虑。本领域技术人员将认识到,在不脱离本发明的精神和范围的情况下,可以实现在此描述的实施例和其它实施例的变化和修改。因此,上面的描述被认为是示例性的而不是限制性的。权利要求中使用的词“包括”不排除其他元件或步骤。不定冠词“一个”不排除复数的重要性。在相互不同的权利要求中记载的某些措施的事实并不表示不能有利地使用这些措施的组合。本发明的范围在以下权利要求和相关的等效物中限定。
Claims (12)
1.一种发光装置,包括磷光体陶瓷,所述磷光体陶瓷包括至少两种发光材料,其特征在于,
其中一种材料具有比其它发光材料的熔点低≥200℃的熔点;以及
这种材料被用作基体材料。
2.根据权利要求1所述的发光装置,其特征在于,所述基体材料具有≤1300℃的熔点。
3.根据权利要求1或2所述的发光装置,其特征在于,所述基体材料是发红光的。
4.根据权利要求1至3中任一项所述的发光装置,其特征在于,所述基体材料具有比所述其它发光材料的熔点低≥400℃的熔点。
5.根据权利要求1至3中任一项所述的发光装置,其特征在于,非基体材料包括具有石榴石结构的材料。
6.根据权利要求1至4中任一项所述的发光装置,其特征在于,不是所述基体材料的其中一种发光材料是发绿光或发黄光的。
7.根据权利要求1至6中任一项所述的发光装置,其特征在于,不是所述基体材料的其中一种发光材料是发蓝光的。
8.根据权利要求1至7中任一项所述的发光装置,其特征在于,所述磷光体陶瓷包括多于一种的不是基体材料的发光材料,并且在所述磷光体陶瓷内存在一个或多个区段或区域,在这些区段或区域本质上仅存在这些“非基体”发光材料中的选择的材料。
9.根据权利要求1至8中任一项所述的发光装置,其特征在于,所述磷光体陶瓷中的所述基体材料的体积分数(以在成品磷光体陶瓷中的体积%/体积%计)是在≥20%和≤99%之间。
10.根据权利要求1至9中任一项所述的发光装置,其特征在于,所述基体材料包括选自以下的材料:
ALn1-x-yEuxM2O8:REy
(Ln1-x-yEux)2MO6:RE2y
(Ln1-x-yEux)2M2O9:RE2y
(Ln1-x-yEux)2M3O12:RE2y
(Ln1-x-yEux)2M4O15:RE2y
(Ln1-x-yEux)6MO12:RE6y
(AE1-2x-yEuxAx+y)3MO6:RE3y
A3AE2(Ln1-x-yEux)3(MoO4)8:REy
Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32
A3AE2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32
其中,对于每个结构独立地,A是碱金属,即选自锂、钠、钾、铷、铯或其混合物,AE是碱土金属,即选自铍、镁、钙、锶、钡或其混合物,Ln是选自钪、钇、镧、钆和镥或其混合物的稀土金属,M是钼、钨或其混合物,RE是选自铽、镝、镨、钕或其混合物的稀土金属,其中0<x≤1并且0≤y≤0.05;
Li3Ba2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A3AE2(Tb1-x-yEuxLny)3(Mo1-zWz)8O32,
A(Tb1-x-yEuxLny)(Mo1-zWz)2O8,
(Tb1-x-yEuxLny)2(Mo1-zWz)O6,
(Tb1-x-yEuxLny)2(Mo1-zWz)2O9,
(Tb1-x-yEuxLny)2(Mo1-zWz)4O15,
(Tb1-x-yEuxLny)2SiO5,
(Tb1-x-yEuxLny)2Si2O7,
A(Tb1-x-yEuxLny)SiO4,
Ba2(Tb1-x-yEuxLny)2Si4O13,
AE2(Tb1-x-yEuxLny)2Si4O13,
Sr3(Tb1-x-yEuxLny)2Si6O18,
AE3(Tb1-x-yEuxLny)2Si6O18,
(Tb1-x-yEuxLny)2GeO5,
(Tb1-x-yEuxLny)2Ge2O7,
A(Tb1-x-yEuxLny)GeO4,
Ba2(Tb1-x-yEuxLny)2Ge4O13,
AE2(Tb1-x-yEuxLny)2Ge4O13,
Sr3(Tb1-x-yEuxLny)2Ge6O18
AE3(Tb1-x-yEuxLny)2Ge6O18
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)O5,
(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)2O7,
A(Tb1-x-yEuxLny)(Ge1-a-bZraHfb)O4,
Ba2(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)4O13,
Sr3(Tb1-x-yEuxLny)2(Ge1-a-bZraHfb)6O18
(Tb1-x-yEuxLny)2(Mo1-zWz)3O12
其中(对于每个结构独立地):
Ln=La,Gd,Lu,Y或其混合物,
A=Li,Na,K,Rb,Cs或其混合物,优选地为Li,
AE=Sr,Ca,Ba或其混合物,优选地为Ba和/或Sr,
x>0且<1并且y≥0且<1,其中1-x-y>0并且a,b≥0且<0.2并且z≥0且≤1,
并且所述非基体材料包括具有石榴石结构的材料。
11.一种制造如权利要求1至10中任一项所述的发光装置的方法,包括以下步骤:
a)提供起始材料,所述起始材料包括以粉末形式的至少一种发光基体材料和至少一种另外的发光材料;
b)可选地进行成型,特别是通过轴向和/或冷等静压和/或流延成型或槽膜工艺和/或热塑工艺(注塑、热浇铸、挤出);
c)将所述起始材料烧结和/或热压成陶瓷;
d)可选地通过热等静压再压缩所烧结的陶瓷;及
e)可选地对所述烧结的陶瓷进行再加工,特别是通过离子束制备工艺,或者通过具有精确的或非精确的切割边缘的机械加工或精细研磨工艺。
12.一种包括根据权利要求1至10中任一项所述的发光装置的系统,所述系统用于以下一个或多个应用中:
-办公室照明系统
-家庭应用系统
-商店照明系统,
-家庭照明系统,
-重点照明系统,
-点照明系统,
-剧院照明系统,
-光纤应用系统,
-投影系统,
-自照明显示系统,
-像素化显示系统,
-分段显示系统,
-警告符号系统,
-医疗照明应用系统,
-指示器符号系统,以及
-装饰照明系统
-便携式系统
-汽车应用
-温室照明系统。
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| DE102015110189.0 | 2015-06-24 | ||
| DE102015110189.0A DE102015110189A1 (de) | 2015-06-24 | 2015-06-24 | Phosphorkeramik |
| DE102015110187.4 | 2015-06-24 | ||
| DE102015110187.4A DE102015110187A1 (de) | 2015-06-24 | 2015-06-24 | Phosphorkeramik |
| PCT/EP2016/064721 WO2016207380A1 (en) | 2015-06-24 | 2016-06-24 | Phosphor ceramic |
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| CN111668579B (zh) * | 2020-06-01 | 2021-09-07 | 惠州威博精密科技有限公司 | 一种5g通讯滤波器介质陶瓷件半成品及其成型方法 |
| DE102020133604B4 (de) | 2020-12-15 | 2025-09-04 | Technologie Manufaktur GmbH & Co. KG | Leuchtstoffkeramik und lichtemittierende Vorrichtungen enthaltend die Leuchtstoffkeramik |
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| JP2018527600A (ja) | 2018-09-20 |
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| US11015118B2 (en) | 2021-05-25 |
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