CN110117418B - 覆盖膜及半导体元件表面的绝缘层的制作方法 - Google Patents

覆盖膜及半导体元件表面的绝缘层的制作方法 Download PDF

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CN110117418B
CN110117418B CN201810204635.1A CN201810204635A CN110117418B CN 110117418 B CN110117418 B CN 110117418B CN 201810204635 A CN201810204635 A CN 201810204635A CN 110117418 B CN110117418 B CN 110117418B
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polyimide layer
layer
polyimide
conductor structures
semiconductor element
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CN110117418A (zh
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林圣钦
吴耀明
陈彦翔
陈忆明
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Taiflex Scientific Co Ltd
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Taiflex Scientific Co Ltd
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Abstract

本发明提供一种覆盖膜及半导体元件表面的绝缘层的制作方法，包括离型层以及设置于离型层上的聚酰亚胺层，聚酰亚胺层包括相对设置的内表面和外表面，外表面直接暴露于大气中，聚酰亚胺层经由包括二胺单体和四羧酸二酐单体的一聚酰亚胺组成物反应所形成，且该聚酰亚胺层还包括架桥剂以及起始剂，其中该二胺单体选自总碳数大于等于36的脂肪族二胺单体，且在温度介于60℃至160℃之间时，聚酰亚胺层的最低粘度小于20000Pa·s。本发明覆盖膜的聚酰亚胺层易薄型化、介电性质佳、杨氏模数低。

Description

覆盖膜及半导体元件表面的绝缘层的制作方法
技术领域
本发明是有关于一种覆盖膜以及半导体元件表面的绝缘层的制作方法。
背景技术
随着电子工业蓬勃发展，聚酰亚胺层因为具有极佳的热稳定性、高耐化性等优异性质，如今已被广泛应用于电子工业上，例如IC晶片保护膜、金属层间绝缘材料、软性电路板及封装材料等。然而，随着电脑、通讯、光电产业的相关产品逐渐朝向轻薄的趋势发展，产业无不追求更高性能表现的材料，因此聚酰亚胺层仍然具有介电性质不佳、吸湿性不佳以及杨氏模数高以致反发力强的缺点需要克服。此外，传统半导体封装结构所使用的聚酰亚胺层还具有不易压合加工、环化温度高以及环化时体积收缩率过大的缺点。此外，对于使用聚酰亚胺层作为半导体元件表面的导体结构间的绝缘层的情况，目前产业中所使用的聚酰亚胺层仍无法填充高深宽比的孔洞（例如：深宽比高于2的孔洞），此实为目前产业中亟待克服的课题。
发明内容
本发明的目的在于解决上述缺点提供一种覆盖膜，其聚酰亚胺层易薄型化、介电性质佳、杨氏模数低。本发明的覆盖膜包括离型层及设置于该离型层上的聚酰亚胺层。聚酰亚胺层包括相对设置的内表面和外表面，其外表面直接暴露于大气中。聚酰亚胺层经由包括二胺单体和四羧酸二酐单体的聚酰亚胺组成物反应所形成，且聚酰亚胺层还包括架桥剂以及起始剂。聚酰亚胺组成物的二胺单体选自总碳数大于等于36以上的脂肪族二胺单体。在温度介于60℃至160℃之间时，聚酰亚胺层的最低粘度小于20000Pa·s。
优选地，该聚酰亚胺层还包括未与聚酰亚胺组成物键结的架桥剂以及起始剂。
优选地，用以生成该聚酰亚胺层的该二胺单体还包括选自羟基、羧基及C=C的基团的二胺单体所组成的群组中的至少一者。
优选地，用以生成该聚酰亚胺层的该二胺单体还包括4, 4’-二氨基二环己基甲烷。
优选地，该聚酰亚胺层在60℃至160℃的热压下，会被填充至深宽比为3的缝隙中。
优选地，该聚酰亚胺层的外表面上未被任何层覆盖。
优选地，该架桥剂包括含有环氧基、异氰酸脂基或烯烃基的化合物且该起始剂包括过氧化物。
本发明另提供一种半导体元件表面的绝缘层的制作方法，包括以下步骤。首先，提供一第一半导体元件，该第一半导体元件的表面具有多个第一导体结构。接着，将第一半导体元件直接接触覆盖膜的聚酰亚胺层。之后，对覆盖膜进行热压工艺，使聚酰亚胺层填满第一导体结构之间的至少一缝隙，使得第一导体结构被该聚酰亚胺层环绕。在进行热压工艺之后，移除离型层。
优选地，该热压工艺的温度介于60℃至160℃之间。
优选地，这些第一导体结构之间的这些缝隙的深宽比大于等于3。
优选地，该第一半导体元件包括晶片。
优选地，这些第一导体结构的组成选自铜、银、锡及上述至少两者所组成的合金所构成的群组。
优选地，在移除该离型层的步骤后，这些第一导体结构被包覆于该聚酰亚胺层中，且在移除该离型层的步骤后，该制作方法另包括：
提供一第二半导体元件，包括一第二部件及设置于该第二部件上的多个第二导体结构，且这些第二导体结构对应于这些第一导体结构而设置；以及
将该第一半导体元件与该第二半导体元件彼此接合，以排开设置于这些第一导体结构以及这些第二导体结构之间的该聚酰亚胺层，致使这些第一导体结构电连接对应的这些第二导体结构。
优选地，该第一部件为印刷电路板、中介板、硅基板或玻璃基板。
优选地，该第二半导体元件包括晶片。
本发明的聚酰亚胺具有可溶性，因此能够涂布于离型层并以160℃的温度进行干燥3分钟以形成聚酰亚胺层，并得到本发明的覆盖膜。此外，本发明的聚酰亚胺层可通过填胶性测试，并且具有可接受的拉伸强度、杨氏模数、伸长率、介电数以及介电损耗。因此，本发明的聚酰亚胺层能够进一步利用上述的方法用以制备半导体元件表面的绝缘层。并且，本发明的聚酰亚胺层在热压工艺温度环境下具有良好的压合流动性，能够取代现有技术的底胶点涂到晶片和基板间再借由毛细作用力流入空隙的覆晶工艺，并且相比使用底胶的覆晶工艺，制作时间较短、填充缝隙能力较佳，也不容易产生气泡。并且，通过上述热压工艺还可以使本发明覆盖膜的聚酰亚胺层填满导体结构之间深宽比大于等于3的缝隙，可应用于半导体封装的介电层、封装体或底胶材料。
附图说明
图1为本发明一实施例的覆盖膜。
图2至图4为本发明第一实施例覆盖膜用以制作半导体元件表面的绝缘层的制作方法的示意图。
图5为本发明第一实施例覆盖膜用以制作封装结构的示意图。
图6至图8为本发明第二实施例覆盖膜用以制作半导体元件表面的绝缘层的制作方法的示意图。
图中：
10、106 覆盖膜； 12、110 离型层； 14、108 聚酰亚胺层； 100、200 第一半导体元件； 102、202 第一部件； 104、204 第一导体结构； 105、205 缝隙； 104a 第一导体结构上表面； 108b 聚酰亚胺层上表面； 112 重布线层； 114 图案化导电层； 116 重布导线；118 介电层； 118a 通孔； 120 导电垫； 122 锡球； 210 第二半导体元件； 212 第二导体结构； 214 第二部件。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
本发明提供一种覆盖膜，包括离型层以及设置于离型层上的聚酰亚胺层。聚酰亚胺层包括相对设置的内表面和外表面，其外表面直接暴露于大气中。换句话说，本发明的覆盖膜可以为仅包括离型层以及聚酰亚胺层的双层结构，且聚酰亚胺层相反于离型层的表面未被任何层覆盖。此外，聚酰亚胺层经由聚酰亚胺组成物反应所形成，该聚酰亚胺组成物包括二胺单体、含有选自羟基、羧基及C=C(烯烃基)的基团的单体及四羧酸二酐单体。此外，聚酰亚胺层中还另残留有架桥剂以及起始剂。其中，聚酰亚胺组成物的二胺单体可采用一种或多种二胺单体，且至少包括长碳链脂肪族的二胺单体，例如是选自总碳数大于等于36的脂肪族二胺单体。由于本发明的聚酰亚胺层通过使用选自总碳数大于等于36的脂肪族二胺单体而被加以合成，因而可达成在温度介于60℃至160℃之间时，聚酰亚胺层的最低粘度小于20000 Pa·s的目的。此外，通过使用选自总碳数大于等于36的脂肪族二胺单体，而使得相应制得的聚酰亚胺层能够同时具有低介电常数、低介电损耗、低吸湿率、低杨氏模数及提高可溶性的性质。以下，将对上述各种组分进行详细说明。
上述的二胺单体包括含有环己烷基的二胺单体，例如是4,4'-二氨基二环己基甲烷(4,4'-diaminodicyclohexyl methane，简称MBCHA)、1,3-二氨甲基环己烷(1,3-diaminomethylcyclohexane)、1,4-二氨甲基环己烷(1,4-diaminomethylcyclohexane)、双氨甲基双环[2.2.1]庚烷(bis(aminomethyl)bicyclo[2.2.1]heptane)、二氨甲基环己基甲烷(4,4'-methylenebis(2-methylcyclohexylamine))。另外，用以反应形成聚酰亚胺层的二胺单体更包括其他的二胺单体，例如2,2’-双[4-(4-氨基苯氧基苯基)]丙烷(2,2’-bis[4-(4-aminophenoxy)phenyl]propane，简称BAPP)、4,4’-二氨基二苯甲烷(4,4’-methylene dianiline)、α,α’-二(4-氨基苯基)-1,4-二异丙基苯(α,α’-bis(4-aminophenyl)-1,4-diisopropylbenzene)、4,4’-二氨基二苯醚(4,4’-oxydianiline)、3,3’-二甲基-4,4’-二氨基联苯(3,3’-dimethyl-4,4’-diaminobiphenyl)或1,4-双(4-氨基苯氧基)苯(1,4-Bis(4-aminophenoxy)benzene)。较佳而言，上述的二胺单体可包括总碳数大于等于36的脂肪族二胺单体，其由油酸等不饱和脂肪酸的二聚体的二聚酸(dimer acid)所衍生的化合物。
上述的聚酰亚胺组成物还包括选自羟基、羧基及C=C的基团的单体，其中包括含有羟基的二胺单体、含有羧基的酸酐单体、含有羧基的二胺单体及含有C=C基团的二胺单体。并且，前述所列举的单体可单独使用或混合使用。值得一提的是，当用以反应形成聚酰亚胺层的聚酰亚胺组成物具有羟基、羧基或C=C的基团时，可以提高聚酰亚胺层的可溶解性，并且能够再交联。
具体而言，含有羟基的二胺单体包括但不限于：3,3’-二 羟基-4,4’-二氨基联苯(3,3’-Dihydroxy-4,4’-diamino-biphenyl，简称HAB)；含有羧基的酸酐单体包括但不限于：偏苯三甲酸酐(trimellitic acidanhydride，简称TMA)；含有羧基的二胺单体包括但不限于：3,5-二氨基苯甲酸(3,5-diaminobenzoic acid，简称DABZ)、6,6’-双氨基-3,3’-甲叉基二苯甲酸(methylene bis(anthranilic acid)，简称MBAA)；含有C=C基团的二胺单体包括但不限于： 2-乙烯基-4,6-二氨基-1,3,5-三嗪(2-vinyl-4,6-diamino-1,3,5-triazine)、2,4-二氨基-6-(异丁烯酰氧基)乙基-1,3,5-三嗪(2,4-diamino-6-(methacryloyloxy)ethyl-1,3,5-triazine)。在另一实施方式中，含有选自羟基、羧基及C=C的基团的单体例如包括偏苯三甲酸酐及3,5-二氨基苯甲酸。
另外，上述用以反应形成聚酰亚胺层的聚酰亚胺组成物中的四羧酸二酐单体可以是所属领域中具有公知常识者所周知的任一四羧酸二酐化合物。具体而言，四羧酸二酐单体包括但不限于：4,4’-氧双邻苯二甲酸酐(Bis-(3-phthalyl anhydride)ether，简称ODPA)、3,3’,4,4’-二苯甲酮四甲酸二酐(3,3’,4,4’-Benzophenonetetracarboxylicdianhydride，简称BTDA)、均苯四甲酸二酐(Pyromellitic Dianhydride，简称PMDA)、双酚A型二醚二酐(4,4’-(4,4’-isopropylidenediphenoxy)bis(phthalic anhydride)，简称BPADA)或3,3’,4,4’-联苯四羧酸二酐(3,3’,4,4’-Biphenyltetracarboxylicdianhydride，简称BPDA)。进一步而言，在本发明中，前述所列举的四羧酸二酐单体可单独使用或混合使用。
本发明的聚酰亚胺层还包括架桥剂以及起始剂。架桥剂包括含有环氧基、异氰酸酯基或烯烃基的化合物。具体而言，架桥剂包括但不限于：酚醛型环氧树脂(phenolnovolactype epoxy resin)、萘型环氧树脂(naphthalene type epoxy resin)或双酚A型环氧树脂(bisphenolA type epoxy resin)。另外，作为含有环氧基的架桥剂可使用市售产品，例如CNE-200EL或PNE-177(CCP长春公司制造)、EPOXY 4700(DIC公司制造)或ESCV-90CR(新日铁化学公司制造)；以及作为含有异氰酸酯基的架桥剂可使用市售产品，例如Desmodur N3600或Desmodur VK10(Bayer公司制造)；以及作为含有烯烃基的架桥剂，例如三烯丙基异三聚氰酸酯(triallyl isocyanurate，简称TAIC)。起始剂包括过氧化物及光起始剂。具体而言，起始剂包括但不限于：过氧化苯甲酰(benzoyl peroxide，简称BPO)、过氧化叔丁醇(tert-Butylhydroperoxide，简称TBH)或过氧化双月桂酰(Dilauroyl peroxide)。
值得说明的是，本发明中架桥剂能够与含有羟基或羧基的单体中的羟基或羧基进行交联反应，而起始剂能够协助含有C=C的单体中的C=C进行交联反应。也就是说，若上述用以反应形成聚酰亚胺层的聚酰亚胺组成物使用了含有羟基或羧基的单体，则选择使用架桥剂；而若上述用以反应形成聚酰亚胺层的聚酰亚胺组成物使用了含有C=C的单体，则选择使用起始剂及加入包含C=C基团的架桥剂。如此一来，用以形成可溶性聚酰亚胺的组成物通过包括含有选自羟基、羧基及C=C的基团的单体以及架桥剂或起始剂，使得经其制得的聚酰亚胺层能够具有良好的耐化性及耐热性。
结合以上所述，本发明的覆盖膜的聚酰亚胺层除了经由上述二胺单体、含有选自羟基、羧基及C=C的基团的单体、四羧酸二酐单体的聚酰亚胺组成物反应而形成，并且还通过上述架桥剂或起始剂进行交联反应。此外，须注意的是，由于聚酰亚胺层中还包括未键结的架桥剂和起始剂，因此在后续的热压工艺中，聚酰亚胺层可以具有适当的流动性，且可以进一步发生聚合反应。也就是说，本发明的覆盖膜的聚酰亚胺层是一种分子量较低的预聚物，其尚未和全部的架桥剂及起始剂进行交联反应并提升分子量。举例而言，上述尚未与聚酰亚胺层完全进行键结的架桥剂和起始剂占聚酰亚胺层中全部树脂的范围为大于0重量百分比且小于或等于50重量百分比，但不以此为限。
另外，在不损及本发明的聚酰亚胺层的效果范围内，用以形成聚酰亚胺层的聚酰亚胺组成物可依需要加入添加剂。所述添加剂包括耐燃剂、着色剂、填充剂或其组合物。值得一提的是，填充剂包括二氧化硅及碳酸钙，能够提升聚酰亚胺层在后续工艺步骤中的流变性及压合工艺中的压合流动性。
本发明的覆盖膜的聚酰亚胺层是由上述聚酰亚胺组成物反应所形成。以下，将对反应步骤进行详细说明。首先，将二胺单体、含有选自羟基、羧基及C=C的基团的单体以及四羧酸二酐单体溶于溶剂中，并进行反应以形成聚酰胺酸溶液。溶剂包括所属领域中具有公知常识者所周知的任一溶剂，包括但不限于：甲苯、二甲苯、环己烷、环己酮、N-甲基吡咯烷酮(NMP)、二甲基乙酰胺、二甲基甲酰胺或其混合物。其中，进行反应的时间例如是介于1小时至6小时之间；聚酰胺酸溶液的固含量例如是介于10%至50%之间，但不限于此。接着，对聚酰胺酸溶液进行环化工艺以形成聚酰亚胺溶液。在此步骤中，环化工艺的工艺温度例如是介于160℃至200℃之间；工艺时间例如是介于1小时至6小时之间；聚酰亚胺溶液的固含量例如是介于10%至50%之间，但不限于此。之后，将上述架桥剂或起始剂加入聚酰亚胺溶液，以形成聚酰亚胺混合溶液。在一实施例中，聚酰亚胺混合溶液可包括可溶性聚酰亚胺、架桥剂、起始剂及溶剂。
接着，将聚酰亚胺混合溶液涂布于离型层上，并以介于100℃至160℃之间的温度干燥3分钟至5分钟，以于离型层上形成本发明的聚酰亚胺层。其中，涂布方式包括但不限于刮刀式涂布、线棒式涂布或网版印刷。另外，离型层例如是以对于后续步骤中形成的聚酰亚胺层提供足够支撑力的离型膜来实现，具有良好的尺寸安定性。离型层可为平光或是哑光，借以调整于后续步骤中形成的聚酰亚胺层的表面粗糙度及光泽度。
根据上述，可以得到本发明的覆盖膜。其结构如图1所示，覆盖膜10包括离型层12及形成于离型层12上的聚酰亚胺层14。由于本发明的覆盖膜10的聚酰亚胺层14是先利用涂布方式而将聚酰亚胺混合溶液形成在离型层12上，之后才进行加热工艺，故相比于现有技术中利用旋涂法制作的聚酰亚胺层而言，本发明的聚酰亚胺层可满足更广的膜厚范围的需求，例如但不限于在1μm至20μm之间。借由涂布方式及涂液固含量的调整，甚至可得到厚度100μm以上的聚酰亚胺层，此为现有技术的旋涂法无法容易得到的厚度。
根据本发明的一实施例，上述的覆盖膜可以用于制作半导体元件表面的绝缘层，尤其是适用于表面具有多个突出导电结构的半导体元件，以下就此实施例加以叙述之。
请参考图2至图5。图2至图4为本发明第一实施例覆盖膜用以制作半导体元件表面的绝缘层的制作方法的示意图。图5为本发明第一实施例覆盖膜用以制作封装结构的示意图。如图2所示，首先提供第一半导体元件100，包括第一部件102及设置于第一部件102上的多个第一导体结构104，且这些第一导体结构104之间具有至少一缝隙105。第一部件102包括但不限于晶片(chip)、处理器(processor)、晶粒(die)、积体电路(IC)或其他主/被动元件相关的元件，且该第一部件102为所属领域中具有公知常识者所周知的上述结构中表面这些第一导体结构104以外的部份。第一导体结构104包括但不限于选自铜、银、锡或及上述至少两者所组成的合金的组合所构成之群组。进一步而言，第一导体结构104可为任何符合半导体元件的机械强度要求的导体结构。
接着，参考图3，将第一导体结构104直接接触本发明覆盖膜106的聚酰亚胺层108。之后，对覆盖膜106进行热压工艺，使聚酰亚胺层108填满第一导体结构104之间的至少一缝隙105，使得第一导体结构104被聚酰亚胺层108环绕。其中，热压工艺的温度可例如介于60°C至160°C之间，借此使聚酰亚胺层108的粘度小于20000Pa·s，而具有适当之流动性。在热压后，再以160℃至200℃的固化温度使聚酰亚胺层108中的架桥剂以及起始剂进一步产生反应，使得高分子链彼此之间进一步产生交联，因而生成热固性的聚酰亚胺层108。
根据上述，本发明半导体元件表面的绝缘层的制作方法通过热压工艺，致使覆盖膜106的聚酰亚胺层108具有足够的压合流动性，而能够填满第一导体结构104之间深宽比大于等于3的缝隙。值得说明的是，覆盖膜106填满第一导体结构104之间深宽比的上限取决于第一导体结构104能够承受热压工艺且不被破坏的强度范围。
接着，移除覆盖膜106的离型层110以暴露出第一导体结构104的上表面104a，而获得如图4所示的结构。在本实施方式中，移除离型层110后，可借由电浆蚀刻或研磨等方式，使第一导体结构上表面104a和聚酰亚胺层上表面108b彼此共平面。
在完成图4所示的步骤后，可以进一步在第一导体结构104及聚酰亚胺层108上形成其他导电结构，其具体实施方式请参照下述。
请参考图5。如图5所示，在完成上述步骤后，可接着在聚酰亚胺层108上形成重布线层112(redistribution layer)，且该重布线层112和第一导体结构上表面104a接触并电性连接。其中，重布线层112包括至少一图案化导电层114、至少一重布导线116、至少一介电层118与至少一通孔118a，并且重布导线116是设置于该通孔118a中。也就是说，重布线层112可包含多个介电层118与对应的多个图案化导电层114、重布导线116及通孔118a，以使线路重布。本实施例中，介电层118使用本发明覆盖膜106的聚酰亚胺层108作为材料，并以上述的热压工艺制得。图5仅绘示一层介电层118和一层图案化导电层114，但本发明不以此为限。接着，选择性地在重布线层112上形成多个彼此分离的导电垫120，并且于各导电垫120上分别形成一锡球122或一金属柱凸块(metal pillar bump)，但不以此为限。其中，导电垫120例如为底部凸块金属(under bump metallization，简称UBM)层，用以提升重布导线116与锡球122之间的粘着性、扩散阻障、焊锡润湿与防止氧化等功能。综上所述，第一部件102内部的导电线路与第一导体结构104、重布线层112以及锡球122电性连接；这些第一导体结构104之间可具有深宽比大于等于3的缝隙并且被聚酰亚胺层108填充；介电层118可选择性地使用本发明的聚酰亚胺层108，以此形成一封装结构。
本发明的覆盖膜并不以上述实施例为限，以下就其他的实施例加以介绍。为了更容易地比较实施例之间的差异，以下将详细描述不同实施例之间的不同之处，并不再对相同的特征作赘述。
请参考图6至图8。图6至图8为本发明第二实施例覆盖膜用以制作半导体元件表面的绝缘层的制作方法的示意图。本实施例中，覆盖膜可用以形成覆晶封装结构或借由热压结合的封装结构。如图6所示，首先提供第一半导体元件200，其包括第一部件202以及多个第一导体结构204。第一半导体元件200可包括一基板，该基板包括印刷电路板、中介板(interposer)、硅基板以及玻璃基板，但不限于此。第一导体结构204可例如为接触垫(contact pad)。接着，将第一导体结构204直接接触本发明覆盖膜106的聚酰亚胺层108，并且对该覆盖膜106进行如前述的热压工艺，使聚酰亚胺层108填满第一导体结构204之间的至少一缝隙205，并且使得第一导体结构204被聚酰亚胺层108环绕。如图7所示，在进行热压工艺之后，移除离型层110。接着，如图8所示，提供第二半导体元件210，包括第二部件214及设置于该第二部件214上的多个第二导体结构212，且这些第二导体结构212对应于这些第一导体结构204而设置。其中，第二部件214包括但不限于晶片、处理器、晶粒、积体电路或其他主/被动元件相关的元件。举例而言，第二半导体元件210可以是本发明第一实施例所述的封装结构，但不以此为限。将第一半导体元件200与第二半导体元件210彼此接合，并排开设置于这些第一导体结构204以及这些第二导体结构212之间的聚酰亚胺层108，致使这些第一导体结构204电连接对应的这些第二导体结构212。需要说明的是，将第一半导体元件200与第二半导体元件210彼此接合时，例如是使用所属领域中具有公知常识者所周知的接合工艺，例如熔融接合(fusion bonding)、金属热压接合(metal thermal compressionbonding)等，但不以此为限，热压时间180秒内，温度为200℃至300℃。在本实施例中，第一导体结构204以及第二导体结构212之间的缝隙被本发明具有良好压合流动性的聚酰亚胺层108填充。热压接合后，再以160℃至200℃的固化温度，例如，使用压力烘箱排除气泡，并且使聚酰亚胺层108中的架桥剂以及起始剂进一步产生反应，使得高分子链彼此之间进一步产生交联，因而生成热固性的聚酰亚胺层108。
为了制作出易薄型化、介电性质佳、杨氏模数低且适合应用于本发明的覆盖膜中的聚酰亚胺层，本发明提出一种聚酰亚胺的组成物，并且以此所制得的聚酰亚胺层可达到上述优点。以下，特举实施例作为本发明确实能够据以实施的范例。
以下借由实施例与比较例来说明本发明覆盖膜的制作方法，以进一步阐明本发明之技术特征。
制备实施例1~2及比较例1的聚酰亚胺层及覆盖膜所使用的主要材料的资讯如下所示。
四羧酸二酐单体：均苯四甲酸二酐(pyromellitic dianhydride，简称PMDA)。
长碳链脂肪族的二胺单体：商品名为PriamineTM 1074-Dimer diamine，日本禾大公司制造，其中主链的碳数为36。
含有选自羟基、羧基及C=C的基团的单体：3,5-二氨基苯甲酸(简称DABZ)，购自锦聿公司；4,4'-二氨基二环己基甲烷(简称MBCHA)，购自TCI公司；2-乙烯基-4,6-二氨基-1,3,5-三嗪(简称VT)，购自四国化成公司。
其他的二胺单体：2,2’-双[4-(4-氨基苯氧基苯基)]丙烷(以下简称BAPP)，购自东信公司。
架桥剂：三环氧丙基异氰脲酸酯(tris(2, 3-epoxy propyl) isocyanurate，简称TEPIC)；三烯丙基异三聚氰酸酯(triallyl isocyanurate，简称TAIC)。
起始剂：过氧化苯甲酰(简称BPO)，见欣实业制造。
溶剂：环己酮，购自胜一化工公司；N-甲基吡咯烷酮(简称NMP)，购自波律公司。
离型膜：商品名为PET-50-SHP-A，购自Fujiko公司。
实施例1：
首先，将10莫耳的四羧酸二酐单体PMDA、6莫耳的总碳数为36的脂肪族二胺单体P1074及3莫耳的二胺单体MBCHA以及0.5莫耳的二胺单体2-乙烯基-4,6-二氨基-1,3,5-三嗪溶入环己酮和NMP的混合物中。接着将所得的混合溶液进行反应2小时，以得到固含量约20%的聚酰胺酸溶液。接着，将该聚酰胺酸溶液在180℃下进行酰亚胺化反应3小时，以得到聚酰亚胺溶液。之后，取出含聚酰亚胺固形物100克的聚酰亚胺溶液并加入5克的架桥剂TEPIC、5克的架桥剂TAIC以及5克的起始剂BPO，以制成聚酰亚胺混合溶液。接着，将聚酰亚胺混合溶液涂布于上述离型层上，并且以约160℃的温度进行干燥3分钟，以制成本发明的聚酰亚胺层。其中，聚酰亚胺层属于预聚物，其尚未和全部的架桥剂和起始剂进行交联反应并提升分子量。
实施例2：
实施例2制备本发明覆盖膜的制作方法与实施例1相同，不同处在于将6莫耳的总碳数为36的脂肪族二胺单体P1074改为9莫耳并且不添加二胺单体MBCHA。
比较例1：
比较例1制备聚酰亚胺层的制作方法与实施例1部分类似，不同处在于将6莫耳的总碳数为36的脂肪族二胺单体P1074改为3莫耳并且不添加二胺单体MBCHA；3莫耳的二胺单体MBCHA改为6莫耳。此外，由于比较例1所形成的聚酰胺酸溶液在180℃下进行酰亚胺化反应3小时之后所生成的聚酰亚胺溶解性不佳，也就是说脱水环化后所形成的该聚酰亚胺无法和前述架桥剂以及起始剂形成聚酰亚胺混合溶液，所以也无法将其涂布于上述离型层。因此，比较例1的聚酰亚胺层是将聚酰胺酸溶液进行脱水环化后直接生成。
之后，分别对实施例1及实施例2的聚酰亚胺层进行杨氏模数、温度流变曲线、介电常数、介电损耗及吸湿率的测定。前述各测试的说明如下，且测试的结果显示于表1中。
依据ASTM-D638的规定，使用测试样板第五类型(type V)，进行拉伸强度、杨氏模数以及伸长率的测定。进行拉伸强度测试时，持续纪录拉力和聚酰亚胺层伸长量的关，直到聚酰亚胺层断裂。在表1中，将聚酰亚胺层断裂时所承受的拉力除以原始样品的截面积便可求得到聚酰亚胺层的拉伸强度；将聚酰亚胺层断裂时的长度减去聚酰亚胺层的原始长度，并除以聚酰亚胺层的原始长度，便可求得拉伸伸长率；根据聚酰亚胺层断裂前所承受的拉力和相应的伸长量以求得拉伸杨氏模数。杨氏模数的数值越低表示聚酰亚胺层的刚性越小。
依据IPC-TM-650 2.5.5.5.1B的规定，使用网路分析仪(型号为ZVB20，由罗德史瓦兹公司(ROHDE & SCHWARZ)制造)分别量测实施例1、实施例2及比较例1的聚酰亚胺层的介电常数及介电损耗，其中量测频率为10GHz。在表1中，数值越低表示聚酰亚胺层的介电性质越好。
接着，以TA厂牌DHR2的旋转式流变仪，选用半径2.5mm的平行板，分别量测实施例1、实施例2的温度流变曲线，并且求得最低的粘度值，如表1所示。
另外，表1中的填胶性是指将上述干燥后的聚酰亚胺层在130℃下，以5kgf/cm2的压力与线距约3密耳(mil)的线路之间进行真空快压约3分钟，并观测聚酰亚胺层填充该线路的间缝隙的能力。其中，当填充线路的间缝隙无气泡产生，定义为通过测试。
表1
Figure DEST_PATH_IMAGE002
由实施例1、2、比较例1及表1可知，实施例1、2的聚酰亚胺具有可溶性，因此能够涂布于离型层并以160℃的温度进行干燥3分钟以形成聚酰亚胺层，并得到本发明的覆盖膜。此外，实施例1、2的聚酰亚胺层可通过填胶性测试，并且具有可接受的拉伸强度、杨氏模数、伸长率、介电数以及介电损耗。因此，实施例1、2的聚酰亚胺层能够进一步利用上述实施例的方法用以制备半导体元件表面的绝缘层。并且，本发明实施例1、2的聚酰亚胺层在热压工艺温度环境下具有良好的压合流动性，能够取代现有技术的底胶(underfill)点涂到晶片和基板间再借由毛细作用力流入空隙的覆晶工艺，并且相比使用底胶的覆晶工艺，制作时间较短、填充缝隙能力较佳，也不容易产生气泡。并且，通过上述热压工艺还可以使本发明覆盖膜的聚酰亚胺层填满导体结构之间深宽比大于等于3的缝隙，可应用于半导体封装的介电层、封装体或底胶材料。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (15)

1.一种覆盖膜，其特征在于，包括：
一离型层；以及
一聚酰亚胺层，设置于该离型层上，该聚酰亚胺层包括相对设置的一内表面和一外表面，该外表面直接暴露于大气中，该聚酰亚胺层经由包括二胺单体和四羧酸二酐单体的一聚酰亚胺组成物反应所形成，其中该二胺单体选自总碳数为36以上的脂肪族二胺单体，且在温度介于60℃至160℃之间时，该聚酰亚胺层的粘度小于20000Pa·s，该聚酰亚胺层填满导体结构之间深宽比大于等于3的缝隙。
2.如权利要求1所述的覆盖膜，其特征在于，该聚酰亚胺层还包括未与聚酰亚胺组成物键结的架桥剂以及起始剂。
3.如权利要求1所述的覆盖膜，其特征在于，用以生成该聚酰亚胺层的该二胺单体还包括选自羟基、羧基及C=C的基团的二胺单体所组成的群组中的至少一者。
4.如权利要求1所述的覆盖膜，其特征在于，用以生成该聚酰亚胺层的该二胺单体还包括4, 4’-二氨基二环己基甲烷。
5.如权利要求1所述的覆盖膜，其特征在于，该聚酰亚胺层在60℃至160℃的热压下，会被填充至深宽比为3的缝隙中。
6.如权利要求1所述的覆盖膜，其特征在于，该聚酰亚胺层的外表面上未被任何层覆盖。
7.如权利要求2所述的覆盖膜，其特征在于，该架桥剂包括含有环氧基、异氰酸酯基或烯烃基的化合物且该起始剂包括过氧化物。
8.一种半导体元件表面的绝缘层的制作方法，其特征在于，包括：
提供一第一半导体元件，包括一第一部件及设置于该第一部件上的多个第一导体结构；
将这些第一导体结构直接接触如权利要求1至7中任一项所述的该覆盖膜的该聚酰亚胺层；
进行一热压工艺，使该聚酰亚胺层填满这些第一导体结构之间的至少一个缝隙，使得这些第一导体结构被该聚酰亚胺层环绕；以及
在进行该热压工艺之后，移除该离型层，再以160℃至200℃的温度固化。
9.如权利要求8所述的半导体元件表面的绝缘层的制作方法，其特征在于，该热压工艺的温度介于60℃至160℃之间。
10.如权利要求8所述的半导体元件表面的绝缘层的制作方法，其特征在于，这些第一导体结构之间的这些缝隙的深宽比大于等于3。
11.如权利要求8所述的半导体元件表面的绝缘层的制作方法，其特征在于，该第一半导体元件包括晶片。
12.如权利要求11所述的半导体元件表面的绝缘层的制作方法，其特征在于，这些第一导体结构的组成选自铜、银、锡及上述至少两者所组成的合金所构成的群组。
13.如权利要求8所述的半导体元件表面的绝缘层的制作方法，其特征在于，在移除该离型层的步骤后，这些第一导体结构被包覆于该聚酰亚胺层中，且在移除该离型层的步骤后，该制作方法另包括：
提供一第二半导体元件，包括一第二部件及设置于该第二部件上的多个第二导体结构，且这些第二导体结构对应于这些第一导体结构而设置；以及
将该第一半导体元件与该第二半导体元件彼此接合，以排开设置于这些第一导体结构以及这些第二导体结构之间的该聚酰亚胺层，致使这些第一导体结构电连接对应的这些第二导体结构。
14.如权利要求13所述的半导体元件表面的绝缘层的制作方法，其特征在于，该第一部件为印刷电路板、中介板、硅基板或玻璃基板。
15.如权利要求13所述的半导体元件表面的绝缘层的制作方法，其特征在于，该第二半导体元件包括晶片。
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