CN103021807A - 晶片粘合方法 - Google Patents

晶片粘合方法 Download PDF

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CN103021807A
CN103021807A CN2012103967506A CN201210396750A CN103021807A CN 103021807 A CN103021807 A CN 103021807A CN 2012103967506 A CN2012103967506 A CN 2012103967506A CN 201210396750 A CN201210396750 A CN 201210396750A CN 103021807 A CN103021807 A CN 103021807A
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洪文斌
白东顺
T.D.弗莱
R.普利吉达
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Abstract

晶片粘合方法，该方法包括：将粘合组合物通过旋涂施加到第一基片或第二基片之一以形成粘合层，所述层为由相同组合物形成的在其厚度上均匀的材料；和将该第一基片和第二基片通过所述粘合层粘合在一起。

Description

晶片粘合方法
背景技术
政府基金 
本发明是在由空军研究实验室(AFRL)授予的第FA8650-05-D-5807号合同的政府资助下完成的。美国政府具有本发明的某些权利。 
技术领域
本发明广泛地涉及新颖的组合物及使用这些组合物形成粘合组合物的方法，所述粘合组合物能在晶片减薄和其它工艺过程中基片将活性晶片支撑在载体或基片上。 
现有技术描述 
晶片(基片)减薄已经被用于散热和辅助集成电路(IC)的电气操作。厚的基片引起电容量的增加，需要更粗的传输线，从而需要大量的IC覆盖面积。基片减薄会提高阻抗，而电容量会降低阻抗，导致传输线粗度的减小，从而导致IC尺寸的减小。因此，基片减薄能促进IC的微型化。 
几何学的限制是基片减薄的另一个诱因。通路孔蚀刻在基片的背面上以促进正面接触。为了使用常见的干蚀刻工艺构造通路，应用了几何限制。对于厚度小于100μm的基片，使用干蚀刻工艺构造直径为30-70μm的通路，其在可接受的时间内形成最少的蚀刻后残留物。对于厚的基片，需要更大的直径。这需要更长的干蚀刻时间并产生更大量的蚀刻后残留物，因此显著地降低了生产能力。更大量的通路还需要更大量的金属镀覆，其是更昂贵的。因此，由于背面处理，可以更快速并更低成本地加工薄基片。 
薄基片还更容易切割和刻划成IC。较薄的基片需要被穿透和切割的材料的量较少，因此需要较少的工作量。不论采用什么方法(锯、划和切断，或者激光烧蚀)，从较薄的基片上都比较容易切割IC基片。大多数半导体晶片在正面操作后减薄。为了便于操作，晶片在其常规的全尺寸厚度，例如600-700μm下加工(即正面设备)。一旦完成后，它们被减薄至100-150μm的厚度。在某些情况下(例如将如砷化镓(GaAs)的混合基片用于高功率设备时)，厚度可以降低至25μm。 
机械基片减薄通过将晶片表面与包含液体浆料的硬且平坦的卧式旋转盘接触来完成。所述浆料包含磨料介质和例如氨、氟或其组合的化学腐蚀剂。所述磨料提供“粗的”基片去除，即减薄，而化学腐蚀剂促进了亚微米级的“抛光”。所述晶片保持与所述介质接触直到一定数量的基片被去除，达到了目标厚度。 
对于等于或大于300μm的晶片厚度，所述晶片用工具固定到位，所述工具利用真空吸盘或其它机械连接装置。当晶片厚度减小到小于300μm时，在进一步减薄和加工过程中很难或不可能保持晶片的连接或处理方面的控制。在某些情况下，可以制造机械设备来连接和固定到减薄的晶片上，但是遭遇了很多问题，尤其是当工艺可能变化时。由于这个原因，所述晶片(“活性”晶片)被安装到一个单独的刚性(载体)基片或晶片上。该基片成为用于进一步减薄和减薄后的加工处理的支撑平台。载体基片由例如蓝宝石、石英、特定玻璃和硅之类的材料组成，通常为1000μm的厚度。基片的选择将取决于与每种材料之间热 膨胀系数(CTE)密切配合的程度。但是，大多数目前可用的粘附方法不具有足够的热稳定性或机械稳定性以承受在背面加工步骤中的高温，例如金属镀覆或绝缘沉积和退火。多数现有方法也具有差的平整度(其造成了整个晶片尺寸的总厚度变化过大)和差的耐化学性。 
一种已经被用来将活性晶片安装到载体基片上的方法是通过热释放胶带。该工艺具有两个主要缺点。第一，所述胶带在活性晶片/载体基片界面上具有有限的厚度均匀性，该有限的均匀性通常不足以用于超薄晶片处理。第二，热释放粘合剂在低温下软化使得粘合的晶片/载体基片的层叠件不能承受在较高温度下进行的许多典型晶片加工步骤。 
另一方面，热稳定的粘合剂通常需要过高的粘合压力或粘合温度来达到足够的熔体流动来形成良好的粘合。同样地，因为所述粘合剂在实际剥离温度下保持过高的粘度，可能需要过大的机械力来分离活性晶片和载体晶片。热稳定的粘合剂也很难被去除而不留下残余物。 
人们需要将活性晶片粘附到载体基片上的新的组合物和基片方法，这些组合物和方法可以承受高的加工温度并允许在工艺的合适步骤中很容易的将晶片和基片相分离。 
发明概述 
本发明通过广泛地提供一种晶片粘合方法克服了现有技术中的缺陷，其包括提供一个包含通过粘合层粘合在一起的第一基片和第二基片的层叠件，并分离第一基片和第二基片。所述粘合层由包含溶解或分散在溶剂体系中的环烯烃共聚物(COC)的组合物形成。 
本发明也提供了一种包含第一基片和第二基片以及粘合层的制品。所述第一基片包含背面和活性面，其包含至少一个活性位点和多种形貌特征。所述第二基片具有粘合面。所述粘合层粘合到第一基片的活性面和第二基片的粘合面。所述粘合层由包含溶解或分散在溶剂体系中的环烯烃共聚物的组合物形成。 
在另一个实施方案中，本发明涉及一种适用于将两种基片粘合到一起的组合物基片。本发明的组合物包含溶解或分散在溶剂体系中的环烯烃共聚物和配料。所述配料选自由增粘树脂、低分子量环烯烃共聚物、及其混合物组成的组。 
附图简要说明 
图1表示根据本发明的两块晶片的减薄和剥离方法； 
图2是实施例中采用的典型工艺步骤的流程图； 
图3描绘了在150℃剥离后的根据本发明的粘合组合物的流变分析结果； 
图4描绘了在200℃剥离后的根据本发明的粘合组合物的流变分析结果；和 
图5描绘了在250℃剥离后的根据本发明的粘合组合物的流变分析结果。 
优选实施方式的详细描述 
更详细地，本发明组合物包含溶解或分散在溶剂体系中的环烯烃共聚物(COC)。基于组合物的总重量作为100重量％，所述共聚物优选以约5重量％-约85重量％的水平存在于组合物中，更优选约5重量％-约60重量％，最优选约10重量％-约40重量％。 
优选的共聚物是热塑性的并优选具有约2,000道尔顿-约200,000道尔顿的重均分子量(MW)，更优选约5,000道尔顿-约100,000道尔顿。优选的共聚物优选具有至少约100℃的软化温度(熔融粘度在3,000Pa·S)，更优选至少约140℃，甚至更优选约160℃-约220℃。合适的共聚物也优选具有至少约60℃的玻璃化转变温度(Tg)，更优选约60℃-约 200℃，最优选约75℃-约160℃。 
优选的环烯烃共聚物由环烯烃和非环烯烃、或基于环烯烃的开环聚合物的重复单体组成。用于本发明的合适的环烯烃选自由基于降冰片烯的烯烃、基于四环十二烯(tetracyclododecene-based)的烯烃、基于双环戊二烯的烯烃、及其衍生物。衍生物包括烷基(优选C1-C20烷基，更优选C1-C10烷基)、亚烷基(优选C1-C20亚烷基，更优选C1-C10亚烷基)、芳烷基(优选C6-C30芳烷基，更优选C6-C18芳烷基)、环烷基(优选C3-C30环烷基，更优选C3-C18环烷基)、醚、乙酰基、芳基、酯、羟基、烷氧基、氰基、酰胺、酰亚胺、以及甲硅烷基取代衍生物。特别优选用于本发明的环烯烃包括选自由 
及上述的组合组成的组的那些，其中每个R1和R2单独地选自由-H和烷基(优选C1-C20烷基，更优选C1-C10烷基)组成的组，每个R3单独地选自由-H、取代和未取代的芳基(优选C6-C18芳基)、烷基(优选C1-C20烷基，更优选C1-C10烷基)、环烷基(优选C3-C30环烷基，更优选C3-C18环烷基)、芳烷基(优选C6-C30芳烷基，更优选C6-C18芳烷基，例如苯甲基、苯乙基和苯丙基等)、酯基、醚基、乙酰基、醇类(优选C1-C10醇)、醛基、酮类、腈类、及其组合组成的组。 
优选的非环烯烃选自由支化和未支化的C2-C20烯烃(优选C2-C10烯烃)组成的组。更优选地，用于本发明地合适非环烯烃具有结构 
Figure BDA00002272157800032
其中每个R4单独地选自由-H和烷基(优选C1-C20烷基，更优选C1-C10烷基)组成的组。特别优选的用于本发明的非环烯烃包括选自由乙烯、丙烯和丁烯组成的组的那些，最优选乙烯。 
制备环烯烃共聚物的方法在现有技术中是已知的。例如，环烯烃共聚物可以通过环状单体和非环单体(例如如下所示的降冰片烯和乙烯)的链聚合来制备。 
上述反应产生了包含交替的降冰片烯基和乙烯基单元的乙烯-降冰片烯共聚物。由该方法制备的共聚物的实例包括由古风罗(Goodfellow)公司和托派司高级聚合物公司(TOPAS Advanced Polymers)生产的TOPAS 
Figure BDA00002272157800042
以及由三井化学生产的APEL 
Figure BDA00002272157800043
制备这些共聚物的合适的方法公开于美国专利No.6,008,298中，其并入此处作为参考。 
环烯烃共聚物也可以通过如下所示的多种环状单体的开环易位聚合随后氢化来制备。 
Figure BDA00002272157800044
由这类聚合反应得到的聚合物可以在概念上被看作乙烯和环烯烃单体(例如如下所示的乙烯和1，3-环戊二烯的交替单元)的共聚物。 
Figure BDA00002272157800045
该方法制备的共聚物的实例包括吉恩化工的ZEONOR 
Figure BDA00002272157800046
以及JSR公司的ARTON 
Figure BDA00002272157800047
制备这些共聚物的合适的方法公开于美国专利No.5,191,026中，其并入此处作为参考。 
相应地，本发明的共聚物优选包含重复单体： 
(I)：
及上述的组合，其中： 
每个R1和R2单独地选自由-H和烷基(优选C1-C20烷基，更优选C1-C10烷基)组成的组，每个R3单独地选自由-H、取代和未取代的芳基(优选C6-C18芳基)、烷基(优选C1-C20烷基，更优选C1-C10烷基)、环烷基(优选C3-C30环烷基，更优选C3-C18环烷基)、芳烷基(优选C6-C30芳烷基，更优选C6-C18芳烷基，例如苯甲基、苯乙基和苯丙基等)、酯基、醚基、乙酰基、醇类(优选C1-C10醇)、醛基、酮类、腈类、及其组合组成的组； 
和 
(II)： 
Figure BDA00002272157800062
其中： 
-----是单键或双键；和 
每个R4单独地选自-H和烷基(优选C1-C20烷基，更优选C1-C10烷基)组成的组。 
聚合物中单体(I)和单体(II)的比率优选从约5∶95至约95∶5，更优选从约30∶70至约70∶30。 
本发明的组合物通过将环烯烃共聚物和其它配料用溶剂体系简单混合形成，优选在室温至约150℃，时间为约1-72小时。 
基于组合物的总重量作为100重量％，所述组合物应当包含至少约15重量％的溶剂体系，优选约30重量％-约95重量％的溶剂体系，更优选约40重量％-约90重量％的溶剂体系，甚至更优选约60重量％-约90重量％的溶剂体系。所述溶剂体系应当具有 约50-280℃的沸点，优选约120-250℃。合适的溶剂包括但不限于甲基乙基酮(MEK)和环戊酮，以及选自由柠檬烯、均三甲苯、双戊烯、蒎烯、双环己烯(bicyclohexyl)、环十二烯、1-叔丁基-3，5-二甲基苯、丁基环己烷、环辛烷、环庚烷、环己烷、甲基环己烷、及其混合物组成的组的烃溶剂。 
基于组合物的总重量作为100重量％，所述组合物中的总的固体水平应当为至少约5重量％，优选约5重量％-约85重量％，更优选约5重量％-约60重量％，甚至更优选约10重量％-约40重量％。 
根据本发明，所述组合物可以包括其它配料，包括低分子量环烯烃共聚物(COC)树脂和/或增粘树脂或松香。所述组合物也可以包括大量选自由增塑剂、抗氧剂、及其混合物组成的组的可选配料。 
当低分子量COC树脂用于所述组合物时，基于组合物的总重量作为100重量％，优选以约2重量％-约80重量％的水平存在于所述组合物中，更优选约5重量％-50重量％，甚至更优选约15重量％-约35重量％。术语“低分子量环烯烃共聚物”是指具有小于约50,000道尔顿的重均分子量(MW)的COC，优选小于约20,000道尔顿，更优选约500-约10,000道尔顿。这类共聚物也优选具有约50℃-约120℃的Tg，更优选约60℃-约90℃，最优选约60℃-约70℃。用于本发明组合物的典型的低分子量COC树脂是可购自托派司高级聚合物公司(Topas Advanced Polymers)的商品名为TOPAS 
Figure BDA00002272157800071
Toner TM(MW8,000)的那些产品。 
当采用增粘剂或松香时，基于组合物的总重量作为100重量％，优选以约2重量％-约80重量％的水平存在于所述组合物中，更优选约5重量％-50重量％，甚至更优选约15重量％-约35重量％。所述增粘剂选自那些与所述环烯烃共聚物化学相容的，这样在所述组合物中不会发生相分离。合适的增粘剂的实例包括但不限于多萜烯树脂(商品名SYLVARESTMTR树脂；亚利桑那化工)、β-多萜烯树脂(商品名SYLVARESTMTR-B树脂；亚利桑那化工)、苯乙烯改性萜烯树脂(商品名ZONATAC NG树脂；亚利桑那化工)、聚合松香树脂(商品名SYLVAROS 
Figure BDA00002272157800072
PR树脂；亚利桑那化工)、松香酯树脂(商品名EASTOTACTM树脂；伊士曼化工)、脂环族烃树脂(商品名PLASTOLYNTM树脂；伊士曼化工，或商品名ARKONTM树脂；荒川化工)、C5脂肪烃树脂(商品名PICCOTACTM树脂；伊士曼化工)、氢化石油附脂(商品名REGALITETM树脂；伊士曼化工)、及其混合物。 
当采用抗氧剂时，基于组合物的总重量作为100重量％，优选以约0.1重量％-约2重量％的水平存在于所述组合物中，更优选约0.5重量％-1.5重量％。合适的抗氧剂的实例包括那些选自由酚类抗氧剂(例如由Ciba以商品名为IRGANOX 
Figure BDA00002272157800073
1010销售的季戊四醇四(3-(3，5-二叔丁基-4-羟苯基)丙酸酯)、亚磷酸盐类抗氧剂(例如由西巴(Ciba)以商品名IRGAFOS 
Figure BDA00002272157800074
168销售的三(2，4-二叔丁基苯基)亚磷酸盐)、亚膦酸盐类(phosphonite)抗氧剂(例如由西巴(Ciba)以商品名IRGAFOX 
Figure BDA00002272157800075
P-EPQ销售的四(2，4-二叔丁基苯基)[1，1-联苯基]-4，4’-二亚磷酸酯)、及其混合物组成的组。 
在替代的实施方案中，优选所述组合物基本上不含有(少于约0.1重量％，优选约0重量％)粘合促进剂，例如二(三甲氧基甲硅烷基乙基)苯、氨丙基三(烷氧基硅烷)(例如，氨丙基三(甲氧基硅烷)、氨丙基三(乙氧基硅烷)、苯基氨丙基三(乙氧基硅烷))、和其它硅烷偶联剂、或其混合物。在一些实施方案中，最终组合物也是热塑性的(即不可交联 的)。因此，在这些替代的实施方案中，所述组合物将基本上不含有(少于约0.1重量％，优选约0重量％)交联剂，例如赛特(Cytec)的POWDERLINK 
Figure BDA00002272157800081
和河西龙专业化学品公司(Hexion Specialty Chemicals)的EPI-CURE1M3200。 
根据一个方面，最终组合物的熔体粘度(综合粘度系数)将优选小于约100Pa·S，更优选小于约50Pa·S，甚至更优选约1Pa·S-约35Pa·S。出于这些测量的目的，所述熔体粘度通过流变静态分析(TA仪，AR-2000，两个直径为25mm的平行板)来测定。此外，所述熔体粘度优选在待测组合物的优选剥离温度下测定。此处所用的术语组合物的“优选剥离温度”定义为组合物熔体粘度低于100Pa·S的温度，并在温度斜坡中1Hz动荡频率动态测量测得。当在组合物的优选剥离温度下测定时，所述组合物也优选具有小于约100Pa的储能模量(G’)，优选小于约50Pa，甚至更优选约1Pa-约26Pa。所述储能模量通过在温度斜坡中1Hz动荡频率动态测量测得。 
所述组合物是热稳定的直到约350℃。在优选剥离温度加50℃的温度下(优选在约200℃-300℃的温度下)一小时后也优选小于约5重量％，更优选小于约1.5重量％的组合物损失，取决于所述组合物。换句话说，在该温度下的组合物中几乎没有热分解发生，如通过此处所述的热重分析(TGA)测定。 
虽然所述组合物可以首先应用到载体基片或者活性晶片，但优选首先应用到活性晶片。可以涂布这些组合物得到凸点晶片应用所需的无气孔的厚膜并达到所要求的整个晶片均匀性。优选的应用方法包括在约500-5000rpm(更优选约1000-3500rpm)的旋转速度、3000-10,000rpm/秒的加速度下旋涂所述组合物，旋转时间约30-180秒。应当被理解的是为了达到特定的厚度，所述应用步骤可以改变。 
涂布后，可以(例如在加热板上)烘烤所述基片以蒸发掉溶剂。典型的烘烤可以在约70-250℃的温度下，优选约80-240℃的温度下进行约1-60分钟，更优选约2-10分钟。烘烤后的膜厚(在形貌最高处)将典型地为至少约1μm，更优选约10-200μm。 
烘烤后，所述载体晶片与之接触并压到本发明组合物层上。所述载体晶片通过在约100-300℃的温度下加热粘合到本发明的组合物上，优选约120-180℃。该加热优选在真空下进行，时间约1-10分钟，粘合力约0.1-约25千牛顿。所述粘合层可以经历背研、金属镀覆、图案化、钝化、成型、和/或晶片减薄中的其它工艺步骤，如下面更详细解释。 
图1(a)表示示例性层叠件10，其包括活性晶片12和载体晶片或基片14的。应当理解层叠件10不是比例显示的，是为了表示的目的已经放大的。活性晶片12具有活性面18。如图1(a)所示，活性面18可以包含多种形貌特征20a-20d。典型的活性晶片12可以包括任意微电子基片。一些可能的活性晶片12的实例包括那些选自由微电机系统(MEMS)设备、显示设备、柔性基片(例如固化环氧基片、可以用来形成图的卷起基片)、化合物半导体、低K介电层、介电层(例如氧化硅、氮化硅)、离子植入层、以及包含硅、铝、钨、硅化钨、砷化镓、锗、钽、亚硝酸钽、SiGe的基片、及上述的材料的混合物组成的组。 
载体基片14具有粘合面22。典型的载体基片14包含选自以下材料：蓝宝石、陶瓷、玻璃、石英、铝、银、硅、玻璃-陶瓷复合物(例如可购自肖特股份有限公司的以商品名Zerodur 
Figure BDA00002272157800082
销售的产品)、及其其组合。 
晶片12和载体基片14通过粘合组合物层24粘合在一起。粘合层24由上述的环烯烃组合物形成，如上所述进行施涂和干燥。如图1(a)所示，粘合层24粘合到晶片12的 活性面18和基片14的粘合面22上。不同于现有技术的胶带，粘合层24是在其厚度上是均匀的(化学相同的)材料。换而言之，整个粘合层24由相同的组合物形成。 
可以理解理解，因为粘合层24可以通过旋涂或喷涂应用到活性面18上，所述粘合组合物会流入到各种形貌特征。而且，所述粘合层24在活性面18的形貌上形成一个均匀的层。为了说明这一点，图1显示了由虚线26构成的平面，其位于底部21并基本上平行于背面16。从该平面到粘合面22的距离由厚度“T”表示。所述厚度“T”在基片14的平面26的长度上变化小于约20％，优选小于约10％，更优选小于约5％，甚至更优选小于约2％，最优选小于约1％。 
如图1(b)所示，可以对所述晶片层叠件进行基片的后续减薄(或其它工艺)，其中12’表示减薄后的晶片12。应当理解所述基片可以被减薄至小于约100μm的厚度，优选小于约50μm，更优选小于约25μm。减薄后，可以进行典型的背面处理，包括背研(backgrinding)、图案化(例如光刻，通孔蚀刻)、钝化、和金属镀覆、及其组合。 
有利地，干燥后的本发明组合物层拥有大量非常理想的性质。例如，所述涂层对真空蚀刻工艺表现出低气体释放性。也就是说，如果15μm厚的组合物膜在80-250℃烘烤2-60分钟(更优选2-4分钟)后，溶剂将被从所述组合物中除去，这样在后续的140-300℃下2-4分钟的烘烤导致膜厚度变化小于约5％，优选小于约2％，甚至更优选小于约1.0％或者甚至0％(称为“膜收缩试验”)。因此，干燥的涂层可以加热至最高约350℃的温度，优选最高约320℃，更优选最高约300℃，而不会在涂层中发生化学反应。在一些实施方案中，所述涂层也可以接触80℃的有机溶剂(例如N-甲基-2-吡咯烷酮)15分钟而不反应。 
所述干燥涂层甚至可以在接触酸或碱时保持粘合完整性。也就是说，具有约15μm厚度的干燥的组合物涂层可以浸入85℃的酸性介质(例如浓硫酸)或碱(例如30wt％的KOH)中约45分钟而保持粘合完整性。粘合完整性可以采用玻璃载体基片，透过玻璃载体基片目视观察粘合组合物层以检查气泡、空洞等来评价。此外，如果不能手工分开活性晶片和载体基片，也说明保持了粘合完整性。 
所需处理发生后，所述活性晶片或基片可以从载体基片上分离。在一个实施方案中，通过加热到足以软化粘合层的温度来分离所述活性晶片和基片。更具体地，所述层叠件被加热至至少约100℃的温度，优选至少约120℃，更优选约150℃-约300℃。这些温度范围表示所述粘合组合物层的优选剥离温度。如图1(c)所示，该加热将引起粘合组合外层软化并形成软化的粘合组合物层24’，在这一点两种基片可以通过例如滑动来分离。图1(c)显示了轴28，其穿过晶片12和基片14，滑动力通常施加在垂直于轴28的方向上。替代滑动，晶片12或基片14可以通过向上提升(即通常远离晶片12或基片14的另一个的方向)从基片14上分离晶片12。 
另外，替代加热软化涂层，所述粘合组合物可以用溶剂溶解。一旦所述涂层被溶解，可以随后分离活性晶片和基片。用于溶解所述粘合层的合适溶剂可以是干燥前组合物组成部分的任意溶剂，例如那些选自由MEK和环戊酮、以及选自由柠檬烯、均三甲苯、双戊烯、蒎烯、双环己烯、环十二烯、1-叔丁基-3，5-二甲苯、丁基环己烷、环辛烷、环庚烷、环己烷、甲基环己烷、及其混合物组成的组的烃溶剂。 
所述粘合组合物无论是被软化或溶解，应当理解可以简单地施加力去滑动和/或提升晶片12或基片14之一来完成分离而保持另一个在大致固定的位置来抵御滑动或提升 力(例如通过同时施加相对滑动或提升力到晶片12和基片14)。这都可以通过常规设备完成。 
任何残留在设备区域的粘合组合物可以通过合适的溶剂冲洗随后旋干容易地除去。合适的溶剂包括干燥前是组合物组成部分的原始溶剂和上面所列的那些在剥离过程中适于溶解组合物的溶剂。与所述溶剂接触5-15分钟后，任何留下的组合物将完全溶解(至少约98％，优选至少约99％，更优选约100％)。也可以接受单独地或与溶剂去除工艺结合使用等离子蚀刻来除去任何残留的粘合组合物。该步骤后，将留下干净的、不含粘合组合物的晶片12’和载体基片14。 
实施例
以下实施例阐述了根据本发明优选的方法。然而，应当理解这些实施例是以说明的方式提供的，不应当视为对本发明整体保护范围的限制。 
实施例1环烯烃共聚物树脂和低分子量COC树脂共混物 
在该实施例中，做了包含环烯烃共聚物树脂和低分子量COC树脂的配方。在一些配方中加入了抗氧剂。 
1、样品1.1 
在该过程中，将1.2克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA00002272157800101
5010，Tg110℃；购自托派司高级聚合物公司(TOPAS Advanced Polymers)，佛罗伦萨，肯塔基)和2.8克低分子量环烯烃共聚物(TOPAS 
Figure BDA00002272157800102
Toner TM，MW8,000，MW/Mn2.0)溶解在6克D-柠檬烯(佛罗里达化工有限公司)中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
2、样品1.2 
在该过程中，将0.75克乙烯-降冰片烯共聚物(TOPAS 8007，Tg78℃)和3.25克低分子量环烯烃共聚物(TOPAS 
Figure BDA00002272157800104
TonerTM)溶解在6克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
3、样品1.3 
对于该过程，将1.519克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA00002272157800105
5013，Tg134℃)和2.481克低分子量环烯烃共聚物(TOPAS  
Figure BDA00002272157800106
Toner TM)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA00002272157800107
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX 
Figure BDA00002272157800108
P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
4、样品1.4 
在该过程中，将1.2克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA00002272157800109
8007)和2.8克低分子量环烯烃共聚物(TOPAS 
Figure BDA000022721578001010
Toner TM)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA000022721578001011
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
5、样品1.5 
对于该过程，将2.365克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA000022721578001013
5013)和1.635克低分子量环烯烃共聚物(TOPAS  
Figure BDA000022721578001014
Toner TM)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA000022721578001015
1010)、以及0.04克膦磷酸盐类抗氧剂(IRGAFOX 
Figure BDA000022721578001016
P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶 液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
6、样品1.6 
在该过程中，将2.2克由开环聚合制备的基于氢化降冰片烯的共聚物(ZEONOR 1060，Tg100℃；购自吉恩化工，路易斯维尔，肯塔基)和1.8克低分子量环烯烃共聚物(TOPAS 
Figure BDA00002272157800112
Toner TM)溶解在5.92克环辛烷(Aldrich，Milwaukee，WI)中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
实施例2环烯烃共聚物树脂和增粘剂共混物 
在该实施例中，做了包含环烯烃共聚物树脂和各种增粘剂共混的配方。与实施例1一样，在一些配方中加入了抗氧剂。 
1、样品2.1 
在该过程中，将0.83克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA00002272157800113
8007)和3.17克氢化石油树脂(REGALITE 
Figure BDA00002272157800114
R1125；购自伊士曼化工有限公司，KingsportTN)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA00002272157800115
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX 
Figure BDA00002272157800116
P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解成溶液。所述溶液中具有约40％的固体。 
2、样品2.2 
对于该过程，将0.7克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA00002272157800117
8007)和3.3克苯乙烯改性萜烯树脂(ZONATA 
Figure BDA00002272157800118
NG98；购自亚利桑那化工，Jackonville FL)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA00002272157800119
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX 
Figure BDA000022721578001110
P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解到溶液中。所述溶液中具有约40％的固体。 
3、样品2.3 
在该配方中，将1.9克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA000022721578001111
5013)和2.1克环脂肪烃树脂(ARKON 
Figure BDA000022721578001112
P-140；购自美国荒川化学公司，Chicago IL)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA000022721578001113
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解到溶液中。 
4、样品2.4 
在该过程中，将2.42克乙烯-降冰片烯共聚物(TOPAS 
Figure BDA000022721578001115
5013)和1.58克环脂肪烃树脂(PLASTOLYN 
Figure BDA000022721578001116
R-1140；购自美国荒川化学公司，Chicago IL)、0.04克酚类抗氧剂(IRGANOX 
Figure BDA000022721578001117
1010)、以及0.04克亚膦酸盐类抗氧剂(IRGAFOX 
Figure BDA000022721578001118
P-EPQ)溶解在5.92克D-柠檬烯中。室温下搅拌所述溶液直到所述配料溶解到溶液中。所述溶液中具有约40％的固体。 
实施例3应用、粘合与剥离、以及分析 
将上述实施例1和2中准备的配方旋涂在各种基片晶片上。烘烤除去溶剂并允许粘合组合物回流，通过加压将第二晶片粘合到各个涂覆的晶片上。图2中示出了用粘合组合物临时晶片粘合的典型过程。测试粘合后晶片的机械强度、热稳定性和耐化学性。所述晶片通过在可接受的温度下手工滑动它们来测试剥离性。剥离后，所述粘合组合物残余物用溶剂冲洗和旋转来清理。 
测试了实施例1和2每个配方的流变性能。所有这些材料都成功地测试了剥离性。测得样品1.1、1.2、2.1和2.2的优选剥离温度为150℃。样品1.3、1.4和2.3的优选剥离 温度为200℃，样品1.5、1.6和2.4的优选剥离温度为250℃。每个样品在其优选剥离温度下的储能模量(G’)和熔体粘度(η*，综合粘度系数)记录如下。每个剥离温度的流变数据也示于图3-5中。 
表1 
  样品编号  储能模量，G’(Pa)   粘度，η*(Pa·S)   剥离温度(℃)
  1.1   25.5   35.0   150
  1.2   9.6   16.7   150
  1.3   8.0   13.9   200
  1.4   3.5   5.1   200
  1.5   16.3   20.1   250
  1.6   8.1   15.1   250
  2.1   24.9   14.5   150
  2.2   1.3   2.4   150
  2.3   21.7   28.7   200
  2.4   5.5   14.1   250
对这些组合物也进行了有关热稳定性和耐化学性的进一步研究。热重分析(TGA)在TA仪器热重分析仪上进行。通过刮下旋涂的和烘烤后的实施例1和2的粘合组合物样品得到TGA样品。对于恒温热重分析测量，在氮气中以10℃/分钟的速率加热样品，直到它们的优选剥离温度加50℃，在此温度保持恒温1小时来测定特定粘合组合物的热稳定性。每个样品的恒温测量记录在下面的表2中。对于扫描热重分析测量，在氮气中以10℃/分钟的速率加热样品，从室温至650℃。 
表2-恒温热重结果-热稳定性(在N2中) 
Figure BDA00002272157800131
从上表可以看出，所有的COC-低分子量COC树脂共混物(实施例1)拥有所需的热稳定性至少直到300℃并表现出最小的质量损失(＜1.5wt％)。当维持在测试温度时，COC-增粘剂共混物(实施例2)具有约5wt％的平均质量损失。然而，如下表3所示，1wt％质量损失的温度高于它们各自的粘合/剥离温度，表明晶片粘合应用的足够耐热性。 
表3-扫描热重结果 
Figure BDA00002272157800132
为了测定耐化学性，使用特定待测粘合组合物粘合两个硅晶片。粘合后的晶片放入85℃的N-甲基2-吡咯烷酮(NMP)或30重量％的KOH化学浴、以及室温的浓硫酸中来测定耐化学性。45分钟后目视观察粘合完整性，并测定粘合组合物对各自相应的化学作用的稳定性。所有粘合组合物保留了粘合完整性。 

Claims (6)

1.晶片粘合方法，该方法包括：
将粘合组合物通过旋涂施加到第一基片或第二基片之一以形成粘合层，所述层为由相同组合物形成的在其厚度上均匀的材料；和
将该第一基片和第二基片通过所述粘合层粘合在一起。
2.权利要求1所述的方法，其中该第一基片为具有包含形貌特征的活性表面的活性晶片，所述粘合层施加于该晶片上。
3.权利要求2所述的方法，其中该粘合组合物流入所述形貌特征之中及流到所述形貌特征之上。
4.权利要求2所述的方法，其中该粘合层在该活性表面的所述形貌上形成均匀层。
5.权利要求1所述的方法，其中施加该粘合层，使得该粘合层的厚度T横跨该第二基片的长度变化小于约20％，优选小于约10％，更优选小于约5％，甚至更优选小于约2％，最优选小于约1％。
6.权利要求1所述的方法，其中该粘合层通过旋涂施加。
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