CN1858924A - 有机发光器件 - Google Patents
有机发光器件 Download PDFInfo
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- CN1858924A CN1858924A CNA2006100785360A CN200610078536A CN1858924A CN 1858924 A CN1858924 A CN 1858924A CN A2006100785360 A CNA2006100785360 A CN A2006100785360A CN 200610078536 A CN200610078536 A CN 200610078536A CN 1858924 A CN1858924 A CN 1858924A
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- 239000000463 material Substances 0.000 claims abstract description 168
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000005540 biological transmission Effects 0.000 claims description 46
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 21
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 claims description 11
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- KMQPLEYEXDZOJF-UHFFFAOYSA-N 1-naphthalen-2-ylanthracene Chemical compound C1=CC=C2C=C3C(C4=CC5=CC=CC=C5C=C4)=CC=CC3=CC2=C1 KMQPLEYEXDZOJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- YOZHUJDVYMRYDM-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-naphthalen-1-yl-n-phenylaniline Chemical compound C=1C=C(C=2C(=CC(NC=3C=CC=CC=3)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 YOZHUJDVYMRYDM-UHFFFAOYSA-N 0.000 claims description 3
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- UIQFAODJHJZOHK-UHFFFAOYSA-N quinolin-2-yl hydrogen sulfate Chemical compound C1=CC=CC2=NC(OS(=O)(=O)O)=CC=C21 UIQFAODJHJZOHK-UHFFFAOYSA-N 0.000 description 2
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- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及有机发光器件(OLED),该发光器件含有包含具有不同电子、空穴传输能力的至少两种材料的混合物的电致发光材料层,并且电子传输层含有三嗪。并且还公开了含有该OLED的显示器件。
Description
技术领域
本发明涉及有机发光器件。
背景技术
有机发光器件(OLED)代表了显示应用领域中比较有发展前景的技术。传统器件结构含有(1)透明前电极;(2)多层有机发光区域(通常至少两层),其含有至少小分子或聚合物有机电致发光材料;以及(3)后电极。OLED通常层压在基板上。前后电极其中之一为电子注入阴极,而另一个为空穴注入阳极。当在电极上施加电压时,从发光区域发出的光经过透明前电极传达给观测者。通常,发光区域含有:(1)靠近阴极的至少一电子传输材料层;(2)靠近阳极的至少一空穴传输材料层;以及(3)位于空穴传输层和电子传输层之间的电致发光材料层。
通过有机发光材料的层迭已经制备了许多OLED。这种器件含有作为电致发光物质的单晶材料,诸如专利号为No.3,530,325的美国专利(在此引入其公开内容作为参考)中所述的单晶蒽。这些类型的器件可能需要100V或者更大数量级的激发电压。
如上所述,OLED通常形成为多层结构。在美国专利No.4,356,429、4,539,507、4,720,432和4,769,292(这里引入其公开作为参考)中公开了具有双层发光区域的OLED,该双层发光区域含有与支持空穴传输的阳极相邻的一有机层以及与支持电子传输的阴极相邻的另一有机层,并且该发光区域用作器件的电致发光区域。
美国专利No.4,769,292公开了一种具有电致发光材料层的传统OLED,该电致发光材料层含有空穴传输层、电致发光层以及向发光层加入荧光掺杂物材料的电子传输层。在其他传统OLED结构中,诸如在美国专利No.4,720,432中所述的OLED结构,该OLED还含有夹在空穴传输层和阳极之间的缓冲层。该空穴传输层和缓冲层的组合形成双层空穴传输区域。这一点在S.A.Van Slyke等人在Appl.Phys.Lett.69,pp.2160-2162(1996)(在此引入其公开作为参考)中的“Organic Electroluminescent Devices with Improved Stability(具有改进稳定性的有机电致发光器件)”中进行了讨论。
还曾经尝试从含有混和层的OLED中获得电致发光,例如,在单层中把空穴传输材料和发射电子传输材料混和在一起的混和层。例如,Kido等人在Appl.Phys.Lett.61,pp.761-763(1992)中发表的“Organic ElectroluminescentDevices Based On Molecularly Doped Polymers”;S.Naka等人在Jpn.J.Appl.Phys.33,pp.L1772-L1774(1994)中发表的“Organic ElectroluminescentDevices Using a Mixed Single Layer(采用混和单层的有机电致发光器件)”;W.Wen等人在Appl.Phys.Lett.71,1302(1997);以及C.Wu等人在IEEETransaction on Electron Devices 44,pp.1269-1281(1997)中提出的“EfficientOrganic Electroluminescent Devices Using Single-Layer Doped Polymer Thin Filmwith Bipolar Carrier Transport Abilities”。该发光材料可以是空穴传输或者电子传输材料其中之一。根据一实施方式,还可以是除空穴传输和电子传输材料以外的可以发光的第三材料。
在美国专利No.5,853,905、No.5,925,980、No.6,130,001(在此引入其公开作为参考)中可以发现由单有机层形成的其他OLED的实施例,该单有机层含有空穴传输材料和电子传输材料。正如S.Naka等人所指出的,这些单混和层OLED不如多层有机发光器件有效。这些仅含有由诸如NPB(N,N’-二(萘-1-基)-N,N’-二苯基-联苯胺)的空穴传输材料和诸如AlQ3(三(8-羟基喹啉)铝)构成的单混和层的器件不稳定并且效率较差。人们认为由于在该混和层中的电子传输材料和空穴诸如材料之间直接接触导致了这些器件的不稳定,这导致:(1)形成不稳定的阳离子电子传输材料;并且(2)该混和层/阴极接触面不稳定。
在商业应用中,对于OLED显示来说高效(例如,对于25mA/cm2的电流密度其驱动电压低于5V)而且足够稳定工作(例如,对于至少为500cd/m2的初始亮度其半衰期大于1000小时)是非常有必要的。在过去具有低驱动电压的小分子OLED已经得到证实(例如,Huang等人,APL 80,139,2002)。但是,该OLED缺乏足够的工作稳定性,可能导致他们不适合商业应用。通过采用混和发光层OLED,已经实现了高工作稳定性,但是驱动电压经常超出预定值,诸如5V。需要既具有低驱动电压又具有足够工作稳定性的OLED。
发明内容
参照各种实施方式,这里公开的有机发光器件含有:(a)阳极;(b)空穴传输层;(c)含有具有不同电子和空穴传输能力的至少两种材料的电致发光材料层;(d)含有三嗪的电子传输层;以及(e)阴极,其中所述电致发光层厚度小于50nm。
根据本发明的另一方面,提供了一种含有至少一有机发光器件的显示器,该有机发光器件含有:(a)阳极;(b)空穴传输层;(c)含有具有不同电子和空穴传输能力的至少两种材料的电致发光材料层;(d)含有三嗪的电子传输层;以及(e)阴极,其中所述电致发光材料层厚度小于50nm。
根据本发明的再一方面,提供了一种有机发光器件,含有:(a)阳极;(b)空穴传输层;(c)含有:(i)电子传输材料;(ii)空穴传输材料;以及(iii)双极传输材料中至少两种的电致发光材料层;(d)含有三嗪的电子传输层;以及(e)阴极,其中所述电致发光材料层厚度小于50nm。
附图说明
图1所示为根据本发明的有机发光器件;以及
图2所示为根据本发明的另一有机发光器件。
具体实施方式
参照图1,在一实施方式中,OLED 10依次含有诸如玻璃的支撑基板20;诸如氧化铟锡的阳极30,其厚度为大约1nm到大约500nm,诸如从大约30nm到100nm;可选缓冲层40,例如酞菁铜染料或者等离子聚合CHF3,厚度为约1nm到大约300nm;有机空穴传输层50,诸如厚度为大约1nm到大约200nm的NPB,例如从大约5nm到大约100nm;含有诸如含有空穴传输/电子传输/双极传输材料构成的混合物的电致发光层60,该层厚度为大约5nm到大约50nm;含有诸如厚度为大约5nm到300nm的三嗪的电子传输层70,例如大约10nm到大约100nm,以及随限接触的低功函金属阴极80。在该阴极80上形成可选的保护层90。如图2所示,根据另一实施方式,在OLED 15中,该支撑基板20与阴极80相邻,并且可选的保护层90与阳极30相邻。
在各种实施方式中,OLED含有支撑基板20。该支撑基板20的示例性实施例含有玻璃等,以及含有诸如MYLAR的聚酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚砜、石英等的聚合物组分。如果其他基板可以有效支撑其他层并且不会***件功能性能也可以选择其他类型基板20。该基板20的厚度范围为从大约25μm到大约1,000μm或者更多,例如根据器件的结构要求,范围可以是从大约50μm到约500μm。
根据各种实施方式,该OLED可以包含邻近基板的阳极30。阳极的适用非限制实施例含有诸如氧化铟锡、氧化锡、金、铂的正电荷注入电极,或者其他的适用材料,诸如导电碳、诸如聚苯胺、聚吡咯等的π-共轭聚合物,其功函数等于或者大于大约4ev(电子伏特),并且具体地,从大约4eV到6eV。该阳极的厚度的范围为从约1nm到约500nm,同时根据该阳极材料的光学常数选择适当范围。阳极厚度的适用范围为大约30nm到大约100nm。
可选地提供有缓冲层40以与阳极相邻。用于便于诸如来自阳极的空穴有效注入并提高阳极和空穴传输层之间粘接性(因此还提高器件工作稳定性)的缓冲层含有诸如聚苯胺及其掺入酸的形式、聚吡咯、聚(对苯乙炔),以及公知的半导体有机材料的导电材料;在美国专利No.4,356,429中公开的卟啉衍生物,该专利在此引入其全部内容作为参考,诸如1,10,15,20-四苯基-21H,23H-卟啉铜(II);酞菁铜、四甲基酞菁铜;酞菁锌;酞菁二氧化钛;酞菁镁等。该缓冲层含有适于用作电子空穴传输材料的叔胺。可以通过诸如汽相沉积或者旋转涂敷的公知方法将以上化合物其中之一形成薄膜制备缓冲层。因此不具体限制缓冲层的厚度,其厚度范围可以在从大约5nm到大约300nm,例如从大约10nm到大约100nm。
在各种实施方式中,该OLED含有含有空穴传输材料的空穴传输层50。该空穴传输材料的适用但非限定实施例含有诸如NPB的芳香叔胺、N,N’-二苯基-N,N’-双(3-甲基苯基)-1,1-联苯基-4,4’-二胺(TPD)、N,N’-二(萘-1-基)-N,N’-二苯基-联苯胺(NPB)、N,N’-双(对联苯基)-N,N’-二苯基联苯胺(BP-TPD),以及在美国专利No.4,539,507中公开的芳香叔胺,在此引入该专利作为参考。适用的芳香叔胺的实施例含有双(4-二甲基氨基-2-甲基苯基)苯基甲烷;N,N,N-三(对甲苯基)胺、1,1-双(4-二-对甲苯基氨基苯基)环己烷;1,1-双(4-二-对甲苯基氨基苯基)-4-苯基环己烷;N,N’-联苯基-N,N’-双(3-甲基苯基)-1,1’-联苯基-4,4’-二胺;N,N’-二苯基-N,N’-双(3-甲基苯基)-1,1’-联苯基-4,4’-二胺;N,N’-二苯基-N,N’-双(4-甲氧基苯基)-1,1’-联苯基-4,4’-二胺;N,N,N’,N’-四-对甲苯基-1,1’-联苯基-4,4’-二胺;N,N’-二-1-萘基-N,N’-二苯基-1,1’-联苯基-4,4’-二胺等。
适于用作空穴传输材料的另一类芳香叔胺为多核芳香胺,诸如N,N-双-[4’-(N-苯基-N-间甲苯基氨基)-4-联苯基]苯胺;N,N--双-[4’-(N-苯基-N-间甲苯基氨基)-4-联苯基]-间甲苯胺;N,N-双-[4’-(N-苯基-N-间甲苯基氨基)-4-联苯基]-对甲苯胺;N,N-双-[4’-(N-苯基-N-对甲苯基氨基)4-联苯基]苯胺;N,N-双-[4’-(N-苯基-N-对甲苯基氨基)-4-联苯基]-间甲苯胺;N,N-双-[4’-(N-苯基-N-对甲苯基氨基)-4-联苯基]-对甲苯胺;N,N-双-(4’-(N-苯基-N-对氯苯基氨基)-4-联苯基)-间甲苯胺:N,N-双-[4’-(N-苯基-N-间氯苯基氨基)-4-联苯基]-间甲苯胺;N,N-双-[4’-(N-苯基-N-间氯苯基氨基)-4-联苯基]-对甲苯胺;N,N-双-[4’-(N-苯基-N-间甲苯基氨基)-4-联苯基]-对氯苯胺;N,N-双-[4’-(N-苯基-N-对甲苯基氨基)-4-联苯基]-间氯苯胺;以及N,N-双-[4’-(N-苯基-N-间甲苯基氨基)-4-联苯基]-1-氨基萘,等。
用于空穴传输层50的其他空穴传输材料含有如N,N′-二咔唑基-4,4′-联苯基(CBP)、4,4′-双(3,6-二甲基咔唑基-9-基)1,1’-二苯基(TPCB)以及4,4’-双(9-咔唑基)-1,1’-联苯基化合物的咔唑。4,4’-双(9-咔唑基)-1,1’-联苯基化合物的示例性实施例含有4,4’-双(9-咔唑基)-1,1’-联苯基和4,4’-双(3-甲基-9-咔唑基)-1,1’-联苯基等。另一类适于空穴传输的材料为吲哚并,诸如5,11-二-萘基-5,11-二氢化吲哚并[3,2-b]咔唑(NIC)。空穴传输层50的厚度范围为大约1nm到大约200nm。根据本发明的另一实施方式,该厚度范围为大约5nm到大约100nm。
这里所公开的OLED含有电致发光层。根据各种实施方式,电致发光材料60含有具有不同电子和空穴传输能力的至少两种材料。可用于电致发光层60的材料含有但不限于空穴传输材料、电子传输材料,以及双极传输材料。各种空穴传输材料、电子传输材料,以及双极传输材料在技术领域中是公知的,对他们进行选择结合从而实现理想的发色性。而且,熟悉本领域的普通技术人员经过常规试验可以很容易地选择能够提供所需发色性的材料。
在各种实施方式中,电致发光层60含有空穴传输材料。适用于电致发光层的空穴传输材料的非限定实施例含有芳香叔胺、多核芳香胺、咔唑以及吲哚并。例如,该电致发光层60可以含有这里所指出的适于空穴传输层50的空穴传输材料其中之一。
电致发光层60还含有至少一电子传输材料,诸如类似AlQ3的金属螯合物以及双(8-羟基喹啉酸合)-(4-苯并基苯酚合)铝盐(BAIQ)、类似4,4′,-双(2,2,-二苯基乙烯基)1,1′-联苯(DPVi)的芪、如2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-噁二唑(PBD),以及诸如含有对三嗪电子传输层指定那些三嗪的4,4’-双-[2-(4,6-二苯基-1,3,5-三嗪基)]-1,1’-联苯(T1)的三嗪。可以采用的电子传输材料的示例性实施例含有但不限于在专利号为No.4,539,507、No.5,151,629和No.5,141,671(在此引入作为参考)的美国专利中公开的8-羟基喹啉。示例性实施例含有双(8-羟基喹啉酸)-(4-苯并苯酚)铝盐(Balq)、三(8-羟基喹啉酸)镓盐;双(8-羟基喹啉酸)镁盐;双(8-羟基喹啉酸)锌盐;三(5-甲基-8-羟基喹啉酸)铝盐;三(7-丙基-8-羟基喹啉酸)铝盐;双[苯并{f}-8-喹啉酸]锌盐;双(10-羟基苯并[h]喹啉酸)铍盐等。
另一类适用于电致发光层60的电子传输材料含有诸如在专利号为No.5,516,577的美国专利中公开的芪衍生物,在此引入该专利作为参考。适用的芪衍生物为4,4′,-双(2,2,-二苯基乙烯基)联苯。再一类适用的电子传输材料为在美国专利No.5,846,666(在此引入作为参考)中所述的金属硫代羟喹啉酸化合物。这些材料含有由双(8-喹啉硫羟酸)锌盐;双(8-喹啉硫羟酸)镉盐;三(8-喹啉硫羟酸)镓盐;三(8-喹啉硫羟酸)铟盐;双(5-甲基喹啉硫羟酸)锌盐;三(5-甲基喹啉硫羟酸)镓盐;三(5-甲基喹啉硫羟酸)铟盐;双(5-甲基喹啉硫羟酸)镉盐;双(3-甲基喹啉硫羟酸)镉盐;双(5-甲基喹啉硫羟酸)锌盐;双[苯并{f}-8-喹啉硫羟酸]锌盐;双[3-甲基苯并{f}-8-喹啉硫羟酸]锌盐;双[3,7-二甲基苯并{f}-8-喹啉硫羟酸]锌盐等构成的金属硫代羟喹啉酸化合物。其他适合材料含有双(8-喹啉硫羟酸)锌盐;双(8-喹啉硫羟酸)镉盐;三(8-喹啉硫羟酸)镓盐;三(8-喹啉硫羟酸)铟盐和双[苯并{f}-8-喹啉硫羟酸]锌盐。
又一类适于电致发光层60的电子传输材料为在美国专利No.5,925,472(在此引入作为参考)中公开的噁二唑金属螯化物。这些材料含有双[2-(2-羟基苯基)-5-苯基-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-苯基-1,3,4-噁二唑]铍;双[2-(2-羟基苯基)-5-(1-萘基)-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-(1-萘基)-1,3,4-噁二唑]铍;双[5-联苯基-2-(2-羟基苯基)-1,3,4-噁二唑]锌;双[5-联苯基-2-(2-羟基苯基)-1,3,4-噁二唑]铍;双(2-羟基苯基)-5-苯基-1,3,4-噁二唑]锂;双[2-(2-羟基苯基)-5-对甲苯基-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-对甲苯基-1,3,4-噁二唑]铍;双[5-(对叔丁基苯基)-2-(2-羟基苯基)-1,3,4-噁二唑]锌;双[5-(对叔丁基苯基)-2-(2-羟基苯基)-1,3,4-噁二唑]铍;双[2-(2-羟基苯基)-5-(3-氟苯基)-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-(4-氟苯基)-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-(4-氟苯基)-1,3,4-噁二唑]铍;双[5-(4-氯苯基)-2-(2-羟基苯基)-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-(4-甲氧基苯基)-1,3,4-噁二唑]锌;双[2-(2-羟基-4-甲基苯基)-5-苯基-1,3,4-噁二唑]锌;双[2-α-(2-羟基萘基)-5-苯基-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-对吡啶基-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-对吡啶基-1,3,4-噁二唑]铍;双[2-(2-羟基苯基)-5-(2-硫代苯基)-1,3,4-噁二唑]锌;双[2-(2-羟基苯基)-5-苯基-1,3,4-硫代噁二唑]锌;双[2-(2-羟基苯基)-5-苯基-1,3,4-硫代噁二唑]铍;双[2-(2-羟基苯基)-5-(1-萘基)-1,3,4-硫代噁二唑]锌;和双[2-(2-羟基苯基)-5-(1-萘基)-1,3,4-硫代噁二唑]铍等。
在不同实施方式中,电致发光层60可以含有双极传输材料,分离地或者替代电子和/或空穴传输材料。适合的双极材料含有如2-(1,1-二甲基乙基)-9,10-双(2-萘基)蒽(TBADN),9,10-二(2-萘基)蒽(DNA),9,10-二(2-苯基)蒽(DPA),9-二(苯基)蒽(BPA),螺旋-BPA和螺旋-DPA,二萘嵌苯,如2,5,8,11-四-t-丁二嵌萘苯(BD2),并四苯,如红荧烯和其他普通烃材料。
在各种实施方式中,电致发光层60含有具有不同电子和空穴传输能力的至少两种材料构成的混合物。所述具有不同电子和空穴传输能力的两种材料可以是任意具有不同空穴迁移率和/或不同电子迁移率的两种材料。通常,如果其空穴迁移率比其电子迁移率高至少约10倍则认为该材料为空穴传输材料。通常,如果其电子迁移率比其空穴迁移率高至少约10倍则认为该材料为电子传输材料。如果其空穴迁移率等于电子迁移率、如果其电子迁移率超过其空穴迁移率小于10倍或者如果其电子迁移率超过其空穴迁移率小于10倍,则认为该材料为双极传输材料。可以从空穴传输材料、电子传输材料和双极传输材料中独立地选择该具有不同电子和空穴传输能力的两种材料,以上已给出其示例性实施例。例如,两种材料可以都是空穴传输材料,两种材料可以都是电子传输材料,两种材料可以都是双极传输材料,一种材料可以是空穴传输材料并且另一种材料是电子传输材料,一种材料可以是空穴传输材料并且另一种材料是双极传输材料,或者一种材料可以是电子传输材料且另一种材料为双极传输材料。在混合物含有两种空穴传输材料的实施方式中,选择两种材料使得一种材料的空穴迁移率至少高于另一种材料空穴迁移率的两倍。在混合物含有两种电子传输材料的实施方式中,选择两种材料使得一种材料的电子迁移率至少高于另一种材料的电子迁移率的两倍。在混合物含有两种双极传输材料的实施方式中,选择两种材料使得一种材料的空穴迁移率至少高于另一种材料的空穴迁移率两倍,和/或一种材料的电子迁移率至少高于另一种材料电子迁移率的两倍。混和区域含有所述两种材料其中之一的体积百分比为约5%到约95%,并且所述两种材料的另一种体积百分比为约95%到约5%。混和区域还选择性地含有体积百分比为约0.01%到约25%的掺杂剂材料。在实施方式中,混和区域含有所述体积百分比为约30%到约70%的两种材料其中之一,并且所述两种材料的另一种体积百分比为约70%到约30%,并且还可以选择性地含有体积百分比为约0.05%到约10%的掺杂剂材料。在其他实施方式中,混和区域含有所述两种材料其中之一的体积百分比为约40%到约60%,并且所述两种材料的另一种体积百分比为约60%到约40%,并且还可以选择性地含有体积百分比为约0.1%到约2%的掺杂剂材料。在其它实施方式中,混和区域的掺杂剂材料的体积量为大约5%到大约20%。
电致发光层60含有至少一可以由于空穴和电子复合而能够发光的材料。该至少一材料可以是荧光或者磷光材料,或者是具有不同电子和空穴传输能力的两种材料中或者其中一种或者两种。另外,该能够发光的至少一材料可以是其它材料。
电致发光层60含有荧光材料。该荧光材料的示例性实施例含有选自香豆素、二氰基亚甲基吡喃、聚甲炔、氧杂苯并蒽、氧杂蒽、吡喃鎓、喹诺酮(carbostyl)、苝和喹吖啶酮衍生物的染料。喹吖啶酮染料的示例性实例含有喹吖啶酮,2-甲基喹吖啶酮、2,9-二甲基喹吖啶酮、2-氯喹吖啶酮、2-氟喹吖啶酮、1,2-苯并喹吖啶酮、N,N’-二甲基喹吖啶酮、N,N’-二甲基-2-甲基喹吖啶酮、N,N’-二甲基-2,9-二甲基喹吖啶酮、N,N’-二甲基-2-氯喹吖啶酮、N,N’-二甲基-2-氟喹吖啶酮、N,N’-二甲基-1,2-苯并喹吖啶酮等。所含荧光物质的重量百分比为占该层重量约0.01%到约10%,诸如重量百分比约1%到约5%。
电致发光层60含有磷光材料,诸如包含产生强自旋-轨道耦合的重金属原子的有机金属化合物,这些内容在Baldo等人在Letters to Nature,395,pp151-154(1998)“Highly efficient organic phosphorescent emission from organicelectroluminescent devices”中公开(在此引入作为参考)。适合的非限制实施例含有2,3,7,8,12,13,17,18-八乙基-21H,23H-膦钯(II)(PtOEP)和三(2-苯基吡啶)铱。
为了获得低驱动电压,电致发光层的厚度为约5nm到约50nm。根据一实施方式,厚度范围为从约10nm到约40nm。在另一实施方式中,厚度范围为从约15nm到约30nm。
这里所公开的OLED含有含有三嗪的电子传输层70。许多三嗪可以用来形成电子传输层70。适用的三嗪含有在专利号为No.6,225,467和No.6,229,012(在此引入作为参考)美国专利中公开的内容。适合的三嗪的非限定性实施例含有4,4’-双-[2-(4,6-二苯基-13,5-三嗪基)]-1,1’-联苯(T1);2,4,6-三(4-联苯基)-1,3,5-三嗪;2,4,6-三[4-(4’-甲基联苯基)]-1,3,5-三嗪;2,4,6,-三[4-(4’-叔丁基联苯基)-1,3,5-三嗪、2,4,6-三[4-(3’,4’-二甲基联苯基)]-1,3,5-三嗪;2,4,6-三[4-(4’-甲氧基联苯基)]-1,3,5-三嗪;2,4,6-三[4-(3’-甲氧基联苯基)]-1,3,5-三嗪;2,4-双(4-联苯基)-6-苯基-1,3,5-三嗪;2,4-双(4-联苯基)-6-间甲苯基-1,3,5-三嗪;4,4’-双-[2-(4,6-二苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4,6-二-对甲苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4,6-二-间甲苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4,6-二-对甲氧基苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4,6-二-间甲氧基苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4-β-萘基-6-苯基-1,3,5-三嗪基)]-1,1’-联苯;4,4’-双-[2-(4,6-二-联苯基-1,3,5-三嗪基)]-1,1’-联苯;4-[2-(4,6-二-联苯基-1,3,5-三嗪基)]-4’-[2-(4,6-二-间甲苯基-1,3,5-三嗪基)]-1,1’-联苯;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]氟;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]-9,9-二甲基芴;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]-9,9-二乙基芴;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]-9,9-二苯基芴;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]-9,10-二氢菲;4,9-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]氧芴;4,9-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]硫芴;2,7-双-[2-(4,6-二-苯基-1,3,5-三嗪基)]-9,9-二甲基-9-硅杂芴等。该电子传输层可以完全由三嗪构成,或者可以含有混和有其他材料的三嗪。例如,如同一日期提交的代理案号为0010.0024的美国专利申请
No.11/122,290中所述(这里引入该公开作为参考),可以在该三嗪中掺杂有机和无机材料其中至少之一。在某些实施方式中,含有三嗪的电子传输层70还可以含有已经公开的对电致发光层60很有用的电子传输材料至少其中之一。在某些实施方式中,该电子传输层70含有体积至少占50%的三嗪。通常,该电子传输层70的厚度在约1nm到约200nm范围内,诸如约5nm到约100nm的,例如在约20nm到约70nm内。
在各种实施方式中,该OLED含有阴极80。阴极80含有任何诸如金属的适用材料。该材料具有高功函组份,例如约4.0eV到约6.0eV。阴极含有低功函组分,诸如功函为约2.5到约4.0eV的金属。通过将低功函金属(约4eV,例如约2eV到约4eV)和至少一其他金属组合得到阴极。
低功函金属与第二或者其他金属的有效比例重量上低于约0.1%到99.9%。低功函金属的示例性实施例含有诸如锂或者钠的碱金属,诸如铍、镁、钙或者钡的IIA族或者碱土金属,以及含有稀土金属和诸如钪、钇、镧、铈、铕、铽、或者锕的锕族金属的III族金属。锂、镁和钙为适用的低功函金属。
阴极80的厚度范围为约10nm到约500nm。美国专利No.4,885,211(这里引入作为参考)的Mg:Ag阴极构成一适用阴极结构。在美国专利No.5,429,884(这里引入作为参考)中描述了另一适用阴极,其中该阴极由具有诸如铝和铟的其他高功函金属的锂合金构成。
可以通过传统方法构造这里公开的OLED。在各种实施方式中,设置诸如玻璃的支撑基板20。在该玻璃上设置阳极30并且该阳极30由厚度为约1nm到约500nm的氧化铟锡构成,例如,从约30nm到约100nm(在整个公开中,厚度范围为所提供实例的厚度范围,也可以选择其他适用厚度)。可以选择性设置和该阳极接触的缓冲层40,并且该缓冲层40可以由厚度为约5nm到约500nm的导电组分或者空穴传输材料构成,例如约10nm到约100nm。在该阳极30或者缓冲层40上设置有机空穴传输层50,该空穴传输层50厚度为约1nm到约200nm,例如约5nm到约100nm。设置电致发光层60与该空穴传输层50接触。设置电子传输层70与电致发光层60接触,该电子传输层70厚度约为5nm到约300nm,例如约10nm到约100nm。含有低功函金属的阴极80与该电子传输层70接触。
根据本公开,这里所公开的OLED的实施方式可以在交流(AC)和/或直流(DC)驱动条件下工作。在某些情况,尤其在高温设备工作条件下,AC驱动条件适于延长工作寿命。适合工作电压为获得至少大约100cd/m2亮度的驱动电流所需的外部施加的驱动电压,并且通常亮度至少约为500cd/m2,诸如亮度为约1000cd/m2。该电压范围为约0.5伏特到约20伏特,诸如约1伏特到约15伏特。根据各种实施方式,工作电压低于约6V,例如低于约5.5V。适合的工作电流范围为约1mA/cm2到约1000mA/cm2,诸如大约10mA/cm2到约200mA/cm2,例如约25mA/cm2。也可以使用该范围之外的工作电压和电流。
实施例
以下实施例为示例性的并非对本发明的限制。
采用物理汽相沉积制造一组有机发光器件。所有器件含有涂敷在玻璃基板上的氧化铟锡和Mg:Ag阴极。所有器件具有位于阳极和阴极之间的三层发光区域,该三层发光区域含有由如下表所述各种组分构成的空穴传输层、电致发光层和电子传输层。在制造完成后,该器件在恒定电流25mA/cm2下工作。在该电流下测量该器件的驱动电压和亮度。然后器件在恒定电流31.25mA/cm2下工作,并测量亮度下降到初始亮度(Lo)的50%所经过的时间,用t1/2表示。然后计算初始亮度为500cd/m2的器件的半衰期(t1/2)。
器件编号 | HTL1 | EL2 | ETL3 | 在25mA/cm2下的效率 | 31.25mA/cm2下的稳定性 | 以小时为单位计算出的初始亮度500cd/m2的t1/2 | |||
亮度(cd/cm2) | 驱动电压(V) | CIE坐标(颜色) | 初始亮度(Lo)(cd/cm2) | t1/2(小时) | |||||
1 | NPB4+5%红荧烯(40nm) | BH25+2%BD2 6(10nm) | T1(45nm) | 576 | 4.46 | 0.200,0.265(蓝) | 703 | 400 | 560 |
2 | NPB+5%红荧烯(40nm) | BH2+T17(9∶1)+2%BD2(10nm) | T1(45nm) | 684 | 4.19 | 0.280,0.346(白) | 830 | 700 | 1160 |
3 | NPB+5%红荧烯(40nm) | BH2+T17(3∶1)+2%BD2(10nm) | T1(45nm) | 622 | 3.8 | 0.389,0.451(黄) | 1150 | 800 | 1840 |
4 | NPB(40nm) | AlQ3 8+2%红荧烯(10nm) | T1(45nm) | 1230 | 3.62 | 0.480,0.511(黄) | 1580 | 150 | 475 |
5 | NPB(40nm) | AlQ3+NPB(1∶1)+2%红荧烯(10nm) | AlQ3(45nm) | 790 | 5.7 | 0.478,0.517(黄) | - | - | - |
6 | NPB(40nm) | AlQ3+NPB(4∶1)+2%红荧烯(10nm) | T1(45nm) | 997 | 3.32 | 0.478,0.518(黄) | 1320 | 700 | 1850 |
7 | NPB(40nm) | AlQ3+NPB(1∶1)+2%红荧烯(10nm) | T1(45nm) | 793 | 3.03 | 0.466,0.529(黄) | 1360 | 500 | 1360 |
8 | NPB(40nm) | AlQ3+NPB(1∶1)+2%红荧烯(10nm) | T1(45nm) | 1330 | 3.6 | 0.466,0.520(黄) | 1570 | 350 | 1100 |
9 | NPB(40nm) | AlQ3+NPB(1∶4)+2%红荧烯(10nm) | T1(45nm) | 944 | 3.27 | 0.462,0.530(黄) | 1150 | 650 | 1500 |
1--空穴传输层
2--电致发光层
3--电子传输层
4--N,N’-二(萘-1-基)-N,N’-联苯基-联苯胺
5--2-(1,1-二甲基乙基)-9,10-双(2-萘基)蒽(也称之为TBADN)
6--2,5,8,11-四-t-丁二嵌萘苯
7--4,4’-双-[2-(4,6-二苯基-13,5-三嗪基)]-1,1’-联苯
8--三(8-羟基喹啉)铝
由于电致发光层仅分别包含BH2和AlQ3且没有第二主材料,因此对照器件1和3表现出低稳定性。比较而言,可能由于电子传输层不含有三嗪,因此对照器件4的驱动电压超过5V。相反,本发明的器件2、3和6-9具有混和电致发光层,体现出大于1000小时的半衰期,并且具有低于5V的驱动电压。
通过这一结果,可以清楚的看到,与对照器件不同,根据本发明实施方式的OLED既显示了低驱动电压(低于5V)又体现了充分的工作稳定性(对于至少500cd/cm2的初始亮度具有大于1000小时的半衰期)。为了获得具有不同发射颜色的不同器件还可以在各种组分构成的OLED器件中采用该实施方式。
对于说明书和所附权利要求书,除非另有说明,在说明书和权利要求中使用的表示数量、百分比或比例的任意数值以及其它数值都可以理解为通过术语“大约”在所有实例中可以修改上述数值。因此,除非具体指出,在说明书和所附权利要求中提到的数字参数为可以根据本公开要获得的理想特性改变的近似值。至少,不希望限定权利要求等同范围的申请,至少应该根据记载的主要数字数量并通过将其应用于普通完整技术中解释该数字参数。
应该注意除非特别以及明确限定为一个指示物,在说明书和所附权利要求中所用到的单数形式“一(a)”、“一个(an)”和“该(the)”含有多个指示物。因此,例如,“一掺杂物”含有两种或者多种掺杂物。希望不限定这里所用到的术语“含有”及其语法变形,从而使得所列出的项目不排除可能替代或者添加到所列项目种的其他可能项目。
尽管描述的是具体的实施方式,但是应用者或其他的熟练技术人员将能够联想到那些目前无法预见或目前可能无法预见的替代方案、修改、变型、改进和基本上等同的技术方案。因此,提交的且可能修改的所附权利要求意欲涵盖所有这些替代方案、修改、改进和基本上等同的技术方案。
Claims (20)
1、一种有机发光器件,含有:
(a)阳极;
(b)空穴传输层;
(c)含有至少两种材料的电致发光材料层,所述至少两种材料具有不同电子和空穴传输能力;
(d)含有三嗪的电子传输层;以及
(e)阴极,
其中所述电致发光材料层的厚度小于50nm。
2、根据权利要求1所述的器件,其特征在于,相对于所述电子传输材料的总体积,存在于所述电子传输层中的三嗪的体积含量至少为大约50%。
3、根据权利要求1所述的器件,其特征在于,所述三嗪为4,4’-双-[2-(4,6-二苯基-13,5-三嗪基)]-1,1’-联苯。
4、根据权利要求1所述的器件,其特征在于,所述三嗪掺杂有无机和有机材料其中至少之一。
5、根据权利要求1所述的器件,其特征在于,所述具有不同电子和空穴能力的两种材料其中至少之一为三(8-羟基喹啉)铝。
6、根据权利要求1所述的器件,其特征在于,具有不同电子和空穴能力的两种材料其中之一为三(8-羟基喹啉)铝并且另一种选自芳香叔胺、蒽、并四苯。
7、根据权利要求6所述的器件,其特征在于,所述芳香叔胺为N,N’-二(萘-1-基)-N,N’-二苯基-联苯胺),所述蒽为2-t-丁基-9,10-二(2萘基)蒽,并且所述并四苯为红荧烯。
8、根据权利要求1所述的器件,其特征在于,所述电致发光材料含有电子传输材料和空穴传输材料。
9、根据权利要求1所述的器件,其特征在于,所述电致发光材料层含有电子传输材料和双极传输材料。
10、根据权利要求1所述的器件,其特征在于,所述电致发光材料层含有空穴传输材料和双极传输材料。
11、根据权利要求1所述的器件,其特征在于,所述电致发光材料层含有由于电子和空穴复合能够发光的至少一材料。
12、根据权利要求11所述的器件,其特征在于,所述能够发光的材料选自荧光材料和磷光材料。
13、根据权利要求1所述的器件,其特征在于,所述器件能够在低于5伏特的驱动电压、至少20mA/cm2的电流密度下工作。
14、根据权利要求1所述的器件,其特征在于,所述器件在初始亮度至少为500cd/m2的情况下具有半衰期至少为1000小时的工作稳定性。
15、根据权利要求1所述的器件,其特征在于,所述电致发光材料层的厚度范围为从约10nm到小于约50nm。
16、根据权利要求1所述的器件,其特征在于,所述电致发光材料层的厚度范围为从约10nm到约30nm。
17、根据权利要求1所述的器件,其特征在于,所述器件发射的光的波长范围为从约400nm到700nm。
18、一种含有至少一有机发光器件的显示器,所述有机发光器件含有:
(a)阳极;
(b)空穴传输层;
(c)含有至少两种材料的电致发光材料层,所述至少两种材料具有不同电子和空穴传输能力;
(d)含有三嗪的电子传输层;以及
(e)阴极,
其中所述电致发光材料层的厚度小于50nm。
19、一种有机发光器件,含有:
(a)阳极;
(b)空穴传输层;
(c)电致发光材料层,含有以下其中至少两种:
(i)电子传输材料;
(ii)空穴传输材料;以及
(iii)双极传输材料;
(d)含有三嗪的电子传输层;以及
(e)阴极,
其中所述电致发光材料层的厚度小于50nm。
20、根据权利要求19所述的器件,其特征在于,所述(i)、(ii)和(iii)中两种的比例范围为5∶95到95∶5。
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US20060265278A1 (en) | 2005-05-18 | 2006-11-23 | Napster Llc | System and method for censoring randomly generated character strings |
US7811679B2 (en) | 2005-05-20 | 2010-10-12 | Lg Display Co., Ltd. | Display devices with light absorbing metal nanoparticle layers |
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2005
- 2005-05-04 US US11/122,288 patent/US8487527B2/en active Active
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2006
- 2006-04-28 GB GB0608494A patent/GB2425886B/en active Active
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- 2006-05-03 DE DE102006020527.8A patent/DE102006020527B4/de active Active
- 2006-05-03 TW TW095115799A patent/TWI322641B/zh active
- 2006-05-04 FR FR0603982A patent/FR2885453B1/fr active Active
- 2006-05-04 KR KR1020060040733A patent/KR100826437B1/ko active IP Right Grant
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103050630A (zh) * | 2011-12-05 | 2013-04-17 | 友达光电股份有限公司 | 电激发光显示面板的画素结构 |
CN103325950A (zh) * | 2012-03-22 | 2013-09-25 | 陶氏环球技术有限责任公司 | 电荷传输层以及包含其的膜 |
CN108470839A (zh) * | 2013-12-31 | 2018-08-31 | 昆山工研院新型平板显示技术中心有限公司 | 一种改善视角特性的顶发射oled器件 |
CN105990528A (zh) * | 2015-02-16 | 2016-10-05 | 上海和辉光电有限公司 | Oled显示面板及oled显示面板制备方法 |
CN105990528B (zh) * | 2015-02-16 | 2018-04-17 | 上海和辉光电有限公司 | Oled显示面板及oled显示面板制备方法 |
Also Published As
Publication number | Publication date |
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FR2885453B1 (fr) | 2008-06-20 |
CN102569661B (zh) | 2015-04-01 |
TW200640286A (en) | 2006-11-16 |
JP2006313909A (ja) | 2006-11-16 |
GB2425886B (en) | 2007-09-26 |
JP4414981B2 (ja) | 2010-02-17 |
TWI322641B (en) | 2010-03-21 |
US20060251919A1 (en) | 2006-11-09 |
GB2425886A (en) | 2006-11-08 |
DE102006020527A1 (de) | 2007-02-15 |
US8487527B2 (en) | 2013-07-16 |
GB0608494D0 (en) | 2006-06-07 |
FR2885453A1 (fr) | 2006-11-10 |
DE102006020527B4 (de) | 2021-10-21 |
KR100826437B1 (ko) | 2008-04-29 |
KR20060115664A (ko) | 2006-11-09 |
CN102569661A (zh) | 2012-07-11 |
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