CN102859741B - 多层叠气密性阻挡层和相关结构以及气密性密封方法 - Google Patents
多层叠气密性阻挡层和相关结构以及气密性密封方法 Download PDFInfo
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Abstract
一种独立多层叠气密片,其包括:第一承载膜(210),在第一承载膜上形成的气密性无机薄膜(220),以及在气密性无机薄膜上形成的第二承载膜(230)。可使用该多层叠片对工件(270)进行气密性密封,可以在独立于多层叠片或工件的形成步骤的步骤中将所述片施加于所述工件。
Description
优先权声明
本申请要求2010年4月20日提交的美国专利申请第12/763541号的权益。该文献内容以及本文提及的出版物、专利和专利文献的全部内容都通过参考结合于此。
技术领域
本发明一般涉及气密性阻挡层,更具体涉及独立多层叠气密性片、相关结构以及形成气密性密封件的方法。
背景技术
气密性阻挡层可用于保护敏感性材料,以免接触各种有害的液体和气体。如本文所用,“气密性”表示完全或基本密封的状态,尤其是针对水或空气的逃逸或进入,不过还设想了针对接触其他液体和气体的保护。
形成气密性阻挡层的方法包括:物理气相沉积(PVD)法,例如溅射或蒸发;或者化学气相沉积(CVD)法,例如等离子体增强CVD(PECVD),其中直接在待保护的装置或材料上形成气密性阻挡层。例如,可使用反应性和非反应性溅射形成气密性阻挡层,例如在室温或升高的温度的工艺条件下形成。反应性溅射联合反应性气体如氧气或氮气进行,导致形成相应的化合物阻挡层(即氧化物或氮化物)。非反应性溅射可使用具有所需组成的氧化物或氮化物靶进行,从而形成具有类似或相关组成的阻挡层。
相对于非反应性溅射,反应性溅射或CVD在经济上是有利的,因为其沉积速率较高。虽然通过反应性溅射能实现提高的生产量,但是其固有的反应特性通常不适用于需要保护的敏感性装置或材料。
鉴于以上情况,非常需要这样的气密性阻挡层,它们具有经济性和装置适应性,能保护敏感性工件如装置、制品或原材料,以免它们不利地接触氧气、水、热或其他污染物。
发明概述
根据本发明的一个方面,提供了一种气密性阻挡层,该阻挡层的形成过程与将其施加于工件的过程分开(decoupled)。气密性阻挡层本身的形成(例如通过物理或化学气相沉积)可涉及氧气、水、溶剂、升高的温度、离子轰击等。通过在第一步骤中形成气密性阻挡层,然后在后续步骤中将该气密性阻挡层施加于工件,可避免在施加气密性阻挡层的过程中使该工件接触侵蚀性或其他有害的工艺条件。
本发明描述了独立多层叠气密性阻挡层,该阻挡层设计成能至少部分包封敏感性装置、制品或材料,所述敏感性装置、制品或材料会因为氧气、湿气、热或其他污染物而劣化。独立多层叠气密性片包括交替结构化形成叠置几何形式的一个或多个无机薄膜以及一个或多个挠性承载膜。具体来说,根据一种实施方式的独立多层叠气密片包括:第一承载膜,具有相对的第一和第二主表面的无机薄膜,以及第二承载膜,其中所述无机薄膜的第一主表面在第一承载膜的表面上形成,第二承载膜在无机薄膜的第二主表面上形成。在其他一些实施方式中,多层叠垫圈包含在合适的垫圈元件上形成的无机薄膜。所述无机薄膜可包含一种或多种氧化物或氮化物,所述氧化物或氮化物包括各种玻璃组成,而承载膜和垫圈元件可包含挠性聚合物材料,例如聚二甲基硅氧烷(PDMS)、聚萘二甲酸乙二醇酯(PEN)或对苯二甲酸乙二醇酯(PET)。
对工件进行气密性密封的方法包括将工件支承在基片上,形成多层叠气密片,将气密片置于工件上,使其在工件外围的基片区域中与基片直接或间接气密性接触,从而对工件进行包封。
可使用多层叠密封组合件对起初在基片表面上形成的装置进行气密性密封,所述多层叠密封组合件包括多层叠气密片和多层叠气密性垫圈。所述多层叠气密性垫圈位于装置外围的基片表面上,所述多层叠气密片位于所述装置上并与所述垫圈气密性接触。
以下详细说明中将提出本发明的其他特性和优点,部分特性和优点对了解详细说明的本领域技术人员而言是显而易见的,或可通过如包括以下详细说明、权利要求以及附图的本文所述实施本发明而认识到。
应该理解,以上一般说明和以下详细说明都提出了本发明的实施方式,为理解要求权利的本发明性质和特性提供概述或框架。包括附图以提供对本发明的进一步理解,附图结合在说明书中并构成说明书的一部分。附图描绘本发明的一些实施方式,与说明书一起用于解释本发明的原理和操作。
附图说明
图1是根据一种实施方式的多层叠气密片的示意图;
图2是使用多层叠气密片的气密性密封装置的示意图;
图3是使用气密性薄膜和气密性阻挡垫圈对装置进行气密性密封的方法的示意图;
图4是使用4层气密片对装置进行气密性密封的方法的示意图。
发明详述
一种多层叠气密片,其包含至少一个承载膜和至少一个在该承载膜上形成的无机薄膜。该气密片可包括双层片、三层片或者具有超过三层的层叠片。根据各种实施方式的示例性多层叠气密片包括双层氧化物/PDMS气密片和三层PEN/氧化物/PDMS气密片。
根据一种实施方式的多层叠气密片的示意图如图1所示。多层叠气密片100包括第一承载膜110,在该第一承载膜110上形成的气密性无机薄膜120,以及在该气密性无机薄膜120上形成的第二承载膜130。在所示实施方式中,无机薄膜120被夹在对应的承载膜110、130之间。任选的第二承载膜130可为无机薄膜120提供保护,适合于将无机薄膜120设置在中性面处或使其略偏向于多层叠气密片的压缩区域。
承载膜可包括塑料膜、聚合物或含有顺应性(即挠性)聚合物的复合膜,所述聚合物是例如聚二甲基硅氧烷(PDMS)、聚萘二甲酸乙二醇酯(PEN)或聚对苯二甲酸乙二醇酯(PET),不过其他材料也是适用的。结合在多层叠气密片中的多个承载膜,包括第一和第二承载膜,可包含相同的聚合物材料或不同的聚合物材料。在一种实施方式中,在包含PEN的第一承载膜上形成无机氧化物薄膜,在该无机氧化物的暴露的主表面上形成PDMS第二承载膜。
所述气密性无机薄膜可包含氧化物或氮化物材料,包括玻璃组合物如870CHM,其为掺杂铌的氧化锡/氟化磷酸锡/五氧化磷玻璃,包含约39.6摩尔%的SnF2、38.7摩尔%的SnO、19.9摩尔%的P2O5和1.8摩尔%的Nb2O5。适用于该无机薄膜的玻璃组合物如共同转让的美国专利第5089446号以及美国专利申请公开第2008/0149924号、第2007/0252526号和第2007/0040501号中所述,这些文献的内容通过参考全文结合于此。
在一些实施方式中,多层叠气密片是能独立存在的,即没有基片的支承。多层叠气密片的总体尺寸可根据应用而变化,但是示例性的总体厚度和面积可分别约为30-1000微米和约1平方厘米至10平方米或更大。在一些实施方式中,单个承载膜的厚度可约为15-500微米(例如,15、25、40、100、150、200、400或500微米),而气密性无机薄膜的厚度可约为0.5-10微米(例如,0.5、1、2、4、6、8或10微米)。为了在使用之前保护多层叠气密片(例如,在运输或储存过程中),可以将一个或多个片包装在适合于保持片的气密完整性的容器中。合适的容器可以是一次性的,或者可以不是一次性的,除了保护气密片免受机械损坏以外,还能提供无菌储存并提供针对辐射损坏的保护。
一种气密性密封的装置的示意图如图2所示。在气密性基片280上形成装置270,该基片是例如玻璃基片,该装置是例如无机发光二极管(OLED)或薄膜太阳能电池。将多层叠气密片200置于该装置上,该气密片包含在第一和第二承载膜210、230之间形成的无机薄膜220。可以围绕多层叠气密片200的外围形成任选的边缘密封件240,例如分配和固化的填充有去湿剂的环氧树脂。在基片上形成边缘密封件,而且该密封件邻接第一承载膜210、第二承载膜230和无机薄膜220中一个或多个膜的侧向边缘表面,从而防止气体或液体的侧向扩散(例如通过第一承载膜210扩散)。
可以在整个结构上形成任选的保护膜或保护片250,从而保护多层叠气密片200,以免发生机械磨损、撕裂等。保护膜250除了为多层叠气密片200提供机械屏障以外,还可设计成使得脆性层(即无机薄膜220)位于中性面处或者位于整个封装件的压缩区域内。在封装件发生挠曲的过程中,这种设计能最大程度减小施加于无机薄膜的拉伸应力,例如在一些实施方式中,在辊到辊工艺中处理所述片。
将多层叠气密片施加于预制工件的过程比同时形成并原位沉积包封层的过程更快。可以在惰性环境中,在室温下将多层叠片直接施加于装置或材料,而不需要真空处理。例如,可以在一开始就在真空室中制造对湿气或氧气敏感的装置,从真空室中取出该装置,并置于惰性环境中,然后永久或暂时地进行保护。由于能在标准温度和压力条件下施加多层叠片,所以周转时间(TACT)短,有助于进行低成本、高效的加工。
除了以上优点以外,通过将多层叠片的形成过程与将其施加于工件的过程分开,可以使密封操作适用于工艺敏感性装置,例如有机发光二极管(OLED)或砷化铜铟镓光伏装置,这些装置不能承受升高的温度或接触氧气。将这两个过程分开,使得可以采用不基于真空的涂覆工艺,例如溶胶-凝胶工艺、纳米复合物的逐层组装工艺、氧化硅纳米颗粒的室温烧结工艺、喷涂工艺、涂刷工艺、辊涂工艺等。其他可以采用的工艺包括将低熔点玻璃热压到耐热塑料基片上,以及将低熔点玻璃料通过带浇铸法浇铸到耐热塑料基片上。可以在采用或不采用施加后烧结步骤的情况下,将气密性多层叠片施加于靶工件。
可使用多层叠气密片来密封具有平面或非平面几何形状的工件。有利的是,气密片能与织构化(例如不平坦)的表面(例如包含台阶特征或微粒的表面)共形。通过选择合适的膜的组合构成多层叠片,可以实现对各种表面几何形状的气密性覆盖。
多层叠气密片除了能与非平面表面共形之外,在将其施加于工件之后,还能进行机械挠曲。能进行机械挠曲的气密片可以弯折、弯曲或以其他方式变形,同时保持其气密性质。这使得可挠曲工件能进行气密性密封。根据一些实施方式,多层叠气密片可位于密封的装置的中性面处,从而尽可能减小当装置封装件发生挠曲时无机薄膜所承受的应力。或者,若装置只需在一个方向挠曲或平放,则多层叠片可位于组装的结构的压缩区域中。
在另一些实施方式中,多层叠气密片可以是光学透明的,使其适合于包封例如食品、医疗器械和药物材料,在这些情况下,不需要打开包装就能看见包装中的内容物是有利的。光学透明性还适合于密封光电装置,例如显示器和光伏装置,这些装置倚赖于光传输。在一些实施方式中,多层叠气密片所具有的光学透明度的特征是透光率大于90%(例如大于90、92、94、96、或98%)。
在另一种实施方式中,可使用多层叠气密片来包封含有液体或气体的工件。示例性的工件包括染料敏化太阳能电池(DSSC)、电润湿显示器和电泳显示器。多层叠气密片可明显抑制工件接触空气和/或湿气,这可有利地防止发生不利的物理和/或化学反应,例如氧化、水合、吸收或吸附,以及这些反应的伴生现象,包括腐化、降解、溶胀、功能降低等。
由于多层叠片具有气密性,所保护的工件的寿命可延长到超过使用常规气密性阻挡层所实现的寿命。
根据一些不同的实施方式,一种形成独立多层叠气密片的方法包括用例如有效量的氧气加上溅射气体(如Ar)对金属靶进行反应性溅射,从而在聚合物基片上形成气密性氧化物薄膜。
另一种形成多层叠气密片的方法包括将870CHM玻璃非反应性溅射到PEN膜上,然后在玻璃的暴露表面上铺置聚二甲基硅氧烷(PDMS)膜。可以对PDMS的厚度进行选择,从而将玻璃膜设置在多层叠片的中性面处。PDMS起到顺应性承载体的作用,使得能将多层片共形施加在非平面或其他形式的不规则表面上。对于具有两个或更多个不同承载膜的多层叠片,可使任何一个承载膜面向(例如接触)工件。
适合于在承载体上形成无机膜的其他方法包括化学气相沉积,等离子体增强化学气相沉积,高速率溅射如HIPIMS,以及蒸发法。随后可以在气密性无机薄膜上形成另一个承载膜。可以单独地或者作为层叠组合件,将另外的层增加到层叠结构上。
多层叠阻挡层可采取如上所述的气密片的形状,例如参见图1和2。根据另外或补充的实施方式,多层叠阻挡层可采取O型环或平垫圈的形状。如以下详细描述的,多层叠阻挡垫圈包括用气密性无机薄膜涂覆的垫圈元件。
一种对工件进行气密性密封的方法可包括按需要施加外围密封件,从而防止湿气或气体通过该多层叠片的承载膜侵入。图3显示一种气密性密封结构,其包括多层叠气密片300、多层叠气密性垫圈315和基片380,它们协同包封在该基片上形成的装置370。如同图1的实施方式,对多层叠气密片300进行设计,将其置于装置370上。在用多层叠气密片300覆盖装置370之前,将多层叠气密性垫圈315设置在包围该装置(即在其外围)的基片380上。多层叠气密性垫圈315是一个独立部件,其包括垫圈元件332,该元件涂覆有气密性无机薄膜322。垫圈元件可包括塑料、聚合物或含有顺应性聚合物的复合膜,所述顺应性聚合物是例如聚二甲基硅氧烷(PDMS)、聚萘二甲酸乙二醇酯(PEN)或聚对苯二甲酸乙二醇酯(PET),不过其他常用垫圈材料如或Buna-N(腈)O形环也是合适的。
仍然参见图3,可以围绕装置外围局部施加热量和压力(如垂直箭头所示),从而在多层叠气密片300和多层叠气密性垫圈315之间,以及在多层叠气密性垫圈315和基片380之间形成气密性密封。因此,第一无机薄膜可以与第二无机薄膜气密性接触,第二无机薄膜可以与基片气密性接触。
若承载膜是可透气塑料膜,则多层叠气密片300上的无机膜320可罩住整个承载膜330,或者若承载膜已经是气密性膜(例如标准玻璃),则无机膜320可以图案化,使得该无机膜不会覆盖装置区域,但仍然密封于多层叠气密性垫圈315。另外,若需要避免多层叠气密片和工件之间的直接接触,则可使用多层叠片作为透明的边缘密封垫圈或外部密封封套。
在一些实施方式中,垫圈元件涂覆有气密性无机薄膜,从而形成多层叠阻挡垫圈。但是,当垫圈元件包含具有足够气密性的材料时,可以使用未涂覆的垫圈元件形成气密性密封。
根据另一种实施方式的多层叠气密片的示意图如图4所示。多层叠气密片400包括气密性无机薄膜420a和第二无机薄膜420b,该气密性无机薄膜420a在第一承载膜410和第二承载膜430之间形成,该第二无机薄膜420b设计成在装置470外围的区域中与基片480气密性接触。可通过如垂直箭头所示,在装置外围的区域中对多层叠气密片400局部施加热量和压力,从而形成气密性密封。任选地,如未示出的实施方式所述,在基片无气密性的实施方式中,可以先在基片表面上形成另外的气密性无机薄膜或多层叠气密片,然后在基片上形成装置,并用多层叠气密片400覆盖该装置。
对工件进行气密性密封的方法可包括在工件上或其周围覆盖、设置、铺置、层叠或粘合多层叠气密片。如本文所用,“用多层叠气密片包封”及其变化形式表示使用该多层叠气密片形成完全或部分包围工件的不渗透空气或液体的阻挡层。
可任选将工件置于基片上并抵靠该基片进行气密性密封,或者将工件气密性密封在该基片内。所述基片可包括平面基片或非平面基片。由气密性材料形成的基片可部分封闭待保护的工件,所述基片可包含例如凹陷部分,该凹陷部分设计用于支承工件。所述基片可包括进口或出口,例如填充口或分配口,工件可通过该进口或出口。在一些实施方式中,可使用层叠气密片对进口或出口进行密封,使得基片的内部(及其内含物)与环境发生气密性隔离。一种示例性的进口或出口可包括法兰。示例性的基片包括玻璃片或聚合物片、金属箔、注射器、安瓿、瓶子和其他容器。多层叠气密片可抵靠这种基片的表面铺置。
在一些实施方式中,可以将去湿剂材料与工件密封在一起。可使用去湿剂材料来清除例如水。在另一种实施方式中,基片可包含用于储存去湿剂的位置,例如将要密封的区域内的凹陷部分。除了将工件支承在基片上以外,还可将去湿剂材料支承在该基片上,然后在工件和去湿剂上设置气密片,从而形成包封的工件。
本发明的另一种实施方式涉及用多层叠气密片和/或多层叠阻挡垫圈保护的工件(例如材料、制品或装置)。受保护的工件具有气密性密封带来的寿命更长的优点,以及包封TACT更快带来的生产成本较低的优点。
实施例
通过以下实施例进一步阐明本发明。
实施例1
用涂覆有约2微米的870CHM材料的约125微米厚的聚萘二甲酸乙二醇酯(PEN)塑料制备两种不同的多层叠气密片。样品1包含沉积后不做处理的CHM涂覆的PEN塑料,而样品2包含于140℃烧结2小时的CHM涂覆的PEN塑料。比较例样品3包含未涂覆的PEN塑料。
通过将两个这种片层叠在一起,使用在有效温度下固化形成密封件的脉冲密封剂围绕外围密封,从而形成测试包。在将这些片完全密封在一起之前,在各个包中插入DrieriteTM材料(硫酸钙)作为指示剂,当有足够的湿气扩散到包中,DrieriteTM会从蓝色变成粉色。在环境湿度下保存90小时之后,比较例样品3中的DrieriteTM为粉色,表示有湿气渗透到包中。另一方面,样品1和样品2的内含物都为蓝色,表示有效的气密性阻挡层对DrieriteTM进行了包封。
本发明揭示了对装置或制品进行气密性密封的新颖产品和方法,而不需要使待保护工件与形成和沉积包封阻挡层的过程之间相适应。所揭示的独立多层叠气密性阻挡层和伴随的包封方法可用于在装置制造过程中对其进行保护。而且,可使用该阻挡层和方法在该装置的使用过程中对其进行临时或永久保护。
如本文所用,单数形式的“一个”、“一种”和“该”包括复数指代物的情况,除非上下文中有另外的清楚说明。因此,例如,对“片”的引用包括具有两个或更多个这种“片”的例子,除非上下文中有另外的清楚说明。
在本文中,范围可以用从“约”一个具体值和/或至“约”另一个具体值表示。表达这种范围时,包括从一个具体值和/或至另一个具体值的例子。类似地,作为约数表示数值时,使用前缀“约”,应理解其具体值形成另一个方面。还应理解,每个范围的端点,无论是与另一个端点相关还是独立于另一个端点,都是有意义的。
除非另外清楚指明,否则,不应认为本文提出的任何方法要求以特定顺序实施其步骤。因此,当方法权利要求未明确指出其步骤应按一定顺序进行,或者名优在权利要求或说明书中具体指出步骤限于一定顺序时,不应推断有任何具体顺序。
还应注意,本文称部件“设计成”或“适应于”特定功能。在这方面,这种部件“设计成”或“适应于”体现具体性质,或以具体方式发挥功能,此类引述为结构性引述,而非预期应用引述。更具体来说,本文关于部件“设计成”或“适应于”某方式的引述表示该部件的现有物理条件,因此应理解为对该部件的结构特性的限定性引述。
对本领域技术人员显而易见的是,可以在不偏离本发明精神和范围的情况下对本发明进行各种修改和变化。由于本发明技术人员可结合本发明的精神和原理对所揭示的实施方式进行修改、组合、子项组合和变化,所以本发明应理解为包括所附权利要求及其等同项范围内的所有内容。
Claims (5)
1.一种用多层叠密封组合件密封的气密性密封的工件,所述多层叠密封组合件包括:
多层叠气密片,其包括在承载膜表面上形成并与所述承载膜表面直接物理接触的第一无机薄膜;和
多层叠气密性垫圈,其包含在垫圈元件的表面上形成的第二无机薄膜,其中工件在基片表面上形成;
将多层叠气密性垫圈设置在工件外围的基片表面上;
将多层叠气密片设置在工件上并与多层叠气密性垫圈气密性接触,以及
其中所述第一无机薄膜包含低熔点玻璃组合物。
2.如权利要求1所述的工件,其特征在于,所述第一无机薄膜与多层叠气密性垫圈气密性接触。
3.如权利要求1所述的工件,其特征在于,所述多层叠气密性垫圈与基片气密性接触。
4.如权利要求1所述的工件,其特征在于,所述第二无机薄膜涂覆所述垫圈元件。
5.一种包封工件的方法,其包括:
将工件支承在基片上;
形成多层叠气密片,该气密片包括承载膜和第一无机薄膜;
独立形成多层叠气密性垫圈,该多层叠气密性垫圈包含涂覆有第二无机薄膜的垫圈元件;
将多层叠气密性垫圈设置在工件外围的基片表面上;
将多层叠气密片设置在工件上并与多层叠气密性垫圈气密性接触,
其中所述第一无机薄膜和第二无机薄膜包含低熔点玻璃组合物。
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TW201514006A (zh) | 2015-04-16 |
TW201144062A (en) | 2011-12-16 |
US8563113B2 (en) | 2013-10-22 |
US9555595B2 (en) | 2017-01-31 |
JP2013525146A (ja) | 2013-06-20 |
KR20150023946A (ko) | 2015-03-05 |
US20140017437A1 (en) | 2014-01-16 |
WO2011133373A3 (en) | 2012-01-19 |
WO2011133373A2 (en) | 2011-10-27 |
KR20130061141A (ko) | 2013-06-10 |
US20110256334A1 (en) | 2011-10-20 |
CN104647851A (zh) | 2015-05-27 |
TWI472428B (zh) | 2015-02-11 |
JP5946140B2 (ja) | 2016-07-05 |
KR101769690B1 (ko) | 2017-08-18 |
CN102859741A (zh) | 2013-01-02 |
KR101715982B1 (ko) | 2017-03-13 |
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