CN101569021A - 用于发光器件的多颗粒发光陶瓷 - Google Patents
用于发光器件的多颗粒发光陶瓷 Download PDFInfo
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- CN101569021A CN101569021A CN200780047857.7A CN200780047857A CN101569021A CN 101569021 A CN101569021 A CN 101569021A CN 200780047857 A CN200780047857 A CN 200780047857A CN 101569021 A CN101569021 A CN 101569021A
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- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
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Abstract
陶瓷体设置在光源所发光的路径中。光源可以包括半导体结构,其包括设置在n型区和p型区之间的发光区。陶瓷体包括多个第一颗粒,其配置成吸收光源发射的光并发射不同波长的光,以及多个第二颗粒。例如,第一颗粒可以是发光材料的颗粒,以及第二颗粒可以是发光材料主基质的颗粒,而无激活掺杂物。
Description
本发明涉及一种波长转换型半导体发光器件。
包括发光二极管(LEDs)、谐振腔发光二极管(RCLEDs)、垂直腔激光二极管(VCSELs)以及边发光激光器的半导体发光器件是目前可用的最有效光源之一。在制造能够在整个可见光谱上工作的高亮度发光器件中,目前所感兴趣的材料系统包括:III-V族半导体,特别是镓,铝,铟和氮的二元、三元及四元合金,也被称为III族氮化物材料。典型地,III族氮化物发光器件由通过金属有机化学气相沉积(MOCVD),分子束外延(MBE)或者其他外延技术在蓝宝石、碳化硅、III族氮化物或其他适合的衬底上外延生长的不同成分和掺杂物浓度的半导体层的叠层来构成。叠层通常包括:在衬底之上形成的掺杂有比如硅的一个或多个n型层、在n型层或多个n型层之上形成的激活区域内的一个或多个发光层、以及在激活区域之上形成的掺杂有比如镁的一个或多个p型层。电接触在n型和p型区上形成。
由于目前商业上可用的III族氮化物器件发射的光通常在可见光谱的较短波长端,因此III族氮化物器件产生的光可以很容易地转换,以生成具有较长波长的光。现有技术中众所周知的是,使用称为发光/荧光的工艺可以将具有第一峰值波长的光(一次光)转换成具有较长峰值波长的光(二次光)。荧光工艺包含通过波长转换材料(例如,磷光体)来吸收一次光,以及激发发射二次光的磷光体材料的发光中心。二次光的峰值波长将取决于磷光体材料。可以选择磷光体材料的类型,以产生具有特定峰值波长的二次光。
图1示出了在美国专利6,351,069中描述的现有技术的磷光体转换型LED 10。LED 10包含在激活时产生蓝色一次光的III族氮化物晶圆(die)12。III族氮化物晶圆12位于反射器杯引线框架14上,并且电耦合至引线16和18。引线16和18将电能传导到III族氮化物晶圆12。III族氮化物晶圆12由包含波长转换材料22的层20(常常是透明树脂)覆盖。用来形成层20的波长转换材料的类型可以根据将由荧光材料22产生的二次光的期望光谱分布来进行改变。III族氮化物晶圆12和荧光层20由透镜24封装。透镜24典型地由透明的环氧或硅树脂制成。
在工作中,电能供给III族氮化物晶圆12,以激活晶圆。晶圆12激活时发射远离晶圆顶面的一次光。一部分所发射的一次光由层20中的波长转换材料22吸收。然后,波长转换材料22发射二次光(即,具有较长峰值波长的转换光)来响应对一次光的吸收。剩余的未吸收部分的所发射一次光与二次光一起传输通过波长转换层。透镜24将按照由箭头26表示的一般通常方向引导未吸收的一次光和二次光,作为输出光。因此,输出光是一种复合光,其由晶圆12发射的一次光和波长转换层20发射的二次光组成。波长转换材料也可以配置成使得极少的或者没有一次光出射器件,如在发射UV一次光的晶圆与发射可见二次光的一种或多种波长转换材料相结合的情况下。
由于III族氮化物LED在较高的功率和较高的温度下工作,所以用在层20中的有机密封剂的透明度趋于退化,这非预期地降低了器件的光提取效率并且潜在地改变了从器件发射的光的外观。
已经提出了波长转换材料的几个可替换的配置,例如,如美国专利6,630,691中所述的在单晶体发光衬底上LED器件的生长,如美国专利6,696,703中所述的薄膜磷光体层,以及如美国专利6,576,488中所述的通过电泳沉积法或者通过美国专利6,650,044中所述的丝网印刷(stenciling)沉积的共形层。这些可替换配置的每一个都还有不足之处。包含粘合材料的磷光体层(例如,通过电泳沉积法或丝网印刷来沉积的磷光体)可能遭受以上参考图1所描述的粘合材料透明度的相同退化。薄膜或者共形磷光体层可能很难处理,因为磷光体层往往是易碎的。
包括粘合剂材料以及易碎磷光体层的磷光体可替换方案是使用在陶瓷片内形成的波长转换材料,这在美国专利申请公开2005-0269582中更详细的描述,通过引用的方式并入于此。其中所述的发光陶瓷片通常是与半导体器件分离形成,然后贴附到完成后的半导体器件上或用作半导体器件的生长衬底的自支撑层。由于发光陶瓷通常除了陶瓷本身以外不需要任何粘合剂材料,并且可能比薄膜或者共形磷光体层更鲁棒性,所以发光陶瓷可以避免现有技术的磷光体层中的至少一些问题。
根据本发明的实施例,陶瓷体设置在光源的路径中。光源可以包含半导体结构,其包括设置在n型区和p型区之间的发光区。陶瓷体包含配置成吸收光源发射的光并且发射不同波长的光的多个第一颗粒以及多个第二颗粒。例如,第一颗粒可以是用掺杂物激活的发光材料,并且第二颗粒可以是不含激活掺杂物的主基质颗粒。这样的多颗粒发光陶瓷可以提供对发光陶瓷内发光颗粒数目和发光陶瓷的其他特性的改进控制。
图1是现有技术的磷光体转换型LED的横截面视图。
图2是设置在半导体发光器件上的透明发光陶瓷的横截面视图。
图3是设置在薄膜半导体发光器件上的多颗粒发光陶瓷的横截面视图;
图4是设置在倒装安装的薄膜半导体发光器件上的多颗粒发光陶瓷的横截面视图;
图5是封装的发光器件的分解视图。
发光陶瓷层可以通过将传统的粉末磷光体烧结(sinstering)成陶瓷片(slab)来制成。由于粉末磷光体原料通常具有均匀的成分和掺杂,所以因而得到的发光陶瓷通常是半透明或者透明的,并且贯穿陶瓷片均匀地掺杂有作为发光中心的激活掺杂剂(activating dopant)。均匀掺杂的发光陶瓷存在一个问题是:发光陶瓷的最小厚度受到可重复制造陶瓷的能力限制。许多磷光体具有优选的掺杂范围,其中磷光体有效吸收和发射光。在其他磷光体布置(如共形层)中,具有优选掺杂级的磷光体粉末沉积成获得期望量的发光中心(luminescentcenter)所需的任何厚度,其生成期望的磷光体转换量以及来自发光二极管的未转换光的泄漏量,从而导致期望的合成光特性。在发光陶瓷(luminescent ceramic)中,如果在工艺要求的最小厚度处的陶瓷中使用优选掺杂级的磷光体粉末导致太多的发光中心,以及因此太多的磷光体转换,那么工艺所要求的厚度可以迫使用比优先级更低的掺杂级。
例如,发射蓝光的发光二极管可以与黄色发光磷光体和红色发光磷光体结合,以获得看起来是白色的合成光。只需少量的红色发光磷光体;如果使用太多的红色发光磷光体,合成光将看起来太红。例如,对于给定的红色磷光体,在发光中心的优选掺杂级,可以在发光陶瓷层20μm的厚度内取得期望的红色发光。然而,由红色发光磷光体形成的发光陶瓷的最小可制造厚度通常是100μm。为了在发光陶瓷100μm厚度内得到期望的红色发光量,必须用具有较低、较小期望的掺杂级的磷光体粉末来形成发光陶瓷。
在图2中示出了透明发光陶瓷存在的第二个问题。透明发光陶瓷30与发光器件12连接。示出了从发光区31发射的两条光线33和34。由于光线33以比光线34相对于发光层表面法线更小的角度来发射,所以光线33“看见”较少发光陶瓷30内的磷光体,且更易于躲避发光陶瓷30,而没有进行磷光体转换。相反,光线34看见更多发光陶瓷30内的磷光体,且在避开发光陶瓷30前更易于进行磷光体转换。因此,假设发光区31发射蓝光并且发光陶瓷30内的磷光体发射黄光,从靠近器件中心发射的光看起来更蓝,而从器件边缘发射的光看起来更黄,这在更多带蓝色光的中心周围导致不希望的淡黄色“光晕”。
根据本发明的实施例,发光陶瓷由至少两类颗粒形成:掺杂有在期望级的激活剂(activator)的发光颗粒,以及任何适当材料的非掺杂颗粒(常常为发光材料晶体基质(crystalline host)的非掺杂颗粒)。在制备陶瓷过程中,掺杂物可以从掺杂发光颗粒扩散到发光材料晶体基质的非掺杂颗粒内,这导致了具有不同掺杂物浓度的非掺杂颗粒和发光颗粒的陶瓷。这种发光陶瓷此处称为多颗粒(mult-grain)发光陶瓷。在一些实施例中,发光颗粒具有在0.2μm和20μm之间的颗粒(grain)尺寸,更优选的在1μm和3μm之间或者5μm和15μm之间。发光材料晶体基质(host)的非掺杂颗粒可以是与发光颗粒相同的尺寸,虽然这不是必须的。多颗粒发光陶瓷内发光颗粒的体积百分比(volume percent)取决于应用,且可以在1%和30%之间,常常在5%和15%之间。可以选择掺杂发光颗粒对非掺杂颗粒的体积百分比,使得完成的多颗粒发光陶瓷具有期望数量的发光中心(luminescentcenter),以及因此具有期望量的磷光体转换。由于多颗粒发光陶瓷内的发光中心总量能够限制在一小部分颗粒上,所以没必要为了控制发光中心的总量而使用低掺杂磷光体。
具有不同基质晶格结构和激活剂离子的许多发光颗粒可以形成到多颗粒发光陶瓷层中。例如,具有通用分子式(Lu1-x-y-a-bYxGdy)3(Al1-z-uGazSiu)5O12-uNu:CeaPrb(其中,0≤x≤1,0≤y≤1,0<z≤0.1,0≤u≤0.2,0<a≤0.2并且0<b≤0.1)的铝石榴石型发光材料,例如,Lu3Al5O12:Ce3+以及Y3Al5O12:Ce3+,其在黄-绿色范围内发光,可以通过将掺杂发光颗粒与非掺杂Y3Al5O12或者Lu3Al5O12颗粒结合来形成多颗粒发光陶瓷。(Sr1-x-yBaxCay)2-zSi5-aAlaN8-aOa:Euz 2+(其中,0≤a<5,0<x≤1,0≤y≤1,并且0<z≤1),例如,Sr2Si5N8:Euz 2+,其在红色范围内发光,可以通过将掺杂发光颗粒与非掺杂Si2Si5N8颗粒结合来形成到颗粒发光陶瓷中。其他绿色,黄色和红色发光材料也可以适用于形成多颗粒发光陶瓷,包括(Sr1-a-bCabBac)SixNyOz:Eua 2+,其中,a=0.002-0.2,b=0.0-0.25,c=0.0-0.25,x=1.5-2.5,y=1.5-2.5,z=1.5-2.5,包括,例如,SrSi2N2O2:Eu2+;(Ca1-x-y-zSrxBayMgz)1-nAl1+a+bSi1-a-bN3-bOb:Mn,其中,0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1,0≤b≤1,0≤n≤1,a≤n,且M是从下以组中选择的金属:Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu或其混合物,包括,例如,Ca(AlSi)2N3:Ce,Eu;(Sr1-u-v-xMguCavBax)(Ga2-y-zAlyInzS4):Eu2+,包括,例如,SrGa2S4:Eu2+;(Sr1-xBax)2SiO4:Eu,其中,0<x≤1,包括,例如,BaSrSiO4:Eu;以及(Ca1-xSrx)S:Eu2+,其中,0<x≤1,包括,例如,CaS:Eu2+,以及SrS:Eu2+。可以选择掺杂发光颗粒对非掺杂颗粒的体积比例,使得完成的多颗粒发光陶瓷具有期望数量的发光中心(luminescencecenter),并且因此具有期望的发光转换量。由于在多颗粒发光陶瓷内发光中心的总量能够限制在一小部分颗粒上,所有没必要为了控制发光中心的总量而使用低掺杂颗粒。
在一些实施例中,多颗粒发光陶瓷包括多于一类的发光颗粒。例如,多颗粒发光陶瓷可以包括在以第一波长发射光的第一类型发光颗粒,例如,黄色或绿色,以及以第二波长发射光的第二类型发光颗粒,例如,红色。在一些实施例中,不同类型的发光颗粒具有相同的主基质(host matrix)但是不同的激活掺杂物。例如,CaAlSiN3颗粒可以掺杂有Ce,用于产生黄色光,以及掺杂有Eu,用于产生红色光。在一个实例中,发光陶瓷中体积百分比80%-99%的发光颗粒是Ca1-x-yMyAl1+a-b+xBbSi1-aN3-aOa:Cex,其中,M=(Mg,Sr,Ba),B=(B,Ga),0.001≤x≤0.02,0≤y≤1,0.0005≤a≤1,0≤b≤1,并且发光颗粒的体积百分比1%-20%为Ca1-x-yMyAl1+a-bBbSi1-aN3-aOa:Eux,其中,M=(Mg,Sr,Ba),B=(B,Ga),0.001≤x≤0.02,0≤y≤1,0.0005≤a≤1,0≤b≤1。尤其,发光陶瓷可以是98%的Ca0.995Al1.055Si0,945N2.95O0.05:Ce0.005及2%的Ca0.998Al1.05Si0,95N2.95O0.05:Eu0.002。另一个实例中,发光陶瓷中体积百分比25%-75%的发光颗粒是(Lu1-x-y-a-bYxGdy)3(Al1-z-uGazSiu)5O12-uNu:CeaPrb,其中,0≤x≤1,0≤y≤1,0<z≤0.1,0≤u≤0.2,0<a≤0.2并且0<b≤0.1,例如,Lu2.985Al5O12:Ce0.15(u=0),其在490和580nm之间的波长范围内发射绿色到黄色光,体积百分比25-75%的发光颗粒是(Lu1-x-y-a-bYxGdy)3(Al1-z-uGazSiu)5O12-uNu:CeaPrb,其中,0≤x≤1,0≤y≤1,0<z≤0.1,0≤u≤0.2,0<a≤0.2并且0<b≤0.1,例如Y2.97Al4.9Si0.1O11.9N0.1:Ce0.03,其在560和640nm之间的波长范围内发射黄色到红色光。
多颗粒发光陶瓷可以通过加热掺杂粉末发光材料以及非掺杂基质材料或者其他适当材料直到粉末颗粒的表面在颗粒的接触点处开始形成强粘合(bond)或者“颈部(neck)”来形成。烧结发生的温度和压力可以取决于所使用的发光材料。例如,具有高掺杂物扩散率的材料可以以比具有较低掺杂物扩散率的材料更低的温度且更高的压力来烧结。在烧结过程中,部分连接的颗粒形成坚硬的结块(agglomerate),该结块进一步地通过颈部进一步生长来减少它的孔隙度。颗粒边界形成并且发生移动,使得一些颗粒的生长以其他颗粒为代价。当孔管道被连接(开口孔)时该烧结阶段继续直到孔隔离(闭口孔)。在烧结(sintering)的最后阶段,孔变得闭合并且沿着颗粒边界缓慢消除直到达到完全密实化。在烧结后,如前所述,多颗粒发光陶瓷可以具有掺杂材料区和非掺杂材料区。掺杂材料区典型地不具有恒定的掺杂物浓度。相反地,这些区通常包括在中心的高掺杂物浓度区域。掺杂区内掺杂物浓度从高掺杂物浓度中心向在其中掺杂区与周围未掺杂材料接触的边缘下降。根据前体(precursor)发光材料颗粒的尺寸,掺杂材料区可以具有100μm一样大的直径。
在(Lu1-x-y-a-bYxGdy)3(Al1-z-uGazSiu)5O12-uNu:CeaPrb(其中,0≤x≤1,0≤y≤1,0<z≤0.1,0≤u≤0.2,0<a≤0.2并且0<b≤0.1,例如Y3Al5O12:Ce3+)的多颗粒发光陶瓷的情况下,陶瓷可以通过将最终Y3Al5O12和Y3Al5O12:Ce3+材料的组成物的粉末二元氧化物进行混合来形成。组成物包括Al2O3,Y2O3,Gd2O3以及CeO2。混合物利用粘合剂来稳定,从而形成具有微粒尺寸(例如,直径在10和400μm之间)的粒状物。如以下几个实例中所述,微粒烧结到包含由非掺杂Y3Al5O12围绕的掺杂Y3Al5O12:Ce3+颗粒的陶瓷内。直径200μm且密度大约为1g/cm3的微粒可以在烧结后形成直径大约40-50μm的陶瓷区。在烧结过程中由微粒形成的磷光体颗粒可以具有在2μm和20μm之间的直径,因此组成的混合物中一个微粒通常形成多个颗粒。在下面实例中更详细描述的可替代方法中,Y3Al5O12:Ce3+多颗粒发光陶瓷可以通过将已经形成的Y3Al5O12:Ce3+晶体颗粒与最终Y3Al5O12材料组成物的混和粉末二元氧化物的非掺杂微粒一起烧结来形成。
如图2所示的黄色光晕问题可以通过增加来自发光陶瓷的散射来减少或消除。散射中心可以由陶瓷制造过程中合并气泡(airpocket)形成,例如通过减少形成发光陶瓷时的温度。
如果陶瓷是全致密的并且无第二物相(phase)的,一些发光材料(特别是Y3Al5O12)是透明的陶瓷型。Ce3+掺杂物可以作为烧结助剂,并且掺杂的Y3Al5O12:Ce3+颗粒可以不散射入射光。因此,在透明的非掺杂Y3Al5O12基质中均匀散布的掺杂Y3Al5O12:Ce3+颗粒可以作为非散射部分。在这样的多颗粒发光陶瓷中,当减少或者消除均匀掺杂的发光陶瓷中的黄色光晕问题时,可以如前所述地选择掺杂的Y3Al5O12:Ce3+颗粒数量来控制散射,从而使光提取最大化。
在一些发光材料(特别是,Y3Al5O12)中,可以调整材料的化学定量关系(stoichiometry)来产生引起散射的材料物相(material phase)。例如,Y3Al5O12中过量的Al或Y可能导致第二材料物相,该第二材料物相可以由于石榴石(garnet)物相与第二物相之间的折射率对比而引起散射。在一个实施例中,体积百分比超过5-10%的氧化铝物相可以在不引入非期望的孔隙度的情况下引入期望的散射量。
不同于共形的磷光体层或设置在透明材料(如,树脂)中的磷光体层,在最终产品中,除了发光材料颗粒和非掺杂颗粒之外,多颗粒发光陶瓷通常具有很少或者没有任何粘合剂材料(如,有机树脂或环氧树脂),从而避免了上述的有机粘合剂材料退化的问题。
多颗粒发光陶瓷可与发光器的任何适当配置一起使用。图3和4示出了设置在生长衬底已从其上去除的两类半导体发光器件上的多颗粒发光陶瓷。
图3示出了设置在生长衬底已从其上去除的半导体发光器件上的多颗粒发光陶瓷。包括设置在n型区和p型区之间的发光区31的半导体结构12经由反射板触头39(常常为p型接触)和一个或多个粘合层41与底座42电气和物理连接。在其上生长半导体结构的生长衬底被去除,从而暴露出在其上设置有第二触头37(通常为n型接触)以及发光陶瓷36的半导体结构12的表面。
发光陶瓷36包括掺杂发光颗粒的区域38,掺杂发光颗粒散布在具有与发光材料相同的晶体结构的未掺杂颗粒的陶瓷基质(matrix)43内,或者适于形成具有掺杂发光颗粒的陶瓷的任何其他适当非掺杂基质内。例如,发光颗粒38可以是Y3Al5O12:Ce3+,其在黄绿色范围内发光,以及非掺杂基质43可以是Y3Al5O12。这样的Y3Al5O12发光陶瓷36可以与具有发射蓝光的激活区31的半导体结构12相结合。发光陶瓷36转换部分由激活区31发射的蓝光,使得由发光中心发射的未转换蓝光和黄光结合看起来是白色的。
图4示出了设置在倒装安装的薄膜半导体发光器件上的两个多颗粒发光陶瓷。在图4的器件内,包括设置在n型区和p型区之间的发光区31的传统半导体结构12在生长衬底上生长。蚀刻去除部分半导体结构,以显露部分所埋藏的导电类型(通常为n型区)。第一导电类型(通常为n型)的触头51在沟道内形成,以及触头(contact)52在第二导电类型材料(通常为p型)的剩余部分上形成。半导体结构12经由每个导电类型的底座连接器55和56与底座57连接。触头51和52可以通过介电质层53相互之间电隔离,所述介电质层53可以例如是空气或者硅的氧化物。去除生长衬底,从而如图4所示暴露出半导体结构12的顶面,在该顶面上设置有第一和第二多颗粒发光陶瓷层45和48。
第一多颗粒发光陶瓷层45包括散布在非掺杂材料46基质内的发光颗粒47。发光颗粒47可以是,例如,Y3Al5O12:Ce3+,其在黄-绿色范围内发光,以及非掺杂颗粒46可以是Y3Al5O12。第二多颗粒发光陶瓷层48包括设置在非掺杂材料50基质内的发光颗粒49。发光颗粒49可以是,例如,CaAlSiN3:Eu,其在红色范围内发光,以及非掺杂基质50可以是,CaAlSiN3。半导体结构12的发光区31可以发射蓝光,例如,使得来自发光区31的未转换光与来自多颗粒发光陶瓷层45和48的光结合,以形成白色合成光。
多颗粒发光陶瓷层可以通过例如,晶片键合,烧结,用有机粘接剂(如,环氧树脂或硅树脂)的薄层胶合,用高标号的无机粘接剂胶合,以及用溶胶凝胶玻璃胶合来贴附到图3和4所示的半导体结构上。
高标号粘接剂的实例包括:高标号光学玻璃,例如Schott玻璃SF59,Schott玻璃LaSF3,Schott玻璃LaSF N18,以及其混合物。这些玻璃可以从Duryea Pa的Schott Glass TechnologiesIncorporated获得。其他高标号粘接剂的实例包括:高标号的硫化玻璃,例如,(Ge,Sb,Ga)(S,Se)硫属玻璃,包括但不限于GaP,InGaP,GaAs和GaN的III-V族半导体,包括但不限于ZnS,ZnSe,ZnTe,CdS,CdSe和CdTe的II-VI族半导体,包括但不限于Si和Ge的IV族半导体和化合物,有机半导体,包括但不限于氧化钨,氧化钛,氧化镍,氧化锌,氧化铟锡以及氧化铬的金属氧化物,包括但不限于氟化镁和氟化钙的金属氟化物,包括但不限于Zn、In、Mg和Sn的金属,钇铝石榴石(YAG),磷化物,砷化物,锑化物,氮化物,高标号有机化合物,以及它们的混合物或合金。在美国专利7,053,419以及7,064,355中详细描述了用高标号无机粘接剂胶合,两者通过引用的方式并入于此。
在美国专利6,642,618中更详细的描述了用溶胶凝胶玻璃胶合,该文献通过引用的方式并入于此。在多颗粒发光陶瓷通过溶胶凝胶玻璃贴附到器件上的实施例中,为了使玻璃的系数与多颗粒发光陶瓷和多颗粒发光陶瓷所贴附的发光器件层的系数更接近的匹配,一种或多种材料(例如,钛,铈、铅、镓、铋、镉、锌、钡或铝的氧化物)可以包含在SiO2溶胶凝胶玻璃中,以提高玻璃的折射系数。
在一些实施例中,多颗粒发光陶瓷用作半导体发光器件的生长衬底,正如美国专利申请公开2005-0269582,美国专利申请序列号11/080,801,发明名称为“Wavelength-Converted Semiconductor LightEmitting Device”,以及美国申请序列号11/290,299,发明名称为“Luminescent Ceramic Element For A Light Emitting Device”中所详述的,它们中每一个通过引用的方式并入于此。
在一些实施例中,多于一种类型的发光颗粒可以包含在多颗粒发光陶瓷中。在一些实施例中,多颗粒发光陶瓷中的发光颗粒不是均匀散布的。例如,发光颗粒可以集中在最接近半导体结构表面的多颗粒发光陶瓷部分。随着距离半导体表面的距离增加,发光颗粒的浓度可能降低。发光颗粒的分级曲线图(grading profile)可以采取任何形式,其包括例如,线性的,阶梯式的,或者幂律曲线,并且可以包括多个恒定发光颗粒浓度的区域或者不包括这样的区域。此外,在一些实施例中,有利的是使分级的曲线图翻转,使得最接近半导体表面的区域具有随着距离器件表面的距离增加而增加的小发光颗粒浓度。
在一些实施例中,器件可以包括与由不同技术(例如,悬浮在粘合剂中并置于器件上,丝网印刷或者沉积为薄膜或者共形层)沉积的另一种发光材料结合的多颗粒发光陶瓷,这如以上背景部分所述。在一些实施例中,多颗粒发光陶瓷可以与不含发光材料的第二陶瓷层一起使用。
多颗粒发光陶瓷能够构造或者模制、研磨、机械加工、热压或者抛光成理想的形状,例如用于增加光提取。例如,多颗粒发光陶瓷可以成形为透镜,例如,半球状透镜或菲涅耳透镜,其粗糙化,或者构造具有光子晶体结构,例如,在陶瓷内形成的孔的周期性晶格。成形的陶瓷层与所贴附的表面相比较,可以更小,或者同样尺寸,或者更大。
虽然这里的实例指的是III族氮化物发光二极管,但是应当理解,本发明的实施例可以延伸到其他发光器件,其包括:例如III族磷化物和III族砷化物等的其他材料系统的器件,以及例如谐振腔LEDs、激光二极管和垂直腔表面激光发射器等的其他结构。
图5为封装的发光器件的分解视图,如美国专利6,274,924中详述的。散热金属块(slug)100放置到插入模制引线框架(leadframe)内。插入模制引线框架是,例如,在提供电路径的金属框架106周围模制的填充塑料材料105。金属块100可以包括可选的反射器杯102。可以是上述实施例中所述的任何一个器件的发光器件晶圆104直接或者经由热传导基座103间接安装到金属块100上。可以增加一个盖108,其可以是光学透镜。
多颗粒陶瓷通常通过准备非掺杂基质材料的粒状物,然后筛选出期望尺寸微粒的粒状物来形成。与非掺杂基质材料分离,准备掺杂发光材料的粒状物,然后对于期望尺寸的微粒进行筛选。非掺杂基质材料和掺杂发光材料的微粒混合,然后形成坯体。任何存在的粘合剂被烧掉,然后陶瓷烧结和机械加工成完工的样式。
多颗粒铈掺杂钇铝石榴石陶瓷的准备过程如下所述:
(a)准备非掺杂Y3Al5O12(YAG)基质前体材料:172.82gY2O3(d50=500nm,99.99%纯度)与127.18gAl2O3(d50=400nm,99.99%纯度)以及0.25g SiO2(硅溶胶AS-30)借助于在异丙醇内球磨进行混合。在混合后,聚乙烯醇缩丁醛(polyvinyl butyral)粘合剂(SekisuiS-LEC)与丙烯乙二醇(propylene glycol)被添加到浆液中,然后浆液通过蒸发进行干燥,以形成具有在100-300μm范围内的微粒尺寸的粒状物(前体I)。
(b)准备掺杂Ce(III)的YAG前体材料:10.000gAl2O3,2.1355gGd2O3(d50=400nm,99.99%纯度),11.9907gY2O3(d50=500nm,99.99%纯度),0.4040g CeO2(99.5%纯度)以及195.06mg水解四乙氧基硅烷混合并颗粒化如上所述形成用于(a)的粒状物。一部分粒状物经过筛选获得100-300μm微粒部分(前体II),另一部分粒状物经过筛选获得20-100μm微粒部分(前体III)。
(c)准备多颗粒陶瓷1:11.40g前体I与1.2725g前体II混合,直到获得统计混合物。混合后的粒状物单轴压入到圆盘内,并且在3500bar通过冷等压来进一步压紧。在空气中1000℃下将粘合剂烧完后,陶瓷在CO气氛中1675℃下烧结2小时。然后,烧结后的陶瓷经过研磨和抛光,以获得具有120μm厚度以及4.54g/cm3(相对密度为99.0%)质量密度的陶瓷晶片。
(d)准备多颗粒陶瓷2:11.40g前体I与1.2725g前体III混合,直到获得统计混合物。混合后的粒状物单轴压入到圆盘内,并且在3500bar通过冷等压进一步压紧。在空气中1000℃下将粘合剂烧完后,陶瓷在CO气氛中1675℃下烧结2小时。然后,烧结后的陶瓷经过研磨和抛光,以获得具有120μm厚度以及4.57g/cm3(相对密度为99.7%)质量密度的陶瓷晶片。
(e)准备多颗粒陶瓷3:11.40g前体物I与1.24g具有12μm平均粒子尺寸的Y2.94Al5O12:Ce0.06磷光体粉末混合,直到获得统计混合物。混合物单轴压入到圆盘内,并且在3500bar通过冷等压进一步压紧。在空气中1000℃下将粘合剂烧完后,陶瓷在H2/N2(5/95)气氛中1650℃下烧结2小时。然后,烧结后的陶瓷经过研磨和抛光,以获得具有120μm的陶瓷晶片。在抛光后,陶瓷晶片在空气中1350℃下退火4小时。
(f)准备均匀掺杂陶瓷4(比较性实例):13.5358gY2O3(d50=500nm,99.99%纯度)与10.000gAl2O3(d50=400nm,99.99%纯度),0.0404g CeO2(99.5%纯度)以及195.06mg水解四乙氧基硅烷(hydrolyzedtetraethoxysilane)借助于在异丙醇(isopropanol)内球磨进行混合。在混合后,聚乙烯醇缩丁醛粘合剂(Sekisui S-LEC)与丙烯乙二醇被添加到浆液中,然后浆液通过蒸发进行干燥,以形成具有在100-300μm范围内的微粒尺寸的粒状物。
在上述实例中所述的发光陶瓷中,由非掺杂材料围绕的掺杂发光材料区的存在由蓝色透射图像来确定,所述蓝色透射图像由在其中陶瓷是非掺杂的较亮区域围绕,其示出了在其中由于掺杂物浓度高而陶瓷发生吸收的较暗区域。陶瓷1的蓝色透射图像上较暗区域比陶瓷2的图像上较暗区域大,这表示在陶瓷2内的掺杂物分布更加均匀并且陶瓷2内的掺杂区域比陶瓷1内的更小,这很可能是由于用于陶瓷2的前体物(precursor)的更小微粒(granule)尺寸。
上述样品的发光特性如下所示:
样品 | 450nm处量子效率 | x | y |
陶瓷1 | 0.93 | 0.4072 | 0.5642 |
陶瓷2 | 0.94 | 0.4072 | 0.5643 |
陶瓷3 | 0.93 | 0.4257 | 0.5515 |
陶瓷4(比较性实例) | 0.95 | 0.4071 | 0.565 |
本发明已经进行了详细描述,本领域技术人员应当理解,给定本发明的公开内容,在不脱离这里所述本发明原理的范围内,可进行各种修改。因此,不意味着本发明的保护范围限制为所说明和描述的特定实施例。
Claims (19)
1.一种器件,其包括:
光源;以及
陶瓷体,设置在光源所发光的路径中,其中,该陶瓷体包括:
多个第一颗粒,配置成吸收由光源发射的第一光以及发射与所述第一光波长不同的第二光;以及
多个第二颗粒。
2.如权利要求1所述的器件,其中,所述光源包括半导体结构,其包括设置在n型区和p型区之间的发光区。
3.如权利要求2所述的器件,其中,所述陶瓷体配置成散射由所述发光区发射的光。
4.如权利要求2所述的器件,其中,所述第二颗粒对于第一光是透明的。
5.如权利要求2所述的器件,其中:
第一颗粒包括主基质和激活掺杂物;以及
第二颗粒包括主基质,但不含任何激活掺杂物。
6.如权利要求2所述的器件,其中,第一颗粒散布在陶瓷体中的多个区域上,其中,所述多个区域由所述第二颗粒分隔。
7.如权利要求6所述的器件,其中;
第一颗粒包括主基质和激活掺杂物;以及
在第一颗粒区域内,接近区域中心的第一颗粒比接近区域边缘的第一颗粒具有更高的激活掺杂物浓度。
8.如权利要求2所述的器件,其中,陶瓷体近一步包括多个第三颗粒,其配置成吸收第一光并发射与第一光和第二光波长不同的第三光。
9.如权利要求8所述的器件,其中:
第一颗粒包括主基质和第一激活掺杂物;
第二颗粒包括主基质,但不含任何激活掺杂物;以及
第三颗粒包括主基质和第二激活掺杂物。
10.如权利要求2所述的器件,其中,陶瓷体设置在半导体结构的表面上。
11.如权利要求2所述的器件,其中,第一光是蓝色并且第二光是黄色或绿色。
12.如权利要求2所述的器件,其中,第一颗粒是(Lu1-x-y-a-bYxGdy)3(Al1-z-uGazSiu)5O12-uNu:CeaPrb,其中0≤x≤1,0≤y≤1,0<z≤0.1,0≤u≤0.2,0<a≤0.2并且0<b≤0.1。
13.如权利要求2所述的器件,其中,第一光是蓝色并且第二光是红色。
14.如权利要求2所述的器件,其中,第一颗粒是(Ca1-x-y-zSrxBayMgz)1-nAl1+a+bSi1-a-bN3-bOb:Mn,其中,0≤x≤1,0≤y≤1,0≤z≤1,0≤a≤1,0≤b≤1,0≤n≤1,a≤n,并且M是从以下组中选择的金属:Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu或其混合物。
15.如权利要求2所述的器件,其中,第一颗粒是Ca(Al,Si)2N3:Ce,Eu。
16.如权利要求2所述的器件,其进一步包括波长转换材料,其设置在发光区发射的光的路径中,该波长转换材料配置成吸收第一光并且发射与第一光波长不同的第三光。
17.如权利要求16所述的器件,其中:
陶瓷体是第一陶瓷体;以及
波长转换材料包含在第二陶瓷体内。
18.如权利要求2所述的器件,其进一步包括:
第一和第二触头,其与n型区和p型区电连接;以及
盖,其设置在发光区之上。
19.如权利要求2所述的器件,其中,半导体结构包括多个III族氮化物半导体层。
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CN113056540A (zh) * | 2018-11-21 | 2021-06-29 | 欧司朗光电半导体有限公司 | 用于制造陶瓷转换器元件的方法、陶瓷转换器元件和光电组件 |
CN114555756A (zh) * | 2019-10-14 | 2022-05-27 | 赢创运营有限公司 | 包含镧系离子诸如Pr3+活化并任选地Gd3+共活化的硅酸盐的蓝光至UV上转换器及其用于表面消毒目的的应用 |
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JP2010514189A (ja) | 2010-04-30 |
US20110084293A1 (en) | 2011-04-14 |
EP2115790A2 (en) | 2009-11-11 |
US20080149956A1 (en) | 2008-06-26 |
WO2008078285A2 (en) | 2008-07-03 |
TW200901506A (en) | 2009-01-01 |
WO2008078285A3 (en) | 2008-09-12 |
US7902564B2 (en) | 2011-03-08 |
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