CN102782086A - 具有发光材料的发光二极管装置 - Google Patents
具有发光材料的发光二极管装置 Download PDFInfo
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- CN102782086A CN102782086A CN201080057770XA CN201080057770A CN102782086A CN 102782086 A CN102782086 A CN 102782086A CN 201080057770X A CN201080057770X A CN 201080057770XA CN 201080057770 A CN201080057770 A CN 201080057770A CN 102782086 A CN102782086 A CN 102782086A
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- chemical formula
- garnet
- luminescent material
- emitting diode
- fluoride compound
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- Led Device Packages (AREA)
Abstract
本发明提供发光二极管装置,其包含布置在衬底(2,12)上的发光二极管(1,11)并且包含波长转换元件(3,13,14)。波长转换元件(3,13)含有作为发光材料的具有石榴石类型晶体结构的Mn4+激活氟化物化合物。Mn4+激活氟化物化合物优选地符合通式{A3}[B2-x-yMnxMgy](Li3)F12-dOd,在该化学式中A代表选自由Na+和K+组成的系列的至少一种元素并且B代表选自由Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和In3+组成的系列的至少一种元素,并且在该化学式中x范围在0.02和0.2之间,y范围在0.0(并且包含0.0)和0.4之间以及d范围在0(并且包含0)和1之间。所述化合物最优选地为{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd。本发明还提供所述材料以及用于其制备的方法。由于所描述的类型和结构的发光材料具有高稳定性以及对潮湿环境的低敏感性,它们可以有利地被用在LED装置的波长转换元件中。
Description
技术领域
本发明涉及一种发光二极管装置,其包含布置在衬底上的发光二极管以及含有Mn4+激活氟化物化合物的波长转换元件。本发明还涉及一种发光材料以及一种用于制备这种发光材料的方法。
背景技术
作为具有用于未来应用的有希望的照明属性的新半导体光源,发光二极管装置(简写为LED装置)是广为知晓的。这些LED装置应最终取代许多比如白炽灯的当前光源。它们在显示灯、警告灯、指示灯和装饰灯中是特别有用的。
发射的光的颜色取决于半导体材料的类型。由诸如GaN的III-V族合金制作的LED由于它们在电磁频谱的绿色到UV范围中产生发射的能力而众所周知。在过去十年,已经发展出将由这种‘蓝色’或‘(近)UV’LED发射的辐射(的部分)转换为更长波长辐射的各种方法。磷光体是用于这种目的的广泛使用的发光材料。这些磷光体是具有高化学纯度和精确控制组成的结晶无机化合物。它们包含使它们成为高效发光材料的少量的特别选择的元素(激活剂)。
除了彩色LED,所谓的‘白色光LED’的发展也是非常重要的。在这个领域中感兴趣的配置是基于转换由蓝色/UV LED生成的光的一部分以及将所述生成的光的该经转换部分与未经转换部分混合,因而获得白色或类似白色的光。在这个领域中,发射蓝色的GaInN LED是最受欢迎的。Ce3+激活钇铝石榴石(YAG-Ce)和Eu2+激活正硅酸盐(BOSE,OSE)是用于此目的的众所周知的磷光体。
同样地比如从专利公开WO2009/012301-A2已知在开篇段落中描述的LED装置。此文献很详尽地描述许多LED装置,其中Mn4+激活氟化物化合物被应用作为这些装置的波长转换元件中的发光材料。许多K2[XF6]:Mn4+(X=Nb或Ta)和K3[XF7]:Mn4+(X=Bi、Y、La或Gd)磷光体化合物的发射和激励频谱被示出。这些发光材料看上去在电磁频谱的红色频谱区域(600-660nm)中表现出窄频带或线发射。这是非常有吸引力的,因为在它们的波长转换元件中包含这种发光材料的LED装置能够产生‘暖白色’光。这是具有低于5000K的比较色温(CTT)的光。
发明内容
已知的LED装置具有若干缺点。要提到的第一缺点是关于在波长转换元件中使用的氟化物化合物,大多数氟化物化合物(或多或少)是有毒性的。第二缺点涉及这些氟化物化合物的处理,因为它们的对潮湿环境较高敏感性的原因,在实践中这种处理是不容易的。这些材料延长暴露于(潮湿)空气导致在材料表面上形成薄的水膜,从而引起(表面)分解。这种不利属性既影响纯材料(导致短的存放时间)又影响它们被应用于其中的LED装置(导致性能随时间降低)。
本发明旨在至少规避已知装置的上述缺陷。
此外,本发明目的是提供具有含有Mn4+激活氟化物化合物的波长转换元件的新LED装置,所述Mn4+激活氟化物化合物毒性较小并且对潮湿环境较不敏感。
另一目的是提供具有用于在LED装置中使用的有吸引力发光属性的新颖类别的Mn4+激活氟化物化合物,所述发光属性应优选地为装置提供产生暖白色光的可能性。
根据本发明,这些和其它目的是通过提供一种发光二极管装置来实现,该发光二极管装置包含:布置在衬底上的发光二极管,以及含有Mn4+激活氟化物化合物作为发光材料的波长转换元件,其中Mn4+激活氟化物化合物具有石榴石类型晶体结构。
本发明是基于发明人获得的下述洞察:具有石榴石类型晶体结构的Mn4+激活氟化物化合物对潮湿环境的敏感性显著低于在WO2009/012301中描述的已知化合物对潮湿环境的敏感性。所描述的化合物不具有石榴石类型晶体结构。发明人还认为,鉴于新发明的发光化合物的化学惰性性质,它们的毒性与所述专利公开中披露的类似的已知化合物相比是低的。发光化合物的这些属性使得它们在LED装置中的应用(在装置生产中以及在装置使用中)更有吸引力。
具有石榴石类型晶体结构的氟化合物可以用下述通式表示:{A3}[B2](C3)F12,其中F代表氟化物以及其中A、B和C代表金属或类似金属的元素的离子。这三种类型的离子分别位于石榴石晶体结构的十二面体、八面体和四面体位上。通常来说,元素A和C为一价的(+)而元素B为三价的(3+)。然而,特别是在八面体位上,利用电荷补偿的取代是有可能的,使得在这些位上也可以发现二价和四价金属离子的组合。
Mn4+和F-离子二者在石榴石结构中的存在被认为对于在电磁频谱的红色频谱区域中提供感兴趣的窄频带或线发射是至关重要的。这意味着大约600nm和大约660nm之间的区域。
根据本发明的LED装置的优选实施例特征在于Mn4+激活氟化物磷光体化合物符合化学式{A3}[B2-x-yMnxMgy](Li3)F12-dOd,在该化学式中A代表选自由Na+和K+组成的系列的至少一种元素并且B代表选自由Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和In3+组成的系列的至少一种元素,并且在该化学式中x范围在0.02和0.2之间,y范围在0.0(并且包含0.0)和0.4之间(即0.0≤y<0.4)以及d范围在0(并且包含0)和1之间(即0≤d<1)。
尽管上述发明洞察原则上可以利用具有石榴石类型晶体结构的所有可能Mn4+激活氟化物化合物,特别是Na+和/或K+在十二面体位上的化合物来实现,Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和/或In3+在八面体位上以及Li+在四面体位上是优选的。基于离子半径考虑结合石榴石的空间结构形成的要求,这些优选化合物被认为形成高度稳定的结晶化合物。
Mn4+离子被认为位于石榴石晶体结构的八面体位上。离子半径计算表明,由于电荷补偿原因,Mg2+优选地存在于相同的晶体位上。优选化合物中Mn4+的数量范围在基于总B3+离子含量的1和10mol%之间。更高数量的Mn4+离子似乎导致高的所谓的‘自淬灭’。如果小于1mol%的Mn4+存在于石榴石结构的八面体位上,则在LED装置中看不到或者几乎看不到任何激活效应。在这种材料中,在Mn4+上的吸收看上去是可忽略的。在5和8mol%之间的Mn4+数量是优选的,因为在这些条件中,自淬灭效应和期望的吸收水平之间达到最佳匹配。
在LED装置的优选实施例中,Mg2+也存在于石榴石结构中的八面体位上。Mn4+的存在导致石榴石结构中电荷不平衡,这可以通过Mg2+的存在来补偿。Mg2+的数量可以选择为比Mn4+的数量略微更宽。因此优选石榴石化合物中Mg2+的数量范围可以在基于总B3+离子含量的0和20mol%之间,其中该范围包括值0mol%。更高数量的Mg2+离子似乎导致例如阴离子空位的晶格缺陷的负面效应。在1和10mol%之间的Mg2+数量是优选的,因为在这些条件中电荷补偿和发光效率二者之间达到最佳匹配。
实践表明F-的数量可以略微偏离12个原子每晶胞单元的化学计量数量。这种偏离用因子d表示,该因子d范围在0(并且包含0)和1之间。强调的是,由于电荷补偿效应,少量的F-也可能被氧代替。如果八面体位的三价离子的少部分被比如Ti4+的更高价离子代替,则情况会是如此。在通常条件下,这将总是低于大约8mol%并且优选地低于4mol%,所有都是基于石榴石结构中F-的总数量。石榴石结构中以F-为代价的O2-的数量增加最通常导致磷光体化合物的发射到更深红色的偏移增加,这是不期望的。
根据本发明的LED装置的更优选实施例特征在于,Mn4+激活氟化物化合物的组成基本上符合化学式{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd。指数的范围为如前所述。根据实验数据得出下述结论,在所描述的更宽广类别的石榴石类型化合物中,这一系列的化合物是非常稳定的。这种稳定性使得这些化合物在LED装置中 (在装置的生产中以及在装置的使用中) 的应用非常有吸引力。
根据本发明的LED装置的另外感兴趣实施例具有下述特征:波长转换元件被形成为陶瓷小板(platelet)。此特征在将用于产生白色光的LED装置中特别有价值。原则上,利用或不利用附加填料材料,通过将所述材料压制成片(sheet),根据某一加热工序烧结这些片,以及比如通过(激光)雕刻和切断从所述烧结的片分割得到期望尺度的小板,可以形成该发光材料。由于以此方式可以制造精确厚度的陶瓷小板,由这种小板形成的波长转换元件在应将(近)UV或蓝色LED光转换为白色光的LED装置中是非常适合的。
根据本发明的LED装置的另一个感兴趣的实施例具有下述特征:波长转换元件被形成为树脂材料的成形本体,其中一定数量的Mn4+激活氟化物化合物被结合在该树脂材料的成形本体中。所述成形本体可以比如形成为透镜或形成为板(plate)。然而,在本发明范围内的其它结构也是有可能的。树脂中具有石榴石类型晶体结构的氟化物化合物的数量可以取决于经转换的光的期望数量、本体的体积等来选择。
本发明还提供一种含有Mn4+激活氟化物化合物的新发光材料。此材料特征在于该化合物具有石榴石类型晶体结构。此组成的材料毒性较小,对潮湿环境具有较低敏感性,并且在电磁频谱的近红色区域(600-660nm)中表现出感兴趣的发射频谱。
特别感兴趣的是符合化学式{A3}[B2-x-yMnxMgy](Li3)F12-dOd的材料,在该化学式中A代表至选自由Na+和K+组成的系列的至少一种元素并且B代表选自由Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和In3+组成的系列的至少一种元素,并且在该化学式中x范围在0.02和0.2之间,y范围在0.0(并且包含0)和0.4之间以及d范围在0(并且包含0)和1之间。此材料可以有利地应用在磷光体涂覆的LED装置中。对于组成基本上符合化学式{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd的发光材料,这尤为成立。由于上述原因,其中Mn4+的数量在1和10mol%之间而Mg2+的数量在1和20mol%之间的发光材料是优选的。然而最优选的是Mn4+含量在5和8.0mol%之间并且Mg2+含量在1和10mol%之间的组成。
本发明的另一个感兴趣的方面涉及一种用于制备如在先前段落中描述的发光材料的方法。该方法特征在于它包含下述步骤:
通过将K2MnF6溶解在含有至少20vol% HF的水中,制备第一水溶液,
按照与石榴石组成对应的摩尔比,制备构成预期石榴石的其余金属的盐的第二水溶液,
混合化学计量数量的两种溶液同时搅拌得到的混合物,以及
从混合物离析得到的石榴石组成。
技术人员将清楚,第一和第二水溶液制备的顺序是不重要的。然而非常优选的是,在混合这些溶液时,在搅拌如此形成的混合物期间将第二溶液添加到第一溶液。应注意,添加的第二溶液的数量被选择为使得在第一溶液中可获得与其它金属的数量成化学计量关系的Mn4+数量,所述其它金属的数量已经是化学计量数量。
优选的是,第一水溶液含有少量的NaHF2。添加此化合物防止部分的Mn4+被还原。在混合溶液以及搅拌混合物大约5分钟之后,得到的混浊溶液被滤出并且用2-丙醇清洗若干次。所获得的粉末随后在真空下在110℃被干燥。为了获得正确颗粒大小,粉末可以在研钵中机械地研磨。如此获得的粉末用X射线分析并且进一步用于根据本发明的LED装置的波长转换元件中。
强调的是,不仅发明的具有石榴石类型晶体结构的Mn4+激活氟化物化合物在它们纯形式中增强LED装置中光的期望性能,而且发明的化合物的复合材料和混合晶体被发现也能如此。复合物被定义为由两种或更多种在有限尺度上可区别的材料组成,例如核壳材料、复合陶瓷或涂覆的颗粒。混合晶体相比之下具有在原子级的构成要素的均匀分布。
本发明因此还涉及{A3}[B2-x-yMnxMgy](Li3)F12-dOd类型石榴石与氧化物石榴石A3B2(CO4)3的复合物,该氧化物石榴石包含但不限于YAG(Y3Al5O12)、Mg3Al2Si3O12或Ca3Al2Si3O12。这些复合物优选地为在{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd类型磷光体颗粒上的氧化物石榴石涂层,或者为核壳材料,其中{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd类型被氧化物石榴石壳围绕。涂层和壳之间的差异主要是相应材料的相对数量,其中涂层小于总材料的10% w/w,在核壳材料中壳可以为50% w/w或者甚至更多。这种涂层材料或核壳材料的优点为相对于潮湿的稳定性增加以及改变磷光体的折射率的选项。随着稳定性增加,还预期毒性将进一步减小。
对于{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd与氧化物石榴石的混合晶体,相同的优点被预期,该混合晶体的通式为(1-a){Na3}[Al2-x-yMnxMgy](Li3)F12-dOd * a A3B2(CO4)3。发现这种混合晶体的形成使能改变激励和发射波长最大值并且影响热淬灭属性。
附图说明
本发明将借助附图通过多个实施例来解释和说明,在附图中
图1示出根据本发明的LED装置的第一实施例,
图2示出根据本发明的LED装置的第二实施例,
图3示出根据本发明第一实施例的发射频谱的图形,
图4示出根据本发明第二实施例的发射频谱的图形,以及
图5示出具有石榴石类型晶体结构的发明的化合物{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12的样品的x射线图样的图形。
具体实施方式
本发明的第一实施例由图1示意性说明。此图示出LED装置的截面图,该LED装置包含连接到衬底(2)的半导体发光二极管(1),衬底(2)有时称为载具。二极管(1)和衬底(2)借助比如焊料或(金属填充)粘合剂的适当连接手段来连接。
二极管(1)为GaInN类型,在工作期间发射具有450nm波长的光。在本实施例中,所述光经由发射表面(4)离开LED(1)。形成为凸透镜形状本体的波长转换元件(3)邻近LED(1)放置。此透镜主要由耐高温硅树脂制成,具有石榴石类型晶体结构的Mn4+激活氟化物化合物的颗粒被结合到该硅树脂中。后一种化合物在透镜中充当发光材料。在本实施例中,所述硅树脂含有16vol% {Na3}[Al1.94Mn0.03Mg0.03](Li3)F12,具有大约10微米的颗粒大小。硅树脂的类型被选择使得其折射率几乎等于磷光体化合物的折射率,即1.34。通过使用(几乎)相同的折射率,LED光通过波长转换元件(3)的散射损耗是尽可能低的。
在可替换实施例中,发明的发光材料与具有匹配折射率的高度透明的氟塑料(例如3M DyneonTM THV2030G或THV220)形成化合物。得到的复合物可以通过已知技术被转印为合适形状。这些形状可以用作LED的功能光学部件或者简单地用作仅仅用于颜色转换的组件。
发光化合物的数量和波长转换元件(3)的尺度被选择为使得所有由LED(1)生成的蓝色光被转换为具有大约630nm的波长的红光。从此处描述的LED装置出射的光的典型发射频谱示于图3。在此图中,发射的强度I(任意单位)被测量为波长λ(nm)的函数。强调的是,为了调适出射的红色LED光的颜色,可以使用其它(已知)类型的附加磷光体。因而,本发明不限于在波长转换元件(3)中仅仅包含石榴石类型晶体结构的单个磷光体的LED装置,这种磷光体与其它(已知)磷光体的混合物也可以被应用。
图2描述设计成生成白色光的LED装置的本发明第二实施例的示意性截面图。此图示出传统的生成蓝色或(近)UV的发光二极管(11),该发光二极管使用焊料凸点(未示出)附连到衬底(12)。衬底(12)在表面上具有金属接触焊盘(未示出),LED(11)电连接到该金属接触焊盘。借助这些焊料焊盘,LED(11)可以连接到电源。在本示例中,LED(11)为AlInGaN类型并且发射具有大约420–470nm的峰值波长的蓝色光。理所当然,在本发明的范围内也可以使用具有其它峰值波长的其它半导体材料。
形成为陶瓷小板(13)和(14)的两个波长转换元件邻近LED(11)放置。小板(13,14)和LED(11)可以借助粘合剂(比如耐高温硅树脂材料或低熔点玻璃)或者借助机械夹紧而相互固定。在本实施例中使用粘合剂。为了保持不希望的吸收尽可能低,LED(11)和元件(13)之间以及元件(13)和元件(14)之间的粘合剂层被制成尽可能薄。
在本实施例中,元件(13)被成形为红色磷光体板,而元件(14)被成形为黄色磷光体板。两种板的表面尺度均与LED(11)的发光表面(15)的表面尺度几乎相同,不过它们可以略微更大而对(白色)出射光没有显著影响。如果LED(11)足够小,来自LED(11)的蓝色辐射的侧面发射可以被忽略。两种元件的厚度典型地在50-300微米的范围。小板的实际厚度当然取决于LED光的频谱功率分布以及小板中存在的磷光体化合物的类型。
在描述的实施例中,元件(13)的红色磷光体小板由具有石榴石类型晶体结构的纯Mn4+激活氟化物磷光体化合物制备而成。为此目的,磷光体化合物基本上符合具有石榴石类型晶体结构的化学式{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12。对于元件(14)的黄色磷光体小板,使用化合物Y3Al5O12:Ce(Ce掺杂的YAG)。
透镜结构形式的光学元件(16)布置在LED(11)以及两个波长转换元件(13,14)上,从而允许LED装置的发射图样的最优化。借助这种光学元件的恰当选择,可以获得朗伯(Lambertian)图样,但是也可以获得允许与光学波导结构良好耦合的图样。还可能设计光学元件(16)使得所生成的白色光的均匀照明分布被获得。这使得本LED装置非常适合于LCD类型应用中的背光照明。
图4示出根据图2的所描述的生成白色光的LED装置的典型发射频谱。在此图中,发射的强度I(任意单位)被测量为波长λ(nm)的函数。该频谱示出在从大约600nm到大约660nm的红色频谱区域中的发射,发射最大值在630nm附近。
如上所述的LED装置的波长转换元件(3,13)中使用的发光材料基本上符合化学式{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12并且具有石榴石类型晶体结构。从含有Mn4+作为掺杂剂的含水HF溶液在室温下作为共沉淀物获得所述材料。对于所述{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12的制备,化学计量数量的开始材料NaCl、LiCl、MgCl2*6H2O和AlCl3*6 H2O以及少量的NaHF2溶解于水并且随后添加到含有K2MnF6的48% HF水溶液。HF溶液中Mn4+的浓度为1mol.%。沉淀物被过滤,用2-丙醇反复清洗,并且随后在真空中在110°C干燥。所获得的产物在研钵中研磨。
图5示出使用Cu-Kα辐射,在沉淀物其中之一的代表性样品上测量的X射线粉末图样谱。在该图中,计数(N)被示为衍射角2西塔(2Theta)的函数。利用这种测量,这些样品可以被认定是具有石榴石类型晶体结构的{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12。在此样品中没有探测到另外的相。
强调的是,有可能使用各种其它开始材料,经由从水溶液的共沉淀来生产本发明的石榴石类型氟化物磷光体。特别是氢氧化物、硝酸盐、醇盐和碳酸盐为用于在共沉淀方法中使用的其它良好的开始材料。其它金属离子盐也可以用作开始材料,比如K+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和/或In3+的盐。当使用这些开始材料时,也可以制备其它组成的具有石榴石类型晶体结构的Mn4+激活氟化物磷光体化合物。
一定数量的如上所述制备的{Na3}[Al1.94Mn0.03Mg0.03](Li3)F12粉末经历进一步强烈的机械研磨,直至平均颗粒大小为大约5微米。随后该粉末被压制成板并且在200℃在炉内在2kbar的轴向压力被烧结。在冷却到室温之后,如此获得的陶瓷板利用激光器来刻划并且切断为单独的小板。这些小板被用作根据本发明的LED装置中的波长转换元件。
尽管本发明已经在图示和前述说明书中详细地说明和描述,这种说明和描述被认为是说明性或示例性的而不是限制性的;本发明不限于所公开的实施例。比如,有可能在下述实施例中操作本发明:其中其它(多个)(光学)元件存在于LED和波长转换元件之间,或者其中多于一个LED结合一个转换元件被操作。
本领域技术人员在实践所要求保护的发明时,通过研究图示、公开内容和所附权利要求,可以理解和达成对所公开实施例的其它变型。在权利要求中,措词"包含"不排除其它元件或步骤,并且不定冠词"一"("a"或"an")不排除多个。在互不相同的从属权利要求中陈述某些措施的纯粹事实并不表示不能有利地使用这些措施的组合。权利要求中的任何附图标记不应解读为限制范围。
Claims (10)
1. 一种发光二极管装置,包含:
布置在衬底(2,12)上的发光二极管(1,11),以及
含有Mn4+激活氟化物化合物作为发光材料的波长转换元件(3,13,14),其中Mn4+激活氟化物化合物具有石榴石类型晶体结构。
2. 根据权利要求1所述的发光二极管装置,其中Mn4+激活氟化物化合物符合化学式{A3}[B2-x-yMnxMgy](Li3)F12-dOd,在该化学式中A代表选自由Na+和K+组成的系列的至少一种元素并且B代表选自由Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和In3+组成的系列的至少一种元素,并且在该化学式中0.02<x<0.2,0.0≤y<0.4以及0≤d<1。
3. 根据权利要求2所述的发光二极管装置,其中Mn4+激活氟化物化合物材料的组成基本上符合化学式{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd。
4. 根据权利要求1、2或3所述的发光二极管装置,其中波长转换元件(3,13)被形成为陶瓷小板。
5. 根据权利要求1、2或3所述的发光二极管装置,其中波长转换元件(3,13)被形成为树脂材料的成形本体,一定数量的Mn4+激活氟化物化合物结合在树脂材料的成形本体中。
6. 一种含有Mn4+激活氟化物化合物的发光材料,其中该化合物具有石榴石类型晶体结构。
7. 根据权利要求6所述的发光材料,其中该组成符合化学式{A3}[B2-x-yMnxMgy](Li3)F12-dOd,在该化学式中A代表选自由Na+和K+组成的系列的至少一种元素并且B代表选自由Al3+、B3+、Sc3+、Fe3+、Cr3+、Ti4+和In3+组成的系列的至少一种元素,并且在该化学式中0.02<x<0.2,0.0≤y<0.4以及0≤d<1。
8. 根据权利要求7所述的发光材料,其中Mn4+激活氟化物化合物的组成基本上符合化学式{Na3}[Al2-x-yMnxMgy](Li3)F12-dOd。
9. 一种用于制备具有根据权利要求6、7或8的组成的发光材料的方法,其特征在于它包括下述步骤:
通过将K2MnF6溶解在含有至少20vol% HF的水中,制备第一水溶液,
按照与石榴石组成对应的摩尔比,制备构成预期石榴石的其余金属的盐的第二水溶液,
混合化学计量数量的两种溶液同时搅拌得到的混合物,以及
从混合物离析得到的石榴石组成。
10. 一种用于制备根据权利要求8的发光材料的方法,其中第一水溶液含有NaHF2。
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JP2013514655A (ja) | 2013-04-25 |
US20150372199A1 (en) | 2015-12-24 |
WO2011073871A2 (en) | 2011-06-23 |
TW201145603A (en) | 2011-12-16 |
RU2012130098A (ru) | 2014-01-27 |
CN102782086B (zh) | 2016-02-17 |
WO2011073871A3 (en) | 2011-09-01 |
JP5698762B2 (ja) | 2015-04-08 |
KR20120104377A (ko) | 2012-09-20 |
EP2513247A2 (en) | 2012-10-24 |
EP2513247B1 (en) | 2013-09-18 |
US20120305972A1 (en) | 2012-12-06 |
US9944849B2 (en) | 2018-04-17 |
US9133390B2 (en) | 2015-09-15 |
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