CN102471681A - 共掺杂的硅氧氮化物 - Google Patents

共掺杂的硅氧氮化物 Download PDF

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Publication number
CN102471681A
CN102471681A CN2010800312624A CN201080031262A CN102471681A CN 102471681 A CN102471681 A CN 102471681A CN 2010800312624 A CN2010800312624 A CN 2010800312624A CN 201080031262 A CN201080031262 A CN 201080031262A CN 102471681 A CN102471681 A CN 102471681A
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compound
multinomial
phosphor
molding
osmium
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CN102471681B (zh
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H·温克勒
R·派特里
T·沃斯格罗内
T·朱斯特尔
D·乌利希
A·卡特尔尼科瓦斯
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Merck Patent GmbH
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Merck Patent GmbH
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Abstract

本发明涉及式(I)的化合物：(Ca，Sr，Ba)6-x(Si1-yMey)3(O1-zMa2z)6N4:Eux (I)其中Me＝Th、Ru和/或Os，Ma＝F和/或Cl，x＜0.5，y＜1且z＜0.1，本发明还涉及这些化合物的制造方法和作为发光物质的用途，还涉及用于转换来自LED的蓝光发射或近UV发射的转换发光物质。

Description

共掺杂的硅氧氮化物
本发明涉及由6-3-6-4碱土金属硅氧氮化物构成的化合物，所述碱土金属硅氧氮化物被钍、钌、锇、氟和/或氯共掺杂，本发明涉及所述化合物的制备，涉及其作为无机发光材料的用途，并涉及用于暖白LEDs或所谓的按需选色用途的LED转换无机发光材料。
按需选色概念是指借助使用一种或多种无机发光材料的pcLED(＝无机发光材料转换LED)产生具有特定色点(colour point)的光。该概念例如用于产生某些企业设计，例如用于照亮的公司标记、商标等。
为了借助LED TV背光实现高的色空间，具有在620纳米-660纳米范围内的最大发射的深红色无机发光材料是必要的。本领域技术人员已知的合适的材料体系是硅氮化物和铝硅氮化物无机发光材料(Xie，Sci.Technol.Adv.Mater.2007，8，588-600)：
1-1-2氮化物，例如CaSiN2:Eu2+(Le Toquin，Cheetham，Chem.Phys.Lett.2006，423，352)，2-5-8氮化物，例如(Ca，Sr，Ba)2Si5N8:Eu2+(Li等人，Chem.Mater.2005，15，4492)，和铝硅氮化物，例如(Ca，Sr)AlSiN3:Eu2+(K.Uheda等人，Electrochem.Solid State Lett.2006，9，H22)。
如上所述的含氮无机发光材料具有一系列缺点，这导致这些材料无法大量供应：特别地，必需的高纯度代表在工业中只有非常努力才能满足的一项挑战。因此，极低浓度的碳或氧导致无机发光材料效率敏感地降低。但是，几乎不可能避免氧杂质，因为甚至原材料，例如Si3N4和金属氮化物(碱土金属氮化物、氮化铕)就无法以无氧形式获得。替代性的原材料，例如金属氢化物，对氧和水分极其敏感，意味着氧也通过这些组分引入无机发光材料中。标准制备法，例如碳热还原和氮化，造成无机发光材料中的碳杂质，使得这种无机发光材料发生灰化，这降低发光度。
Sohn等人，Journ.o(Electr.Soc.155(2)，J58-J61(2008)首次描述了硅氧氮化物Sr6Si3O6N4:Eu。
因此，本发明的目的是将上述6-3-6-4碱土金属硅氧氮化物改性，以使这些化合物实现更高的光效率。
出乎意料地，已经发现，如果用钍、钌、锇、氟和/或氯进行共掺杂，可以满足进一步提高红色硅氧氮化物无机发光材料(Ca，Sr，Ba)6Si3O6N4:Eu的转换效率的的要求，这种提高在经济上是重要的。
因此，本发明涉及铕掺杂的6-3-6-4碱土金属硅氧氮化物类型的化合物，该化合物还包含来自钍、铷、锇、氟和/或氯的共掺杂剂。
“6-3-6-4碱土金属硅氧氮化物”是指复合物M6Si3O6N4:Eu2+，其中M代表碱土金属或多种碱土金属的混合物。
优选的是式I的化合物
(Ca，Sr，Ba)6-x(Si1-yMey)3(O1-zMa2z)6N4:Eux    (I)
其中
Me＝Th、Ru和/或Os
Ma＝F和/或Cl
x＜0.5
y＜1且
z＜0.1。
优选地，x值等于0.003至0.2，y值(其代表共掺杂剂Me的原子浓度)等于0.0001至0.2，z值等于0.0005至0.03。
更优选地，x＝0.005至0.15和/或y＝0.001至0.02。
本发明的式I的化合物或无机发光材料与具有相同组成但没有共掺杂剂钍、铷、锇、氟和/或氯的那些相比具有较高的发光度，这可以借助本领域技术人员已知的理论解释。通过卤化物存在造成的较高晶格质量产生这种较高发光度。该卤化物非常可能造成扩散势垒降低，离子在固态反应中必须克服该扩散势垒才能占据固体结构中的所需晶格位置。重金属Th、Ru或Os很可能通过所谓的重原子效应造成提高的无机发光材料吸收。
本发明化合物的粒度为50纳米至30微米，优选1微米至20微米，更优选2至15微米。
本发明还涉及能够如下所述获得的化合物：通过固态扩散法将含有氮化硅、铕和钙和/或锶和/或钡的原材料与至少一种含钍、锇、钌、氟和/或氯的共掺杂剂混合，所述共掺杂剂可任选包含选自碱金属或碱土金属卤化物或硼酸盐化合物的助熔剂；然后进行热后处理。
本发明还涉及制备铕掺杂的6-3-6-4碱土金属硅氧氮化物型化合物的方法，该方法具有下述工艺步骤：
a)通过混合至少4种选自含氮化硅、铕、钙、锶、钡、钍、铷、锇、氟和/或氯的材料的原材料，制备被含钍、铷、锇、氟和/或氯的材料共掺杂的Eu掺杂的6-3-6-4碱土金属硅氧氮化物，
b)热后处理所述被钍、铷、锇、氟和/或氯共掺杂的化合物。
c)用HCl溶液和KOH溶液洗涤所述经热后处理的化合物。
如上所述，用于制备该化合物的原材料由氮化硅(Si3N4)、氢化钙和氟化铕以及至少一种含Th、Ru、Os、F和Cl的共掺杂剂构成。除优选的氮化物、氢化物和氟化物外，合适的原材料还包括其它无机和/或有机物质，例如氰氨化物、二氰氨化物、氰化物、草酸盐、丙二酸盐、富马酸盐、碳酸盐、柠檬酸盐、抗坏血酸盐和乙酰丙酮化物。
上文提到的热后处理(见工艺步骤b)在还原条件下，例如用合成气体(例如90/10)、纯氢和/或在含或不含上述气氛的氨气氛中，进行数个小时。煅烧过程中的温度为1000℃至1800℃，优选1400℃至1600℃，持续许多小时(优选8小时)。
还优选将该无机发光材料转移到高压烧结炉中，并在此在40至70巴和1400至1600℃的温度煅烧6至10小时。
还优选在真空中对该无机发光材料施以热等静压制。
另外优选先用HCl、然后用KOH洗涤该无机发光材料，这除去无定形SiO2。这种洗涤步骤有利地提高该无机发光材料的发射强度及吸收。
借助上文提到的方法，可以制造任何所需外形的本发明化合物或无机发光材料，例如球粒、薄片和结构化材料和陶瓷。这些形状根据本发明概括在术语“成形体”下。该成形体优选是“无机发光体”。
因此，本发明还涉及包含本发明化合物的成形体，其具有粗糙表面，该表面载有纳米粒子和/或下述粒子：该粒子包含含或不含选自铕、锇、钌、钍、氟和/或氯的掺杂剂的本发明化合物，所述纳米粒子包含SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物。
在另一优选实施方案中，该成形体在与LED芯片相对的面上具有结构化(例如，锥体形)的表面(参见WO 2008/058619，Merck，其整个范围经此引用并入本申请的文本中)。这能从该无机发光材料中耦合输出尽可能多的光。
该成形体上的结构化表面如下制造：之后用已结构化的合适的材料涂覆，或在之后的步骤中通过(光)平版印刷法、蚀刻法或通过利用能量或材料束或机械力作用的写入法。
在另一优选实施方案中，本发明的成形体在与LED芯片相对的面上具有粗糙表面，该表面载有包含SiO2、TiO2、Al2O3、ZnO2、ZrO2和/或Y2O3或这些材料的组合的纳米粒子，和/或下述粒子：该粒子具有式I的无机发光材料复合物，含或不含选自Th、Ru、Os、F和/或Cl的掺杂剂。在本文中，粗糙表面具有最多几百纳米的粗糙度。涂覆表面具有可降低或防止全反射、并且可以更好地从本发明无机发光材料中耦合输出光的优点(参见WO 2008/058619，Merck，其整个范围经此引用并入本申请的文本中)。
本发明的成形体还优选在背向芯片的表面上具有折射率匹配的层，这简化了初级辐射和/或无机发光体发出的辐射的耦合输出。
在另一优选实施方案中，该成形体具有连续表面涂层，该连续表面涂层由SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物和/或无活化剂铕的式I的化合物构成。这种表面涂层的优点在于，涂料折射率的合适分级能使折射率与环境匹配。在这种情况下，无机发光材料表面处的光散射降低，且更大比例的光可进入无机发光材料，并在此被吸收和转换。此外，由于全内反射降低，折射率匹配的表面涂层能从该无机发光材料中耦合输出更多光。
此外，如果必须将无机发光材料包封，则连续层是有利的。为了对抗无机发光材料或其部分对直接环境中的扩散水或其它材料的敏感性，这可能是必要的。用封闭壳包封的另一原因是将实际无机发光材料与芯片中产生的热热解耦。这种热导致无机发光材料的荧光产额降低，并也可能影响荧光的颜色。最后，这种类型的涂层能够通过防止无机发光材料中发生的晶格振动传播到环境中来提高无机发光材料的效率。
此外，该成形体优选具有多孔表面涂层，该多孔表面涂层由SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物和/或含或不含选自Eu、Th、Ru、Os、F和/或Cl的掺杂剂的式I的化合物构成。这些多孔涂层提供进一步降低单层的折射率的可能性。这种类型的多孔涂层可通过如WO 03/027015中所述的三种常规方法制造，其整个范围经此引用并入本申请的文本中：玻璃蚀刻(例如钠钙玻璃(参见US 4019884))、施用多孔层、以及多孔层和蚀刻操作的组合。
在另一优选实施方案中，该成形体具有带有官能团的表面，所述官能团有利于与环境、优选由环氧或有机硅树脂构成的环境的化学键合或物理结合。这些官能团可以是例如经由氧基键合、并能与基于环氧化物和/或有机硅的粘合剂的成分形成连接的酯或其它衍生物。这种类型的表面具有促进无机发光材料均匀合并到粘合剂中的优点。此外，可由此将该无机发光材料/粘合剂体系的流变性质以及适用期调节至特定程度。由此简化混合物的加工。在这方面，如果静电相互作用在体系之间经由电荷波动或部分电荷发挥作用，则使用术语物理结合。
由于施用到LED芯片上的本发明无机发光材料层优选由有机硅和均匀无机发光材料粒子的混合物构成，且该有机硅具有表面张力，因此这种无机发光材料层在微观层面上不是均匀的，或该层的厚度并非处处恒定。
通过常规方法，由相应的金属盐和/或稀土盐制备作为另一优选实施方案的薄片状无机发光材料。在EP 763573和WO 2008/058620中详细描述了该制备方法，其整个范围经此引用并入本申请的文本中。这些薄片状无机发光材料可以如下制备：通过在水分散体或悬浮液中的沉淀反应，用无机发光材料层涂覆具有非常大的径厚比、原子级平滑表面和可调厚度的天然或合成的高度稳定的载体或基底，包括例如云母、SiO2、Al2O3、ZrO2、玻璃或TiO2薄片。除云母、ZrO2、SiO2、Al2O3、玻璃或TiO2或其混合物外，该薄片也可以由无机发光材料本身构成或由一种材料组成。如果薄片本身仅充当无机发光材料涂层的载体，后者必须由可透过来自LED的初级辐射、或吸收该初级辐射并将这种能量传递给无机发光材料层的材料构成。将薄片状无机发光材料分散在树脂(例如有机硅或环氧树脂)中，并将该分散体施用到LED芯片上。
薄片状无机发光材料可以在大工业规模下以50纳米至大约20微米、优选150纳米至5微米的厚度制备。直径在此为50纳米至20微米。其通常具有1∶1至400∶1、特别是3∶1至100∶1的径厚比(直径与粒子厚度的比率)。薄片大小(长度×宽度)取决于布置。薄片也适合作为转换层内的散射中心，特别是在它们具有特别小的尺寸时。
可以在本发明的薄片状无机发光材料的朝向LED芯片的表面上提供对LED芯片发出的初级辐射具有抗反射作用的涂层。这导致该初级辐射的反向散射降低，从而能使初级辐射更好地耦合到本发明的无机发光体中。
适用于此用途的是例如，折射率匹配的涂层，其必须具有下述厚度d：d＝[LED芯片的初级辐射的波长/(4×无机发光陶瓷的折射率)]，参见例如Gerthsen，Physik[物理]，Springer Verlag，第18版，1995。该涂层也可以由光子晶体构成，其也包括薄片状无机发光材料表面的结构化以实现某些功能。
本发明陶瓷体形式的成形体是与WO 2008/017353(Merck)(其整个范围经此引用并入本申请的文本中)中描述的方法类似地制造的。在这种方法中，如下制备无机发光材料：混合相应的原材料和掺杂剂，然后施以等静压制，并以均匀、薄和无孔的薄片形式直接施用到芯片表面上，或与芯片隔开一定距离(远程无机发光材料概念)。各自的布置尤其取决于LED器件的构造，本领域技术人员能够选择有利的布置。因此不存在该无机发光材料的激发和发射的位置依赖性变化，这意味着带有无机发光材料的LED发射具有恒定颜色的均匀光锥并具有高的光输出。可以在大的工业规模下，例如，以厚度几百纳米至大约500微米的薄片形式制造陶瓷无机发光体。薄片大小(长度×宽度)取决于布置。在直接施用到芯片上的情况下，应根据芯片大小(大约100μm×100μm至数平方毫米)选择薄片尺寸，在合适的芯片布置(例如倒装芯片布置)的情况下或相应地，芯片表面的尺寸超出大约10％-30％。如果在成品LED上安装该无机发光材料薄片，则所有发出的光锥都穿过该薄片。
可以用轻金属或贵金属，优选铝或银，涂覆该陶瓷无机发光体的侧面。该金属涂覆的作用在于，光不会从该无机发光体中侧向射出。侧向射出的光会降低从LED中耦合输出的光流。在等静压制产生杆或薄片后的工艺步骤中进行陶瓷无机发光体的金属涂覆，其中可任选在金属涂覆之前将该杆或薄片切至必要尺寸。为此，例如用包含硝酸银和葡萄糖的溶液润湿侧面，然后在高温下暴露在氨气氛下。在该方法中例如在侧面上形成例如银涂层。
或者，无电金属化法也合适，参见例如Hollemann-Wiberg，Lehrbuchder anorganischen Chemie[无机化学教科书]，Walter de Gruyter Verlag，或Ullmannsder chemischen Technologie[Ullmann化学技术百科全书]。
如果必要，可以使用水玻璃溶液将陶瓷无机发光体固定到LED芯片的基板上。
在另一实施方案中，该陶瓷无机发光体在与LED芯片相对的面上具有结构化(例如，锥体形)的表面。这能从该无机发光体中耦合输出尽可能多的光。通过使用具有结构化压板的压模进行等静压制，并由此将结构压印到该表面中，制造无机发光体上的结构化表面。如果目的是制造尽可能薄的无机发光体或薄片，则结构化表面是合意的。压制条件是本领域技术人员已知的(参见J.Kriegsmann，Technische keramische Werkstoffe[工业陶瓷材料]，第4章，Deutscher Wirtschaftsdienst，1998)。重要的是，所用压制温度为要压制的物质的熔点的2/3至5/6。
本发明还涉及制造成形体、优选无机发光体的方法，其具有下述工艺步骤：
a)通过混合至少4种选自含氮化硅、铕、钙、锶、钡、钌、钍、锇、氟和/或氯的材料的原材料，制备被含钍、铷、锇、氟和/或氯的材料共掺杂的铕掺杂的6-3-6-4碱土金属硅氧氮化物，
b)热后处理所述被钍、铷、锇、氟和/或氯共掺杂的化合物，并形成具有粗糙表面的成形体，
c)用包含SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物的纳米粒子，或用包含本发明化合物的纳米粒子，涂覆所述表面。
此外，本发明的无机发光材料的可激发性贯穿宽的范围，该范围为大约350纳米至530纳米，优选430纳米至大约500纳米。这些无机发光材料因此不仅适合被发射UV或蓝光的初级光源(例如LEDs)或常规放电灯(例如基于Hg的放电灯)激发，也适用于如利用在451纳米的蓝色In3+光线的光源。
本发明还涉及照明装置，其具有至少一个最大发射在250纳米至530纳米、优选350纳米至大约500纳米范围内的初级光源。440至480纳米的范围特别优选，初级辐射被本发明化合物或无机发光材料部分或完全转换成较长波长的辐射。这种照明装置优选发白光或发射具有特定色点的光(按需选色原理)。本发明的照明装置的优选实施方案描绘在图1至7中。
在本发明的照明装置的一个优选实施方案中，光源是发光的氮化镓铝铟，特别具有式IniGajAlkN的氮化镓铝铟，其中0≤i，0≤j，0≤k，且i+j+k＝1。这种类型的光源的可能形式是本领域技术人员已知的。它们可以是具有各种结构的发光LED芯片。
在本发明照明装置的另一优选实施方案中，光源是基于ZnO、TCO(透明导电氧化物)、ZnSe或SiC的发光装置或基于有机发光层(OLED)的装置。
在本发明照明装置的另一优选实施方案中，光源是表现出电致发光和/或光致发光的源。该光源也可以是等离子体或放电源。
可以将本发明的无机发光材料分散在树脂(例如环氧或有机硅树脂)中，或在合适的尺寸比下，直接置于初级光源上，或根据用途，远离初级光源布置(后一种布置也包括“远程无机发光技术)。远程无机发光技术的优点是本领域技术人员已知的并例如在下述出版物中揭示：JapaneseJourn.of Appl.Phys.第44卷，No.21(2005)，L649-L651。
在另一实施方案中，优选通过光导布置实现照明装置在无机发光材料和初级光源之间的光耦合。因此可以将初级光源安装在中心位置，并借助光导装置(例如光导纤维)与无机发光材料光耦合。由此，可以获得适合照明意图的仅由一种或不同的无机发光材料(可将它们布置而形成光幕)和与初级光源耦合的光波导管构成的灯。由此，可以在有利于电气安装的位置安装强的初级光源，并且无需进一步使用电缆而是仅通过铺设光波导管就可以在任何所需位置安装包含与光波导管耦合的无机发光材料的灯。
本发明还涉及本发明化合物和成形体作为无机发光材料或无机发光体的用途。
本发明还涉及本发明的化合物用于部分或完全转换发光二极管发出的蓝光或近紫外光发射的用途。
本发明的化合物还优选用于将蓝光或近紫外光发射转换成可见白光辐射。本发明的化合物还优选用于根据“按需选色”概念将初级辐射转换成特定色点。
本发明的式I的化合物可以单独使用，或与本领域技术人员熟悉的下述无机发光材料混合使用：
Ba2SiO4:Eu2+、BaSi2O5:Pb2+、BaxSri1-xF2:Eu2+、BaSrMgSi2O7:Eu2+、BaTiP2O7、(Ba，Ti)2P2O7:Ti、Ba3WO6:U、BaY2F8Er3+，Yb+、Be2SiO4:Mn2+、Bi4Ge3O12、CaAl2O4:Ce3+、CaLa4O7:Ce3+、CaAl2O4:Eu2+、CaAl2O4:Mn2+、CaAl4O7:Pb2+，Mn2+、CaAl2O4:Tb3+、Ca3Al2Si3O12:Ce3+、Ca3Al2Si3Oi2:Ce3+、Ca3Al2Si3O，2:Eu2+、Ca2B5O9Br:Eu2+、Ca2B5O9Cl:Eu2+、Ca2B5O9Cl:Pb2+、CaB2O4:Mn2+、Ca2B2O5:Mn2+、CaB2O4:Pb2+、CaB2P2O9:Eu2+、Ca5B2SiO10:Eu3+、Ca0.5Ba0.5Al12O19:Ce3+，Mn2+、Ca2Ba3(PO4)3Cl:Eu2+、CaBr2:Eu2+在SiO2中、CaCl2:Eu2+在SiO2中、CaCl2:Eu2+，Mn2+在SiO2中、CaF2:Ce3+、CaF2:Ce3+，Mn2+、CaF2:Ce3+，Tb3+、CaF2:Eu2+、CaF2:Mn2+、CaF2:U、CaGa2O4:Mn2+、CaGa4O7:Mn2+、CaGa2S4:Ce3+、CaGa2S4:Eu2+、CaGa2S4:Mn2+、CaGa2S4:Pb2+、CaGeO3:Mn2+、CaI2:Eu2+在SiO2中、CaI2:Eu2+，Mn2+在SiO2中、CaLaBO4:Eu3+、CaLaB3O7:Ce3+，Mn2+、Ca2La2BO6.5:Pb2+、Ca2MgSi2O7、Ca2MgSi2O7:Ce3+、CaMgSi2O6:Eu2+、Ca3MgSi2O8:Eu2+、Ca2MgSi2O7:Eu2+、CaMgSi2O6:Eu2+，Mn2+、Ca2MgSi2O7:Eu2+，Mn2+、CaMoO4、CaMoO4:Eu3+、CaO:Bi3+、CaO:Cd2+、CaO:Cu+、CaO:Eu3+、CaO:Eu3+、Na+、CaO:Mn2+、CaO:Pb2+、CaO:Sb3+、CaO:Sm3+、CaO:Tb3+、CaO:Tl、CaO:Zn2+、Ca2P2O7:Ce3+、-Ca3(PO4)2:Ce3+、-Ca3(PO4)2:Ce3+、Ca5(PO4)3Cl:Eu2+、Ca5(PO4)3Cl:Mn2+、Ca5(PO4)3Cl:Sb3+、Ca5(PO4)3Cl:Sn2+、-Ca3(PO4)2:Eu2+，Mn2+、Ca5(PO4)3F:Mn2+、Cas(PO4)3F:Sb3+、Cas(PO4)3F:Sn2+、-Ca3(PO4)2:Eu2+、-Ca3(PO4)2:Eu2+、Ca2P2O7:Eu2+、Ca2P2O7:Eu2+，Mn2+、CaP2O6:Mn2+、-Ca3(PO4)2:Pb2+、-Ca3(PO4)2:Sn2+、-Ca3(PO4)2:Sn2+、-Ca2P2O7:Sn，Mn、-Ca3(PO4)2:Tr、CaS:Bi3+、CaS:Bi3+，Na、CaS:Ce3+、CaS:Eu2+、CaS:Cu+，Na+、CaS:La3+、CaS:Mn2+、CaSO4:Bi、CaSO4:Ce3+、CaSO4:Ce3+，Mn2+、CaSO4:Eu2+、CaSO4:Eu2+，Mn2+、CaSO4:Pb2+、CaS:Pb2+、CaS:Pb2+，Cl、CaS:Pb2+，Mn2+、CaS:Pr3+，Pb2+，Cl、CaS:Sb3+、CaS:Sb3+，Na、CaS:Sm3+、CaS:Sn2+、CaS:Sn2+，F、CaS:Tb3+、CaS:Tb3+，Cl、CaS:Y3+、CaS:Yb2+、CaS:Yb2+，Cl、CaSiO3:Ce3+、Ca3SiO4Cl2:Eu2+、Ca3SiO4Cl2:Pb2+、CaSiO3:Eu2+、CaSiO3:Mn2+，Pb、CaSiO3:Pb2+、CaSiO3:Pb2+，Mn2+、CaSiO3:Ti4+、CaSr2(PO4)2:Bi3+、-(Ca，Sr)3(PO4)2:Sn2+Mn2+、CaTi0.9Al0.1O3:Bi3+、CaTiO3:Eu3+、CaTiO3:Pr3+、Ca5(VO4)3Cl、CaWO4、CaWO4:Pb2+、CaWO4:W、Ca3WO6:U、CaYAlO4:Eu3+、CaYBO4:Bi3+、CaYBO4:Eu3+、CaYB0.8O3.7:Eu3+、CaY2ZrO6:Eu3+、(Ca，Zn，Mg)3(PO4)2:Sn、CeF3、(Ce，Mg)BaAl11O18:Ce、(Ce，Mg)SrAl11O18:Ce、CeMgAl11O19:Ce:Tb、Cd2B6O11:Mn2+、CdS:Ag+，Cr、CdS:In、CdS:In、CdS:In，Te、CdS:Te、CdWO4、CsF、Csl、CsI:Na+、CsI:Tl、(ErCl3)0.25(BaCl2)0.75、GaN:Zn、Gd3Ga5O12:Cr3+、Gd3Ga5O12:Cr，Ce、GdNbO4:Bi3+、Gd2O2S:Eu3+、Gd2O2Pr3+、Gd2O2S:Pr，Ce，F、Gd2O2S:Tb3+、Gd2SiO5:Ce3+、KAI11O17:Tl+、KGa11O17:Mn2+、K2La2Ti3O10:Eu、KMgF3:Eu2+、KMgF3:Mn2+、K2SiF6:Mn4+、LaAl3B4O12:Eu3+、LaAlB2O6:Eu3+、LaAlO3:Eu3+、LaAlO3:Sm3+、LaAsO4:Eu3+、LaBr3:Ce3+、LaBO3:Eu3+、(La，Ce，Tb)PO4:Ce:Tb、LaCl3:Ce3+、La2O3:Bi3+、LaOBr:Tb3+、LaOBr:Tm3+、LaOCl:Bi3+、LaOCl:Eu3+、LaOF:Eu3+、La2O3:Eu3+、La2O3:Pr3+、La2O2S:Tb3+、LaPO4:Ce3+、LaPO4:Eu3+、LaSiO3Cl:Ce3+、LaSiO3Cl:Ce3+，Tb3+、LaVO4:Eu3+、La2W3O12:Eu3+、LiAlF4:Mn2+、LiAl5O8:Fe3+、LiAlO2:Fe3+、LiAlO2:Mn2+、LiAl5O8:Mn2+、Li2CaP2O7:Ce3+，Mn2+、LiCeBa4Si4O14:Mn2+、LiCeSrBa3Si4O14:Mn2+、LiInO2:Eu3+、LiInO2:Sm3+、LiLaO2:Eu3+、LuAlO3:Ce3+、(Lu，Gd)2Si05:Ce3+、Lu2SiO5:Ce3+、Lu2Si2O7:Ce3+、LuTaO4:Nb5+、Lu1-xYxAlO3:Ce3+、MgAl2O4:Mn2+、MgSrAl10O17:Ce、MgB2O4:Mn2+、MgBa2(PO4)2:Sn2+、MgBa2(PO4)2:U、MgBaP2O7:Eu2+、MgBaP2O7:Eu2+，Mn2+、MgBa3Si2O8:Eu2+、MgBa(SO4)2:Eu2+、Mg3Ca3(PO4)4:Eu2+、MgCaP2O7:Mn2+、Mg2Ca(SO4)3:Eu2+、Mg2Ca(SO4)3:Eu2+，Mn2、MgCeAlnO19:Tb3+、Mg4(F)GeO6:Mn2+、Mg4(F)(Ge，Sn)O6:Mn2+、MgF2:Mn2+、MgGa2O4:Mn2+、Mg8Ge2O11F2:Mn4+、MgS:Eu2+、MgSiO3:Mn2+、Mg2SiO4:Mn2+、Mg3SiO3F4:Ti4+、MgSO4:Eu2+、MgSO4:Pb2+、MgSrBa2Si2O7:Eu2+、MgSrP2O7:Eu2+、MgSr5(PO4)4:Sn2+、MgSr3Si2O8:Eu2+Mn2+、Mg2Sr(SO4)3:Eu2+、Mg2TiO4:Mn4+、MgWO4、MgYBO4:Eu3+、Na3Ce(PO4)2:Tb3+、NaI:Tl、Na1.23KO.42Eu0.12TiSi4O11:Eu3+、Na1.23K0.42Eu0.12TiSi5O13·xH2O:Eu3+、Na1.29K0.46Er0.08TiSi4O11:Eu3+、Na2Mg3Al2Si2O10:Tb、Na(Mg2-xMnx)LiSi4O10F2:Mn、NaYF4:Er3+、Yb3+、NaYO2:Eu3+、P46(70％)+P47(30％)、SrAl12O19:Ce3+、Mn2+、SrAl2O4:Eu2+、SrAl4O7:Eu3+、SrAl12O19:Eu2+、SrAl2S4:Eu2+、Sr2B5O9Cl:Eu2+、SrB4O7:Eu2+(F，Cl，Br)、SrB4O7:Pb2+、SrB4O7:Pb2+、Mn2+、SrB8O13:Sm2+、SrxBayClzAl2O4-z/2:Mn2+、Ce3+、SrBaSiO4:Eu2+、Sr(Cl，Br，I)2:Eu2+在SiO2中、SrCl2:Eu2+在SiO2中、Sr5Cl(PO4)3:Eu、SrwFxB4O6.5:Eu2+、SrwFxByOz:Eu2+，Sm2+、SrF2:Eu2+、SrGa12O19:Mn2+、SrGa2S4:Ce3+、SrGa2S4:Eu2+、SrGa2S4:Pb2+、SrIn2O4:Pr3+、Al3+、(Sr，Mg)3(PO4)2:Sn、SrMgSi2O6:Eu2+、Sr2MgSi2O7:Eu2+、Sr3MgSi2O8:Eu2+、SrMoO4:U、SrO·3B2O3:Eu2+，Cl、β-SrO·3B2O3:Pb2+、β-SrO·3B2O3:Pb2+，Mn2+、α-SrO·3B2O3:Sm2+、Sr6P5BO20:Eu、Sr5(PO4)3Cl:Eu2+、Sr5(PO4)3Cl:Eu2+，Pr3+、Sr5(PO4)3Cl:Mn2+、Sr5(PO4)3Cl:Sb3+、Sr2P2O7:Eu2+、β-Sr3(PO4)2:Eu2+、Sr5(PO4)3F:Mn2+、Sr5(PO4)3F:Sb3+、Sr5(PO4)3F:Sb3+，Mn2+、Sr5(PO4)3F:Sn2+、Sr2P2O7:Sn2+、β-Sr3(PO4)2:Sn2+、β-Sr3(PO4)2:Sn2+，Mn2+(Al)、SrS:Ce3+、SrS:Eu2+、SrS:Mn2+、SrS:Cu+，Na、SrSO4:Bi、SrSO4:Ce3+、SrSO4:Eu2+、SrSO4:Eu2+，Mn2+、Sr5Si4O10Cl6:Eu2+、Sr2SiO4:Eu2+、SrTiO3:Pr3+、SrTiO3:Pr3+，Al3+、Sr3WO6:U、SrY2O3:Eu3+、ThO2:Eu3+、ThO2:Pr3+、ThO2:Tb3+、YAl3B4O12:Bi3+、YAl3B4O12:Ce3+、YAl3B4O12:Ce3+，Mn、YAl3B4O12:Ce3+，Tb3+、YAl3B4O12:Eu3+、YAl3B4O12:Eu3+，Cr3+、YAl3B4O12:Th4+，Ce3+，Mn2+、YAlO3:Ce3+、Y3Al5O12:Ce3+、Y3Al5O12:Cr3+、YAlO3:Eu3+、Y3Al5O12:Eu3r、Y4Al2O9:Eu3+、Y3Al5O12:Mn4+、YAlO3:Sm3+、YAlO3:Tb3+、Y3Al5O12:Tb3+、YAsO4:Eu3+、YBO3:Ce3+、YBO3:Eu3+、YF3:Er3+，Yb3+、YF3:Mn2+、YF3:Mn2+，Th4+、YF3:Tm3+，Yb3+、(Y，Gd)BO3:Eu、(Y，Gd)BO3:Tb、(Y，Gd)2O3:Eu3+、Y1.34Gd0.60O3(Eu，Pr)、Y2O3:Bi3+、YOBr:Eu3+、Y2O3:Ce、Y2O3:Er3+、Y2O3:Eu3+(YOE)、Y2O3:Ce3+，Tb3+、YOCl:Ce3+、YOCl:Eu3+、YOF:Eu3+、YOF:Tb3+、Y2O3:Ho3+、Y2O2S:Eu3+、Y2O2S:Pr3+、Y2O2S:Tb3+、Y2O3:Tb3+、YPO4:Ce3+、YPO4:Ce3+，Tb3+、YPO4:Eu3+、YPO4:Mn2+，Th4+、YPO4:V5+、Y(P，V)O4:Eu、Y2SiO5:Ce3+、YTaO4、YTaO4:Nb5+、YVO4:Dy3+、YVO4:Eu3+、ZnAl2O4:Mn2+、ZnB2O4:Mn2+、ZnBa2S3:Mn2+、(Zn，Be)2SiO4:Mn2+、Zn0.4Cd0.6S:Ag、Zn0.6Cd0.4S:Ag、(Zn，Cd)S:Ag，Cl、(Zn，Cd)S:Cu、ZnF2:Mn2+、ZnGa2O4、ZnGa2O4:Mn2+、ZnGa2S4:Mn2+、Zn2GeO4:Mn2+、(Zn，Mg)F2:Mn2+、ZnMg2(PO4)2:Mn2+、(Zn，Mg)3(PO4)2:Mn2+、ZnO:Al3+，Ga3+、ZnO:Bi3+、ZnO:Ga3+、ZnO:Ga、ZnO-CdO:Ga、ZnO:S、ZnO:Se、ZnO:Zn、ZnS:Ag+，Cl-、ZnS:Ag，Cu，Cl、ZnS:Ag，Ni、ZnS:Au，In、ZnS-CdS(25-75)、ZnS-CdS(50-50)、ZnS-CdS(75-25)、ZnS-CdS:Ag，Br，Ni、ZnS-CdS:Ag+，Cl、ZnS-CdS:Cu，Br、ZnS-CdS:Cu，I、ZnS:Cl-、ZnS:Eu2+、ZnS:Cu、ZnS:Cu+，Al3+、ZnS:Cu+，Cl-、ZnS:Cu，Sn、ZnS:Eu2+、ZnS:Mn2+、ZnS:Mn，Cu、ZnS:Mn2+，Te2+、ZnS:P、ZnS:P3-，Cl-、ZnS:Pb2+、ZnS:Pb2+，Cl-、ZnS:Pb，Cu、Zn3(PO4)2:Mn2+、Zn2SiO4:Mn2+、Zn2SiO4:Mn2+，As5+、Zn2SiO4:Mn，Sb2O2、Zn2SiO4:Mn2+，P、Zn2SiO4:Ti4+、ZnS:Sn2+、ZnS:Sn，Ag、ZnS:Sn2+，Li+、ZnS:Te，Mn、ZnS-ZnTe:Mn2+、ZnSe:Cu+，Cl、ZnWO4。
下述实施例旨在例证本发明。但是，它们无论如何不应被视为限制。该组合物中可用的所有化合物或组分是已知和可购得的，或可通过已知方法合成。实施例中所示的温度始终以℃计。此外，当然地，在说明书和在实施例中，该复合物中各组分的添加量始终合计为100％。所给出的百分比数据应始终在给定背景下考量。但是，它们通常总是涉及所示分量或总量的重量。
实施例
实施例1：5克Sr5.94Eu0.06Si3O6N4的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.8112克SrC2O4(AlfaAesar，95％)、0.0689克Eu2O3(Treibacher，99.99％)和0.9159克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例2：5克Sr5.94Eu0.06Si3O5.88N4F0.24的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.6736克SrC2O4(AlfaAesar，95％)、0.0689克Eu2O3(Treibacher，99.99％)、0.0984克SrF2(Aldrich，99.998％)和0.9159克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例3：5克Sr5.94Eu0.06Si3O5.88N4Cl0.24的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.6168克SrC2O4(AlfaAesar，95％)、0.0683克Eu2O3(Treibacher，99.99％)、0.1231克SrCl2(Alfa Aesar，99.5％)和0.9081克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例4：5克Sr5.82Th0.06Eu0.06Si3O6N4的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.6444克SrC2O4(AlfaAesar，95％)、0.0686克Eu2O3(Treibacher，99.99％)、0.1030克ThO2(Merck，99％)和0.9119克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例5：5克Sr5.82Os0.06Eu0.06Si3O6N4的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.6658克SrC2O4(AlfaAesar，95％)、0.0688克Eu2O3(Treibacher，99.99％)、0.0869克OsO2(Alfa Aesar，Os 83％min)和0.9148克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例6：5克Sr5.82Ru0.06Eu0.06Si3O6N4的制备
在充有干燥N2的手套箱中在玛瑙研钵中将6.7129克SrC2O4(AlfaAesar，95％)、0.0693克Eu2O3(Treibacher，99.99％)、0.0524克RuO2(Alfa Aesar，99.9％)和0.9213克α-Si3N4(UBE，99％)充分相互合并。将由此获得的粗制物质混合物转移到Mo箔衬里的Al2O3皿中。将该混合物在N2/H2/NH3气氛下在1200-1600℃加热8小时。
实施例7：来自实施例1-6的无机发光材料的高压烧结
在每种情况下，将5克来自实施例1-6的化合物引入Mo坩锅，并转移到高压烧结炉中。在40-70巴的氮气压下和以5-10K/min的加热升温速率将样品在其中加热至1400-1600的温度。保持时间为6-10小时。
实施例8：来自实施例1-6的无机发光材料的热等静压制
在每种情况下，将5克来自实施例1-6的化合物引入等静热压机中。将该热压机置于真空下，并将温度升至200℃。然后将温度以5-10K/min升至1400-1600℃，同时将压力调节至50至200MPa的值。保持时间为6-10小时。
实施例9：来自实施例1-8的无机发光材料的洗涤
在每种情况下，将5克来自实施例1-8的化合物悬浮在100毫升1摩尔盐酸中，并在室温下搅拌3小时。然后抽吸滤除残留物，并用去离子水洗涤直至中性。然后将洗过的残留物悬浮在100毫升1摩尔KOH溶液中，并进一步搅拌30分钟。然后抽吸滤除残留物，并再用去离子水洗涤直至中性。
表1：Sr5.94Eu0.06Si3O6N4:Eu(作为参照)和本发明的共掺杂无机发光材料的光学性质
Figure BDA0000130070850000161
附图描述
下面参照许多实施例更详细解释本发明。附图显示下列：
图1：显示InGaN类型的COB(芯片直接贴装)封装件，其充当白光光源(LED)(1＝半导体芯片；2，3＝电接点；4＝转换无机发光材料；7＝板)。将无机发光材料分布在粘合剂透镜上，该粘合剂透镜同时代表次级光学元件并作为透镜影响发光特性。
图2：显示InGaN类型的COB(芯片直接贴装)封装件，其充当白光光源(LED)(1＝半导体芯片；2，3＝电接点；4＝转换无机发光材料；7＝板)。无机发光材料直接位于LED芯片上，分布在薄粘合剂层中。可以在其上设置由透明材料构成的次级光学元件。
图3：显示充当白光光源(LED)的Golden Dragon
Figure BDA0000130070850000162
封装件(1＝半导体芯片；2，3＝电接点；4＝在具有反射体的空腔内的转换无机发光材料)。该转换无机发光材料分散在粘合剂中，混合物填充空腔。
图4：显示SMD封装件(表面安装封装件)，其中1＝外壳；2，3＝电接点；4＝转换无机发光材料。该半导体芯片完全被本发明的无机发光材料覆盖。该SMD设计的优点在于，其具有小的设计并因此适合装入传统灯中。
图5：显示发光二极管的示意图，其中1＝半导体芯片；2，3＝电接点；4＝转换无机发光材料；5＝接合线，其中无机发光材料在粘合剂中以顶球形式施用。这种形式的无机发光材料/粘合剂层可以充当次级光学元件，并可以影响例如光传播。
图6：显示发光二极管的示意图，其中1＝半导体芯片；2，3＝电接点；4＝转换无机发光材料；5＝接合线，其中无机发光材料以分散在粘合剂中的薄层形式施用。可以容易地在该层上施用充当次级光学元件的另一组件，例如透镜。
图7：显示另一应用的实施例，其原则上从US-B 6,700,322中获知。本发明的无机发光材料在此与OLED一起使用。光源是有机发光二极管31，由实际有机薄膜30和透明基底32构成。薄膜30特别发射例如由PVK:PBD:香豆素(PVK，聚(N-乙烯基咔唑)的缩写；PBD，2-(4-联苯基)-5-(4-叔丁基苯基)-1，3，4-噁二唑的缩写)产生的初级蓝光。该发射被由本发明的无机发光材料的层33形成的覆盖层部分地转换成黄色的次级发射光，因此通过初级和次级发射光的混色在总体上实现白色发光。OLED基本由在两个电极之间的至少一层发光聚合物或所谓的小分子构成，这两个电极由本身已知的材料构成，例如ITO(氧化铟锡的缩写)作为阳极，和高反应性金属(例如Ba或Ca)作为阴极。也常常在电极之间使用多个层，它们充当空穴传输层或在小分子领域中，也充当电子传输层。所用的发光聚合物是例如聚芴或聚螺环材料。

Claims (23)

1.铕掺杂的6-3-6-4碱土金属硅氧氮化物类型的化合物，它还包含选自Th、Ru、Os、F和/或Cl的共掺杂剂。
2.根据权利要求1的化合物，其特征在于式I
(Ca，Sr，Ba)6-x(Si1-yMey)3(O1-zMa2z)6N4:Eux    (I)
其中
Me＝Th、Ru和/或Os
Ma＝F和/或Cl
x＜0.5
y＜1且
z＜0.1。
3.根据权利要求1和/或2的化合物，其特征在于x＝0.003至0.2，y＝0.0001至0.2且z＝0.0005至0.03。
4.根据权利要求1至3中的一项或多项的化合物，其特征在于x＝0.005至0.15和/或y＝0.001至0.02。
5.根据权利要求1至4的一项或多项的化合物，其可如下获得：通过固态扩散法将含氮化硅、铕和钙和/或锶和/或钡的原材料与至少一种含钍、锇、钌、氟和/或氯的共掺杂剂混合，然后热后处理。
6.制备根据权利要求1至5的一项或多项的化合物的方法，其具有下述工艺步骤：
a)通过混合至少4种选自含氮化硅、铕、钙、锶、钡、钍、钌、锇、氟和/或氯的材料的原材料，制备被含钍、钌、锇、氟和/或氯的材料共掺杂的铕掺杂的6-3-6-4碱土金属硅氧氮化物，
b)热后处理所述被钍、钌、锇、氟和/或氯共掺杂的化合物，
c)用HCl溶液和KOH溶液洗涤所述经过热后处理的化合物。
7.成形体，包含根据权利要求1至5的一项或多项的化合物，所述成形体的特征在于其具有粗糙表面，该表面载有纳米粒子和/或如下所述的粒子：该粒子包含具有或不具有选自铕、钍、钌、锇、氟和/或氯的掺杂剂的根据权利要求1至5的一项或多项的化合物，所述纳米粒子包含SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物。
8.成形体，包含根据权利要求1至5的一项或多项的化合物，所述成形体的特征在于其具有连续表面涂层，该连续表面涂层由SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物和/或不具有活化剂铕的根据权利要求1至5的一项或多项的化合物构成。
9.成形体，包含根据权利要求1至5的一项或多项的化合物，所述成形体的特征在于其具有多孔表面涂层，该多孔表面涂层由SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物和/或具有或不具有选自铕、钍、钌、锇、氟和/或氯的掺杂剂的根据权利要求1至5的一项或多项的化合物构成。
10.成形体，包含根据权利要求1至5的一项或多项的化合物，所述成形体的特征在于表面带有下述官能团：该官能团有利于与环境、优选由环氧或有机硅树脂构成的环境的化学键合或物理结合。
11.制造根据权利要求8至10的一项或多项的成形体的方法，该方法具有下述工艺步骤：
a)通过混合至少4种选自含氮化硅、铕、钙、锶、钡、钍、钌、锇、氟和/或氯的材料的原材料，制备被含钍、钌、锇、氟和/或氯的材料共掺杂的铕掺杂的6-3-6-4碱土金属硅氧氮化物，
b)热后处理所述被钍、钌、锇、氟和/或氯共掺杂的化合物，
c)用包含SiO2、TiO2、Al2O3、ZnO、ZrO2和/或Y2O3或其混合氧化物的纳米粒子、或用包含具有或不具有掺杂剂的根据权利要求1至5一项或多项的化合物的纳米粒子涂覆表面。
12.根据权利要求11的方法，其特征在于在工艺步骤b)后进行用HCl溶液和KOH溶液洗涤的步骤。
13.照明装置，具有至少一个初级光源，所述至少一个初级光源的最大发射在250纳米至530纳米、优选350纳米至500纳米范围内，其中该辐射被根据权利要求1至10的一项或多项的化合物和/或无机发光体部分地或完全地转换成较长波长的辐射。
14.根据权利要求13的照明装置，其特征在于所述光源是发光的氮化镓铝铟，特别具有式IniGajAlkN的氮化镓铝铟，其中0≤i，0≤j，0≤k，且i+j+k＝1。
15.根据权利要求13的照明装置，其特征在于所述光源是基于ZnO、TCO(透明导电氧化物)、ZnSe或SiC的发光装置。
16.根据权利要求13的照明装置，其特征在于所述光源是基于有机发光层的材料。
17.根据权利要求13的照明装置，其特征在于所述光源是等离子体或放电灯。
18.根据权利要求13至17的一项或多项的照明装置，其特征在于无机发光材料直接位于所述初级光源上和/或远离所述初级光源。
19.根据权利要求13至18的一项或多项的照明装置，其特征在于无机发光材料和初级光源之间的光耦合是通过光导布置实现的。
20.至少一种根据权利要求1至5的一项或多项的化合物的用途，用作无机发光材料。
21.至少一种根据权利要求1至5的一项或多项的化合物的用途，用作将发光二极管发出的蓝光或近紫外光部分地或完全地转换的转换无机发光材料。
22.至少一种根据权利要求1至5的一项或多项的化合物的用途，用作根据按需选色概念将初级辐射转换成特定色点的转换无机发光材料。
23.根据权利要求7至10的一项或多项的成形体的用途，用作无机发光体。
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