CN104220398B - 包含转化磷光体和具有负的热膨胀系数的材料的复合陶瓷 - Google Patents

包含转化磷光体和具有负的热膨胀系数的材料的复合陶瓷 Download PDF

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CN104220398B
CN104220398B CN201380017859.7A CN201380017859A CN104220398B CN 104220398 B CN104220398 B CN 104220398B CN 201380017859 A CN201380017859 A CN 201380017859A CN 104220398 B CN104220398 B CN 104220398B
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composite ceramics
expansion
conversion phosphor
light source
thermal coefficient
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CN104220398A (zh
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H·温克勒
T·朱斯特尔
J·普利瓦
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Merck Patent GmbH
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Merck Patent GmbH
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Abstract

本发明涉及包含转化磷光体和其它材料的复合陶瓷，其特征在于所述其它材料具有负的热膨胀系数，及其制备方法。此外，本发明还涉及本发明复合陶瓷优选在白光源中作为发射转化材料的用途，和光源、照明装置和显示器件。

Description

包含转化磷光体和具有负的热膨胀系数的材料的复合陶瓷
本发明涉及复合陶瓷及其制备方法。此外，本发明还涉及本发明复合陶瓷作为发射转化材料的用途，优选用作白光源中的发射转化材料，以及涉及光源、照明装置和显示器件。
现有技术公开了当它们用蓝光谱区或UV区中的光激发时显示出可见光发射的各种化合物。这些所谓的转化磷光体以粉末形式或者作为陶瓷用于光源中。熟知的转化磷光体为YAG:Ce(铈掺杂的钇铝石榴石)或LuAG:Ce(铈掺杂的镥铝石榴石)，由于它们在受蓝光激发时在黄色光谱区中发射，其使白光源成为可能。
如果转化磷光体以粉末的形式使用，则它们具有这一缺点：由光源发射的光的高反向散射，使得“包装收益(package gain)”(光源中的可能包装密度)以及因此的效率降低。由于包含转化磷光体的粉末中的散射系数取决于粒度，尝试通过纳米颗粒的合成而降低不想要的散射效应。然而，纳米颗粒形式的掺有稀土元素的转化磷光体的使用通常产生由于强表面缺陷导致的差发光性能，和由于小粒度导致的强聚集。尽管粉末形式使用的某些转化磷光体，例如YAG:Ce或LuAG:Ce显示出由于低散射效应而导致的良好效力，然而，此处的光量子产率仍能够改进。
陶瓷形式的转化磷光体例如适于将高能辐射如X射线和γ辐射转化成可见光。这类闪烁体陶瓷通常用稀土元素掺杂，例如由Lu2SiO5:Ce或Gd2O2S:Ce,Pr组成。然而，各种铈掺杂的陶瓷也可例如作为转化磷光体用于光源如LED(发光器件)(WO 2007/107915)中以实现某些色分布。陶瓷的使用通常产生比粉末情况下更高的光量子产率，但从蓝光至黄光的转化效率通常仍非常低，因为大量能量作为热损失。现有技术公开了用于LED中的掺杂的YAG陶瓷，特别是稀土元素掺杂的(WO 2008/012712)。特别地，各种掺杂的稀土元素石榴石化合物的发射(US 2010/0277673 A1)也作为背光用于LCD(液晶显示器)中。试图找到显示出高光量子产率和高效率的作为固态光源的转化体的发光陶瓷。由于大多数转化磷光体如YAG:Ce具有低导热率，作为热损失的能量不能容易地消散。该热应力导致陶瓷中的缺陷和裂纹形成，导致导热率甚至进一步下降，这又导致散射能力极大地提高。包含这类陶瓷作为发射转化材料的光源的效率在操作过程中显著降低。
需要除高光量子产率和高效率外，还促进光源的长寿命的转化磷光体。
因此，本发明的目的是提供用于光源的发射转化材料，其具有高效率和高光量子产率，并且能够生产具有长寿命的光源。
令人惊讶的是，已经发现，包含转化磷光体和具有负的热膨胀系数的其它材料的复合陶瓷提供所有这些所述优点。
“复合陶瓷”中的术语“复合”意欲考虑其微结构具有至少两种粒子类型的情况。第一粒子类型由转化磷光体形成，另一粒子类型由所述其它材料形成。这里所述其它材料意欲通过具有负的热膨胀系数而补偿转化磷光体材料的热膨胀。
在本申请中，术语“转化磷光体”意指吸收电磁谱的特定波长区，优选蓝光或UV区，特别是蓝光谱区中的辐射，并发射电磁谱的另一波长区的可见光的材料。
在本申请中，术语“发射转化材料”意指包含至少一种转化磷光体和任选其它材料，优选具有负的热膨胀系数的材料的材料。
转化磷光体优选为含Ce、含Eu和/或含Mn的材料。含Ce、含Eu和/或含Mn的材料优选为无机陶瓷材料，其中一些晶格格位特别优选被Ce3+、Eu2+、Eu3+和/或Mn2+或Mn4+离子占据。
含Ce、含Eu和/或含Mn的材料中的Ce、Eu和/或Mn的含量优选为0.01-5原子％，优选0.01-5原子％，更优选0.05-3原子％，基于含Ce、Eu和/或含Mn的材料中的在晶格格位代替Ce、Eu和/或Mn的原子的总数，例如基于YAG中的Y。
根据本发明优选的含Ce、含Eu和/或含Mn的材料为本身是本领域技术人员已知的适合作为发光二极管中的转化磷光体的那些。这些特别是硅酸盐，例如原硅酸盐、氧原硅酸盐(oxyorthosilicates)、二硅酸盐(disilicates)、sialone、硅氧氮化物(silicooxynitrides)、硅氮化物(siliconitrides)、铝酸盐、石榴石，以及其它三元和四元氧化物和氮化物。
特别优选含Ce、含Eu和/或含Mn的材料为含Ce、含Eu和/或含Mn的石榴石。根据本发明，石榴石优选意指具有以下形式的化学组成的成岩矿物：
E3G2(TO4)3
其中：
E为被8个氧阴离子围绕的二价或三价阳离子；
G为被6个氧阴离子围绕的二价、三价或四价阳离子，优选三价阳离子；且
T为被4个氧阴离子围绕的三价或四价阳离子。
根据本发明，石榴石优选为含Ce石榴石。根据本发明，这优选意指其中一些阳离子E已被Ce3+离子代替的石榴石。为了简便起见，含Ce石榴石在本申请中缩写为E3G2(TO4)3:Ce。
E3G2(TO4)3:Ce中的E优选选自Y、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu或其混合物。E3G2(TO4)3:Ce中的G和T优选相互独立地选自Al、Sc、Ga或其混合物。作为选择，G和T也可代表组合Mg/Si或Mg/Ge或其混合物，其中Mg和四价元素Si或Ge则以相同摩尔比例存在。
“热膨胀系数”意指描述物质在温度变化时尺寸变化方面的行为的特征量。造成该行为的效应是热膨胀。热膨胀取决于所用物质，即为物质特异性材料常数。它的度量单位为K-1。如果它是正的，则物质随着温度提高而膨胀。如果它是负的，则物质的尺寸随着温度提高而降低。由于在许多物质的情况下，热膨胀并非在整个温度范围内均匀地进行，热膨胀系数本身也是温度相关的，因此，其是对于特定参照温度或特定温度范围而言的。就本发明而言，热膨胀系数如下测定：由于热膨胀系数α高度取决于陶瓷的微结构，复合物的α值必须借助膨胀计通过实验测定。使用推杆膨胀计，根据DIN 51045标准测量复合陶瓷在热作用下的长度变化。也相应地测定存在于复合陶瓷中并根据本发明具有负的热膨胀系数的所述其它材料的热膨胀系数。
在本发明中，在20-200℃的温度变化的情况下，所述其它材料的负的热膨胀系数优选为1*10-6至12*10-6K-1，特别优选3*10-6至10*10-6。
本发明复合材料中具有负的热膨胀系数的所述其它材料优选为钨酸盐或钼酸盐或其混合氧化物。所述其它材料特别优选选自Al2W3O12、Y2W3O12、YAlW3O12、ZrW2O8、Al2Mo3O12、Y2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、Y2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、Y2MoW2O12、YAlMoW2O12或其混合物。
此处还优选将具有负的热膨胀系数的材料涂覆。合适的涂料为例如无机氧化物，例如氧化铝或氧化硅。
转化磷光体与所述其它材料的摩尔比优选为1:0.5-10:1，优选1:1-5:1。精确的摩尔比尤其取决于转化磷光体的热膨胀系数和所述其它材料的热膨胀系数如何相对于彼此作用。转化磷光体通常具有正热膨胀系数，因此随着温度提高而膨胀。为补偿该膨胀，所用所述其它材料为具有负的热膨胀系数的材料。所述其它材料的膨胀系数应为负的以达到转化磷光体的膨胀系数为正的程度。在该理想情况下，两种材料应以0.9:1-1:0.9的摩尔比使用。两种组分的摩尔比应彼此调整至转化磷光体的正膨胀系数大于所述其它材料的负膨胀系数的绝对值(modulus)的程度。换言之，复合陶瓷中两种组分的摩尔比应近似地与它们的热膨胀系数的绝对值之比成正比。
本发明还涉及制备复合陶瓷，优选本发明复合陶瓷的方法，所述方法包括以下步骤：
a)提供转化磷光体；
b)提供具有负的热膨胀系数的材料；
c)将步骤a)和b)中提供的两种组分混合以得到混合物；和
d)将混合物烧结。
根据本发明，步骤a)中提供的转化磷光体应以与对本发明复合陶瓷给出的完全相同的方式定义。这里转化磷光体优选以粉末形式提供。这里转化磷光体粉末的平均粒度优选为0.1-1μm。
步骤b)中提供的具有负的热膨胀系数的材料在这里应以与对复合陶瓷定义的所述其它材料完全相同的方式定义。它也优选以粉末形式使用且它的平均粒度优选为1-10μm。
在本发明方法的步骤c)中，将步骤a)和b)中提供的材料相互混合。粉末可以以干状态或者通过加入溶剂以悬浮液的形式相互混合。合适的溶剂为常规溶剂，例如乙醇或异丙醇。步骤c)中的混合优选在球磨机中进行。优选继续混合直至粉末的平均粒度为0.1-1μm。此处有帮助的是使用特定添加剂以对抗聚集体的形成。对于氧化物粉末，通常使用所谓的聚电解质，例如Darvan(Vanderbilt)、Dolapix(Zschimer&Schwertz)、KD1(Uniqema)。
在混合以后，可进一步加工所得粉末混合物。优选将粉末混合物在两个步骤中单轴且等静压压制成薄圆盘的形式，其中压制压力为100-300MPa。
根据本发明，步骤d)中的烧结在合适的温度下进行。如果步骤a)中的转化磷光体无涂层地提供，则烧结在低于具有负的热膨胀系数的材料的熔点的温度进行。已发现，如果烧结温度为具有负的热膨胀系数的材料的熔融温度的2/3-5/6，则实现良好结果。如果转化磷光体带有在加工条件下稳定的惰化涂层，则在本发明这一方案中，烧结也可熔融温度区域或者略高于该温度的温度进行。烧结优选在800-1600℃，更优选1000-1600℃的温度下进行。烧结优选在烧结炉中进行。烧结优选在保护气体气氛(N2或Ar)，作为选择，在还原气氛如合成气体(forming gas)下进行。
本发明还涉及制备复合陶瓷，优选本发明复合陶瓷的可选方法，所述方法包括以下步骤：
a')将转化磷光体用铝氧化物涂覆；
b')将步骤a')中所得的涂覆转化磷光体与含W或含Mo组分混合以得到混合物；和
c')将步骤b')中所得混合物在1000-1600℃，优选1400-1600℃的温度下烧结。
根据本发明，步骤a')中提供的转化磷光体应以对本发明复合陶瓷给出的完全相同的方式定义。转化磷光体在这里优选以粉末形式提供。转化磷光体粉末的平均粒度在这里优选为1-10μm。
所用铝氧化物可以为能够在步骤c')的烧结时与含W或含Mo化合物形成具有负的热膨胀系数的材料的任何氧化铝化合物。所用铝氧化物优选为Al2O3，特别优选作为γ-晶型。
含W或含Mo组分意指可通过烧结与铝氧化物反应形成具有负的热膨胀系数的材料的无机化合物。所用含W或含Mo组分优选为WO3或MoO3。具有负的热膨胀系数的材料在本文中应以与对复合陶瓷定义的所述其它材料完全相同的方式定义。
可选制备方法在步骤c')中得到其中转化磷光体粒子被具有负的热膨胀系数的材料围绕的复合陶瓷。
此外，本发明涉及本发明复合陶瓷或通过本发明方法制备的复合陶瓷作为发射转化材料的用途。
由于复合陶瓷中转化磷光体的存在，复合陶瓷还具有可将一种激发波长的光/辐射转化成另一波长的光的性能。因此，发射转化材料优选用于光源中。特别优选光源为LED(发光二极管)或者包含LED。此外，优选光源发射白光。
此外，本发明因此还涉及包含本发明陶瓷组分或通过本发明方法制备的复合陶瓷的光源。光源可具有其中来自初级光源的光通过转化磷光体转化的任何类型。然而，优选光源为LED或者包含LED。
在本发明LED的情况下，用于“磷光体转化LED”的术语pc-LED也是常用的。
初级光源可以为半导体芯片，基于ZnO、TCO(透明导电氧化物)、ZnSe或SiC的发光装置，基于有机发光层(OLED)的装置或者等离子体或放电源，优选半导体芯片。这类光源的可能形式也是本领域技术人员已知的。
如果初级光源为半导体芯片，则优选发光氮化铟铝镓(InAlGaN)，特别是式IniGajAlkN的那些，其中0≤i、0≤j、0≤k且i+j+k＝1。
光源中所用的复合陶瓷优选以均匀的薄且无孔片的形式直接施用于芯片形式的初级光源表面上。这具有这一优点：不发生转化磷光体的激发和发射的位置依赖性变化，导致用其装配的光源发射均匀且颜色恒定的光锥且具有高光输出。如果需要的话，陶瓷发射转化模制品形式的复合陶瓷可固定在芯片基底上，例如使用水玻璃溶液固定。
在一个优选实施方案中，陶瓷发射转化模制品形式的复合陶瓷具有在与半导体芯片相反的那侧上的结构化(例如金字塔形)表面。因此，可从陶瓷发射转化模制品中耦合出尽可能多的光。陶瓷发射转化模制品上的结构化表面优选例如在等静压压制的情况下通过具有结构化压板且因此将结构压印在表面中的压模制备。如果要制备尽可能最薄的陶瓷发射转化模制品或片，结构化表面是理想的。压制条件是本领域技术人员已知的(参见J.Kriegsmann，Technische keramische Werkstoffe[Industrial Ceramic Materials]，第4章，Deutscher Wirtschaftsdienst，1998)。
此外，本发明涉及包含至少一个本发明光源的照明装置，特别是用于显示器件的背光的光源。这类照明装置主要用于背光显示器件，特别是液晶显示器件(LC显示器)中。因此，本发明还涉及这类显示器件。
在本发明照明装置的同样优选变化方案中，发射转化材料(复合陶瓷)与初级光源(特别是半导体芯片)之间的光耦合优选通过光导装置进行。因此，可将初级光源安装在中心位置上并通过光导器件如光学纤维光学耦连于发射转化材料。这样，可实现适于光需求的灯，其仅由一种或多种可排列形成光幕(light screen)的不同转化磷光体和连接在初级光源上的光波导组成。这样，可将强初级光源置于对电组装有利的位置上并安装包含发射转化材料的灯，其在任意所需位置，不用进一步的电缆仅通过铺设光导而耦连于光波导。该概念也称为“远程概念”或“远程磷光体概念”。所述陶瓷磷光体可以以使得用于光激发的光源与本发明陶瓷模制品相距一段距离的方式安装在灯中。
以下实施例和图意欲说明本发明。然而，它们决不应被视为限定性的。可用于制备中的所有化合物或组分是已知或市售的，或者可通过已知方法合成。
附图说明
图1：图1显示对比材料YAG:Ce以及如实施例3a中所制备的由Y3Al5O12:Ce和Al2W3O12(3:1)组成的复合陶瓷的发射光谱。该光谱用Edinburgh Instruments FL900荧光分光计，使用Xe中压灯(Osram)作为激发源记录。
图2：图2显示对比材料YAG:Ce以及如实施例3b中所制备的由Y3Al5O12:Ce和YAlW3O12(3:1)组成的复合陶瓷的发射光谱。该光谱用Edinburgh Instruments FL900荧光分光计，使用Xe中压灯(Osram)作为激发源记录。
实施例：
实施例1：制备由Y3(Al1-aSia/2Mga/2)5O12:Ce和Al2W3O12组成的复合陶瓷
分别制备用于复合陶瓷的粉末组分，即铝酸钇和钨酸铝。所用原料为金属硝酸盐Y(NO3)3、Al(NO3)3、Ce(NO3)3用于铝酸钇，以及在氨中的Al(NO3)3和WO3用于钨酸铝，每种情况下将所述组分混合以得到均匀溶液。溶液中的金属阳离子通过加入络合剂(例如三胺(trisamine))而稳定，然后蒸发以得到固体残余物。干残余物的进一步加热导致引燃和海绵状前体结构的形成。将该前体在800-1000℃的温度下煅烧并转化成软聚集体形式的化合物Y3-xCexAl5O12和Al2W3O12。将Al2W3O12粉末通过湿化学方法用Al2O3涂覆，其中涂覆方法通过在混合反应器中将异丙醇铝在醇介质中水解而实现，其中加入氨作为催化剂。
在随后步骤中，将两种粉末混合，其中第二组分的体积比例为10-60体积％，并考虑最终陶瓷的膨胀测量而确定。
在两个步骤中以薄圆盘的形式单轴且等静压压制混合粉末，其中压制压力为100-300MPa。随后的烧结在空气中以多步骤方法实现，其中温度在1000-1600℃范围内。将烧结的陶瓷使用金刚石悬浮液研磨并通过picolaser切成与激发源匹配的尺寸。
实施例2：制备由Y3(Al1-aSia/2Mga/2)5O12:Ce和YAlW3O12(3:1)组成的复合陶瓷
通过陶瓷方法分别制备用于复合陶瓷的粉末组分，即镁-和硅掺杂的铝酸钇和钨酸钇铝。将细粉形式的金属氧化物混合、在800-1200℃的温度下煅烧并合成。将YAlW3O12粉末通过湿化学方法用Al2O3涂覆，其中涂覆方法通过在混合反应器中将异丙醇铝在醇介质中水解而实现，其中加入氨作为催化剂。将Y3(Al1-aSia/2Mga/2)5O12:Ce粉末精细研磨并与Al2O3涂覆的YAlW3O12粉末混合。将混合物通过两步单轴和等静压压制以薄圆盘的形式成型，其中压制压力为100-300MPa。随后的烧结在空气中以多步骤方法实现，其中温度为1000-1600℃。将烧结陶瓷使用金刚石悬浮液研磨并通过picolaser切成与激发源匹配的尺寸。
实施例3：由YAG:Ce和钨酸盐(实施例3a：Al2W3O12；实施例3b：AlYW3O12)制备复合陶瓷的具体实验程序
步骤1.YAG:Ce粉末通过自燃方法制备，其中将金属硝酸盐水溶液与三(羟甲基)氨基甲烷(TRIS：M＝121.14g/mol)混合，干燥，然后引燃。将黑色前体在1000℃下煅烧并在方法中转化成细颗粒无色粉末。
将8.4594g(0.02524mol)Y2O3溶于10ml的HNO3中并用H2O补充至约250ml。然后加入46.8913g(0.08421mol)的Al(NO3)3*9H2O和0.03256g(0.00005mol)的Ce(NO3)3*9 H2O并溶解。将TRIS加入均匀溶液中，并用H2O补充至约500ml。在加热以后，将H2O蒸发，并将残余物引燃。将前体在干燥箱中干燥12小时，在研钵中研磨，然后在炉中在1000℃下煅烧1小时。
步骤2.Al2W3O12粉末通过陶瓷方法制备，其中将细颗粒氧化物Al2O3和WO3混合并在两步骤中处理，首先在1000℃的温度下，然后在1100℃下处理(中间在研钵中研磨)。
将1.019g(0.01mol)的Al2O3(纳米级)与6.955g(0.003mol)的WO3用乙醇研磨(玛瑙研钵)。将悬浮液干燥并在研钵中均化，然后在1000℃下烧结12小时，在研钵中研磨并在空气中在1100℃下煅烧12小时。
步骤3.AlYW3O12粉末通过陶瓷方法由氧化物Al2O3、WO3和Y2O3制备，其中将所有氧化物粉末一起在研钵中研磨并在两步骤中在空气中在1000℃(6小时)和1100℃(12小时)下处理。
将0.5098g(0.005mol)的Al2O3(纳米级)与6.955g(0.003mol)的WO3和1.129g(0.005mol)的Y2O3在乙醇中研磨。将悬浮液干燥并在研钵中均化，然后在1000℃下烧结12小时，在研钵中研磨并在空气中在1100℃下煅烧12小时。
步骤4.借助Al2W3O12粉末或AlYW3O12粉末的混合物制备包含YAG:Ce和上述金属钨酸盐之一的复合陶瓷。为此，将Y2.997Ce0.003Al5O12粉末(90-99重量％)和每种情况下一种钨酸盐(1-10重量％)在乙醇中(在玛瑙研钵中)研磨，干燥，用几滴压制助剂聚乙烯醇润湿(在玛瑙研钵中)，然后单轴(约100MPa)和等静压(约300MPa)压制以得到片(厚度约2.5mm，直接约12mm)，在空气中干燥，最后在两个步骤中烧结，首先在1000℃下12小时，然后在1100℃下2小时。得到陶瓷模制品。
对比例A：制备不包含具有负的热膨胀系数的材料的复合陶瓷
为比较，由YAG:Ce和Al2O3制备复合材料，其中YAG:Ce通过自燃方法制备。所用第二组分为Al2O3纳米粉末(Degussa)。在粉末混合(有利地以1:1体积比)以后，以类似于上述实施例的方式制备陶瓷圆盘。
对比例B：
作为第二对比材料，制备包含YAG:Ce与未掺杂YAG的陶瓷。YAG:Ce粉末通过共沉淀方法制备，其中所用原料为金属硝酸盐Y(NO3)3、Al(NO3)3、Ce(NO3)3，且所用沉淀剂为NH4HCO3。将产生的沉淀物通过在800℃下煅烧和在1000℃下烧结而转化成YAG:Ce。在剧烈研磨以后，YAG:Ce变成细颗粒并适于与以类似方式制备的YAG混合。将混合物通过两步骤单轴且等静压压制成型成薄圆盘，其中压制压力为100-300MPa。随后的烧结在空气中以多步骤方法实现，其中温度为1000-1600℃。将烧结的陶瓷使用金刚石悬浮液研磨并通过picolaser切成与激发源匹配的尺寸。
实施例4：以实施例3a和3b以及对比例A和B的复合陶瓷制造LED
实施例4a：远程磷光体装置
将由本发明复合陶瓷组成的具有5mm直径和0.1mm厚度的片置于填充有液体硅氧烷OE 6550(Dow Corning)的SMD LED(芯片峰值波长450nm，操作电流强度350mA，空腔操作直径5.5mm)上，从而将圆形空腔密封。然后将组件储存在150℃的烘箱中1小时，期间硅氧烷硬化并强结合在LED和陶瓷片上。
实施例4b：芯片级转化装置
直接放置具有1×1mm正方形尺寸和0.1mm厚度的陶瓷磷光体片以借助一滴硅氧烷OE 6550(Dow Corning)安装在SMD倒装LED的1×1mmLED芯片(芯片峰值波长450nm，操作电流强度350mA)上。在硅氧烷在150℃下经1小时硬化以后，将LED的其余空腔用硅氧烷OE6550(Dow Corning)浇铸，并将整个组件在150℃下储存1小时以使硅氧烷硬化。
实施例5：发射强度
在图1和2中，根据本发明实施例3a和3b的复合陶瓷显示出与对比例A和B的YAG:Ce陶瓷相比较低的强度，预期这是由于YAG:Ce磷光体在复合陶瓷中是稀形式的。光谱用Edinburgh Instruments FL900荧光分光计记录，其中所用激发源为Xe中压灯(Osram)。
实施例6：寿命
根据实施例1、2和3的本发明复合陶瓷的优点可参考在发光二极管中的长期使用证明。本发明材料与来自现有技术的陶瓷相比显示出在使用中降低的裂化。因此，效率较慢下降，且陶瓷可以以良好效率更长时间使用。

Claims (13)

1.包含转化磷光体和其它材料的复合陶瓷，其特征在于所述其它材料具有负的热膨胀系数，其涂覆有无机氧化物，且其选自Al2W3O12、YAlW3O12、Al2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、YAlMoW2O12及其混合物，其中转化磷光体为含Ce石榴石。
2.根据权利要求1的复合陶瓷，其中含Ce石榴石具有式E3G2(TO4)3:Ce，其中E选自Y、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu或其混合物，且G和T各自相互独立地选自Al、Sc、Ga或其混合物，或者G和T一起代表组合Mg/Si或组合Mg/Ge，其中Mg和Si或Mg和Ge分别以相同摩尔比例存在。
3.根据权利要求1或2的复合陶瓷，其中在20-200℃范围内的温度变化的情况下，所述负的热膨胀系数在1*10-6-12*10-6K-1范围内。
4.根据权利要求1或2的复合陶瓷，其中转化磷光体与所述其它材料的摩尔比为1:0.5-10:1。
5.根据权利要求4的复合陶瓷，其中转化磷光体与所述其它材料的摩尔比为1:1-5:1。
6.根据权利要求1的复合陶瓷，其中无机氧化物为氧化铝或氧化硅。
7.制备根据权利要求1-6中任一项的复合陶瓷的方法，其包括以下步骤：
a)提供转化磷光体，该转化磷光体为含Ce石榴石；
b)提供具有负的热膨胀系数的材料，其涂覆有无机氧化物，且其选自Al2W3O12、YAlW3O12、Al2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、YAlMoW2O12及其混合物；
c)将步骤a)和b)中提供的两种组分混合以得到混合物；和
d)将混合物烧结。
8.根据权利要求7的方法，其特征在于烧结在具有负的热膨胀系数的材料的熔融温度的2/3-5/6范围内的温度进行。
9.根据权利要求7的方法，其中无机氧化物为氧化铝或氧化硅。
10.根据权利要求1-6中任一项或者根据权利要求7-9中任一项的方法制备的复合陶瓷作为发射转化材料的用途。
11.根据权利要求10的用途，其中发射转化材料用于光源中。
12.光源，其包含根据权利要求1-6中任一项或者根据权利要求7-9中任一项的方法制备的复合陶瓷和初级光源。
13.包含至少一个根据权利要求12的光源的照明装置。
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