CN1170383A - 多色有机发光装置 - Google Patents

多色有机发光装置 Download PDF

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CN1170383A
CN1170383A CN95196807A CN95196807A CN1170383A CN 1170383 A CN1170383 A CN 1170383A CN 95196807 A CN95196807 A CN 95196807A CN 95196807 A CN95196807 A CN 95196807A CN 1170383 A CN1170383 A CN 1170383A
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metal
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琳达·S·萨波切克
史蒂芬·R·福里斯特
保罗·E·伯罗斯
丹尼斯·M·麦克卡蒂
马克·E·汤普森
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Abstract

一种多色有机发光装置(29)采用纵向堆积的由有机化合物构成的双异结构装置层。纵向堆积的结构是在由具有透明ITO涂层(35)的玻璃基(37)或类似的金属上形成的。纵向堆积的三个LED双异结构装置(20,21,22)结构每一个均采用适宜的有机材料构造,通过电池(30,31,32)施加向上的偏压,其中来自这些电池的电流进入阳极端(40,41,42)并最终流至阴极端(43)。结果,光从每一个LED(20,21,22)发出。进行堆积时应使具有最长波长的双异结构在堆积体的顶部。这构成了发射红光的装置在顶部,而发射蓝光具有最短波长的装置在底部,而发射绿光的装置在堆积体的中部。顶部金属层(26I)为透明的,随之为金属接点层(26M),这两层构成层(26)。每一层(26)与相邻的层(26)被有机EL层(20E,21E,22E)和空穴迁移层(20T和22H)分开。

Description

多色有机发光装置
                       发明领域
本发明涉及多色有机发光装置,具体而言,涉及用于平板电子显示器的发光装置。
                       背景技术
电子显示器是现代社会传送信息必不可少的手段,它可用在电视机、计算机终端及其它应用中。没有任何其它的介质可提供其速度、多功能性及相互作用。已知的显示技术包括等离子显示器、发光二极管(LED),薄层场致发光显示器等。
主要的非发射技术利用了一类有机分子的电子光学性质,即液晶(LC)或液晶显示器(LCD)。LCD操作相当可靠,但其对比度和分辨率较低,需要高能后照光。活性基质显示器采用多个晶体管,每一只能够激活单一的LC像素。无可置疑,与平板显示器相关的技术具有重要意义,同时该技术也在不断取得进展。可参见:“Flat Panel Displays”,ScientificAmerican,March,1993,90-97页,S.W.Depp和W.E.Honard。该文章指明,到1995年,仅平板显示器预期的市场将为40-50亿美元。任何有利的显示技术应能提供高分辨率的金色显示器,具有良好的发光性及有竞争力的价格。
彩色显色器以三种主颜色红(R)、绿(G)和蓝(B)运行。采用有机薄膜材料的表现红、绿、蓝发光装置(LED)已取得了显著的进步。这些薄膜材料是在真空条件下沉积的。此项技术在世界各地的许多地方得以发展,许多研究机构目前对其进行继续研究。
目前,最热门的高效有机发射结构被称之为双异结构LED,如图1A所示,且如现有技术所述。该结构与采用GaAs或InP的无机LED极为相似。
图1A的装置中,由铟锡氧化物(ITO)的薄层11深敷在玻璃载体层10上,层10与11形成基底8。此后,在ITO层11上沉积薄的(100-500埃)、有机的,主要为空穴迁移层(HTL)12。再在HTL层12上面再沉积薄(通常50埃-100埃)的发射层(EL)13。如果层太薄将使膜缺乏连续性,而膜太厚又会产生太大的内电阻,需高能量来操作。发射层(EL)13对100-500埃厚度的电子迁移层14(ETL)发出的电子及来自HTL层12的空穴提供重组位点。ETL材料的特点是其电子淌度大大高于空穴的淌度。在下述文献中公开了现有技术中ETL、EL和HTL材料的实例:“OrganicElectroluminescent MultiColor Image Display Device,”issued on March15,1994 to Tang et al.
通常,EL层13用高荧光染料进行掺杂以调整色彩,并增加LED的场致发光效率。通过沉积金属接点15、16及顶电极17完成图1A所示的装置。接点15、16通常由铟或Ti/Pt/Au构成。电极17通常为双层结构,它由直接与有机ETL层14接触的合金如Mg/Ag 17′及厚的高功能金属层17″构成,如Mg/Ag上的金(Au)或银(Ag)。厚金属17″为不透明的。当在顶电极17与接点15、16间施加适宜的偏压时,通过玻璃基底10产生光发射,图1A的LED装置的发光外量子效率为0.05-4%,其取决于发射的颜色及其结构。
另一种已知的有机发射结构被之为单杂结构,如图1B所示,且如现有技术所述。该结构与图1A所示的结构相比,其差异在于EL层13也用作ETL层,从而除去了图1A中的ETL层14。但是,为了有效地工作,图1B的装置必须采用具有优良电子迁移能力的EL层13,否则必须包括图1A装置中所示的单独的ETL层14。
目前,在绿LED中可观察到最高的效率。此外,可实现3-10伏的驱动电压。这些早期的非常有前途的显示技术使用了非晶形或高度多晶的有机层。无疑这些结构限制了穿过膜的载流子淌度,依次也限制了电流并增加了驱动电压。由多晶态引起的晶体的迁移和增长为此结构明显的不成功因素。电极接触退化也是明显的失败原因。
图1C显示的是另一种已知的LED装置,为单层(聚合物)LED的典型剖面图。如图所示,该装置包括玻璃载体层1,在其上涂敷有薄ITU层3,由它们构成基底在ITU层3上面形成例如一层旋转涂敷聚合物的有机层5。其提供了如前所述HTL、ETL和EL层各层的功能。在有机层5上形成金属电极层6。金属通常为Mg、Ca或其它常用的金属。
在USP5,294,870(Tang等)中公开了采用有机化合物用于发光像素的多色场致发光图像显示装置的实例。该专利给出了多种发光像素,其包含一种在发蓝光的显像素区域中用于发射蓝光的有机介质。荧光介质在横向上与发蓝光的亚像素区域隔开。荧光介质吸收有机介质发出的光,并在不同的亚像素区域发出红光和绿光。掺杂荧光染料的发射红或绿光的材料对来自蓝亚像素区域的蓝光的吸收效果弱于直接由红或绿LED形成的材料。其原因在于,效率为(对EL的量子效率)*(对荧光的量子效率)*(1-透光度)的乘积。因此,这种显示器的缺陷即为对于每一种发射的颜色需要相互隔开的不同的亚素区域。
                      发明简述
本发明的目的是提供一种采用几种类型的有机场致发光介质且每种发射截然不同颜色的多色有机发光装置。
本发明的另一个目的是提供在高清晰度多色显示器中有机介质以堆积的构型设置的装置,这样任何一种颜色均可从显示器的一般区域发射。
本发明的另一个目的是提供一种三色有机发光装置,其性能极为可靠,生产相当便宜。
本发明的再一个目的是提供这样的一种装置,该装置通过类似于用在场致发光二极管中的那些有机材料的生长而完成,从而得到高度可靠、紧凑、有效的有机LED,用于GB显示时仅需要较低的驱动电压。
在本发明的一种实施方案中,多色有机发光装置(LED)结构包括至少一个第一有机LED和第二有机LED,一个堆积在另一个上面,优选为三个,从而形成层压结构,每一LED间通过透明的导电层分隔开,使得每一个装置能接收独立的偏压而通过堆积体(stack)发光。
                  附图简述
图1A为根据现有技术典型的有机双杂结构发光装置(LED)的截面图。
图1B为根据现有技术典型的有机单杂结构发光装置(LED)的截面图。
图1C为根据现有技术已知的单层聚合物LED结构的截面图。
图2A、2B和2C分别为根据本发明的实施方案一体式三色像素采用结晶的有机发光装置(LED)的截面图。
图3-11显示了可用于包含在产生各种颜色的活性发光层中的各种有机化合物。
图12(A-E)说明本发明用于生产多色LED的荫罩(shadow masking)方法。
图13(A-F)说明本发明用于生产多色LED的干蚀方法。
图14A显示了本发明的一种实施方案中采用堆积构型的多色LED。
图14B显示了本发明另一个实施方案中气密封装(package)的截面图。
图14C为图14B沿14C-14C的截面图。
图15为采用本发明的LED装置及显示器驱动电路图的RGB显示器的方框图。
图16显示了本发明的另一个实施方案的LED装置,将堆积LED的数目扩大至N,其中N为整数1、2、3…N。
                     发明详述
图1A已作过描述,其为现有技术的双异结构有机发光装置。图1A装置的基本结构用于本发明的描述。
参看图2A,示出了本发明一种实施方案中高度紧密一体式RGB像素结构的示意截面,该结构是通过生长的或真空沉积的有机层完成的。在本发明的一个实施方案中,基于能在各种材料(包括金属和ITO)上生长有机材料,我们可以构造出表示为20、21和22的LED双异结构(DH)的堆积体。为了更好地说明,在图2A的实例中,LED20被看作堆积体的底部,LED21为其中部,LED22为其顶部。同样,图2A中堆积体是垂直定向的,但LED也可以反向定向。在其它实施方案中,单异结构(SH)LED(见图1B)或聚合物基LED装置(见图1C)的堆积体可视为DHLED可行的替代品,SH装置与DH装置同样可用于发光器。另外,包含真空沉积的和聚合发光材料组合的SH和DH装置被认为属于本发明的保护范围内。
每一个装置结构如装置20均由HTL层20H构成,它真空沉积或生长或沉积在ITO层35的表面上。顶层ETL层20T与HTL层20H间夹着EL层20E,如图2A装置的结构所示。ETL层20T及其它所述的ETL层由有机材料构成,如M(8-羟基喹啉酸盐)n(M=金属离子;n=2-4)。其它适宜的有机ETL材料的实例参见USP5,294,870(Tang等)。在ETL层20T的顶部形成薄的半透明低功函(优选<4eV)金属层26M,其厚度一般小于50埃。适宜的材料包括Mg、Mg/Ag和As。在金属层26M的顶部沉积另一种透明的薄的导电ITO层26I。(以下为方便起见,金属层26M和ITO层26I的双层结构被称之为ITO/金属层26)。每一双异结构装置如20、21和22均具有底部的HTL层,其形成于ITO26I或35的透明导电层之上。然后沉积EL层,再沉积另一层ETL。因其组成和最小厚度,HTL、ETL、ITO、金属和有机EL层均是透明的。各ETL层的厚度可为50-1000埃;各EL层的厚度可为50-200埃;各ETL层的厚度可为50-1000埃;各金属层26M的厚度可为50-1000埃;各ITO层26I和35的厚度可为1000-4000埃。从最佳情况考虑,每一层的厚度最好为上述范围的下限值。因此,每一LED20、21和22(除去ITO/金属层)的厚度优选接近200埃。
如果由SH LED装置而非DH LED装置用于提供LED20、21、22,如图1B中SH前面所描述的那样,ETL层和EL层由单一一层如层13提供。该层13通常为喹啉酸铝。如图2B所示,EL层20E、21E和22E分别同时提供EL层和ETL层的功能。但是,相对于图2B的SH LED堆积体,图2A中DH LED堆积体的优点是,DH LED堆积体允许较薄的总体结构,具有较高的效率。
在图2A和2B中,即使每一LED的中心之间有所偏移,但从每一装置发出的总的光束在LED20、21和22间基本上是重合的。当光束在同心构型中重合时,接近玻璃基底的发射或非发射装置相对远离玻璃基底的发射装置来说是透明的。但是,二极管20、21和22相互间无需偏离,它们之间可同心地相互堆积,而从每一装置发出的光融洽入整体上说相互间是同心重合的。以下在讨论装置构造方法时会描述图12E中所述的同心构型。需要注意的是,在偏心和同心构型的功能方面,它们不存在差异。每一个装置通过玻璃基底37以基本上全向的模式发光。通过控制穿越堆积体29中三种LED的电压可在任何时间对特定的像素提供理想的综合发射颜色和亮度。因此,每一LED如22、21和20均可分别同时用光束如R、G和B赋能,如经图2A和2B示意的透明层赋能且通过其可见。每一DH结构20、21和22根据所加适当的偏压而发射不同颜色的光。双异结构LED20发射蓝光。双异结构LED21发射绿光,而双异结构LED22发射红光。单独一种LED20、21和22或其不同的组合被活化可选择性地获得各像素所需要颜色的光,其部分取决于在每一LED20、21和22上电流的大小。
在图2A和2B的实例中,分别由电池32、31和30向LED20、21和22加向上的偏压。电流从每个电池32、31和30的正极端分别流入其相应的LED20、21和22的阳极40、42、42,通过各个装置的诸层后,从用作阴极的极端21、22和43流至每一电池32、31和30的负极。结果,光从每一LED20、21和22发出。LED装置20、21和22通过一装置(未示出),将电池32,31和30分别与其相应的LED选择性开启或关闭连接而选择性地赋能。
在本发明的实施方案中,如图2A和2B所示,用于LED22的顶ITO接点26I为透明的,使得所显示的三色装置可用于平视显示。但是,本发明的另一种实施方案中,顶接点26I是由厚金属形成的,如Mg/Ag、In、Ag或Au,以反射向上发射的光返回基底13,显著地增加装置的效率。同样,通过在玻璃基底37与ITO层35间形成多层不导电薄膜以提供抗反射表面可增加整个装置的效率。需要三套抗反射层,其中每一种在从各层发射的波长下形成抗反射涂层。
在另一个实施方案中,图2A的装置以相反或反转的方式构造,使发射的光从堆积体的顶部发出而非如前所述的从底部发出。参看图2,反转结构的实例是用厚的反射金属层38代替ITO层35。通过交换HTL层20H和ETL层20T,同时EL层20E仍夹在20H与20T中间,从而形成蓝LED20。进而,金属接点层26M沉积在ITO层26I的顶部。与反转的蓝IED20相同,堆积体的绿LED21和红LED22部分分别以反转层构造(HTL和EL层交换,随后反转金属和ITO层)。需要指出,在反转结构中,蓝装置20必须在顶部,而红装置22则必须在底部。同样,电池30、31和32的极性也要反转。结果,分别通过装置20、21和22的电流当施以向前的发光偏压时以与图2A实施方案相反的方向流动。
在该实例中,截面图中的装置为台阶形。透明的接点区(ITO)26I允许对堆积体中的每一像素分别施以偏压,进而,该材料也可用在加工步骤中的蚀刻步骤。分别对每一DH LED结构20、21和22施以偏压可将像素输出的波长调节至如CIE(Commission Intemationale de lEclairage/Intemational Commission of Illumination)颜色标准定义的可见光光谱的各种理想颜色。蓝发射LED20位于堆积体的底部,它是三种装置中最大的。蓝LED在底部是因其对红光和绿光均是透明的。最后,将要描述的是使用透明的ITO/金属层26的材料“分隔”(“Partitioning”)以便利生产该装置。与有机化合物相关的真空生长和构造方法是非常独特的方面,它使得有可能制造图2A、2B和2C所示的像素LED装置。图2A、2B和2C所示的纵向上分层可用最小可能的面积来构造三种颜色像素,因而使这些想法用于高清晰度显示器。
如图2A、2B和2C所示,每一个DH结构20、21和22可同时或分离地分别以箭头B、G和R所示发光。需要指出,基本上从每一LED20、21和22的整个横向部分发光,其中箭头R、G和B分别并不代表实际发光的宽度。这样,通过眼睛感觉不同的颜色和色调以综合R、G和B颜色的增减。这在采色视觉和显示比色素领域是公知的。在所示的偏移结构中,红、绿和蓝光束基本上重合。如果装置制得足够小,如约50微米或更小,可从堆积体生产任何一种颜色。但是,很显然一种颜色源于一种像素。
用在DH结构中的有机材料一种在另一种顶上生长,或在纵向上堆积,最长波长装置22为红光在顶部,而最短波长装置20为蓝光在底部。以这种方式,可减少在像素或装置中的光吸收。每一DH LED装置由ITO/金属层26(具体而言,半透明金属层26M和铟锡氧化物层26I)分开。ITO层26I可通过金属沉积进一步处理以对暴露的ITO表面上提供严格的接点区,如接点40、41、42和43。这些接点40、41、42和43是由铟、铂、金、银或合金如Ti/Pt/Au、Cr/Au或Mg/Ag构造的。使用常规的金属沉积或气相沉积对接点的沉积技术也是公知的。接点如40、41、42和43能分开堆积体中每一LED的偏压。有机LED材料与透明电极26I间的重要的化学差异使电极起蚀刻停止层作用。这使得在装置加工期间对每一像素进行有选择的蚀刻和暴露。
每一LED20、21、22均具有其自己的偏压源,在该实例中示意为电池32、31和30,其使每一LED能发光。可以理解,可分别以适宜的信号用来代替电池30、31和32。如公知的那样,LED需要最小的域电压以发光(每一DH LED),因此该活化电压由电池符号示意显示。
EL层20E、21E、22E可由有机化合物构造,有机化合物的选择依据其生产各主要颜色及中间体的能力进行。有机化合物通常选自三价金属喹啉酸盐配合物、三价金属桥的喹啉酸盐配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮化物配合物、金属二齿配位体配合物、双磷酸(bisphosphonates)配合物、二价金属马来腈二硫戊环配合物、分子电荷转移配合物、芳和杂环聚合物和稀土混合螯合物,如下所述。
三价金属喹啉酸盐配合物如图3中结构式所示,其中M为三价金属离子,选自周期表第3-13族和镧系元素。Al3+、Ga3+和In3+为优选的三价金属离子。
图3中R包括氢、取代和未取代的烷基、芳基和杂环基。烷基可为直链或支链,优选具有1-8个碳原子。适宜的烷基实例为甲基和乙基。优选的芳基为苯基,R为杂环基的实例包括吡啶基、咪唑基、呋喃基和噻吩基。
R是烷基、芳基和杂环基可被至少一个取代基取代,取代基选自:芳基、卤素、氰基、烷氧基,优选具有1-8个碳原子。优选的卤素为氯。
图3中基团L代表一种配位体,包括吡啶甲基甲基酮、取代和未取代的水杨醛(如用巴比土酸取代的水杨醛),式R(O)CO-的基团(其中R定义如上)、卤素、式RO-的基因(R定义如上)、喹啉化合物(如8-羟基喹啉)及其衍生物(如巴比土酸取代的喹啉化合物)。由图3所示结构式覆盖的优选配合物为M是Ga+3,L是氯的配合物。这些化合物发蓝光。当M为Ga+3,L为羧酸甲酯时,配合物在蓝至蓝/绿区域发光。使用巴比土酸取代的水杨酸或巴比土酸取代的8-羟基喹啉为L基可预计发射黄或红光。采用喹啉酸盐作L基团可发射绿光。
可用于本发明的三价金属桥连喹啉配合物如图4A和4B所示。这些配合物产生绿光,与现有技术装置中采用的三喹啉酯(图3中L为喹啉酯的配合物)比较显示出优异的环境稳定性。用于这些配合物中的三价金属离子M如上定义,优选Al+3、Ga+3或In+3。图4A中的基团Z的结构式为SiR,其中R如前定义。Z也可为式P=O的基团,其形成了磷酸酯。
席夫碱二价金属配合物包括图5A和5B所示的那些,其中M′为二价金属,选自周期表第2-12族,优选Zn(参见:Y、Hanada,等,“BlueElectroluminescence in Thin Films of Axomethin-Zinc Complexes”,Japanese Journal of Applied Physics Vol.32,PP.L511-L513(1995))。基团R1选自图5A和5B所示的结构式。基团R1优选通过胺或吡啶基团的氢与配合物的金属配位。X选自氢、烷基、烷氧基,每一个均具有1-8个碳原子,芳基、杂环基、磷酰基、卤素和胺。优选的芳基为苯基,优选的杂环基选自:吡啶基、咪唑基、呋喃基和噻吩基。X基团影响席夫碱二价金属配合物在有机溶剂中的溶解度。图5B所示的特定的席夫碱二价金属配合物在波长为520nm处发射。
本发明EL层中采用的锡(IV)金属配合物发绿光。这些配合物包括式SnL1 2L2 2的配合物,其中L1选自水杨醛、水杨酸或喹啉化合物(如8-羟基喹啉)。L2包括前述对所有R基团的定义,除氢之外。例如,当L1为喹啉化合物,L2为苯基的锡(IV)金属配合物的发射波长(λem)为504nm,该波长是在固态下测量光致发光得到的。
锡(IV)金属配合物还包括图6中结构式的那些配合物,其中Y为硫或NR2,R2选自氢和取代或未取代的烷基和芳基。烷基可为直链或支链,优选具有1-8个碳原子。优选的芳基为苯基。对烷基和芳基进行取代的取代基包括1-8个碳原子的烷基和烷氧基、氰基和卤原子。L3选自烷基、芳基、卤化物、喹啉化合物(如8-羟基喹啉)、水杨醛、水杨酸及马来腈二硫戊环化合物(“mnt”)。当A为S,Y为CN,L3为“mnt”时,预计发射介于红和橙之间的光。
图7所示的M(乙酰丙酮化物)3配合物产生蓝光。金属离子M选自周期表3-13族和镧系元素的三价金属。优选的金属离子为Al+3、Ga+3和In+3。图7中基团R定义同图3中对R的定义。例如当R为甲基、M选自Al+3、Ga+3和In+3时,在固态下测量光致发光得到的波长分别为415nm、445nm和457nm(见J.Kido等,“Organic Electroluminescent Devices UsingLanthanide Complexes”,Journal of Alloys and Compounds,Vol,92,pp.30-33(1993)。
本发明的金属二齿配位体配合物通常产生蓝光。
这些配合物通式为MDL2 4,其中M选自周期表第3-13族和镧系元素的三价金属。优选的金属离子为Al+3、Ga+3、In+3和Sc+3。D为图8A所示的双齿配位体。具体说来,二齿配位体D包括2-吡啶甲基酮、2-喹哪啶基(quinaldyl)酮和2-(邻苯氧基)吡啶酮,其中图8A中的基团R如前定义。
L4的优选的基团包括乙酰丙酮化合物;式OR3R的化合物,其中R3选自Si、C、R选自如上定义相同的基团;3,5-二(叔丁基)苯酚;2,6-二(叔丁基)苯酚;2,6-二(叔丁基)甲酚;和H2Bpz2,后面的化合物分别如图8B-8E所示。
例如,在固态下测量光致发光得到的Al(吡啶甲基甲基酮)双(2,6-二叔丁基)苯氧化物)的波长(λem)为420nm。上述化合物的甲酚衍生物的波长也是420nm。Al(吡啶甲基甲基酮)双(OSiPh3)和Sc(4-甲氧基-吡啶甲基甲基酮)双(乙酰丙酮化物)的波长均为433nm,而Al[2-(邻苯氧基)吡啶]双(2,6-二(叔丁基)苯氧化物]的波长为450nm。
可用于本发明EL层的另一类化合物为双膦酸化合物。双膦酸化合物由下式表示:
               M2 x(O3P-有机-PO3)y
M2为金属离子。当x为y均为1时,它是四价金属离子如Zr+4、Ti+4和Hf+4。当x为3且y为2时,金属离子M2为二价,包括例如Zn+2、Cu+2和Cd+2。上式中术语“有机”是指能与膦酸基双官能化的芳香族或杂环族荧光化合物。
优选的双膦酸化合物包括图9A、9B所示的那些,如亚苯基亚乙烯基双膦酸化合物。具体而言,图9A示出了β-苯乙烯基1,2-二苯乙烯双膦酸和图9B示出了4,4′-二苯基二(乙烯基膦酸),其中R如前定义,R4选自取代和未取代的烷基,优选其具有1-8个碳原子,和芳基。优选的烷基为甲基和乙基,优选的芳基为苯基。优选的取代烷基和芳基的取代基包括至少一个选自芳基、卤原子、氰基、烷氧基(优选具有1-8个碳原子)的取代基。
二价金属马来腈二硫戊环(nmt)配合物的结构式如图10所示。二价金属离子M3包括所有具有+2电荷的金属离子,优选过渡金属离子如Pt+2、Zn+2和Pd+2。Y1选自氰基和取代或未取代的苯基。优选的苯基的取代基选自烷基、氰基、氯和1,2,2-三氰基乙烯基。
L5代表无电荷的基团。优选的L5基因包括P(OR)3和P(R)3,其中R定义如上,或L5可为一种鳌合配位体,如2,2′-二吡啶基,菲咯啉;1,5-环辛二烯;或双(二苯基膦基)甲烷。
表1示出了这些化合物的各种组合的发射波长的代表性实例,如以下文献给出的:C.E.Johnson et al.,“Luminescent Iridium(I),Rhodium(I),and Platinum(II)Dithiolate Complexes”,Journal of theAmerican Chemical Society,Vol.105,pg.1795(1983)。
               表I
    配合物 波长*
[铂(1,5-环辛二烯)(mnt)] 560nm
[铂(P(OEt)3)2(mnt)] 566nm
[铂(P(OPh)3)2(mnt)] 605nm
[铂(双(二苯基膦基)甲烷)(mnt)] 610nm
[铂(PPh3)2(mnt)] 652nm
*在固态下测量光致发光得到的波长。
用于本发明EL层的分子电荷迁移配合物为包含与电子给体结构配位的电子受体结构的那些化合物。图11A-11E示出了各种适宜的电子受体,其可与图11F-11J所示电子给体结构中的一种形成电荷迁移配合物,图11A和11H中基团R定义同前。
这些电荷迁移材料膜是这样制备的:以两个池中分别蒸发给体和受体分子至基体上;或者直接蒸发预先制得的电荷迁移配合物。发射波长可从红至蓝,取决于何种受体与何种给体偶合。
在固态下发荧光的芳香化合物和杂环化合物的聚合物可用于本发明的EL层。这些聚合物可用于产生各种不同颜色的发射。表II给出了适宜的聚合物的实例及其发射的颜色。
          表II
    聚合物 发射颜色
聚(对苯乙烯) 蓝至绿
聚(二烷氧基亚苯基亚乙烯) 红/橙
聚(噻吩)
聚(苯)
聚(苯基乙炔) 黄至红
聚(N-乙烯基咔唑)
用于本发明的稀土混合鳌合剂包括键合至二齿芳族或杂环配位体的任何镧系元素(如La、Pr、Nd、Sm、Eu和Tb)。二齿配位体用于迁移载体(如电子),但不吸收发射能。因此,二齿配位体用于迁移能量于金属。稀土混合鳌合物中配位体的实例包括水杨醛和其衍生物、水杨酸、喹啉化合物、席夫碱配位体、乙酰丙酮化合物、菲咯啉、联吡啶、喹啉和吡啶。
空穴迁移层20H、21H和22H可由卟啉化合物组成。此外,空穴迁移层20H、21H和22H可至少具有一种空穴迁移芳族叔胺,该化合物至少包含一个仅与碳原子键合的三价氮原子,至少其中之一为芳环的环原子。例如,芳族叔胺可为芳基胺,如一芳基胺、二芳基胺、三芳基胺或聚芳基胺。其它适宜的芳族叔胺以及所有的卟啉化合物公开于USP5,294,870(Tang等),该文献的所有内容引入本文作参考,只要这种教导不与本文内容矛盾。
可以通过下述两种方法之一完成本发明堆积的有机LED三色像素的制备:荫罩法和干蚀法,为了进行说明,两种所述方法均假定双异结构LED构造,即对每一种活化发射层仅采用一层有机化合物层,光从底部玻璃基底表面发出。应当理解,本领域的技术人员只需对所述方法进行轻微改变即可构造出对每一种活化发射层具有多个有机化合物层的多杂质结有机LED,和/或反转结构(光从堆积体的顶部表面发出)。
图12(A-E)说明本发明荫罩法的步骤。欲用ITO层52涂敷的玻璃基底50首先进行清洁,即将基底50浸在沸腾的三氯乙烯或类似的氯代烃中约5分钟。随后在丙酮中漂洗约5分钟,然后在甲醇中约5分钟。然后用超高纯(UHP)氮气吹干基底50。采用的所有有机溶剂均优选“电子级”。清洁后,采用常规的溅射法或电子束法在真空中于基底50上形成ITO层52。
然后按照下述过程在ITO层52上构造蓝发射LED55(见图12B)。荫罩73设置在预定的ITO层52的外部。荫罩73和其它荫罩法中采用的掩蔽应在加上步骤中不将装置暴露于水气、氧气和其它污染物的条件下引入和除去,上述成分会减少装置的使用寿命。采用如下作法实现这一点:在用氮气或惰性气体充入的环境中变化掩蔽,或通过遥控处理技术在真空环境下将掩蔽置于装置表面上。通过荫罩73的开口,在不暴露于空气即真空下顺序将50-100埃厚的空穴迁移层(HTL)54和50-200埃厚的蓝发射层(EL)56沉积(图12B所示)。将厚度优选50-1000埃的电子迁移层(ETL)58沉积在EL56上。然后,在ETL58上面沉积半透明金属层60M,其优选由10%Ag和90%Mg层组成,或为其它低功函金属或金属合金层。层60M非常薄,优选小于100埃。层54、56、58和60M可根据任何常规沉积技术进行沉积,如气相沉积、离子束沉积、电子束沉积、溅射和激光烧蚀。
然后通过常规的溅射或电子束方法在金属层60M上形成厚度约1000-4000埃的ITO接点层60I。为方便起见,夹心层60M和60I将被称之为并显示成单层60,其与图2的层26基本相同。每层60的低功函金属部分60M与在其下面的ETL层直接接触,而ITO层60I与在其上面的HTL层接触。注意,整个装置的构造过程最好在保持真空条件下完成,步骤之间不中断真空。
图12C示出了绿发射LED65,其构造在层60的顶部,过程与用于构造蓝发射LED55的荫罩和沉积技术基本相同。LED65包含HTL62、绿发射层64和TEL66。在ETL层66上沉积第二薄(厚度<100埃,薄至足以半透明,但不能失去电连续性)的金属层60M,随之是另一1000-4000埃厚的ITO层60I,以形成第二夹心层60。
图12D为使用类似的荫罩和金属沉积方法在层60(具体在60I上面)上面构造的红发射LED75。红发射LED75由HTL70、红发射EL72和ETL74组成。在LED75上形成层60I与60M的顶夹心层60。类似如上图2实施方案所述。在另一种实施方案中,顶部透明ITO层60I可被适宜的金属电极代替,其另一作用是将向上的光反射回去通过基底50,从而降低装置顶部的光损失。每一ETL层74、66和58的厚度为50-200埃;每一HTL层54、62和70的厚度为100-500埃;每一EL层56、64和72的厚度为50-1000埃。为了最佳亮度和效率,应使包含ITO/金属层的每一层尽可能接近上述范围的下限值。
然后,优选在一个步骤中在ITO层52上形成电接点51和59、在ITO金属层60的ITO部分60I上形成电接点88、89、92、94和96。这些电接点可为铟、铂、金、银或其混合物如Ti/Pt/Au、Cr/Au、Mg/Ag。在掩蔽装置的其余部分后可通过气相沉积或其它适宜的金属沉积技术沉积这些金属。
荫罩方法中最后的步骤是如图12E用绝缘层97防护(overcoat)整个装置,除了被掩蔽的金属接点51、59、88、89、92、94和96之外。绝缘层97对水分、氧气和其它污染物是不透性的,从而防止了LED的污染。绝缘层97可为通过电子束、溅射或热磁增强或等离子体增强CVD沉积的SiO2,氮化硅如Si2N3或其它绝缘体。所用的沉积技术应不会使装置的温度升至高于120℃,因为高温会降低LED的特性。
图13(A-F)示出了本发明构造LED堆积体的干蚀方法。参看图13A,以与上述荫罩方法相同的方式首先清洁玻璃基底102。然后使用常规的溅射或电子束方法在真空中在玻璃基底102上沉积ITO层101。然后在ITO层101的整个表面上使用常规真空沉积技术或聚合物旋涂或喷涂技术沉积HTL104、蓝E105、ETL106和含金属层107M及ITO层107I的夹心层,各层厚度通常与荫罩法中的厚度相同。ITO/金属夹心层107由厚度小于100埃、直接沉积在ETL层106上的低功函金属层107M及于金属层107M上厚度为1000-4000埃的ITO层107I组成。在ITO层107I的整个顶表面上,使用低温等离子体CVD沉积1000埃-2000埃厚的氮化硅或二氧化硅掩蔽材料108的层。然后在氮化硅层108上沉积正光抗蚀剂层109如HPR1400J。如图13B所示,使用标准光刻方法暴露并除去光抗蚀剂层109的外部110(见图13A)。相应于底部ITO层101区域的暴露的外部110被暴露并电接触。参看图13C,相应于除去光抗蚀剂区域的氮化硅层108的外部区域111(图13B定义)使用CF4∶O2等离子体除去。然后,使用离子磨技术或另一种等离子体蚀刻方法,除去ITO/金属层107I和107M的暴露的外面部分。再采用O2等离子体分别顺序除去ETL层106、EL层105和HTL层104相应暴露的外面部分,同样也除去图13D所示其余的光抗蚀剂层109。最后,再次采用CF4∶O2等离子体除去氮化硅掩蔽108,得到图13D所示的蓝LED构型。
采用相同顺序的干蚀方法步骤构造在蓝LED顶部的绿LED115,只是SiNx150如图所示被涂盖,随之如图13E所示的光抗蚀剂掩蔽113,从而掩蔽ITO层101的外面部分。然后沉积HTL层114、绿EL层116等(见图13F)。再采用相同用于蓝LED构造的光刻和蚀刻技术完成绿LED115的形成。随后,使用基本上相同的干蚀方法在绿LED的顶上形成红LED117。与图12E中层97类似的钝化层119的适当的图形沉积在LED堆积体上以暴露电接点,如荫罩方法所述。采用光抗蚀剂掩蔽以允许对钝化层119中的孔洞蚀刻。以后,金属152沉积在孔洞中,最后通过卸走(lift-off)方法除去光抗蚀剂层和过量的金属。
不论采用荫罩法、干蚀法或其它方法中何种方法,在LED堆积体构造完后,必须对堆积体进行适当的包装以实现可接受的装置性能和可靠性。图14(A-C)说明了本发明实施包装的实施方案,以对本发明多至4个多色LED装置进行气密封装。图14(A-B)中采用之标号与图12E中相同技术特征的标号相同。可也以采用图13F的几乎相同的结构进行封装。参看图14A,在采用绝缘层97如SiNx除护整个装置后,使用已知的蚀刻/光掩蔽技术形成入口孔120、122和124暴露蓝、绿和红LED(有机发光二极管)装置的最顶层金属层60M′、60M″和60M。因而,采用常规的方法步骤,在从暴露的金属层60M′、60M″和60M至铟焊接凸面边缘132、133和134的路径上沉积适宜的金属循环路径126、128和130(通常为金)。类似地,经形成的金属(如金)循环路径135提供阳极端,以具有接触ITO层52的内端及终止在铟焊接凸面边缘136的外端,均由常规方法提供。然后用附加的绝缘材料如SiNx防护装置,以与沿着边缘暴露的焊接凸面132、133、134和136形成绝缘的盖。以这种方式,易于采用常规技术或如下描述的本发明的包装实施方案来封装有机LED装置。
参考附图14A、14B和14C,对本发明的另一个实施方案,描述在一种封装构型下于共同基底50上四个多色LED装置的制造方法。起始原料包括用铟锡氧化物(ITO)152防护层涂敷的玻璃基底50。采用下述步骤以得到封装的多色有机LED组合:
1.以同心的方带环图案(square band ring pattern)掩蔽ITO层52以在ITO层52顶部,用常规技术沉积SiO2层138(可采用其它图案)。
2.使用获得上述图12E或13F和14A的结构的方法,以SiO2层138上区域140中形成分享共同层的4个三色LED堆积体。
3.经荫罩沉积金属接点170-181;每一个终止于SiO2层138上的外端,提供外部电连接或粘合垫170-181。注意,图14A中接点126,128和130相同于接点170-181中每三个连接接点。每三个接点为一组,即170-172,173-175,176-178,179-181,终止于其内端或其它端,分别提供了与四个有机LED装置每一个的金属层60M′、60M″的电子连接。另一金属接点182经荫罩沉积在对所有四个LED装置ITO层52的边缘,提供普通的阳极连接。注意,如果通过适当的掩蔽和蚀刻,四个LED装置以完全独立的层制得,四个阳极接点将分别必须提赋能以多路转换方式操作的后一种排列。在本实施例中所述的多色LED排列为非多路转换排列。
4.采用溅射或等离子体增强CVD或电子束沉积技术,以连续的离开暴露的粘合垫170′-180′带或环中经荫罩沉积第二SiO2层184。
5.以连续的带或环186在第二SiO2层或带84上沉积Pb-Sn或其它低温熔化焊剂。
6.在盖玻璃188的底部上沉积金属环190,其与焊缝环186同心。
7.在组件上安装盖玻璃188,如图14B所示,金属环190与焊缝环186相对。
8.将组件放在惰性气氛如干燥氮气中,加热熔化焊缝环186得到空气紧密封,惰性气体捕集在内部区域192中。
参看图15,示出了显示器194,其为RGB有机LED显示器,点195被省。完整的显示器194包含多个像素如196。像素以XY矩阵设置覆盖涂有ITO的玻璃基片的整个表面面积。每一个像素包括一个如图2所示的堆积的LED结构。代替固定的偏压部件如电池30、31和32(如图2),图2中标记的末端线如蓝(B)、绿(G)和红(R)被引出并与适宜的横向与纵向扫描处理仪197和198相连,处理由显示器发生器199控制,发生器可为一个TV单元。因此,每一个LED矩阵具有至少两个轴(X、Y),每一LED位于至少两个轴的交叉处。同样,X轴可代表横轴,Y轴代表纵轴。公知可将电视信号如NTSC信号转化成彩色显示器的颜色成分R、G和B。采用红、绿、蓝为主要颜色的计算机用监视器也是公知的。通过横和纵轴扫描技术驱动和控制该装置也是公知的。采用典型的XY扫描技术如使用XY寻址可对沉积在显示器表面上的像素结构的整体排列进行扫描。这些技术用在实际的矩阵显示器中。
按照所需要的信号量可使用脉冲宽度调制来选择性地对每一DHLED像素的红、绿和蓝输入赋能。以这种方式,在显示器的每一线中的每一LED可选择性地进入并寻址,并通过多种手段通过脉冲宽度调制信号或通过阶梯发生电压施加偏加,使这些装置发射单一颜色或多种颜色,从而从所说结构发出的光产生预定形状和颜色的图像。同样,也可逐次对XY轴的每一条轴扫描,并对矩阵中所选择的任一LED进行逐次赋能以发射出光而产生纵向逐次产生的具有颜色的图像。选择的LED中的任一个可同时被赋能。
如上所表明,图2所示的纵向层压技术可在极小的区域内构造三色DH LED像素。这可提供高清晰高的显示器,如每英寸为300-600线的分辨率或更大。使用现有技术将不可能获得如此高的分辨率,现有技术中产生不同颜色的发射层或荧光介质相互间在横向上是隔开了。
基于现代标准,可以提供如图2所示的LED装置,其有效面积小于可使数百的像素二极管在横向和纵向上堆积在一平方英寸的区域内。因而,此构造技术可实现极高的分辨率及高光亮度。
图16中示出了本发明另一个多色LED装置的实施方案,该装置包括多至N个单个LED的堆积体,其中N为整数1,2,3…N。根据未来技术的状态,N将为实际限定的值。使用图12(A-E)所述的荫罩法步骤或图13(A-F)所述干蚀法可提供堆积的N级LED。图16的堆积体的基底或底部为如图13F所示的玻璃基底102,在基底102上面形成ITO层101。紧接着为第一LED层,随后的LED装置每一个均依次包括ITO层101HTL层154、EL层156、ETL层158、金属层160、ITO层162。第N级LED装置164进一步包括于最上面ITO层162上形成的最顶层金属层(见图13F的层152)。如图13F的彩色堆积体,在堆积体上沉积钝化层119。每一ED装置入每一EL层156所用的材料可选择以对相应的LED提供特定的颜色。如在三色装置中,较短波长(蓝)的装置必须低于较长波长(红)装置,以避免红发射层吸收光。对各LED所选的颜色及堆积的LED的实际数目取决于具体应用和所需的颜色及能提供的遮蔽能力。这种多色装置也可用在光通讯网络,其中使用由堆积体中给定装置发出的不同波长传送每一不同的光通道。发射光内在的同心特性可偶合几种波长进入单一的单传送纤维。在实际的这种堆积体中,入口孔在每一装置的ITO层162下方形成,随之适宜的金属化定位以便于封装和电连接至堆积体中的每一LED装置,其过程类似于图14A、14B和14C中的堆积的多色LED装置。
这种装置可用于提供任何尺寸的低成本、高分辨率、高亮度的全色平板显示器。这拓宽了本发明的范围至小至几个毫米大至建筑物大小的显示器。显示器上产生的图像根据单个LED的尺寸可为全色的文字式或说明式。
本领域的技术人员可以认识到如上所述的本发明的实施方案可做各种改变。这种改变仍属本发明权利要求的精神及保护范围内。例如,在本发明的另一实施方案中,多色堆积的LED装置如上述图2的三色装置可从图1C所示聚合物装置形成LED20而提供,或从沉积的金属磷酸化合物膜来提供,而并不具有真空中沉积的所有的三层。两种其它的堆积LED可通过气相沉积形成。

Claims (111)

1.一种多色发光装置(LED)结构,包含:
至少多个相互堆积的第一和第二发光有机装置,从而形成层压结构,每一LED通过透明导电层相互分开,使每个装置接受单独的偏压以通过整个堆积体发光。
2.权利要求1的多色发光装置结构,其中每一个所说的LED在施加偏压时发出不同波长的光并产生不同的颜色。
3.权利要求1的多色发光装置结构,包括至少第一至第三分别相互堆积的发光装置。
4.权利要求3的多色发光装置结构,其中所说的第一装置发射蓝色(B),所说的第二装置发射绿色(G),所说的第三装置发射红色(R)。
5.权利要求4的多色发光装置结构,其中所说的装置沿纵轴由底部向上以下列次序堆积,其中第一装置发蓝色,位于所说发蓝光装置的上表面顶部的第二装置发绿色,位于所说绿发光装置的上表面顶部的第三装置发红色,由此当结构纵向排列时,所说的波长最短的蓝发光装置是在波长最长的红发光装置的底部。
6.权利要求1的多色发光装置结构,其中每一LED装置为由有机材料构成的透明的双异结构(DH)装置。
7.权利要求1的多色发光装置结构,其中每一LED装置为由有机材料构成的透明的单异结构装置。
8.权利要求6的多色发光装置结构,其中所说的透明导电层包括铟锡氧化物(ITO)。
9.权利要求7的多色发光装置结构,其中所说的透明导电层包括铟锡氧化物(ITO)。
10.权利要求3的多色发光装置结构,其中所说的至少第一、第二和第三有机LED是在共同基底上以连续次序堆积的。
11.权利要求10的多色发光装置结构,其中所说的基底是在所说的LED结构的底部,所说的第三有机LED最顶层是由铟锡氧化物(ITO)材料组成的,该材料作为对下面的金属材料层的接点。
12.权利要求6的多色发光装置结构,其中所说的透明导电层包含金属层,其功函小于约4电子伏特,和在所说金属层上的ITO层。
13.权利要求6的多色发光装置结构,其中所说的有机材料选自:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
14.权利要求13的多色发光装置结构,其中三价金属喹啉配合物具有下结构式:
Figure A9519680700031
其中,R选自氢、取代和未取代的烷基、芳基和杂环基,L为一种配位体,其选自吡啶甲基甲基酮、取代和未取代的水杨醛;式R(O)CO-的基团,其中R如上定义;卤素;式RO-的基团,其中R如上定义;和喹啉化合物及其衍生物。
15.权利要求13的多色发光装置结构,其中金属二齿配位体配合物具有下结构式:
Figure A9519680700032
其中M选自周期表第3-13族和镧系元素的三价金属,D为二齿配位体,L4选自乙酰丙酮化合物;式OR3R的化合物,其中R3为Si或C,R选自氢、取代和未取代的烷基、芳基、杂环基;3,5-二(叔丁基)苯酚;2,6-二(叔丁基)苯酚;2,6-二(叔丁基)甲酚及下式的化合物:
16.权利要求15的多色发光装置结构,其中D选自2-吡啶甲基酮、2-喹哪啶基酮和2-(邻苯氧基)吡啶酮。
17.权利要求13的多色发光装置结构,其中席夫碱二价金属配合物选自具有下述结构式的那些化合物:
Figure A9519680700042
其中M1为周期表第2-12族的二价金属,R1选自基团:
Figure A9519680700043
其中X选自氢、具有1-8个碳原子的烷基、具有1-8个碳原子的烷氧基、芳基、杂环基、膦基、卤素和胺。
18.权利要求13的多色发光装置结构,其中芳香和杂环聚合物选自聚(对苯乙烯)、聚(二烷氧基苯乙烯)、聚(噻吩)、聚(苯)、聚(苯乙炔)、聚(N-乙烯基咔唑)。
19.权利要求13的多色发光装置结构,其中稀土混合螯合物包含键合至二齿配位体芳基或杂环基上的镧系元素。
20.权利要求19的多色发光装置结构,其中二齿配位体芳族或杂环基选自水杨醛和其衍生物、水杨酸、喹啉化合物、席夫碱配位体、乙酰丙酮化合物、菲咯啉、联吡啶、喹啉和吡啶。
21.权利要求19的多色发光装置结构,其中二价金属马来腈二硫戊环配合物具有下结构式:其中M3为具有+2价电荷的金属,Y1选自氰基,取代和未取代的苯基,L5为不带电荷的基团。
22.权利要求21的多色发光装置结构,其中L5为式P(OR)3或P(R)3的基团,其中R选自氢、取代和未取代的烷基、芳基及杂环基。
23.权利要求13的多色发光装置结构,其中双膦酸配合物的结构式为M2 x(O3P有机-PO3)y,其中M2为金属离子,有机代表一种能与膦酸基双官能化的芳香族或杂环族荧光化合物。
24.权利要求13的多色发光装置结构,其中三价金属桥连喹啉配合物具有下结构式:
Figure A9519680700061
其中,M为三价金属离子,Z选自SiR或P=O,其中R选自氢、取代和未取代的烷基、芳基及杂环基。
25.权利要求13的多色发光装置结构,其中锡(iv)金属配合物具有下式SnL1 2L2 2,其中L1选自水杨醛、水杨酸及喹啉化合物,L2选自取代和未取代的烷基芳基和杂环基。
26.权利要求13的多色发光装置结构,其中分子电荷迁移配合物包含一种与电子给体配合的电子受体。
27.权利要求1的多色发光装置结构,其中所说的装置按照其相应的发射波长和吸收特性以一种次序堆积。
28.权利要求2的多色发光装置结构,其中在纵向上,最长波长LED是在堆积体的顶部,随之为连续较短波长的LED,最短波长LED在堆积体的底部。
29.一种多色发光装置结构,包含:
一层透明基底层,其表面上沉积第一透明导电涂层;
在所说的第一透明导电涂层上沉积的第一发光装置;
沉积在所说的第一装置上与所说的第一涂层不接触的第二透明导电涂层;
在所说的第二涂层的表面上沉积的第二发光装置;
沉积在所说的第二装置上与所说的第二涂层不接触的第三透明导电涂层;
在所说的第三涂层的表面上沉积的第三发光装置;
沉积在所说的第三装置上与所说的第三涂层不接触的另一导电涂层。
30.权利要求29的多色发光装置结构,其中所说的第一、第二、第三和第四导电涂层适于分别接收各个偏压源。
31.权利要求29的多色发光装置结构,其中所说装置和导电层被沉积而形成一种阶梯状,所说的透明基底的长度比所说的第一装置长,所说的第一装置的长度比所说的第二装置长,所说的第二装置的长度比所说的第三装置长,其中,每一步均被所述的适于所说的装置结构施加操作电压的各导电涂层覆盖,其中所说的第一至第三透明导电涂层允许通过任一所说装置分别发射光以通过所说的透明基底层。
32.权利要求29的多色发光装置结构,其中所说的另一导电涂层包括将向上的直射光反射返回所说基底的第三种金属。
33.权利要求32的多色发光装置结构,其中所说的另一导电层进一步包含一种相当薄的铟锡氧化物(ITO)层,其位于所说的厚金属层与所说的第三装置表面之间,且不与第三层接触,所说的ITO层用作接点,用于所说第三发光二极管装置的基础金属材料层。
34.权利要求29的多色发光装置结构,其中所说透明基底为玻璃,所说的第一导电涂层为铟锡氧化物(ITO),每一个所说的第二、第三和另一导电涂层是由沉积于一种低功函金属层上的ITO层组成。
35.权利要求29的多色发光装置结构,其中每一个所说的装置为双杂结构(DH),当施加偏压时,第一装置发蓝光(B),第二装置发绿光(G),第三装置发红光(R)。
36.权利要求35的多色发光装置结构,其中每一个DH结构由有机化合物组成。
37.权利要求29的多色发光装置结构,其中每一个所说的装置为单杂结构(SH),当施加偏压时,第一装置发蓝光(B),第二装置发绿光(G),第三装置发红光(R)。
38.权利要求29的多色发光装置结构,其中每一个所说的装置为聚合物结构,当施加偏压时,第一装置发蓝光(B),第二装置发绿光(G),第三装置发红光(R)。
39.一种多色显示器,包含:
多个以纵横排列的多色发光装置像素结构,以提供具有每个像素结构的显示表面,其至少由一个多色发光装置结构组成,其中每一装置结构包含相互堆积的第一、第二和第三发光装置(LED)以形成一个层压结构,每一个LED被透明的导电层分隔开,藉此所说的显示器可经所说的导电层施加偏压以使所说的多色发光装置发光。
40.权利要求39的多色显示器,其中所说的第一LED发蓝光(B),所说的第二LED发绿光(G),所说的第三LED发红光(R)。
41.权利要求39的多色显示器,其中每一LED装置为双杂结构(DH)装置,其在所说装置中能使所用的有机化合物发光。
42.权利要求39的多色显示器,其中每一LED装置为单杂结构(SH)装置,其在所说装置中能使所用的有机化合物发光。
43.权利要求39的多色显示器,其中每一LED装置为聚合物结构装置,其在所说装置中能使所用的有机化合物发光。
44.权利要求39的多色显示器,其中在一玻璃基底上纵横排列的所说的多个多色装置结构涂敷有薄的透明ITO层,在所说基底上堆积每一像素的第一、第二和第三LED装置,形成分开的像素位置。
45.一种多色发光装置(LED)结构的构造方法,其包含下列步骤:
在透明的基底上形成第一透明导电层;
在所说的第一透明导电层上沉积第一空穴迁移层;
在所说的第一空穴迁移层上沉积第一有机发射层以提供第一种发射颜色;
在所说的第一发射层上沉积第一电子迁移层;
在所说的第一电子迁移层上沉积第二透明导电层,所说的第二透明导电层适于接收第一偏压;
在所说的第二透明导电层上沉积第二空穴迁移层;
在所说的第二空穴迁移层上沉积第二有机发射层以提供第二种发射颜色;
在所说的第二发射层上沉积第二电子迁移层;以及
在所说的第二电子迁移层上沉积第三透明导电层,所说的第三透明导电层适于接收第二偏压。
46.权利要求45的方法,还包括在沉积所说的第一空穴迁移层之前,荫罩所说第一透明导电层一区域以暴露所说的第一透明导电层的所说区域的步骤,从而使得能在所说第二透明导电层与所说第一透明导电层的所说区域之间施加第一偏压。
47.权利要求45的方法,还包括刻蚀所说第一空穴迁移层一区域以暴露所说的第一透明导电层一部分的步骤,从而使得能在所物第二透明导电层与所说第一透明导电层的所说暴露部分之间施加第一偏压。
48.一种气密封装的多色发光装置(LED)的构造方法,其包含下列步骤:
在透明的基底上形成第一透明导电层;
遮蔽所说的第一透明导电层以沉积SiO2层而形成同心的构型;
在所说的第一SiO2层的一部分上形成至少一个多色LED,每一个包括至少相互堆积的第一和第二有机发光装置(LED),以在所说的第一SiO2层上形成层压结构;
经荫罩沉积多个金属接点或循环回路,每一个的一端靠近所说的第一SiO2层的外缘,而其另一端在所说至少一个多色LED的单个偏压电极上;
经荫罩沉积与第一SiO2层同心的第二SiO2层的环,其在所说的多个金属接点部分的外部的上面,但离开经暴露的所说的一端;
在所说的第二SiO2环的上面并与之同心沉积低温熔化的焊剂环;
在盖玻璃的底部沉积金属环,其位置与所说的焊剂一致;
在所说的基底上安装所说的盖玻璃及至少一个多色LED,所说的焊剂的环与所说的在盖玻璃上的金属环相对;
将所说的组件放置在惰性气体中;和
将焊剂环加热以熔化焊剂形成空气紧密封,并将所说的惰性气体包封在所说盖玻璃底部及下面的基底间的内部。
49.权利要求48的方法,其中所说的多色LED形成步骤进一步包括在所说的SiO2层上形成多个多色LED装置。
50.权利要求48的方法,其中所说的惰性气体包括干燥氮气。
51.权利要求48的方法,其中所说的第一透明层包括铟锡氧化物(ITO)。
52.权利要求51的方法,进一步包括在靠近所说ITO层边缘和其上面沉积金属接点作为阴极的步骤。
53.权利要求49的方法,进一步包括在靠近所说第一透明导电层边缘和其上面沉积金属接点作为阴极的步骤。
54.权利要求53的方法,其中所说的第一透明层包括铟锡氧化物(ITO)。
55.一种多色可赋能的发光结构,包含:
至少三层导电材料;
一种透明的可赋能的发光装置(LED),其位于相邻的所说导电材料层之间,从而所说的LED与位于每两个所说LED间的所说的导电材料层之一相互堆积,而其它的导电材料层位于所说的LED的外面;
在所说相邻的LED与所说外层之一之间设置的导电材料层基本上是透明的;和
在每一个导电材料层上面用于与对每一个所说LED进行选择性赋能的连接偏压相连的部件。
56.权利要求55的结构,其中第一个所说的LED发射不同颜色。
57.权利要求56的结构,其中所说的LED以纵向排列进行堆积。
58.权利要求57的结构,进一步包括:
在所说的堆积体中的第三个LED;
所说的LED中中间的一个操作发出预定波长的光;
其它的LED之一操作发出较长波长的光;
最低的LED操作发出较短波长的光。
59.权利要求57的结构,进一步包括:
一个透明基底;
通过所说的透明基底负载所说的LED与导电材料层的堆积体,其次序相应于所说LED发射的光波的长度;和
所说发射最短波长的LED最接近所说的透明基底,从而当赋能时从每一个所说的LED发射的光通过其它LED和通过所说的透明基底传送。
60.权利要求59的结构,进一步包括:
位于所说发射最短波长的LED和所说透明基底之间的抗反射材料层,从而当赋能时,从每一个所说的LED发射的光不会从所说的透明基底反射。
61.权利要求59的结构,进一步包括:
在邻近发射最长波长的LED处的反射材料层,用于将从所说LED发射的光反射回所说基底。
62.权利要求55的结构,其中所说的导电材料层包括铟锡氧化物(ITO)和一种金属。
63.权利要求62的结构,其中所说的金属的功函小于4电子伏特。
64.权利要求55的结构,进一步包括:
一个透明基底;
通过所说的透明基底负载所说的LED与导电材料层的堆积体,其次序相应于所说LED发射的光波的长度;和
所说发射最短波长的LED最接近所说的透明基底,从而当赋能时,从每一个所说的LED发射的光通过其它LED和通过所说的透明基底在基本减少吸收下传送。
65.权利要求64的结构,进一步包括:
位于所说发射最短波长的LED和所说透明基底之间的抗反射材料层,从而当赋能时,从每一个所说的LED发射的光不会从所说的透明基底反射。
66.权利要求64的结构,其中所说的导电材料层包括铟锡氧化物(ITO)和一种金属。
67.权利要求66的结构,其中所说的金属的功函小于4电子伏特。
68.权利要求64的结构,进一步包括:
在邻近发射最长波长的LED处的反射材料层,用于将从所说LED发射的光反射回所说基底。
69.权利要求55的结构,其中所说的每一个LED均为双异结构。
70.权利要求55的结构,其中所说的每一个LED均为单异结构。
71.一种可赋能的光发射结构,包含:
一种透明基底;
负载于所说基底上基本透明的第一导电材料层;
负载于所说基本透明的第一导电材料层上的透明的可赋能的发光装置(LED),所说的LED包括发射层;
负载于所说LED上的第二导电材料层;和
当赋能时,所说的LED操作以产生光并通过所说的透明基底传送。
72.权利要求71的结构,其中所说的第一和第二层包括铟锡氧化物。
73.权利要求72的结构,其中第二层进一步包含功函小于4电子伏特的金属层。
74.权利要求73的结构,其中所说的金属选自镁、砷和镁/金合金。
75.权利要求71的结构,进一步包括:
所说的第二导电材料层基本上是透明的;
负载于所说第二导电材料层上的透明的可赋能的第二发光装置(LED),所说的第二LED包括发射层;
负载于所说第二LED上的第三导电材料层;和
当赋能时,所说的第二LED操作以产生光并通过所说的第一LED和通过透明基底传送。
76.权利要求71的可赋能发光结构,其中所说的发射层包括选自以下材料中的至少一种:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
77.一种多色可赋能的发光显示器,包含:
多个可赋能的发光结构;
所说结构的每一个包含多个透明的发光装置(LED),它们相互堆积;
当赋能时,所说的结构中的每一个LED操作以产生不同颜色的光;和
用于对每一个所说结构中的至少一个LED选择性地赋能的部件,在每一个发光结构中的LED或LED组被赋能由其决定由每一个所说的发光结构产生的颜色,从而从所说结构发出的光产生预定图形和颜色的图像。
78.权利要求77的显示器,其中所说的可赋能的发光结构以一种排列方式设置,所说的排列方式包括至少两个轴,每一个所说的发光结构位于至少两个轴的交叉处。
79.权利要求78的显示器,其中所说的轴定义为横轴和纵轴。
80.权利要求78的显示器,其中所说用于对每一个所说结构中的至少一个LED选择性地赋能的部件包括:
用于选择结构及在这些欲赋能的结构中LED的部件;和
用于逐次地扫描每一个轴的部件,从而使所说的用于对至少一个LED选择性地赋能的部件能沿所说的轴扫描,在所说轴的交叉处所说LED中所选的一个被逐次赋能以发光,从而逐次产生所说的图像和所说的颜色。
81.权利要求77的显示器,其中所说用于对每一个所说结构中的至少一个LED选择性地赋能的部件包括:
用于基本上逐次地赋能所说的LED的部件,其是在所说的结构中,从而由所说的结构逐次地产生所说的图像和所说的颜色。
82.权利要求77的显示器,其中操作用于对所说LED选择性地赋能的部件,以同时对所选结构中之一的LED进行赋能,从而通过所选结构中之一的所选的LED之一同时产生所说的图像和所说的颜色。
83.权利要求77的显示器,其中每一个所说结构进一步包括:
一个透明基底;
所说的每一LED具有底部和顶部,并限定了LED的堆积体具有的底部和顶部,所说的堆积体负载于所说的透明的基底上;
基本透明的第一导电材料层,所说的第一层设置在所说底部LED和所说透明基底之间;
至少一层基本透明的第二导电材料层,所说的第二层设置在相邻的LED之间;
第一导电材料层,所说的第一层设置在所说邻近顶部LED的顶部处;和
所说的每一导电材料层上用于与偏压连接以选择性地对每一所说LED进行赋能的部件。
84.权利要求83的显示器,其中每一基本透明的导电材料层和导电材料层包括一层铟锡氧化物。
85.权利要求83的显示器,其中每一基本透明的导电材料层和导电材料层包括一层金属层和一层铟锡氧化物。
86.权利要求85的显示器,其中所说的金属的功函小于约4电子伏特。
87.权利要求83的显示器,进一步包括:
设置在所说近顶部LED顶点的导电材料层上的反射材料层,从而从所说的LED发出的光由所说的反射材料层反射通过所说的透明基底。
88.权利要求87的显示器,进一步包括:
所说的LED的堆积体负载于所说的透明基底上,其次序相应于所说LED发射的光的波长;和
所说发射最短波长的LED最接近所说的透明基底,从而当赋能时从每一个所说的LED发射的光通过其它LED和通过所说的透明基底传送。
89.权利要求88的显示器,进一步包括:
位于所说发射最短波长的LED和所说透明基底之间的抗反射材料层,从而当赋能时,从每一个所说的LED发射的光不会从所说的透明基底反射。
90.权利要求77的显示器,进一步包括:
一层透明基底;
每一个所说的LED具有顶部和底部;
至少两层基本上透明的导电材料层,其中一层设置在所说透明基底上;
在所说每一结构中所说LED之一的底部负载于所说基本上透明的导电材料一层之上;
其它基本透明的导电材料层设置在其余LED之间,从而所说的LED限定了堆积体;
负载于所说堆积体顶部的导电材料层是离所说的透明基底最远的;和
在所说的基本透明的导电材料层上和所说的导电材料层上选择与偏压连续以选择性地对所说每一LED进行赋能的部件。
91.权利要求90的显示器,其中所述的每一基本透明的导电材料层和导电材料层包括一层铟锡氧化物。
92.权利要求90的显示器,其中所述的每一基本透明的导电材料层和导电材料层包括一层金属层和一层铟锡氧化物。
93.权利要求92的显示器,其中所说的金属的功函小于约4电子伏特。
94.权利要求90的显示器,进一步包括:
设置在所述邻近顶部LED顶点的基本透明的导电材料层上的反射材料层,从而光由所说的反射材料层反射通过所说的透明基底。
95.权利要求94的结构,其中
通过所说的透明基底负载所说的LED的堆积体,其次序相应于所说LED发射的光波的长度;和
所说发射最短波长的LED最接近所说的透明基底,从而当赋能时从每一个所说的LED发射的光通过其它LED和通过所说的透明基底传送。
96.权利要求95的结构,进一步包括:
位于所说发射最短波长的LED和所说透明基底之间的抗反射材料层,从而当赋能时,从每一个所说的LED发射的光不会从所说的透明基底反射。
97.权利要求77的结构,其中所说的多个LED包括:
三个LED;
每一个所说的LED为双异结构(DH);
当赋能时操作最接近透明基底的LED以发射蓝光;
当赋能时操作最远离透明基底的LED以发射绿光;
当赋能时操作其它LED以发射红光。
98.权利要求97的的多色发光显示器,其中所说的每个LED包括含有机材料的发射层,有机材料选自:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
99.权利要求77的的显示器,其中所说的多个LED包括:
三个LED;
每一个所说的LED为单异结构(SH);
当赋能时操作最接近透明基底的LED以发射蓝光;
当赋能时操作最远离透明基底的LED以发射绿光;
当赋能时操作其它LED以发射红光。
100.权利要求99的的多色发光显示器,其中所说的每个LED包括含有机材料的发射层,有机材料选自:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
101.一种多色可赋能的发光结构的构造方法,包含下述步骤:
提供一层透明基底;
提供在所说透明基底上的基本透明的第一导电材料层;
提供在所说基底上的透明的第一发光二极管(LED),当赋能时所说的第一LED操作以发射第一种预定波长的光;
提供在所说第一LED上的基本透明的第一导电材料层;
提供在所说基本透明的第二导电层上的透明的第二发光二极管(LED),当赋能时所说的第二LED操作以发射第二种预定波长的光,其波长比第一种预定波长的光的波长长;和
在所说第二(LED)上的导电层。
102、权利要求101的方法,其中
所说的提供所说的第一和第二LED的步骤包括通过下述步骤形成每一LED的步骤:
在所说的基本透明的第一和第二导电层上沉积空穴迁移层;
在所说的空穴迁移层上沉积发射层;
在所说的发射层上沉积电子迁移层。
103.权利要求102的方法,其中所说的每个发射层包括的材料选自:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
104.权利要求103的方法,其中每一层基本透明的导电材料层和导电材料层包括一层铟锡氧化物。
105.权利要求102的方法,进一步包括:
提供在所说LED之间基本透明的金属层的步骤;和
在所说的基本透明的金属层上的所说的基本透明的导电材料层的步骤。
106.权利要求105的方法,其中所说的金属的功函小于约4电子伏特。
107.权利要求105的方法,其中所说的金属选自镁、砷和镁/金合金。
108.权利要求101的方法,其中所说的导电材料层具有用于反射所说LED发出的光通过所说透明基底的反射表面。
109.权利要求101的方法,进一步包括如下步骤:
在所说基本透明的每一导电材料层和所说的每一导电材料层上提供电接点,从而每一层可与偏压源连接。
110.一种透明的可赋能的发光装置(LED),包含:
一发射层,空穴迁移层和电子迁移层;
所说的发射层设置在所说空穴迁移层与电子迁移层之间;
基本上透明的第一导电材料层,第二导电材料层,所说的第一层在所说的空穴迁移层上面,所说的第二层在所说的电子迁移层上面;和
所说的每个发射层由以下材料组成,该材料选自:三价金属喹啉配合物、三价金属桥连喹啉配合物、席夫碱二价金属配合物、锡(IV)金属配合物、金属乙酰丙酮配合物、金属二齿配位体配合物、双膦酸配合物、二价金属马来腈二硫戊环配合物、分子电荷迁移配合物、芳香和杂环聚合物和稀土混合螯合物。
111.权利要求110的装置,其中
所说的发射层的厚度不超过约200埃;
所说的空穴迁移层的厚度不超过约1000埃;和
所说的电子迁移层的厚度不超过约1000埃。
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US5721160A (en) 1998-02-24
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