CN1237627C - 一种有机器件的制造方法 - Google Patents
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Abstract
本发明涉及有机器件的布图方法,更具体地说,涉及利用压模的布图方法。在衬底(602)上淀积有机材料第一层(608),接着淀积第一电极层(608)。然后将具有升高部分(506)的第一布图压模(500)压到第一电极层(608)上。使得第一布图压模(500)的升高部分(506)接触第一电极层(608)的部分。除去布图压模(500),以便除去与第一布图压模(500)的升高部分接触的第一电极层(608)。在本发明的一个实施例中,然后在第一电极层上淀积第二有机层,接着淀积第二电极层。将具有升高部分的第二布图压模压到第二电极层上,以便除去与第二布图压模的升高部分接触的第二电极层的部分,最好用粘结剂材料(508)例如金属覆盖布图压模。
Description
本申请是1999年11月23日申请的美国专利申请序列号No.09/447,793的延续部分,这里引入其全文作为参考。
技术领域
本发明涉及薄膜的布图方法,更具体地说涉及利用压模的布图方法。
背景技术
在如平板显示器的应用方面,使用薄膜、当有电流激励时发射光的有机光发射器件(OLED)变成了越来越普遍的技术。普通的OLED结构包含双异质结构、单异质结构和单层,如在PCT申请WO96/19792所描述的,这里引入WO96/19792作为参考。
为了形成OLED阵列,必须布图构成材料。可以通过光致抗蚀剂法实现上述布图,如Shieh在美国专利No.5,641,611和Burrows et al在美国专利No.6,013,528中所公开的。也可以使用遮光板(shadowmask)来布图,如在未审的美国专利申请No.09/182636中所公开的。遮光板必须足够厚以便提供机械强度,这样,限制了布图能够实现的分辨率。其它的布图方法也已经采用,例如准分子激光烧蚀和保形掩模。
这些已知的布图方法在某些环境中是令人满意的,但仍然希望更精确、更快和更经济的布图方法。
发明内容
本发明涉及有机器件的布图方法,更具体地说,涉及利用压模的布图方法。在衬底上淀积第一有机材料层,接着淀积第一电极层。然后将具有升高部分的第一布图压模压到第一电极层上,使得第一布图压模的升高部分接触第一电极层的部分。移去布图的压模,以便除去与第一布图压模的升高部分接触的第一电极层的部分。在本发明的一个实施例中,然后在第一电极层上淀积第二有机层,接着淀积第二电极层,将具有生高部分的第二布图压模压到第二电极层上,使得第二布图压模的升高部分接触第二电极层的部分,移去第二布图压模,以便除去与第二布图压模的升高部分接触的第二电极层的部分。最好用粘结剂材料例如金属覆盖布图压模。
具体地说,提供一种制造有机器件的方法,包括:(a)在衬底上形成底电极,在底电极上淀积包括有机材料的第一层;(b)在所述第一层上淀积包括电极材料的第二层;(c)将具有凸起部分和凹陷部分的布图的压模压到第二层上,其中第二层在压模的凸起部分和压模的凹陷部分之间的接合区域破裂;和(d)除去布图的压模。
根据本发明的上述方法,其中布图的压模包括硅。
根据本发明的上述方法,其中布图的压模具有覆盖有粘结剂材料的凸起部分。
根据本发明的上述方法,其中粘结剂材料包括金属或金属合金。
根据本发明的上述方法,其中粘结剂材料包括胶水。
根据本发明的上述方法,其中第一层进一步包括有机空穴传输层和有机发射层。
根据本发明的上述方法,其中在淀积第一层之前,布图所述有机空穴传输层。
根据本发明的上述方法,其中使用此方法来制造有机光发射器件的无源阵列,每个器件具有由第三层形成的底部电极、由第一层形成的有机光发射层和由第二层形成的顶部电极。
根据本发明的上述方法,其中第三层包括电极材料。
根据本发明的上述方法,其中第三层由金属或金属氧化物构成。
根据本发明的上述方法,其中第二层由金属或金属氧化物构成。
本发明还提供一种用于有机器件布图的压模,包括覆盖有粘结剂材料的凸起部分。
根据本发明的上述压模,其中粘结剂材料包括金属。
根据本发明的上述压模,其中粘结剂材料包括金属合金。
根据本发明的上述压模,其中布图的压模包括硅。
本发明还提供一种制造有机器件的方法,包括:(a)在衬底上淀积第一有机层;(b)在第一有机层上淀积第一电极层;(c)将具有粘结剂覆盖的凸起部分的第一布图压模压到第一电极层上,使得第一布图压模的凸起部分接触第一电极层的多个部分;(d)除去第一布图压模,以便除去与第一布图压模的凸起部分接触的第一电极层的部分;(e)在第一电极层上淀积第二有机层;(f)在第二有机层上淀积第二电极层;(g)将具有粘结剂覆盖的凸起部分的第二布图压模压到第二电极层上,使得第二布图压模的凸起部分接触第二电极层的多个部分;(h)除去第二布图压模,以便除去与第二布图压模的凸起部分接触的第二电极层的部分。
根据本发明的上述方法,还包括步骤:(i)在第二电极层上淀积第三有机层;(j)在第三有机层上淀积第三电极层;(k)将具有粘结剂覆盖的凸起部分的第三布图压模压到第三电极层上,使得第三布图压模的凸起部分与第三电极层的多个部分接触;(l)除去第三布图压模,以便除去与第三布图压模的凸起部分接触的第三电极层的部分。
根据本发明的上述方法,还包括步骤:在步骤(d)之后,步骤(e)之前,除去通过在步骤(d)中除去第一电极层的部分而露出的第一有机层的部分;在步骤(g)之后,步骤(h)之前,除去通过在步骤(g)中除去第二电极层的部分而露出的第二有机层的部分。
根据本发明的上述方法,其中通过反应离子蚀刻除去第一有机层的部分。
根据本发明的上述方法,其中通过结合CF4和O2的反应离子蚀刻除去第一有机层的部分。
根据本发明的上述方法,其中通过利用O2的反应离子蚀刻除去第一有机层的部分。
根据本发明的上述方法,其中粘结由冷焊导致。
根据本发明的上述方法,其中布图压模包括硅。
根据本发明的上述方法,其中粘结剂材料包括金属或金属合金。
根据本发明的上述方法,其中粘结剂材料包括胶水。
本发明还提供一种制造有机器件的方法,包括:(a)在衬底上淀积第一有机层;(b)在第一有机层上淀积第一电极层;(c)将具有凸起部分的第一布图压模压到第一电极层上;(d)除去第一布图压模;(e)在第一电极层上淀积第二有机层;(f)在第二有机层上淀积第二电极层;(g)将具有凸起部分和凹陷部分的第二布图压模压到第二电极层上,其中第二电极层在压模的凸起部分和压模的凹陷部分之间的接合区域破裂;(h)除去第二布图压模。
附图说明
图1显示了适于使用本发明的压模的截面图。
图2显示了根据本发明布图之前的样品的截面图。
图3显示了用来布图类似于图2样品的图1的压模的截面图。
图4显示了布图之后图3的样品的平面图。
图5显示了如在例子中显示的通过冷焊接着移走的布图工艺,将具有金属层的硅印模压到未布图的OLEDs上以得到布图的OLEDs。
图6显示了230μm直径点图的光学显微照片。
图7显示了当通过电流强度于电压之间的关系特性和通过量子效率与电流强度之间关系测量时,通过遮光板技术布图的OLEDs和通过本发明的压印技术布图的OLEDs的比较结果。
图8显示了宽55μm的横剖图形的SEM图像。
图9显示了420μm×420μm像素的有源矩阵的光学显微照片。
图10显示了单和多像素的场致发光的CCD照片。
图11是玻璃衬底的弹性变形和印模的升高部分的横向扩张的示意图。
图12显示了根据本发明实施例局部制造的器件。
图13显示了进一步加工之后图12的局部制造的器件。
图14显示了进一步加工之后图13的局部制造的器件。
图15显示了进一步加工之后图14的局部制造的器件。
图16显示了进一步加工之后图15的局部制造的器件。
图17显示了进一步加工之后图16的局部制造的器件。
图18显示了进一步加工之后图17的局部制造的器件,以制造完全的器件。
图19显示了图18的顶视图。
图20显示了在通过边缘掩膜得到的器件的边缘处,金属层的连接说明。
图21显示了实际器件的电流与电压之间的关系。
图22显示了实际器件的量子效率与电流之间的关系。
具体实施方式
在接着的工艺和附图中,将参考说明的实施例描述本发明。
下面提供了一种利用压模布图电子器件的方法。在衬底的顶部制造此器件。在根据本发明布图之前,可以利用本领域已知的技术在衬底上形成布图层或第一电极。然后,在衬底和其上存在的任何布图层或电极上淀积有机材料覆盖层。然后,在有机层上淀积金属电极材料覆盖层(“顶部电极层”)。顶部电极层可以是例如阴极层或阳极层。可选择的第一电极也可以是阴极层或阳极层。最好如果顶部电极层是阴极层,那么第一电极是阳极层,反过来亦然。
所述电子器件例如可以是有机光发射器件(OLED),如在美国专利No.5,707,745所描述的,这里引入作为参考。
用具有升高和凹陷部分的压模布图覆盖层,形成希望的图形。根据一个实施例,将压模压到覆盖层上,使得压模的升高部分挤压衬底上的底层。结果,有机层将变形,顶部电极层将在压模的升高和凹陷部分之间的接合处破裂。压模的升高部分可以用一种材料覆盖,使得顶部电极层的底部粘到压模上,并且当压模升起时除去该底部。当压模的升高部分没有覆盖材料,使得顶部电极层的底部粘到压模上时,压模的压力引起顶部电极层破裂,然而,顶部电极的剩余层仍留在布图的电子器件的部分上。
由硬的物质形成压模。最好,压模由容易布图的物质构成。根据本发明可以用来形成压模的合适的材料包含硅、玻璃、石英和硬金属。在试验室硅是最好压模材料,因为它坚硬,并且能容易布图。然而,对于大量生产来说,可以有更合适的不同的材料。
图1显示了适用于本发明的压模100的截面图。压模100具有由硬的物质形成的体102。体102具有凹陷部分104和升高部分106。凹陷部分104和升高部分106可以利用本领域已知的技术形成,例如硅布图和蚀刻工艺。升高部分106用覆盖层108覆盖。覆盖层108适于很好地粘到体102上。覆盖层108也适于很好地粘到材料例如金属和铟锡氧化物(ITO)上。例如,覆盖层108可以是金属或其它的压敏粘合剂。具体地说,如果采用金属,它应该是与从有机材料表面搬走的金属成分几乎一样的金属。在压力下,这些类似的金属形成了强的冷焊连接。
图2显示了根据本发明在布图之前的样品200的截面图。样品200具有由适于提供支撑的材料制成的衬底202。衬底202可以由任何合适的材料制成,包含玻璃、聚合物和胶质玻璃。衬底202可以是刚性的、挠性的、不透明的或透明的。最好,衬底202由如玻璃或塑料的材料制成。利用本领域已知的技术在衬底202上淀积由导电材料制成的底部电极204。最好,底部电极204由透明导电材料例如ITO制成。在一个实施例中,可以利用本领域已知的技术将底部电极204布图为带,如下面参考图4进一步详细讨论的。有机层206是淀积在底部电极204上的覆盖层。有机层206可以包括单层或者多层。例如,有机层206可以包括单或双异质结构OLED的多个有机层,如在美国专利No.5,707,745中所描述的,这里引入作为参考。顶部电极层208是淀积在有机层206上的覆盖层。顶部电极层208由如金属、金属合金或者ITO的导电材料制成。
图3显示了用来将样品300布图为OLEDs阵列的图1的压模100的截面图,样品300与图2的样品200类似。图3的衬底302、底部电极304、有机层306(包括区域306a和306b)和顶部电极层308(包括顶部电极308a和区域308b)对应于图2的衬底202、底部电极204、有机层206和底部电极层208。
将压模100压到样品300上,压模100的升高部分106接触样品300的上部。顶部电极层308的区域308b粘到覆盖层108上,并且当压模100从样品300升起时除去。顶部电极308a(顶部电极层308的遗留部分)不粘到压模上。
图4显示了如参考图3的描述布图之后样品300的许多可能的不同平面图中的一个。在图4中,示出了无源显示器。具体地说,图3是图4通过线3’的截面。在淀积有机层306和顶部电极层308之前,和在由压模100压样品300之前,利用本领域已知的技术将底部电极304布图为带状。加压后,布图顶部电极层308以形成顶部电极308a。由于已经通过压模100除去了顶部电极层308的区域308b,因此露出了区域306a。
在本发明的一个实施例中,图4所示的样品300形成一个3×2电子器件阵列。具体地说,在底部电极304和顶部电极308a的交叉点处制造了电子器件402、404、406、408、410和412。利用本领域已知的无源矩阵编址技术,每个电子器件都可以通过控制底部电极304和顶部电极308a的电压来独立地编址。
应理解,本发明可以用来制造比这里具体描述的器件阵列更大的有机器件阵列。此外,通过本领域已知的淀积各种下转换层可以制造多色显示器。例如,有机层206可以由发射蓝光的材料制成,在淀积底部电极204之前,可以在衬底202上淀积布图的蓝-至-绿和蓝-至-红下转换层。可以布图这些下转换层,使得最后制造的有机器件的阵列形成三色像素,每个像素都包括三个有机器件--一个发射蓝光的没有下转换层的器件,一个发射绿光的具有蓝-至-绿下转换层的器件,一个发射红光的具有蓝-至-红下转换层的器件。
有机材料层可以通过若干任何装置发射光。光的发射通常称为“荧光”。具体的发光机理包含荧光现象和荧光性。对本发明来说,在任何实施例中都可以采用任何类型的荧光。
例子
根据本发明进行通过后淀积模压来直接微布图OLED显示器的方法。具体地说,布图未布图的OLED,通过将带有金属层的布图的硅印模(即压模)压到未布图的OLED上,使得选择性地搬走OLED的阴极层。在后淀积模压法中,印模包含金属覆盖层,当此金属覆盖层和阴极彼此接触时,此金属覆盖层冷焊到未布图的OLED的阴极上。当从OLED移去印模时,以基本上相同的图形从OLED选择性地除去了阴极,其中在印模上放置了金属。
在本例中,采用图5所示的布图工艺。首先,在整个衬底区域602上真空淀积未布图的小微点OLED结构,此小微点OLED结构具有阳极604、一个或多个有机层606和阴极608。在膜淀积之前,给玻璃衬底602预涂覆~1500厚、清洗透明导电(20Ω/)铟锡氧化物(ITO)阳极被清洗,接着进行2分钟的氧等离子处理(31RF功率,50sccm的氧流速,100mTorr室压)。此OLED是单异质结构器件,具有500厚的作为空穴传输材料的4,4’-双[N-(1-萘基)-N-苯基-氨基]联苯(α-NPD)的空穴传输层和500厚的既作为电子传输又作为光发射材料的三-(8-羟基喹啉)铝(Alq)的电子传输和光发射层。用300厚的Ag层覆盖由400厚的Mg:Ag合金构成的阴极。
为了布图OLEDs,形成印模(或压模)500。在形成印模中,利用传统的光刻处理硅晶片。利用SiO2作为掩模,通过氯基反应例子蚀刻(RIE)和通过湿蚀(HF-HNO3-CH3COOH混合物蚀刻)蚀刻晶片。对于湿蚀,采用7%∶70%∶23%(HF∶HNO3∶CH3∶COOH)的蚀刻剂成分,蚀刻速度为2μm/分钟。在硅印模上得到的图形是希望的OLED图形的负相图。用金属覆盖层708覆盖硅印模702,金属覆盖层708具有厚50的Cr粘结层和通过传统的电子束蒸发淀积的150-200厚的Ag层。
为了建立OLED图形,将印模压到未布图的OLEDs上,以便诱发OLED阴极和印模上的银之间的冷焊。利用Instron DynamicTesting System(型号8501)进行加压,它利用液压传动装置施加压力。将衬底和印模放在下圆柱形压板上,通过向固定的上压板移动下压板来施加压力。随着时间,施加的力从零线性增加到最大,最大的力和斜率由计算机控制。整个实验过程中,采用大约10mm×10mm的玻璃衬底602。
图6a和6b显示了230μm直径的点图形的结果。ITO层没有被布图,最大压力为~35kN,相应于~290Mpa的平均压力。斜率为1kN/s,达到最大压力之后,在压力下保持样品5分钟。采用具有~10μm的蚀刻深度的硅印模。选择此深度以努力防止由于玻璃衬底的可能变形而可能使印模无意的接触到阴极层。对于更大的图形来说,这方面的考虑尤其重要。如图6a和6b所示,实现高效率的图形转移。
图7比较了通过本技术布图的1mm直径的OLEDs和利用传统的遮光板技术布图的OLEDs。图7显示了电流密度与电压之间的关系和外量子效率与电流密度之间的关系。V10定义为对应于10mA/cm2的电流密度的电压。图7显示了通过此方法没有导致明显的退化。
图8a和8b显示了通过本方法得到的宽55μm的横向图形。阴极没有明显的剥离。应注意有些有机材料也被除去。
这些实验中的OLEDs的布图是在实验室的环境条件下进行的。因此印模和OLEDs都没有收到保护使其免受灰尘、氧、水蒸汽等的影响。
为了说明将本方法应用到平板显示器的可能性,制造了一个具有420μm×420μm像素尺寸的无源矩阵。首先,通过传统的光刻和湿蚀得到~1500厚的ITO层的平行线。进行清洗步骤之后,依次在布图的ITO层(如上所述)淀积有机单异质结构和阴极层。然后,用具有平行线图形的印模垂直压衬底,以便得到无源矩阵。在加压过程中施加的最大力为~8kN(即~380Mpa的压力),斜率为1kN/s。达到最大力之后,在压力下保持样品5分钟。图9a和9b显示了得到的图形。图10a和10b分别显示了接通单个和多个像素的CCD相片。对于图10a和10b中接通单个像素来说,整个行和整个列都被微弱地接通。然而,相信这是由于反向漏电流而导致的,是器件固有的问题。
当使两个固体表面接触时(例如印模上的金属层和OLED的阴极),当界面间隙降低到临界值以下时,它们可以彼此连接,生成单一固体。因此,为了通过此技术实现好的图形,施加的力应当足够高以便将界面间隙降低到临界值以下。
还应当考虑阴极层中的应力分布。此问题可以考虑硅印模和玻璃衬底之间具有有限的摩擦力的弹性接触问题。在接触区的边缘处,正常的接触应力是非常大的。一般认为由于高度集中的正常应力,使得在接触区的边缘处局部削弱了阴极层。而且,由于相当高的施加力,应考虑阴极和有机层的塑性变形。
当施加的力逐渐增加时,由施加的力和泊松比确定,印模的升高部分横向延伸。参见图11,希望有助于局部减弱。因此,结果,当印模从OLEDs分离时,沿着减弱的边界出现裂痕,产生尖锐的图形边缘。施加的力应当足够高以便将银层的界面间隙降低到临界值以下,而且沿着接触区边缘使金属层局部减弱。确定的优选压力为大约250Mpa至大约400Mpa。
当将印模施加给器件时,器件的衬底会弯曲,使得器件弯曲到压模的凹陷部分中。器件和压模的凹陷部分之间的接触是不希望的,且会导致应该除去的层留在器件上。为了避免这种接触,可以控制各种参数。例如,更硬的衬底和施加给压模更小的力是可以用来消除这种接触的两个因素。如果采用挠性衬底,如果需要,可以在刚性支撑结构上安装此衬底。还可以采用其它的方法以保持挠性衬底足够的刚性,以便保持希望的公差。另一个重要的因素是压模的几何形状。具体地说,通过增加凹陷部分的深度,或者通过减小升高部分之间的间隙,可以避免这种接触。确信每1毫米间隙最好为10微米深度,以避免这种接触,尽管上述比例可以随着具体的衬底和力而变化。
通过模压的全色OLED
在本发明的一个实施例中,可以用布图的压模进行几个不同的布图步骤。结果,可以制造如全色OLED显示器的器件。例如,可以制造如图12-18所示的全色OLED。
图12显示了部分制造的器件1200。衬底1220具有利用传统的布图法在其上制造的第一电极1225和绝缘带1227。然后在打底结构上淀积有机覆盖层1230和电极覆盖层1240。然后将具有升高部分1212和凹陷部分1214的布图的压模1210压到器件1200上。然后以与前面关于图1-3所描述的方式类似的方式布图电极覆盖层1240。
图13显示了进一步处理了之后图12所显示的部分制造的器件1200。具体地说,布图压模1210已经压到器件1200上并且已经除去。电极覆盖层1240的除去的部分1240b已经粘到压模1210上,并且由压模1210除去。有机覆盖层1230的除去部分1230b已经粘到压模1210上,并且已经由压模1210除去。有机覆盖层1230的部分1230c留在器件1200上,但通过除去部分1240b而保持露出状态。第一可供使用的有机层1230a留在器件1200上,与第一电极1225电接触。第二电极1240a也留在器件1200上,与第一有机层1230a电接触。
图13示出了粘到压模1210上的有机覆盖层1230的除去部分1230b和留在器件1200上的有机覆盖层1230的部分1230c。然而,根据各个层的粘结,给第二电极层1240的部分1240b打底的有机覆盖层1230的部分可以完全被压模1210除去,即,移去压模1210之后没有留下部分1230c。还可以是,给第二电极层1240的部分1240b打底的有机层1230的部分可以全部留在器件1200上,即没有部分1230b。
图14显示了进一步处理之后部分制造的图13的器件1200。压模1210升起之后留下的任何有机覆盖层1230的部分1230c都已经被除去。可以通过任何适当的且不会毁坏器件1200的技术来除去部分1230c。具体地说,应当选择除去的工艺以使对电极1240a的损伤最小,所用的任何试剂都应当不与电极1240a起反应。最好,使用反应离子蚀刻来除去部分1230c。可以采用CF4和O2的组合或者仅用O2的反应离子蚀刻。当部分1230c包含Alq时最好采用CF4和O2的组合。通过这种组合可以快速除去。可以淀积薄的金保护层作为电极1240a的一部分,以为除去工序提供保护,尤其是当采用CF4和O2的反应离子蚀刻时。
绝缘带1227可以在用压模1210、1520和1710压的过程中防止第一电极1220和其它的电极之间可以形成的短路。绝缘带1227平行于第二电极1540a延伸,可以由任何提供适当保护的不导电材料制成。最好,绝缘带1227由SiNx或者SiO2制成。绝缘带1227不是必须的,如果即使没有绝缘带1227,上述短路的形成在可接受的公差内,也可以从器件1200省略绝缘带1227。
图15显示了进一步处理之后部分制造的图14的器件1200。有机覆盖层1530和电极层1540已经淀积在打底层上。布图的压模1510位于器件1200的上面,布图的压模1510具有升高部分1512和凹陷部分1514。采用与图12-14所描述的处理类似的处理以便除去与压模1510的升高部分1512对应的有机覆盖层1530和电极层1540的部分。
图16显示了进一步处理之后,尤其是已经移去压模1510并且已经除去了任何遗留的暴露的有机覆盖层1530的部分之后,图15的部分制造的器件1200。有机覆盖层1530的第二可供使用的有机层1530a留在器件1200上,与第一电极1225电接触。第三电极1540a留在器件1200上,与第二可供使用的有机层1530a电接触。有机覆盖层1530的残余部分1530d和电极覆盖层1540的残余部分1540d也留在第二电极1240a的顶部。
图15和16显示了在先前制造的可供使用的有机层1230a和第二电极层1240a上具有凹陷部分1514的压模1510。这些凹陷部分导致了残余部分1530d和1540d的制造。对于器件1200的工作来说,这些残余部分不是必须的。然而,确信在最后将作为器件1200的功能部件的先前制造的区域具有凹陷部分例如凹陷部分1514能使在接着的压工序过程中对这些先前制造的功能部件的损害最小,上述功能部件例如有可供使用的有机层1230a和第二电极1240a。如果先前制造的功能部件可以耐印模的压力,且仍然在希望的参数内起作用,也可以不以这种方式来保护它们。
图17显示了进一步处理之后图16的部分制造的器件1200。在打底层上已经淀积了有机覆盖层1730和电极层1740。布图的压模1710位于器件1200的上方,压模1710具有升高部分1712和凹陷部分1714。用与图12-14所描述的类似的工艺除去与压模1710的升高部分1712对应的有机覆盖层1730和电极覆盖层1740的部分。
图18显示了进一步处理之后图17的器件1200,以得到最后制造的器件。具体地说,已经移走压模1710,并且已经除去了任何遗留的第二有机层1730的暴露部分。有机覆盖层1730的第三可供使用的有机层1730a留在了器件1200上,与第一电极1225电接触。第四电极1740a留在器件1200上,与第三可供使用的有机层1730a电接触。有机覆盖层1730和残余部分1730d和电极覆盖层1740的残余部分1740d也留在第三电极1540a以及残余部分1540d的顶上。
图19显示了图18的器件的顶视图。图12-18是由图19沿线1得到的截面图。为了清楚,图19中只示出了可供使用的电极即第一电极1225、第二电极1240a、第三电极1540a和第四电极1740a。如图18所示,这些电极中的几个实际上被残余层覆盖,在图19中没有示出。
最好,电极覆盖层1540和1740的任何残余部分即残余部分1540d和1740d都与直接在下面延伸且与它们平行的可供使用电极层电连接,以避免不希望的电浮置电极覆盖层的残余部分,和/或避免残余有机部分的电压差。具体地说,参考图18,第二电极1240a最好电连接到正好在第二电极1240a上的残余部分1540d和残余部分1740d。同样,第三电极1540a最好电连接到正好在第三电极1540a上的残余部分1740d。此电连接可以通过许多方式来实现。图20显示了一种通过边缘研磨实现此连接的可能的方式。具体地说,利用在中心具有一个大开口的遮光板电极覆盖层1230、1240、1530、1540、1730和1740,使得遮蔽器件1200的边缘。用来淀积电极覆盖层1240、1540和1740的掩模具有比用来电极有机覆盖层1230、1530和1730的开口更大的开口。结果,在器件1200的边缘处,残余部分1540d和1740d与第二电极1230电接触。第三电极1530同样与其覆盖的残余部分1740d电接触。
与残余部分1530d和1730d叠加的电极1230a和1530a之间的电接触也可以在不使用边缘掩模、通过在器件的边缘驱动导电棒穿过电极和任何叠加的残余部分来实现。
当电流流过可供使用的有机层1230a、1530a和1730a时,它们发射光。具体地说,当在第一电极1225和第二电极1240a之间施加电流时,第一可供使用的有机层1230a发射光。当在第一电极1225和第三电极1540a之间施加电流时,第二可供使用的有机层1530a发射光。当在第一电极1225和第二电极1240a之间施加电流时,可供选择的有机层1230a发射光。图18所示的器件1200可以是全色OLED。例如,可供使用的有机层1230a可以发射红光,可供使用的有机层1530a可以发射绿光,可供使用的有机层1730可以发射蓝光。
尽管用简化的有机层和电极说明的本发明的各种实施例,但另外的层和子层也可以存在。例如,可供使用的有机层1230a可以包括如参考图2所描述的多个子层。另外的层还可以存在。例如,还可以有孔注入层,例如Forrest et al在美国专利No.5,998,803中所描述的,这里引入作为参考。电极和有机层之间存在这种孔注入层会妨碍电极和有机层之间的物理接触,但不会改变电极和有机层电接触的事实。还可以存在本领域已知的另外层。
图12-20的实施例可以使用与图1-11一样的压模、材料和工艺参数来实施。
最好,每个有机层和每个电极都大约1000厚。尽管可以使用其它任何合适的透明电极,但第一电极1225最好是ITO。最好,第二电极1240a、第三电极1540a和第四电极1740a包括大约1000厚的覆盖有大约100厚的Au层的Mg/Ag合金层,Mg/Ag合金层。然而,也可以采用任何合适的电极,例如LiF/Al电极。
在图12-20的实施例中,在模压过程中,压模应当适当定位。具体地说,在图15和17所示的模压过程中,压模应当根据器件1200上已有的结构精确定位。此对准可以利用本领域已知的技术例如利用通过器件底部突出的IR光的光学对准、利用光散射的基准对准和任何其它适当的技术来实施例。从而电极覆盖层干扰这种对准技术,在淀积过程中可以采用边缘掩模以提供器件的没有金属淀积覆盖的区域。
进一步的例子
在一个衬底上依次制造两个OLEDs阵列。尽管没有使用模压,但在两个阵列的制造中间通过反应离子蚀刻除去有机层。这表面第一阵列不受暴露于反应离子蚀刻的负面影响,第二阵列可以顺利地利用已经暴露于反应离子蚀刻的底电极来制造。
具体地说,得到用ITO层覆盖的传统衬底。此ITO层没有被布图,并且在每个阵列中作为每个器件的普通的底部电极(阳极)。结果,此例不是要说明每个像素都分别编址的阵列,而是说明可以制造工作的OLEDs。在ITO层上覆盖淀积500厚的α-NPD层,接着淀积500厚的Alq层,以形成传统的单异质结构OLED的有机层。然后仅第一阵列的顶部电极(阴极)通过遮光掩模淀积。限定第一阵列小于衬底的一半。
测量器件的第一阵列的特性。图21显示了这些器件的电流与电压之间的关系,图22显示了量子效率与电流之间的关系。具体地说,图21的线2110和2115显示了电流与电压之间的关系,图22的线2210和2215显示了量子效率与电流之间的关系。
然后采用结合CF4和O2的反应离子蚀刻来除去露出的有机层,即,器件的第一阵列的没有被顶部电极覆盖的有机层部分。然后再次测量器件的第一阵列的特性。图21的线2120和2125显示了电流和电压之间的关系,图22的线2220和2225显示了量子效率与电流之间的关系。线2120和2125与线2110和2115的接近以及线2220和2225与线2210和2215的接近表示反应离子蚀刻不会负面影响第一阵列中的器件。
然后在包含器件的第一阵列的整个衬底上淀积厚500第二α-NPD层,接着淀积500厚的第二Alq层,以形成传统的单异质结构OLED有机层。然后通过遮光掩模将第二阵列的顶部电极淀积到衬底的没有被第一阵列占据的部分。
测量器件的第二阵列的特性。图21的线2130和2135显示了电流与电压之间的关系,图22的线2230和2235显示了量子效率与电流之间的关系。线2130和2135与线2120和2125的接近以及线2230和2235与线2210和2215的接近表明利用底部电极可以顺利地制造OLED,其中底部电极已经预先用有机材料覆盖,然后用反应离子蚀刻清洗。
然后采用结合CF4和O2的反应离子蚀刻来除去露出的有机层,即,器件的第二阵列的没有被顶部电极覆盖的有机层部分。此反应离子蚀刻还除去了淀积在器件的第一阵列上的有机材料。然后再次测量器件的第二阵列特性。对于器件的第二阵列来说图21的线2140和2145显示了电流与电压之间的关系,图22的线2240和2245显示了量子效率与电流之间的关系。而且再次测量了器件的第一阵列特性。图21的线2150和2155显示了器件的第一阵列的电流和电压之间的关系,图22的线2250和2255显示了器件的第一阵列的量子效率与电流之间的关系。
图21上线2140、2145、2150和2155与其它线的接近以及图22上线2240、2245、2250和2255与其它线的接近表明第二反应离子蚀刻不会负面影响两个阵列中的器件。
结论
本发明的方法与先前报导的布图技术相比具有几个优点。例如,本方法非常经济,因为印模是可再利用的。在印模具有金属层的实施例中,通过湿蚀除去金属层之后可再利用此印模。本发明的方法还提供了高的产量,像显示面板这样的大面积可以在一个步骤中布图。
另外,本发明的方法还适于利用挠性塑性衬底的滚动(roll-to-roll)制造工艺。通过使用滚轮印模,由于降低了接触面积,可以用更小的力来施加最佳压力,因此对于挠性衬底来说可以更容易地进行大面积布图。本发明可以简单、经济和高效地制造OLEDs和其它的电子器件,例如可以用来制造平板显示器。
与本发明的其它实施例相比,图12-20的实施例提供了几个未预料到的和有利的特征。图12-20的实施例使得将不同的有机层引入到相同阵列中的不同器件中。例如,可供使用的有机层1230a可以和可供使用的有机层1530a不同,结果与可供使用的有机层1730a也不同。这样,就可以在不用下转换层的情况下制造全色显示器。使用多个印模是图12-20的实施例中一个预料不到和有利的特征。另一个是能够在模压之后除去残余有机层而不毁坏已经存在的器件,使得可以利用通过上述除去步骤而露出的第一电极1225来制造进一步的器件。
上面已经参考具体的例子和最佳实施例,应理解本发明并不限于这些例子和实施例,具体地说,本发明不限于OLEDs,它可以应用到更宽范围的各种电子器件中。另外,关于OLEDs,本发明也不限于所描述的具体例子和实施例,因此,本领域技术人员应当清楚,所要求的本发明包含从这里描述的具体的例子和最佳实施例作出的各种变化。
Claims (26)
1.一种制造有机器件的方法,包括:
(a)在衬底上形成底电极,在底电极上淀积包括有机材料的第一层;
(b)在所述第一层上淀积包括电极材料的第二层;
(c)将具有凸起部分和凹陷部分的布图的压模压到第二层上,其中第二层在压模的凸起部分和压模的凹陷部分之间的接合区域破裂;和
(d)除去布图的压模。
2.权利要求1的方法,其中布图的压模包括硅。
3.权利要求1的方法,其中布图的压模具有覆盖有粘结剂材料的凸起部分。
4.权利要求3的方法,其中粘结剂材料包括金属或金属合金。
5.权利要求3的方法,其中粘结剂材料包括胶水。
6.权利要求1的方法,其中第一层进一步包括有机空穴传输层和有机发射层。
7.权利要求1的方法,其中在淀积第一层之前,布图所述底电极。
8.权利要求1的方法,其中使用此方法来制造有机光发射器件的无源阵列,每个器件具有底电极、由第一层形成的有机光发射层、和由第二层形成的顶电极。
9.权利要求4的方法,其中金属或金属合金冷焊于第二层的多个部分。
10.权利要求1的方法,其中底电极包括由金属和金属氧化物构成的组中选出的电极材料。
11.权利要求1的方法,其中第二层由金属或金属氧化物构成。
12.一种用于有机器件布图的压模,包括覆盖有粘结剂材料的凸起部分。
13.权利要求12的布图的压模,其中粘结剂材料包括金属。
14.权利要求12的布图的压模,其中粘结剂材料包括金属合金。
15.权利要求12的布图的压模,其中布图的压模包括硅。
16.一种制造有机器件的方法,包括:
(a)在衬底上淀积第一有机层;
(b)在第一有机层上淀积第一电极层;
(c)将具有粘结剂覆盖的凸起部分的第一布图压模压到第一电极层上,使得第一布图压模的凸起部分接触第一电极层的多个部分;
(d)除去第一布图压模,以便除去与第一布图压模的凸起部分接触的第一电极层的部分;
(e)在第一电极层上淀积第二有机层;
(f)在第二有机层上淀积第二电极层;
(g)将具有粘结剂覆盖的凸起部分的第二布图压模压到第二电极层上,使得第二布图压模的凸起部分接触第二电极层的多个部分;
(h)除去第二布图压模,以便除去与第二布图压模的凸起部分接触的第二电极层的部分。
17.权利要求16的方法,还包括步骤:
(i)在第二电极层上淀积第三有机层;
(j)在第三有机层上淀积第三电极层;
(k)将具有粘结剂覆盖的凸起部分的第三布图压模压到第三电极层上,使得第三布图压模的凸起部分与第三电极层的多个部分接触;
(l)除去第三布图压模,以便除去与第三布图压模的凸起部分接触的第三电极层的部分。
18.权利要求16的方法,还包括步骤:
在步骤(d)之后,步骤(e)之前,除去通过在步骤(d)中除去第一电极层的部分而露出的第一有机层的部分;
在步骤(g)之后,步骤(h)之前,除去通过在步骤(g)中除去第二电极层的部分而露出的第二有机层的部分。
19.权利要求18的方法,其中通过反应离子蚀刻除去第一有机层的部分。
20.权利要求19的方法,其中通过结合CF4和O2的反应离子蚀刻除去第一有机层的部分。
21.权利要求19的方法,其中通过利用O2的反应离子蚀刻除去第一有机层的部分。
22.权利要求16的方法,其中粘结由冷焊导致。
23.权利要求16的方法,其中布图压模包括硅。
24.权利要求16的方法,其中粘结剂材料包括金属或金属合金。
25.权利要求16的方法,其中粘结剂材料包括胶水。
26.一种制造有机器件的方法,包括:
(a)在衬底上淀积第一有机层;
(b)在第一有机层上淀积第一电极层;
(c)将具有凸起部分的第一布图压模压到第一电极层上;
(d)除去第一布图压模;
(e)在第一电极层上淀积第二有机层;
(f)在第二有机层上淀积第二电极层;
(g)将具有凸起部分和凹陷部分的第二布图压模压到第二电极层上,其中第二电极层在压模的凸起部分和压模的凹陷部分之间的接合区域破裂;
(h)除去第二布图压模。
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