CN1784572A - 涂有发光材料的纳米粒子的uv光源 - Google Patents

涂有发光材料的纳米粒子的uv光源 Download PDF

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CN1784572A
CN1784572A CN200480012512.4A CN200480012512A CN1784572A CN 1784572 A CN1784572 A CN 1784572A CN 200480012512 A CN200480012512 A CN 200480012512A CN 1784572 A CN1784572 A CN 1784572A
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T·杰斯特
A·G·H·梅杰斯
D·伯特拉姆
H·－H·贝奇特
H·F·博尔纳
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Koninklijke Philips NV
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Abstract

描述了一种包括光波导板、UV光源和用于将UV光耦合到光波导板内的装置的发光体，并且其中光波导板被提供有包含一种或多种发光材料的覆盖层，该发光材料被直接施加或可被嵌入在合成树脂材料的球形粒子内。这些发光材料将波长为300～400nm的UV光转换成波长为420～480nm的可见光。覆盖层具有10～5000nm的厚度并显示出＜20％的光反射。

Description

涂有发光材料的纳米粒子的UV光源
本发明涉及通过使用纳米粒子形式的无机和/或有机发光材料层将光耦合输出光波导板而产生的发光体。
通过利用散射耦合输出光的光发射是一种广泛使用的技术。微米范围内的光散射粒子早已用于光的有效分布并使光导片具有不透明的外观。这产生的是半透明的而不是透明的光源。
在许多应用中，具有透明光源应是有优势的。这可通过用纳米粒子将光耦合输出光波导板来实现。为该目的，光在光波导板的边缘处被耦合，通过全内反射被分布在片内，并且接着在涂在光波导上面的具有合适的特性的粒子层处通过散射被耦合输出光波导板。如果正确选择了粒子尺寸、层的折射率和厚度，那么可获得光学透明性。
本发明的优点在于提供用于设计平光源，包括它们的透明性、从光源发射的颜色及其自然色的新的机会。
对于平光源来说，以及尤其对于用作光波导板并被光散射层覆盖的透明片来说，存在无数可能的应用。例如，用这种方法制造许多用于背光LCD的光源。在所有上述应用中，散射层被优化以给光源提供最大可能的耦合输出和均匀性。
用于散射光的粒子直径通过Mie理论限定。散射通常通过与覆盖层内的粒子的直径和充填密度成比例的散射参数S来设计。散射参数在恒定波长处是粒子直径的函数并且它随着粒子尺寸的减小而增加，当粒子尺寸接近零时到达最大值并最终返回零。普通光源使用具有高散射功率的粒子涂敷，在这种情况下，使用接近Mie最大值的直径的粒子或厚层。
结果是高达70％的光被耦合输出并且光源看起来不透明。如果粒子尺寸小于散射光的最佳值，那么层变得越来越透明。同时，这降低了光的耦合输出。然而，如果光波导内的光吸收小，那么由于光子可被耦合输出采用的太多种可能方式的原因，耦合输出仍足够高。
本发明涉及一种发光体，该发光体包括光波导板1、UV光源2和用于将UV光耦合到光波导板内的装置，该片被提供有包含一种或多种发光材料的覆盖层3，该发光材料被直接施加或可被嵌入合成树脂材料的球形粒子内并将波长为300～400nm的UV光转换成波长为420～480nm的可见光，合成树脂材料的粒子具有在10和500nm之间的直径并显示出＜20％的光反射。
覆盖层内的这些发光材料一方面使光耦合输出光波导板，并且另一方面将UV光转换成更长波长的可见光。一种或多种无机或有机发光材料可被嵌入合成树脂材料的球形粒子内。
光散射粒子的发光材料特性也可用于制造发射白光的平的、透明的光源。
施加到光波导板的覆盖层通常厚20～5,000nm。荧光管用作主光源以将光耦合到光波导板内。然而，也可用作主光源的是AlxGayInzN LED装置pf，其中x、y和z可采用0和1之间的值，并且x+y+z的和为1。
为制造根据本发明的发射白光的发光体，可使用表1所示的在聚合前驱物内溶解的有机发光材料。为产生白光，将来自表1的两种或多种合适的发光材料混合在一起并溶解在聚合物前驱物内。聚合物前驱物在这种情况下利用一种方法被聚合，在该方法中，得到尺寸在5和500nm之间的球形纳米珠，正如例如通过BASF向公共查阅公开的德国申请198 41 842和199 08 013所描述的一样。优选聚合物前驱物在这种情况下为聚甲基丙烯酸甲酯，这是因为它对直到尺寸为300nm的粒子是透明的。其它合适的聚合物是聚乙烯、聚氯乙烯、聚四氟乙烯、聚苯乙烯或聚碳酸酯。用这种方法得到的纳米珠接着被施加给光波导以提供20～5,000nm的层厚。适合于根据本发明的发光体的发光材料在表1中示出。
表1
  发光材料   发射颜色   发射波长(nm)
  路玛近F紫570   蓝   425
  香豆素120   蓝   440
  香豆素152   绿   520
  路玛近F黄083   绿   490，520
  路玛近F黄ED206   黄   555
  路玛近F橙240   橙   545，575
  路玛近F红300   红   615
使用粒子尺寸在纳米范围的无机发光材料也非常适合于制造根据本发明的发光体。在这种情况下，它们的粒子尺寸应在1和300nm之间的范围内。纳米粒子接着以覆盖层的形式施加给光波导，在这种情况下，层厚应优选在20和5,000nm之间。合适的无机发光材料颜料是氧化物、硫化物或氮化物以及具有晶格的半导电材料，具有高折射率的颜料例如MgWO4、CaWO4、Y2O3(n≈1.9)、CaS、SrS(n≈2.1)或ZnS(n≈2.4)是尤其优选的。这些颜料借助Eu2+、Ce3+、Eu3+、Tb3+、Pr3+、Mn2+、Ag+、Pb2+、Cu2+或Bi3+被活化，或具有导通态和价态之间的直接光允许跃迁。在后者的情况下，粒子尺寸的减小导致发射特性的改变。尤其是随着粒子尺寸的减小，发射能增加即发射颜色从红经过黄和绿到蓝偏移。这种无机发光材料优选通过胶体化学型的合成来制造。尤其优选的无机发光材料在表2中列出。
表2
  发光材料颜料   颜色  在(nm)处发射   色点x   色点y
  Sr2P2O7:Eu   紫  420   0.17   0.01
  CaWO4   青白  420   0.17   0.1
  CaWO4:Pb   青白  440   0.18   0.21
  (Ba1-xSrx)5(PO4)3(F，Cl):Eu   蓝  450   0.15   0.07
  ZnS:Ag   蓝  450   0.15   0.05
  BaMAl10O17:Eu   蓝  453   0.15   0.07
  BaMgAl10O17:Mn，Eu   蓝绿  453,515   *   *
  Sr4Al14O25:Eu   蓝绿  490   0.14   0.35
  MgWO4   青白  480   0.24   0.34
  SrAl2O4:Eu   绿  520   0.14   0.35
  ZnS:Cu   绿  530   0.31   0.61
  SrGa2S4:Eu   绿  535   0.27   0.69
  CePO4:Tb   绿  545   0.34   0.58
  Y3Al5O12:Ce   黄  560   0.45   0.53
  (Y1-x-yGdxLuy)3(Al1-yGay)5O12:Ce   黄  520-580**   **   **
  ZnS:Mn   橙  590   0.58   0.42
  (Y1-xGdx)2O3:Bi，Eu   红  612   0.65   0.34
  Y(V1-xPx)O4:Eu   红  620   0.66   0.33
  Y2O3:Eu   红  620   0.66   0.33
带*标记的色点依赖于活化剂/共同活化剂的浓度比。带**标记的发射波长和色点依赖于相应的阳离子比。
在它们的带内具有直接间隙即被称为量子点的优选发光材料的综述可在表3中得到。这些是具有固有粘度的自发光粒子。
表3
  周期表的II-VI族 CdSe，CdTe，ZnS，ZnTe，ZnSe，CdS，HgS，HgSe，HgTe，CdSeS，CdTeSe，CdTeS，ZnSSe，ZnTeSe，ZnSTe，CdZnSe，CdZnTe，CdZnS
  周期表的III-V族 GaAs，GaP，GaSb，GaN，InN，InP，InAs，InSb，InGaP，InGaAs，InGaN，AlInGaN，AlInGaP，AlInGaAs
  周期表的IV族 Si，Ge
  核-外壳(一种材料的核，不同材料的外壳) (CdSe)ZnS，(CdTe)ZnS，(CdSe)CdS，(CdTe)CdS，(InP)ZnS，(InN)GaN
发射白光的光源可通过使用包含蓝和黄橙发光材料或蓝、绿和红发光材料的发光材料的混合物得到。上述的最优选实例是：
1.        Sr4Al14O25:Eu和ZnS:Mn
2.        BaMgAl10O17:Mn，Eu和ZnS:Mn
3.        ZnS:Ag，ZnS:Cu和YVO4:Eu
4.        BaMgAl10O17:Eu和Y3Al5O12:Ce
5.        BaMgAl10O17:Eu和(Y1-x-yGdxLuy)3(Al1-yGay)5O12:Ce
6.        BaMgAl10O17:Eu，CePO4:Tb和Y(V1-x-yPx)O4:Eu
7.        BaMgAl10O17:Eu，CePO4:Tb和Y2O2S:Eu
8.        (Ba1-xSrx)5(PO4)3(F，Cl):Eu和Y3Al5O12:Ce
9.        (Ba1-xSrx)5(PO4)3(F，C1):Eu和(Y1-x-yGdxLuy)3(Al1-yGay)5O12:Ce
耦合到光波导内的主光(primary light)通常具有在300和400nm之间的波长。它可借助AlxGayInzN LED装置或借助包含UV发光材料的荧光灯产生。在这种情况下优选发光材料是LaPO4:Ce(320nm)、(Y，Gd)PO4:Ce(345nm)、BaSi2O5:Pb(350nm)或SrB4O7:Eu(370nm)。
根据权利要求的发光体具有一系列重要优点：
-发射光的颜色通过光波导的涂层被确定并可容易地通过改变发光材料或发光材料的混合物被修改；
-由于与白光相比UV光借助非常小的粒子被更强烈地散射，因此可容易地得到高透明性的平光源；
-平光片可以是无色的，或者如果耦合输出光的层包含具有可见区内的吸收的发光材料，那么可用相应颜色的发光材料着色。
可采用很多方式使用它们。一种可能性是它们用于照亮汽车顶内衬(lining)以及另一种是它们用于照亮窗户。
参考下文所描述的实例，本发明的这些和其它方面将变明显并被阐明。
在附图中：
图1示出了平透明光源的发射谱，从Al0.57Ga0.5In0.05N LED装置发射的光传播到该平透明光源中并且从该平透明光源处光通过包含BaMgAl10O17:Eu、CePO4:Tb和YVO4:Eu的混合物的层被耦合输出。
图2示出了具有LED作为其主光源的透明光源的结构示意图。
图3示出了具有荧光灯作为其主光源的透明光源的结构。
图4示出了其中耦合输出光的层放置在两个光导之间的透明光源的结构示意图。
实例
聚甲基丙烯酸甲酯片在一侧上涂有包括BaMgAl10O17:Eu、CePO4:Tb和YVO4:Eu的纳米粒子混合物的悬浮液。这三种发光材料的浓度被如此调节以便当它们借助UV光被激发时得到白光谱。
聚甲基丙烯酸甲酯片以这种方式堆叠以便按图4所示的方式形成夹层。设置在光波导的边缘处的Al0.57Ga0.5In0.05N LED装置用作主光源。发射光的光谱在图1中示出。这种光源的彩色再现在4,000K的色温下约为90。
参考数字列表
1光波导板
2 UV光源
3覆盖层

Claims (10)

1.一种包括光波导板(1)、UV光源(2)和用于将UV光耦合到光波导板内的装置的发光体，其特征在于光波导板被提供有包含一种或多种发光材料的覆盖层3，该发光材料被直接施加或可被嵌入在合成树脂材料的球形粒子内并将波长为300～400nm的UV光转换成波长为420～480nm的可见光，合成树脂材料的粒子具有在10和500nm之间的直径并显示出＜20％的光反射。
2.如权利要求1所述的发光体，其特征在于覆盖层包含可被嵌入在合成树脂材料的球形粒子内的一种或多种无机发光材料。
3.如权利要求1所述的发光体，其特征在于覆盖层包含可被嵌入在合成树脂材料的球形粒子内的一种或多种有机发光材料。
4.如权利要求1～3所述的发光体，其特征在于可被嵌入在合成树脂材料的球形粒子内的发光材料转换带有颜色的或白光的UV光。
5.如权利要求1～4所述的发光体，其特征在于施加到光波导板的覆盖层产生20～5000nm的层厚。
6.如权利要求1～5所述的发光体，其特征在于荧光管用作主光源。
7.如权利要求1～5所述的发光体，其特征在于AlxGayInzN LED装置用作主光源，其中x、y和z可采用0和1之间的值并且x+y+z的和为1。
8.如权利要求1～7所述的发光体，其特征在于包含合成树脂材料的球形粒子的覆盖层施加到放置在两个或多个光波导板之间的薄膜上。
9.如权利要求1～8所述的发光体的用途，其特征在于它用于照亮汽车顶内衬。
10.如权利要求1～8所述的发光体的用途，其特征在于它用于照亮窗户。
CN200480012512.4A 2003-05-09 2004-05-03 涂有发光材料的纳米粒子的uv光源 Pending CN1784572A (zh)

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