CN101488480A - 间层电介质和预施涂的模片连接粘合剂材料 - Google Patents
间层电介质和预施涂的模片连接粘合剂材料 Download PDFInfo
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- CN101488480A CN101488480A CNA2008101733589A CN200810173358A CN101488480A CN 101488480 A CN101488480 A CN 101488480A CN A2008101733589 A CNA2008101733589 A CN A2008101733589A CN 200810173358 A CN200810173358 A CN 200810173358A CN 101488480 A CN101488480 A CN 101488480A
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Abstract
本发明涉及间层电介质材料和预施涂的模片连接粘合剂,更具体地预施涂的模片连接粘合剂(如芯片或其它衬底施涂的模片连接粘合剂),施涂间层电介质材料到衬底上以制备低K介电半导体芯片的方法,施涂预施涂的模片连接粘合剂到芯片和其它表面上的方法,和由其制备的用于连接微电子电路的组件。
Description
本申请是母案03814094.2的分案申请,母案申请日为2003年6月17日,名称为“间层电介质和预施涂的模片连接粘合剂材料”。
发明背景
发明领域
本发明涉及间层电介质材料和预施涂的模片连接粘合剂,更具体地预施涂的模片连接粘合剂(如芯片或其它衬底施涂的模片连接粘合剂),施涂间层电介质材料到衬底上以制备低K介电半导体芯片的方法,施涂预施涂的模片连接粘合剂到芯片和其它表面上的方法,和由其制备的用于连接微电子电路的组件。
相关技术的简要描述
双马来酰亚胺在热固性树脂的光谱中占据显着位置,和许多双马来酰亚胺可市购。双马来酰亚胺已经用于模塑件和粘合剂接合物,耐热复合材料,和高温涂料的生产。更近来,Henkel Loctite Corporation已经商业化许多部分基于某些双马来酰亚胺用于连接半导体芯片到电路板的产品,它们接收来自微电子封装工业中的有利响应。这些产品描述于一篇或多篇如下文献中:U.S.专利Nos.5,789,757(Husson),6,034,194(Dershem),6,034,195(Dershem)和6,187,886(Husson)。
低-k介电材料(或间层电介质,"ILD′s")在高级集成电路制造的末来发展中起重要作用,能够实现铜互连在亚-0.18微米制造工艺中的应用。ILD′s用于集成电路制造以将铜互连与它们的周围部分隔绝,在互连之间保证较少的串扰。由于它引起电路中的故障,串扰集成电路制造中的通常问题。当集成电路持续设计为越来越小时,串扰变得甚至更突出。和ILD′s是此设计倾向的重要方面以最大化一直更复杂集成电路的效率。
工业界的许多人甚至希望ILD′s作为氧化硅绝缘体的潜在后继物。然而,在降低内部封装应力方面迄今为止报导较少的进展,该应力导致ILD裂纹故障。
因此需要提供具有优异介电性能的ILD′s以最小化串扰。此外,需要提供采用这样ILD′s组装的电子组件和提供增强物理性能的这样电子组件的制造方法。
也需要采用预施涂的形式,如其芯片施涂或衬底施涂版本,提供模片连接粘合剂材料。这样的版本会消除许多贮存,分配,装卸和加工问题,当在包括模片连接粘合剂材料的可流动形式反应性粘合剂中分配时出现这些问题。
此外,在更极端的环境,如那些高温条件中,半导体器件在焊剂回流循环期间可曝露于该条件,其中无引线的焊剂用于建立电互连,需要在预施涂的模片连接粘合剂材料中使用甚至比以上提及的马来酰亚胺更刚硬的材料。
预施涂的粘合剂它们自身不是新的商业产品。例如,HenkelLoctite在预施涂的螺纹锁(threadlocker)粘合剂中具有实质性生意,它涉及(甲基)丙烯酸酯工业,用于与螺母和螺栓组合体连接,可由光固化机理、热固化机理、或其结合,与非必要的次级厌氧固化机理固化。也参见国际专利申请No.PCT/US00/07494;和U.S.专利Nos.2,928,446,4,325,985,4,632,944和5,300,608。
然而,迄今为止在商业中还没有采用在其上用于应用的预施涂模片连接粘合剂材料的制造制品,如半导体芯片或半导体芯片而没有由可流动模片连接粘合剂材料伴随的中间工艺步骤,特别是在粘合剂材料的反应性组分完全或部分基于双马来酰亚胺的情况,或对于如下情况的极端环境:模片连接粘合剂材料的反应性组分完全或部分基于苯并噁嗪。
发明概述
本发明在一个方面涉及制造制品,和特别地,提供用于连接到载体衬底和与载体衬底电互连的半导体芯片(或芯模片)。半导体芯片含有第一表面和第二表面,第一表面含有在其上以预定图案布置的用于提供与载体衬底电接通的电接触,及第二表面含在其层或一部分上布置的,优选作为膜的预施涂的模片连接粘合剂材料。
或者,半导体芯片可以为芯片形式,即为体形式,从该形式可以从芯片切线单个半导体芯片。
在本发明此方面的一个实施方案中,模片连接粘合剂材料所需地包括以液体形式或固体形式的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物,该化合物当为液体形式时与热塑性弹性体结合使用和当为固体形式时非必要地包括热塑性弹性体。模片连接粘合剂材料可包括另外的材料,该另外的材料可以与含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物共固化,如(甲基)丙烯酸酯官能化的材料、乙烯基官能化材料、乙烯基醚官能化的材料等。
当含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物在预施涂的模片连接粘合剂材料中以液体形式使用时,它可以是B阶段的,如通过曝露于电磁光谱中的辐射,以使得它在最终固化之前不可流动。
注意到,模片连接粘合剂材料可包括以液体形式或固体形式的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物。
如同以液体形式销售的Henkel Loctite双马来酰亚胺模片连接粘合剂材料,本发明的预施涂模片连接粘合剂材料产生固化的模片连接组合物,该模片连接组合物显示高度所需的物理性能的结合,该物理性能包括快速固化,低水吸收和低介电常数。和采用以上一般提及的粘合剂材料类型预施涂的制造制品具有如下的增加优点:有用而没有当采用可流动粘合剂材料加工时采用的通常加工步骤,该通常的加工步骤另外设计用于相似的应用。
在本发明的另一方面,模片连接粘合剂材料所需地包括含苯并噁嗪的化合物。
本发明提供涉及避免最终用户的分配,装卸和贮存问题的优点,使用含有预施涂到其表面的粘合剂材料的半导体芯片,该最终用户特别地尝试组装微电子器件。
本发明进一步提供组装半导体器件的方法,该方法包括提供半导体芯片与这样的模片连接粘合剂材料,配合半导体芯片与载体衬底以形成配合的组件,和曝露配合的组件于足以固化模片连接粘合剂材料的温度条件,因此粘合半导体芯片到载体衬底。或者或另外,可以将模片连接材料预施涂到如下部分上:位于载体衬底,如另一个芯模片或电路板上的一个或多个金属化接触、或键合、垫。根据本发明的含马来酰亚胺、衣康酰胺或NA酰亚胺的预施涂模片连接粘合剂材料的固化条件可包括对约150℃-约200℃的温度曝露约0.25分钟-约2分钟。
此外,在另一方面本发明提供间层电介质材料,该间层电介质材料基于含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物或基于含苯并噁嗪的化合物,和由其制造的半导体芯片。
附图简述
图1是在与衬底的组装之前,在本发明一个实施方案中的预施涂模片连接半导体芯片的简要表示。
图2是包括组装到衬底的图1半导体芯片的电路组件的简要表示。
图3是在本发明进一步的实施方案中,包括组装到芯片尺寸封装的半导体芯片的电路组件的简要表示。
图4是芯片背侧施涂的简要表示。
图5是芯片背侧施涂的简要表示。
图6是衬底施涂的简要表示。
图7是半导体芯片与间层电介质材料的简要表示。
图8是堆迭模施涂的简要表示,其中上部半导体芯片由模片连接粘合剂材料预施涂。
图9是在与半导体芯片组装之前,在本发明的一个实施方案中预施涂的模片连接载体衬底的简要表示。
图10是堆迭模施涂的简要表示,其中下部半导体芯片由模片连接粘合剂材料预施涂。
发明详述
参考附图,其中在其整个几个视图中同样的参考特征表示同样的部件,与电路组件50相关显示和描述预施涂的模片连接粘合剂材料,如图1和2所示。一般来说,电路组件50包括形式为预施涂的模片连接电路芯片60的半导体芯片,和载体衬底,如电路板衬底70。
预施涂的模片连接电路芯片60可以连接到电路板衬底以外的载体衬底,如热片或散热片,或热扩展器。热片,散热片或热扩展器可以至少部分从用于消散热量的材料,如AlSiC、阳极化铝等构成。
电路芯片60包括芯模片62。半导体芯片,或芯模片62可以由本领域已知的任何材料,如硅、锗等构成。芯模片62也可以采用材料涂敷,该材料能够钝化环境腐蚀,如聚酰亚胺、聚苯并环丁烷、氮化硅基材料。在图1或2中未显示钝化涂料。
衬底70也可以由本领域已知的任何材料,如以下物质构成:包括Al2O3、SiN3、和Al2O3-SiO2的陶瓷衬底;耐热树脂,如聚酰亚胺的衬底或带;玻璃增强环氧类物质的衬底;丙烯腈-丁二烯-苯乙烯("ABS")的衬底;酚类衬底等。衬底70包括在衬底表面74上的电路,该电路包括多个电接触垫76。
芯模片62包括相对的第一和第二表面,包括芯片表面64作为第一表面和连接表面68作为第二表面。在芯片表面64上提供电路,该电路包括多个电接触垫,如金属化接触垫66,它以预定的图案布置。这些电接触垫可连接到衬底70的接触垫76。通过如由导线80建立的在芯模片62上每个接触垫66和衬底70的接触垫76之间的键合,提供在芯模片62上的电路和衬底70上的电路之间的电互连和接通。可以在模片连接材料的固化之前或,更优选之后通过结合导线80到接触垫76建立电互连。尽管本图为展示本发明的目的而显示在芯模片62上的两个导线80和在衬底70上的两个相应接触垫76,理解导线结合和接触垫76的数目可以根据特定的所需用途和电路芯片的特定配置变化,和在此展示的具体配置不应当考虑为本发明的限制。
在本发明中,芯模片62包括形式为芯片表面64上接触垫66的金属化电接触,和包括在芯模片62与衬底70组装之前在相对连接表面68上预施涂的模片连接粘合剂材料90。
导电体可以是凸块,和焊接剂可以基本没有引线,如在工业中的增加倾向那样。在对适当固化条件的曝露之后,预施涂的模片连接粘合剂材料90提供电路组件50,该电路组件具有高粘合强度用于粘合芯模片62到衬底70。通常,通过对足以促进模片连接材料90的固化的高温条件的曝露,这样的粘合通过以固体形式形成完全固化的材料而发生,用于连接和粘合芯模片62到衬底70。
本发明进一步提供组装形式的电路组件50,如图2所示,其中芯模片62已经与衬底70配合,和曝露于适当的条件以引起模片连接材料90连接和粘合芯模片62到衬底70。同样,通过在接触垫66和接触垫76之间建立的电互连,如通过焊接或另外在其间结合导线80,芯模片62然后可以与衬底70电互连。
本发明因此在一个实施方案中提供形式为电路芯片的制造制品,该电路芯片含有能够提供与载体衬底电接通的第一表面,它希望电互连到该载体衬底,和第二表面,该第二表面与第一表面相对,和含有位于其至少一部分上的预施涂的模片连接粘合剂材料。直接提供模片连接粘合剂材料到芯模片表面上,消除与分配体积和温度的生产问题,和也消除贮存,装卸和保存期限问题。即预施涂的模片连接粘合剂材料的最终用户不再需要使用复杂的分配设备和用于这样材料应用的低温贮存容器。反而,最终用户现在可以使用根据本发明,含有在其表面至少一部分上预施涂的模片连接粘合剂材料的半导体芯片或半导体芯片和具有增加容易和产量组装半导体器件。
由模片连接粘合剂材料预施涂的半导体芯片也使最终用户能够实施更严格的封装设计标准。即由于与已知粘合剂对比从这样预施涂的模片连接粘合剂材料的降低流出和渗出,可以实现在模边缘和结合处之间的更严格允许误差。此外,半导体芯片现在可以更容易堆迭[参见如U.S.专利Nos.5,140,404(Fogal),5,177,632(Fogal),5,323,060(Fogal)和6,465,893(Khandros)],使得可以降低半导体器件的总体尺寸,或至少在长度和宽度方向中保持基本相同,还可以急剧增加堆迭半导体芯片的绩效能力。(参见图8和10.)
另外,鉴于通常模片连接粘合剂材料要求更严格的控制以在薄切线的结合期间避免截口蠕变和接触结合衬污染,当使用预施涂的模片连接粘合剂时不需要这样的预防措施。
预施涂的粘合剂材料也可以用于代替模垫上的焊剂掩模涂料,即预施涂的粘合物用作载体衬底,如电路板、保护器和粘合剂两者。由模堆迭物的厚度由焊剂掩模厚度的数量变薄,此方案能够制造甚至更薄的半导体器件封装。
在可以达到芯模片和衬底之间足够粘合和在这样集成的组件使用期间在其间提供适当性能的任何厚度和数量下,将模片连接材料(a)预施涂到电路芯片相对表面的至少一部分68上(图1)或(b)预施涂到在电接触垫76之间电接触垫76的至少一部分74A上(图9)。
预施涂的模片连接材料在本发明的一个方面中可以是热固性树脂组合物,该组合物在一个实施方案中包括以液体形式的含马来酰亚胺的化合物,如在以下文献中描述和要求的那样:U.S.专利Nos.5,789,757(Husson),6,034,194(Dershem),6,034,195(Dershem)和6,187,886(Husson),每个文献的公开内容因此在此引入作为参考。在另一个实施方案中,预施涂的模片连接材料包括含衣康酰胺或NA酰亚胺的化合物。
如上所述,预施涂的模片连接粘合剂材料可包括另外的材料,该另外的材料可以与含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物共固化,如(甲基)丙烯酸酯官能化的材料、乙烯基官能化的材料、乙烯基醚官能化的材料等,和/或热塑性弹性体,该热塑性弹性体当与含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物混合时有助于形成膜。
此处在预施涂的模片连接半导体芯片(而不是例如堆迭模施涂或预施涂的模片连接载体衬底)的上下文中所述,在到半导体芯片或芯片的第二表面上的布置之前,模片连接粘合剂材料应当为可流动的形式。因此,当使用液体形式的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物时,得到的模片连接粘合剂材料应当可流动。当以固体形式使用含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物时,需要升温半导体芯片或芯片,模片连接粘合剂材料,或与反应性或惰性种类的稀释剂混合,以形成其分散体的溶液和然后将这样的分散体溶液布置到半导体芯片或芯片的第二表面上。
预施涂的模片连接粘合剂材料也可以包括至少一种用于含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物的固化引发剂。
马来酰亚胺,NA酰亚胺,和衣康酰亚胺包括分别具有如下结构I,II和III的那些化合物
其中:
m=1-15,
p=0-15,
每个R2独立地选自氢或低级烷基,和
J是包括有机或有机硅氧烷基的单价或多价部分,及其两种或多种的结合。
马来酰亚胺,衣康酰亚胺和NA酰亚胺的更具体代表包括相应于结构I,II和III的那些,其中m=1-6,p=0,R2独立地选自氢或低级烷基,和J是选自如下的单价或多价基团:烃基、取代烃基、含杂原子的烃基、取代的含杂原子的烃基、亚烃基、取代亚烃基、含杂原子的亚烃基、取代的含杂原子的亚烃基、聚硅氧烷、聚硅氧烷-聚氨酯嵌段共聚物、及其两种或多种的结合,非必要地包含一种或多种选自如下的连接部分:共价键、-O-、-S-、-NR-、-O-C(O)-、-O-C(O)-O-、-O-C(O)-NR-、-NR-C(O)-、-NR-C(O)-O-、-NR-C(O)-NR-、-S-C(O)-、-S-C(O)-O-、-S-C(O)-NR-、-S(O)-、-S(O)2-、-O-S(O)2-、-O-S(O)2-O-、-O-S(O)2-NR-、-O-S(O)-、-O-S(O)-O-、-O-S(O)-NR-、-O-NR-C(O)-、-O-NR-C(O)-O-、-O-NR-C(O)-NR-、-NR-O-C(O)-、-NR-O-C(O)-O-、-NR-O-C(O)-NR-、-O-NR-C(S)-、-O-NR-C(S)-O-、-O-NR-C(S)-NR-、-NR-O-C(S)-、-NR-O-C(S)-O-、-NR-O-C(S)-NR-、-O-C(S)-、-O-C(S)-O-、-O-C(S)-NR-、-NR-C(S)-、-NR-C(S)-O-、-NR-C(S)-NR-、-S-S(O)2-、-S-S(O)2-O-、-S-S(O)2-NR-、-NR-O-S(O)-、-NR-O-S(O)-O-、-NR-O-S(O)-NR-、-NR-O-S(O)2-、-NR-O-S(O)2-O-、-NR-O-S(O)2-NR-、-O-NR-S(O)-、-O-NR-S(O)-O-、-O-NR-S(O)-NR-、-O-NR-S(O)2-O-、-O-NR-S(O)2-NR-、-O-NR-S(O)2-、-O-P(O)R2-、-S-P(O)R2-、-NR-P(O)R2-,其中每个R独立地是氢、烷基或取代烷基、及其两种或多种的结合。
当一种或多种上述单价或多价基团包含一个或多个上述连接部分以形成马来酰亚胺、NA酰亚胺或衣康酰亚胺基团的“J”附加物时,如容易由本领域技术人员认可的那样,可以产生很多种连接部分,例如,烷氧基、硫代烷基、氨基烷基、羧基烷基、烯氧基、硫代烯基、氨基烯基、羧基烯基、炔氧基、硫代炔基、氨基炔基、羧基炔基、环烷氧基、硫代环烷基、氨基环烷基、羧基环烷基、环烯氧基、硫代环烯基、氨基环烯基、羧基环烯基、杂环、氧杂环、硫代杂环、氨基杂环、羧基杂环、芳氧基、硫代芳基、氨基芳基、羧基芳基、杂芳基、杂芳氧基、硫代杂芳基、氨基杂芳基、羧基杂芳基、烷芳氧基、硫代烷芳基、氨基烷芳基、羧基烷芳基、芳烷氧基、硫代芳烷基、氨基芳烷基、羧基芳烷基、芳烯氧基、硫代芳烯基、氨基芳烯基、羧基芳烯基、氧烯基芳基、硫代烯基芳基、氨基烯基芳基、羧基烯基芳基、氧芳基炔基、硫代芳基炔基、氨基芳基炔基、羧基芳基炔基、氧炔基芳基、硫代炔基芳基、氨基炔基芳基或羧基炔基芳基、氧亚烷基、硫代亚烷基、氨基亚烷基、羧基亚烷基、氧亚烯基、硫代亚烯基、氨基亚烯基、羧基亚烯基、氧亚炔基、硫代亚炔基、氨基亚炔基、羧基亚炔基、氧亚环烷基、硫代亚环烷基、氨基亚环烷基、羧基亚环烷基、氧亚环烯基、硫代亚环烯基、氨基亚环烯基、羧基亚环烯基、氧亚芳基、硫代亚芳基、氨基亚芳基、羧基亚芳基、氧烷基亚芳基、硫代烷基亚芳基、氨基烷基亚芳基、羧基烷基亚芳基、氧芳基亚烷基、硫代芳基亚烷基、氨基芳基亚烷基、羧基芳基亚烷基、氧芳基亚烯基、硫代芳基亚烯基、氨基芳基亚烯基、羧基芳基亚烯基、氧烯基亚芳基、硫代烯基亚芳基、氨基烯基亚芳基、羧基烯基亚芳基、氧芳基亚炔基、硫代芳基亚炔基、氨基芳基亚炔基、羧基芳基亚炔基、氧炔基亚芳基、硫代炔基亚芳基、氨基炔基亚芳基、羧基炔基亚芳基、亚杂芳基、氧亚杂芳基、硫代亚杂芳基、氨基亚杂芳基、羧基亚杂芳基、含杂原子的二价或多价环状部分、含氧杂原子的二价或多价环状部分、含杂硫代原子的二价或多价环状部分、含氨基杂原子的二价或多价环状部分、含羧基杂原子的二价或多价环状部分、二硫化物、磺酰胺等。
在另一个实施方案中,设想用于本发明实施的马来酰亚胺,NA酰亚胺,和衣康酰亚胺具有结构I,II,和III,其中m=1-6,p=0-6,和J选自饱和直链烷基或支链烷基,非必要地包含非必要取代的芳基部分作为烷基链上的取代基或作为烷基链主链的一部分,和其中烷基链含有至多约20个碳原子;
具有如下结构的硅氧烷:-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-、-(C(R3)2)d-C(R3)-C(O)O-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-O(O)C-(C(R3)2)e-、或-(C(R3)2)d-C(R3)-O(O)C-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-C(O)O-(C(R3)2)e-,其中:
每个R3独立地是氢、烷基或取代烷基,
每个R4独立地是氢、低级烷基或芳基,
d=1-10,
e=1-10,和
f=1-50;
具有结构[(CR2)r-O-]f-(CR2)s-的聚烯化氧,
其中:
每个R独立地是氢、烷基或取代烷基,
r=1-10,
s=1-10,和
f如上所定义;
具有如下结构的芳族基团:
其中:
每个Ar是含有3-10个碳原子的单取代、二取代或三取代芳族或杂芳族环,和
Z是:
饱和直链亚烷基或支链亚烷基,非必要地包含饱和环状部分作为亚烷基链上的取代基或作为亚烷基链主链的一部分,或
具有结构-[(CR2)r-O-]q-(CR2)s-的聚烯化氧,
其中:
每个R独立地是氢、烷基或取代烷基,r和s每个如上所定义,和q为1-50;
具有如下结构的二或三以代芳族部分:
其中:
每个R独立地是氢、烷基或取代烷基,
t为2-10,
u为2-10,和
Ar如以上所定义;
具有如下结构的芳族基团:
其中:
每个R独立地是氢、烷基或取代烷基,
t=2-10,k=1、2或3,
g=1-约50,
每个Ar如上所定义,
E是-O-或-NR5,其中R5是氢或低级烷基;和
W是直链或支链烷基、亚烷基、亚烷氧基、烯基、亚烯基、亚烯氧基、酯、或聚酯、具有如下结构的硅烷:-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-、-(C(R3)2)d-C(R3)-C(O)O-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-O(O)C-(C(R3)2)e-、或-(C(R3)2)d-C(R3)-O(O)C-(C(R3)2)d-[Si(R4)2-O]f-Si(R4)2-(C(R3)2)e-C(O)O-(C(R3)2)e-,其中:
每个R3独立地是氢、烷基或取代烷基,
每个R4独立地是氢、低级烷基或芳基,
d=1-10,
e=1-10,和
f=1-50;
具有结构-[(CR2)r-O-]f-(CR2)s-的聚烯化氧
其中:
每个R独立地是氢、烷基或取代烷基,
r=1-10,
s=1-10,和
f如以上所定义;
非必要地包含选自如下的取代基:羟基、烷氧基、羧基、腈、环烷基或环烯基;
具有结构的R7-U-C(O)-NR6-R8-NR6-C(O)-(O-R8-O-C(O)-NR6-R8-NR6-C(O))v-U-R8-的尿烷基团,其中:
每个R6独立地是氢或低级烷基,
每个R7独立地是含有1-18个碳原子的烷基、芳基、或芳烷基,
每个R8是在链中含有至多约100个原子的烷基或烷氧基,非必要地由Ar取代,
U是-O-、-S-、-N(R)-、或-P(L)1,2-,
其中R如以上所定义,和其中每个L独立地是=O、=S、-OR或-R;和
v=0-50;
多环烯基;或其任何两种或多种的混合物。
当处于液态时,含马来酰亚胺、NA酰亚胺和/或衣康酰亚胺的化合物含有连接到单价基团J的官能团,或由多价基团J分隔的官能团,单价基团或多价基团的每一个具有足够的长度和支化以使含马来酰亚胺、NA酰亚胺和/或衣康酰亚胺的化合物为液体。
分别在结构I,II和III的这样含马来酰亚胺,NA酰亚胺和衣康酰亚胺的化合物的更具体叙述中,每个R独立地是氢或低级烷基,-J-包括支链烷基、亚烷基、烯化氧、亚烷基羧基或亚烷基酰氨基种类,这些种类具有足够的长度和支化以使马来酰亚胺、NA酰亚胺和/或衣康酰亚胺化合物为液体,和m是1、2或3。
含马来酰亚胺的化合物可以选自如下文献中描述和要求的那些:U.S.专利Nos.5,789,757(Husson),6,034,194(Dershem),6,034,195(Dershem)和6,187,886(Husson),每篇文献的公开内容因此在此引入作为参考,和由如下文献描述的那些:U.S.专利Nos.6,063,828(Ma),6,265,530(Herr),6,281,314(Tong)和6,316,566(Ma),每篇文献的公开内容也因此在此引入作为参考。
在此采用的
"烷基"表示含有1-约20个碳原子,优选2-10个碳原子的烃基;"取代烷基"包括进一步带有一个或多个取代基的烷基,该取代基选自羟基、烷氧基、巯基、环烷基、取代环烷基、杂环、取代杂环、芳基、取代芳基、杂芳基、取代杂芳基、芳氧基、取代芳氧基、卤素、氰基、硝基、氨基、酰氨基、C(O)H、酰基、酰氧基、羧基、氨基甲酸酯、磺酰基、磺酰胺、磺酰基等;
"环烷基”表示包含3-约8个碳原子的环状含环基团,和"取代环烷基”表示进一步带有一个或多个以上说明的取代基的环烷基;
"烯基”表示含有至少一个碳-碳双键,和含有2-约12个碳原子的直链或支链烃基,和"取代烯基”表示进一步带有一个或多个以上说明的取代基的烯基;
"环烯基”表示包含3-约8个碳原子的环状含环基团,和"取代环烯基”表示进一步带有一个或多个以上说明的取代基的环烯基;
"亚烷基”表示含有1-约20碳原子,优选2-10碳原子的二价烃基,和"取代亚烷基"包括进一步带有一个或多个以上说明的取代基的亚烷基;
"亚烷氧基”表示亚烷基部分,其中亚烷基部分的一个或多个亚甲基单元由氧原子代替;
"芳基”表示含有6-约14碳原子的芳族基团,和"取代芳基”表示进一步带有一个或多个以上说明的取代基的芳基;
"亚烯基”表示含有至少一个碳-碳双键,和含有2-约12碳原子的二价,直链或支链烃基,和"取代亚烯基”表示进一步带有一个或多个以上说明的取代基的亚烯基;和
"亚烯氧基”表示表示亚烯基部分,其中亚烯基部分的一个或多个亚甲基单元由氧原子代替。
用于本发明实施中设想使用的预施涂模片连接粘合剂材料或间层电介质材料的特别所需马来酰亚胺化合物包括,例如具有如下结构的马来酰亚胺:
结构I的优选马来酰亚胺树脂包括硬脂基马来酰亚胺、油基马来酰亚胺和二十二烷基马来酰亚胺、1,20-双马来酰亚氨基-10,11-二辛基-二十烷等、以及其结合物。
在本发明的另一方面,预施涂的模片连接粘合剂材料可包括含苯并噁嗪的化合物。
在预施涂的模片连接粘合剂材料包括含苯并噁嗪的化合物的情况下,预施涂的模片连接粘合剂材料也可包括(ii)环氧树脂或环硫化物树脂组分;(iii)一种或多种噁唑啉组分、氰酸酯组分、酚组分、硫代酚组分、丙烯腈-丁二烯共聚物组分、聚酰亚胺组分、和聚酰亚胺/硅氧烷组分;和(iv)非必要地,固化剂。它这些另外的组分与苯并噁嗪一起在预施涂的模片连接粘合剂材料中采用时,特别需要存在环氧,组分(iii)存在和不仅仅是酚组分。
苯并噁嗪可以选自包括如下结构的基质:
其中:
L是非必要的间隔部分,如亚烷基或硅氧烷连接部分、氢、直接键、O、C=O、S、O=S=O、C、CH、CH2、CR9R10及R9和R10是烷基、卤素取代的烷基、芳基或烷芳基;
Ar是非必要取代的亚芳基;
Q是具有如下结构的噁嗪环或其胺盐:
及在噁嗪环的位置5和6以稠合方式键合到Ar,
其中:
Sp是非必要的,和如果存在的话,是C1-C6亚烷基间隔部分,
n是1或2,
m是非必要的,和如果存在的话,是1-4,
x和y每个独立地是0-4,和
R11,R12,或R13的至少一个是可聚合的部分,如由L-(Ar(Qn))m表示的苯并噁嗪。
苯并噁嗪也可以由结构R11 x—Ar(Q)n包括:
其中:
Ar是非必要取代的亚芳基;
Q是具有如下结构的噁嗪环或其胺盐:
及在噁嗪环的位置5和6以稠合方式键合到Ar,
其中:
Sp是非必要的,和如果存在的话,是C1-C6亚烷基间隔部分,
n是1或2,
x和y每个独立地是0-4,和
R11,R12,或R13的至少一个是可聚合的部分。
此外,苯并噁嗪可以由如下结构包括
其中O是1-4,X是直接键(当O是2时)、烷基(当O是1时)、亚烷基(当O是2-4时)、羰基(当O是2时)、硫醇(当O是1时)、硫醚(当O是2时)、亚砜(当O是2时)、和砜(当O是2时),和R14是烷基、或芳基。
在更具体的实施方案中,苯并噁嗪组分由如下结构包括:
其中X选自直接键、CH2、C(CH3)2、C=O、S=O和O=S=O、S,及R14和R15相同或不同和选自甲基、乙基、丙基、或丁基和芳基。
在还更具体的实施方案中,苯并噁嗪由如下结构包括:
其中R14和R15相同或不同及选自甲基、乙基、丙基、丁基或芳基。
苯并噁嗪组分可包括一种或多种如下物质:
其中R14,R15和R16相同或不同和选自甲基、乙基、丙基、丁基或芳基。
例如,具体的多官能苯并噁嗪包括
因此,苯并噁嗪组分可包括多官能苯并噁嗪、单官能苯并噁嗪、及其结合物。
单官能苯并噁嗪包括
其中R14选自甲基、乙基、丙基、丁基或芳基,如甲基。
当加入稀释剂时,需要稀释剂是反应性稀释剂,该反应性稀释剂与含马来酰亚胺、NA酰亚胺、和衣康酰亚胺的化合物或含苯并噁嗪的化合物结合,形成热固性树脂组合物。这样的反应性稀释剂包括单官能和多官能醇的丙烯酸酯和甲基丙烯酸酯、如在此极大详细描述的乙烯基化合物、苯乙烯类单体(即,衍生自乙烯基苄基氯与单,二或三官能羟基化合物的反应的醚)等。
相应于乙烯基或多乙烯基化合物的特别优选类别反应性稀释剂包括通式:
其中q是1、2或3,
每个R独立地选自氢或低级烷基,
每个Q独立地选自醚、酮、酯或相反酯,和
Y是单价部分或多价连接部分。
多价连接Y典型地选自以上的J。
由以上一般结构包括的例示乙烯基或多乙烯基化合物包括硬脂基乙烯基醚、二十二烷基乙烯基醚、二十烷基乙烯基醚、异二十烷基乙烯基醚、异二十四烷基乙烯基醚、聚(四氢呋喃)二乙烯基醚、四甘醇二乙烯基醚、三-2,4,6-(1-乙烯氧基丁烷-4-氧-1,3,5-三嗪、双-1,3-(1-乙烯氧基丁烷-4)-氧羰基-苯(或者称为双(4-乙烯氧基丁基)间苯二甲酸酯;以商品名"VECTOMER"4010购自HoneywellInternational Inc.,Morristown,NJ)、在合适钯催化剂存在下通过在低级乙烯基醚和高分子量二醇之间的乙烯基交换制备的二乙烯基醚、非必要氢化的二取代聚丁二烯、非必要氢化的二取代聚异戊二烯、非必要氢化的二取代聚[(1-乙基)-1,2-乙烷]等。优选的二乙烯基醚包括硬脂基乙烯基醚、二十二烷基乙烯基醚、二十烷基乙烯基醚、异二十烷基乙烯基醚、聚(四氢呋喃)二乙烯基醚、在合适钯催化剂存在下通过在低级乙烯基醚和高分子量二醇之间的乙烯基交换制备的二乙烯基醚等。
另外,相应于结构XXIV的二乙烯基化合物,其中-Q-是酯和Y是含有约12-约500个碳原子的高分子量支链亚烷基,是有用的热固性树脂组合物,甚至在双马来酰亚胺树脂不存在下。当与合适数量的至少一种自由基引发剂和至少一种偶合剂结合时,这些二乙烯基醚权树脂单独能够形成热固性树脂组合物,该组合物显示优异的物理性能,该性能包括快速固化速率和低水吸收。
当然,模片连接材料可包括结构XXIV的乙烯基化合物和含马来酰亚胺、NA酰亚胺、或衣康酰亚胺的化合物或含苯并噁嗪的化合物的结合物,以得益于物理性能的高度所需结合,该物理性能包括快速固化速率和低水吸收两者。
所需地,预施涂的模片连接粘合剂材料可进一步包括可以与其共固化的热塑性弹性体,特别是当马来酰亚胺、衣康酰胺和NA酰亚胺为液体形式时。在此采用的"可共固化”表示热塑性弹性体的如下能力:经受与大分子单体如含马来酰亚胺、衣康酰胺和NA酰亚胺的化合物的共聚,以形成三维聚合物网络。
设想用于本发明实施的热塑性弹性体典型地是嵌段共聚物。嵌段共聚物含有至少一个通式(A-B)或(A-B-A)的单元,其中A是非弹性体聚合物嵌段和B是弹性体聚合物嵌段。设想用于本发明实施的嵌段共聚物优选具有低介电常数。此外,热塑性塑料包括烯属不饱和的侧和/或末端单元,和因此能够与模片连接材料中的其它组分固化。
非弹性体聚合物嵌段(A)可以是一种或多种非必要取代芳族烃的聚合产物,该芳族烃包含至少一个烯属不饱和的单元。设想用于本发明实施的芳族烃包括,例如,非必要取代的苯乙烯、非必要取代的茋等。设想用于本发明非必要使用的取代基包括例如,烷基、烯基、炔基、羟基、烷氧基、烯氧基等。在优选的实施方案中,芳族烃是非必要取代的苯乙烯。
弹性体聚合物嵌段(B)典型地是非必要取代的烯烃单体和/或非必要取代的共轭二烯烃单体的聚合或共聚产物。设想用于本发明实施的烯烃单体典型地包含2-约20个碳原子。优选,烯烃单体包含2-约12个碳原子。在特别优选的实施方案中,烯烃单体包括,例如,乙烯、丙烯、丁烯、异丁烯、丙烯腈、(甲基)丙烯酸酯等。最优选,烯烃单体是丙烯腈。
设想用于本发明实施的共轭二烯烃单体典型地包含4-约20个碳原子。优选,共轭二烯烃单体包含4-约12个碳原子。在特别优选的实施方案中,共轭二烯烃单体包括,例如,丁二烯、异戊二烯、二甲基丁二烯等。最优选,共轭二烯烃单体是丁二烯。
设想使用的热塑性弹性体包括,例如,聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-聚二甲基丁二烯-聚苯乙烯嵌段共聚物、聚丁二烯-聚丙烯腈嵌段共聚物等。优选,嵌段共聚物是聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物或聚丁二烯-聚丙烯腈嵌段共聚物。
当采用热塑性弹性体时,模片连接材料典型地包含约10wt%-约95wt%热塑性弹性体,约5wt%-约90wt%含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物,或含苯并噁嗪的化合物,和约0.2wt%-约2.0wt%固化引发剂,其中wt%是基于组合物的总重量。优选,含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物,或含苯并噁嗪的化合物以约10wt%-约80wt%存在。
也可以包括固化引发剂,和所需包括的是自由基引发剂时,由对约70℃-约180℃的温度,或对电磁光谱中的辐射曝露而激发。在此采用的术语"自由基引发剂”表示在对足够能量(如光、热量等)曝露时,分解成至少两种不带电荷的物质的任何化学物质,但该每种具有至少一个未配对的电子。
热自由基固化引发剂包括例如,过氧化物(如过氧酸酯,过氧碳酸酯,氢过氧化物,烷基过氧化物,芳基过氧化物等)、偶氮化合物等。设想用于本发明实施的目前优选过氧化物包括过氧化二枯基、过氧化二苯甲酰、过氧化2-丁酮、过苯甲酸叔丁酯、过氧化二叔丁基、2,5-双(叔丁基过氧)-2,5-二甲基己烷、双(叔丁基过氧异丙基)苯、氢过氧化叔丁基等。设想用于本发明实施的目前优选偶氮化合物包括2,2′-偶氮双(2-甲基丙腈)、2,2′-偶氮双(2-甲基丁腈)、1,1′-偶氮双(环己腈)等。
辐射自由基固化引发剂(或,光敏引发剂)包括例如,以商品名"IRGACURE"和"DAROCUR"购自Vantico,Inc.,Brewster,纽约的那些,如"IRGACURE"184(1-羟基环己基苯基酮)、907(2-甲基-1-[4-(甲基硫代)苯基]-2-吗啉代丙烷-1-酮)、369[2-苄基-2-N,N-二甲基氨基-1-(4-吗啉代苯基)-1-丁酮]、500(1-羟基环己基苯基酮和二苯酮的结合物)、651(2,2-二甲氧基-2-苯基苯乙酮)、1700[双(2,6-二甲氧基苯甲酰基-2,4,4-三甲基戊基)膦氧化物和2-羟基-2-甲基-1-苯基-丙烷-1-酮的结合物]和"DAROCUR"1173(2-羟基-2-甲基-1-苯基-1-丙烷)和4265(2,4,6-三甲基苯甲酰基二苯基-膦氧化物和2-羟基-2-甲基-1-苯基-丙烷-1-酮的结合物);以"CYRACURE"商品名购自Dow Chemical的光敏引发剂,如"CYRACURE"UVI-6974(混合六氟锑酸三芳基锍盐)和UVI-6990(混合六氟磷酸三芳基锍盐);和可见光[蓝色]光敏引发剂,d1-樟脑醌和"IRGACURE"784DC。
另外的光敏引发剂可以选自以商品名"ESACURE"和"SARCAT"购自Sartomer,Inc.,Exton,Pennsylvania的那些。例子包括"ESACURE"KB1(苯偶酰二甲基缩酮)、"ESACURE"EB3(苯偶姻和丁基醚的混合物)、"ESACURE"TZT(三甲基二苯酮共混物)、"ESACURE"KIP100F(羟基酮)、"ESACURE"KIP150(聚合物羟基酮)、"ESACURE"KT37("ESACURE"TZT和KIP150的共混物)、"ESACURE"KT046(三苯基膦氧化物,"ESACURE"KIP150和TZT的共混物)、"ESACURE"X33(2-和4-异丙基噻吨酮,4-(二甲基氨基)苯甲酸乙酯和"ESACURE"TZT的共混物)、"SARCAT"CD 1010[六氟锑酸三芳基锍(碳酸丙烯酯中的50%)]、"SARCAT"DC 1011[六氟磷酸三芳基锍(50%碳酸正丙烯酯)]、"SARCAT"DC 1012(六氟锑酸二芳基碘鎓)、和"SARCAT"K185[六氟磷酸三芳基锍(在碳酸丙烯酯中的50%)]。
光敏引发剂包括含非亲核抗衡离子的三芳基锍和二芳基碘鎓盐和芳基重氮鎓盐,它们的例子包括六氟磷酸4-甲氧基苯重氮鎓、四氟硼酸苯重氮鎓、氯化二苯基碘鎓、六氟磷酸二苯基碘鎓、六氟磷酸4,4-二辛氧基二苯基碘鎓、四氟硼酸三苯基锍、六氟磷酸二苯基甲苯基锍、六氟砷酸苯基二甲苯基锍、和六氟锑酸二苯基-硫代苯氧基苯基锍。
当然,可以使用这样光敏引发剂的结合,如本领域技术人员认为适当的那样。
在此采用的术语"偶合剂”表示化学物质,该化学物质包含一套能够键合到矿物质和/或有机表面的官能团和也包含另一套能够键合模片连接粘合剂材料中反应性材料的反应性官能团。偶合剂因此促进模片连接材料对它要施涂到其上的衬底的连接。
设想用于本发明实施的例示偶合剂包括硅酸酯、金属丙烯酸盐(如,甲基丙烯酸铝)、钛酸酯(如,钛甲基丙烯酰氧基乙酸乙酸酯三异丙醇盐)、或包含可共聚基团和螯合配体(如,膦,硫醇,乙酰乙酸酯等)的化合物。一般采用约0.1-10wt%至少一种偶合剂的范围(基于有机相的总重量),及约0.5-2wt%的范围是所需的。
某些所需的偶合剂包含可共聚官能(如,乙烯基部分,丙烯酸酯部分,甲基丙烯酸酯部分,苯乙烯部分,环戊二烯部分等),以及硅酸酯官能两者。偶合剂的硅酸酯部分能够与衬底矿物质表面上存在的金属氢氧化物缩合,同时可共聚官能能够与本发明粘合剂组合物中的其它反应性组分共聚。这样偶合剂的例子是低聚物硅酸酯偶合剂,如聚(甲氧基乙烯基硅氧烷)。
预施涂的模片连接粘合剂材料可进一步包括约20-90wt%填料,基于预施涂的模片连接组合物的总重量。设想用于本发明实施的填料可以非必要是传导性的(导电和/或导热)。设想用于本发明实施的导电填料包括,例如,银、镍、金、钴、铜、铝、石墨、银涂敷的石墨、镍涂敷的石墨、这样金属的合金等、以及其混合物。在此可以使用填料的粉末和薄片形式两者。在薄片形式中,填料的厚度小于约2微米,及平面尺寸为约20-约25微米。在此采用的薄片的表面积为约0.15-5.0m2/g和堆积密度为约0.4-约5.5g/cc。在粉末形式中,填料粒子的直径为约0.5-30微米,如约20微米。
当存在时,典型地使用预施涂的模片连接材料约1wt%-约95wt%的填料,其中wt%是基于组合物的总重量。
设想在此使用的导热填料包括,例如,氮化铝、氮化硼、碳化硅、金刚石、石墨、氧化铍、氧化镁、二氧化硅、氧化铝等。
应当由采用螯合剂、还原剂、非离子润滑剂、或这样试剂混合物的处理使导热和/或导热填料基本没有催化活性金属离子。这样的处理描述于U.S.专利No.5,447,988,该文献在此全文明确引入作为参考。
非必要地,可以使用导电或导热的填料。可以希望这样的填料向配制剂赋予一些其它性能,例如,固化组合物的降低热膨胀、降低的介电常数、改进的韧性、增加的疏水性等。这样填料的例子包括全氟化烃聚合物(即,TEFLON)、热塑性聚合物、热塑性弹性体、云母、煅烧的二氧化硅、玻璃粉末、间隔片元件等。
预施涂的模片连接粘合剂材料可进一步包含其它添加剂,如防沫剂、流平剂、染料、和颜料。
可以由模版印刷、丝网印刷或喷涂将模片连接粘合剂材料施涂到半导体芯片(参见如图1-3)以形成预施涂的模片连接电路芯片。分别参见图4-6。此外,可以由模版印刷、丝网印刷或喷涂将模片连接粘合剂材料施涂到半导体芯片以外的衬底上(参见图9)以形成预施涂的模片连接电路芯片。和可以将模片连接粘合剂材料施涂到中间衬底,如晶片划线带或膜、晶片支持带或膜上,它们用于传输在带或膜上预施涂的模片连接粘合剂材料用于转移到半导体芯片或其它衬底上。
在模版印刷或丝网印刷到预划线晶片上的情况下,可以采用模片连接粘合剂材料均匀地涂敷晶片。在晶片划线期间,划线锯然后通过预施涂的模片连接粘合剂材料层和晶片完全切割。
在模版印刷或丝网印刷到预划线晶片的情况下,制备含有窗孔的模版或丝网,该窗孔设计用于部分,或完全覆盖单个模或半导体芯片。具体地,模版或丝网的边带用于保持模片连接粘合剂材料就位。即,不需要模片连接粘合剂材料进入划线范围,它会促进模放置期间的模分离。设计边带的宽度,或相反,窗孔的尺寸使得在模放置之后,可以达到目标湿粘结层和模片连接粘合剂材料可以在模以下形成所需高度的嵌条。
在模版印刷或丝网印刷到层压衬底上的情况下,制备含有窗孔的模版或丝网,该窗孔设计用于部分覆盖模垫。具体地,丝网或模版的边带用于在模放置之后保持模片连接粘合剂材料就位。设计边带的宽度,或相反,窗孔的尺寸使得在模放置之后,可以达到湿粘结层和预施涂的模片连接粘合剂材料可以在模以下形成所需高度的嵌条,及由导电互连的预施涂模片连接粘合剂材料引起的润湿最小到无。
在施涂到层压衬底上的情况下,可以采用模片连接粘合剂材料达到"零间隙粘结层"。例如,首先在模垫上制造没有焊剂掩模层的层压材料。因此,模垫区域的高度相对于非模垫区域低等于焊剂掩模层厚度的深度,它典型地是约1密耳。然后使用模版印刷或丝网印刷由模片连接粘合剂材料填充这些凹陷的模垫。
优选,施涂一定数量的模片连接粘合剂材料直到施涂粘合剂材料的表面与焊剂掩模层齐平。凹陷的模垫不完全由模片连接粘合剂材料填充入;使用一定数量的模片连接粘合剂材料使得在模放置之后,模片连接粘合剂材料在模以下流动以覆盖先前曝露的模垫底部。此方法允许半导体封装制造商达到更装的封装件而不改变粘结层粘合剂。
在将模片连接粘合剂材料预施涂在半导体芯片以外的衬底上的情况下,衬底可以是层压材料(如上所述)、陶瓷、引线架、热片或热扩展器(如上所述)、或中间衬底(也如上所述)。
参考图9,将模片连接粘合剂材料90A预施涂到载体衬底70上以形成预施涂的模片连接载体衬底60A。当将半导体芯片62的粘合表面68A与预施涂的模片连接载体衬底60A接触和建立电连接时,如通过从半导体芯片62上的电接触垫66结合导线80到载体衬底70上的电接触垫76,形成电路组件50。
在喷涂的情况下,薄半导体芯片是所需的衬底,在其上用于涂敷模片连接粘合剂材料。这些薄半导体芯片的厚度为约2-3密耳。尽管一旦合适地支持而是机械强健的,即,以它们的未支持形式结合到柔性衬底上和被包覆或过度模塑,从这些晶片衍生物薄小片是脆性的和相当容易断裂。因此有利的是在进行这样操作的同时,施涂模片连接粘合剂材料到薄晶片上的方法施加最小的力量。
在使用任何上述方法施涂模片连接粘合剂材料到晶片或模上之后,然后可以将粘合剂材料干燥以除去如果存在的溶剂,或冷却以固化粘合剂材料。
尽管可以选择在模片连接粘合剂材料可固化组分固化开始以下的任何温度,在约100℃的温度下典型的干燥时间可以是约30分钟。时间长度可依赖于模片连接粘合剂材料表面在选择的温度下变成无粘性要求的时间而变化。
在模片连接粘合剂材料表面无粘性之后(通过干燥或冷却,或B阶段,如上所述)的任何时间,可进行芯片键合。
适用于固化预施涂的模片连接粘合剂材料,特别是包含含有马来酰亚胺、NA酰亚胺、和衣康酰亚胺的化合物的那些粘合剂材料的条件包括将预施涂的模片连接粘合剂材料经受至少约175℃但小于约300℃的温度约0.5-约2分钟。在7.6mm x 7.6mm模的情况下,典型的芯片键合设定是在约约100℃的温度下,使用500cN展开的约10秒时间。可以采用各种方式,如采用内联快速固化站如由Nihon Sanso制造的那些、在模结合器上安装的受热台、或由EFOS Novacure IR单元提供的IR束完成此快速,短持续时间加热。对于包含苯并噁嗪化合物的预施涂的模片连接粘合剂材料,尽管通常可能需要更长的时间,如约1小时,相同的温度条件可用于固化粘合剂材料。
在堆叠模组件的情况下(如在U.S.专利Nos.5,140,404,5,286,679,5,323,060,和6,465,893中所述,每篇文献的公开内容在此明确引入作为参考),有利地在模放置之后加热模以熔融模片连接粘合剂材料,特别是在存在可固化热塑性组分的情况下,以允许衬底的改进润湿,它要放置在该衬底上。可以由通过模套爪脉冲热量加热模,它末来可用于膜的模结合器,如由ESC制造的那些。在薄模的情况下,该模薄由于研磨工艺期间残余机械应力的积累典型地翘曲,在某些温度以上加热模具有退火模和降低翘曲的效果。
图8和10显示分别要在堆叠模组件110,110A中堆叠的两个模的横截面视图。这两种配置中的差异在于在图8中,将模片连接粘合剂材料90在堆叠模组件110中上半导体芯片112的下表面68上预施涂,而在图10中,将模片连接粘合剂材料90A在堆叠模组件110A的下半导体芯片114上表面64A上预施涂。参考图8,堆叠模组件110包括形式为预施涂的模片连接电路芯片112(含有芯模片62和在其上布置的预施涂的模片连接粘合剂90)的半导体芯片,和另一个芯模片62A,在芯模片62A的处理表面64A上,预施涂的模片连接电路芯片112连接到该芯模片62A。预施涂的模片连接电路芯片112含有结合垫66和结合导线80,它通过芯模片62A上的结合垫66A电连接到芯模片62A。结合导线80A从结合垫66A延伸到另一个芯模片(未显示)或电路板(未显示)用于电互连。
注意到在此讨论的芯模片62可以提供为单个芯模片,或可以提供为芯片尺寸封装。因此,在图3中所示的还进一步实施方案中,提供芯片尺寸封装160的电路组件150。芯片尺寸封装在本领域已知用于电路与电路板衬底的电连接。在本实施方案中,电路组件150包括相似于图2所示实施方案中显示的结构,区别在于芯模片62由芯片尺寸封装160代替。例如,电路组件150包括电路板衬底70,电路板衬底70包括在其上的接触垫76。将衬底70连接到芯片尺寸封装160,它可包括例如,连接到单独载体衬底或插入层的芯模片,,如本领域已知的那样。在这样的实施方案中,采用先前描述中关于电路芯片60说明的相似方式,接触垫66和/或导线80可以在单独载体衬底上提供或在插入层上提供。另外,采用与先前描述相似的方式,通过模片连接材料90将芯片尺寸封装160连接到衬底70。
本发明也提供采用粘合剂连接本发明的制造制品到载体衬底,如芯模片或电路板的方法。方法包括:
a.提供本发明的制造制品;
b.提供载体衬底;
c.联接本发明的制造制品与载体衬底以形成组件,其中本发明的制造制品和载体衬底由预施涂的模片连接粘合剂材料分隔;和
d.曝露这样形成的组件以足以固化预施涂的模片连接粘合剂材料的温度条件。
在本发明的另一方面,马来酰亚胺,衣康酰胺和NA酰亚胺具有使它们适于用作ILD的物理性能情况,该ILD用于硅模的制造。通常以它们的液体形式,这些马来酰亚胺,衣康酰胺和NA酰亚胺具有足够低的粘度,该粘度能够实现旋涂。此外,如需要可以通过加热或与以上讨论的反应性稀释剂结合进一步降低它们的粘度,用于旋涂更薄的ILD。同样,在固体形式中,可以将这样的马来酰亚胺,衣康酰胺和NA酰亚胺加热或与稀释剂结合,以允许旋涂。这些马来酰亚胺,衣康酰胺和NA酰亚胺具有高热降解温度和高均聚开始,它们允许由加热的稀化。由于马来酰亚胺,衣康酰胺和NA酰亚胺可以通过对电磁光谱中的辐射,如UV固化,可以达到到一些分辩率的光刻法。马来酰亚胺,衣康酰胺和NA酰亚胺的固化产物具有尖的热降解点,它允许清洁和清晰的激光烧蚀。
图7在横截面中显示半导体芯片100,其中ILD 108的层在第一和第二导电层106,106A之间显示,更具体地,半导体芯片100从硅衬底102形成,它已经曝露于氧化气氛中的高温条件使得氧化硅层104形成为在其上的半导体层104。半导体层104显示电子源103,以及电子槽103A,和闸107,它通过调节电压控制电子的流动。在半导体层上布置的层105在此图中从硼磷硅酸盐玻璃制备,它可以由化学气相沉积工艺施涂。由于形成具有不规则表面的半导体层104,此硼磷硅酸盐玻璃表面使那些不规则物变平。显示的下一个层是第一导电层106,在此显示为从铜构造。此导体层106可含有在其上涂敷的耗散屏障(未显示)。在第一导电层106的顶部上是ILD层,在其顶部上是第二导电层106A。最后在图7中显示钝化层101。通常旋涂钝化层101。在第二导电层106A和第一导电层106之间是通道109A,它通过ILD层108形成使得电子可流动。和在第一导电层106和半导体层106A之间是用于相同目的另一个通道109。
因此,广而言之本发明在此方面提供半导体芯片,该半导体芯片包括硅衬底,半导体层层,至少两个导体层,在其两个之间是包括一种或多种含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物,或一种或多种含苯并噁嗪的化合物的间层电介质。
现在通过参考如下非限制性实施例更详细地描述本发明。
实施例
在第一实施例中,使用苯乙烯-丁二烯嵌段共聚物,KRATON D-1102作为热塑性弹性体组分,和十八烷基马来酰亚胺和X-BMI(10,11-二辛基-二十烷的1,20-双马来酰亚氨基衍生物)作为马来酰亚胺,制备用于预施涂到半导体芯片的模片连接粘合剂材料。从以下表1叙述的组分制备用于预施涂的模片连接的粘合剂材料。
表1
十八烷基马来酰亚胺 1.0g
KRATON D-1102 2.5g
X-BMI1 1.5g
RICON 1302 0.2g
硅烷偶合剂3 0.2g
过氧化二枯基 0.05g
二甲苯 5.0g
TEFLON填料 6.9g
1.X-BMI(10,11-二辛基-二十烷的1,20-双马来酰亚氨基衍生物),根据U.S.专利No.5,973,166中说明的过程制备,该文献的公开内容在此明确引入作为参考。
2.采用马来酸酐20%接枝的聚丁二烯(Sartomer)
3.专用含硅烷偶合剂。
将十八烷基马来酰亚胺溶于二甲苯,和将KRATON D-1102加入和允许在加入剩余组分之前溶解。
将膜流延到玻璃衬底上和干燥过夜。然后将硅模放置到膜上,和将膜涂敷的衬底加热到80℃的温度下1-3秒。将此组件最终在80℃的温度下固化30分钟。
在校准的Dage 2400模剪切测试仪上评价膜模片连接组合物的室温模剪切和热模剪切。结果以下显示于表2,相比于QMI536,模片连接产物,购自Henkel Loctite Corporation,LaJolla,加利福尼亚,该产物包括与以上采用的相同双马来酰亚胺结合物。同样包括在表2中的是在将固化组合物经受85℃/85%湿度条件24hrs时间之后的模剪切数值。
表2
配制剂 | 室温模剪切(磅) | 热模剪切(245℃)(磅) |
QMI536,初始 | 59.1 | 24.4 |
配制剂1,初始 | 88.9 | 25.9 |
QMI536,24hrs,85/85 | 52.6 | 23.9 |
配制剂1,24hrs,85/85 | 79.6 | 24.6 |
以上显示的结果展示与不以预施涂,不可流动形式的类似可流动模片连接组合物相比,配制剂1具有优异的模剪切强度。
在第二个实施例中,使用含苯并噁嗪的化合物用于模片连接材料制备两个样品。以下在表3中按份数说明配制剂2和3每个的组分。
表2
苯并噁嗪4 2 1.5
RICON1302 0.2 0.2
硅烷偶合剂3 0.1 0.1
树脂5 0.5 0.5
环氧物6 -- 0.5
丙酮 2 2
TEFLON填料 2 2.2
4.相信从双酚F,硫代二苯酚,苯胺和甲醛制备,和以商品名XU3560US购自Vantico。
5.专用羟基官能化芳族树脂
6.ARALDITE 7097US。
配制剂2和3制备如下。与环氧物一起,将苯并噁嗪在室温下溶于丙酮(用于配制剂3)。向此物质中采用搅拌在室温下加入树脂,RICON130和硅烷偶合剂。最后,将TEFLON填料加入和充分混合以形成平滑,乳状糊剂。
象配制剂1,将配制剂2和3流延到载玻上成膜。将由配制剂2和3涂敷的载玻片曝露于95-125℃的温度下约10-60分钟的时间,和允许冷却到室温。一旦在室温下,将半导体芯片放置在每个配制剂涂敷的载玻片上,和芯片和衬底一起在95-125℃的温度下以连接芯片到衬底。然后将配制剂175℃的温度下固化1小时的时间。
一旦固化之后,评价配制剂2和3的剪切强度。因此,由配制剂2连接的300密耳玻璃基模在室温下显示62.8Kg-f,和在245℃下显示3.3Kg-f,和由配制剂3连接的那些在室温下显示56.4Kg-f,和在245℃下显示2.7Kg-f。
配制剂2和3也经受差示扫描量热法以测定它们的开始温度,固化峰和固化能量。观察配制剂2以具有190℃的开始温度,而观察配制剂3以具有195℃的开始温度。配制剂2展示214℃的固化峰,而配制剂3展示222℃的固化峰。配制剂2也展示171.75J/g的固化能量,而配制剂3显示91.7J/g的固化能量。
Claims (33)
1.制品,包括:
(a)含有第一表面和第二表面的芯模片,及第一表面含有在其上以预定图案布置的电接触;和
(b)位于芯模片第二表面的层或一部分上的B阶段模片连接粘合剂材料,和其中在B阶段之前,模片连接粘合剂材料包括:
(i)一种或多种以液体形式与热塑性弹性体结合的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物。
2.制品,包括:
(a)含有第一表面和第二表面的芯模片,及第一表面含有在其上以预定图案布置的电接触;和
(b)位于芯模片第二表面的层或一部分上的模片连接粘合剂材料,和其中模片连接粘合剂材料包括:
(i)一种或多种非必要地与热塑性弹性体结合的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物。
3.制品,包括:
(a)含有第一表面和第二表面的芯模片,及第一表面含有在其上以预定图案布置的电接触;和
(b)位于芯模片第二表面的层或一部分上的模片连接粘合剂材料,和其中模片连接粘合剂材料包括:
(i)一种或多种非必要地与热塑性弹性体结合的含苯并噁嗪的化合物。
4.权利要求3的制造制品,其中模片连接粘合剂材料进一步包括
(ii)环氧树脂或环硫化物树脂组分;
(iii)非必要地,一种或多种如下物质:噁唑啉组分、氰酸酯组分、酚组分、硫代酚组分、聚酰亚胺/硅氧烷组分、含马来酰亚胺的组分、含NA酰亚胺的组分、和含衣康酰胺的组分;和
(iv)非必要地,固化剂。
5.权利要求3的制造制品,条件是在组分(ii)是环氧类的情况下,组分(iii)存在和不仅仅是酚组分。
6.根据权利要求1的制造制品,其中在制造制品芯模片的第一表面上的电接触提供与载体衬底的电接通,它要连接到该衬底上。
7.根据权利要求1的制造制品,其中电接触包括焊接凸块。
8.根据权利要求2的制造制品,其中在制造制品芯模片的第一表面上的电接触提供与载体衬底的电接通,它要连接到该衬底上。
9.根据权利要求2的制造制品,其中电接触包括焊接凸块。
10.根据权利要求3的制造制品,其中在制造制品芯模片的第一表面上的电接触提供与载体衬底的电接通,它要连接到该衬底上。
11.根据权利要求3的制造制品,其中电接触包括焊接凸块。
12.根据权利要求3的制造制品,其中电接触包括基本没有引线的焊接凸块。
13.根据权利要求3的制造制品,其中电接触包括熔点大于约200℃的焊接凸块。
15.根据权利要求14的制造制品,其中J包括具有足够长度和支化以使马来酰亚胺、NA酰亚胺和/或衣康酰亚胺化合物为液体的支链烷基、亚烷基、烯化氧、亚烷基羧基或亚烷基酰氨基,和m是1、2或3。
16.根据权利要求1或2的制造制品,其中热塑性弹性体包括具有至少一个通式(A-B)或(A-B-A)单元的嵌段共聚物,其中A是非弹性体聚合物嵌段和B是弹性体聚合物嵌段。
22.根据权利要求14的制造制品,其中预施涂的模片连接粘合剂材料包括含马来酰亚胺的化合物、含衣康酰亚胺的化合物或含NA酰亚胺的化合物,这些化合物包括结构I,II和III,其中
m=1-6,
p=0,
R2独立地选自氢或低级烷基,和
J是选自如下的单价或多价基团:烃基、取代烃基、含杂原子的烃基、取代的含杂原子的烃基、亚烃基、取代亚烃基、含杂原子的亚烃基、取代的含杂原子的亚烃基、聚硅氧烷、聚硅氧烷-聚氨酯嵌段共聚物、及其两种或多种的结合,非必要地包含一种或多种选自如下的连接部分:共价键、-O-、-S-、-NR-、-O-C(O)-、-O-C(O)-O-、-O-C(O)-NR-、-NR-C(O)-、-NR-C(O)-O-、-NR-C(O)-NR-、-S-C(O)-、-S-C(O)-O-、-S-C(O)-NR-、-S(O)-、-S(O)2-、-O-S(O)2-、-O-S(O)2-O-、-O-S(O)2-NR-、-O-S(O)-、-O-S(O)-O-、-O-S(O)-NR-、-O-NR-C(O)-、-O-NR-C(O)-O-、-O-NR-C(O)-NR-、-NR-O-C(O)-、-NR-O-C(O)-O-、-NR-O-C(O)-NR-、-O-NR-C(S)-、-O-NR-C(S)-O-、-O-NR-C(S)-NR-、-NR-O-C(S)-、-NR-O-C(S)-O-、-NR-O-C(S)-NR-、-O-C(S)-、-O-C(S)-O-、-O-C(S)-NR-、-NR-C(S)-、-NR-C(S)-O-、-NR-C(S)-NR-、-S-S(O)2-、-S-S(O)2-O-、-S-S(O)2-NR-、-NR-O-S(O)-、-NR-O-S(O)-O-、-NR-O-S(O)-NR-、-NR-O-S(O)2-、-NR-O-S(O)2-O-、-NR-O-S(O)2-NR-、-O-NR-S(O)-、-O-NR-S(O)-O-、-O-NR-S(O)-NR-、-O-NR-S(O)2-O-、-O-NR-S(O)2-NR-、-O-NR-S(O)2-、-O-P(O)R2-、-S-P(O)R2-、-NR-P(O)R2-,其中每个R独立地是氢、烷基或取代烷基、及其两种或多种的结合。
23.根据权利要求1或2的制造制品,其中含马来酰亚胺、衣康酰亚胺或NA酰亚胺的化合物包括分别连接到单价基团上的马来酰亚胺官能团、衣康酰亚胺官能团、或NA酰亚胺官能团,或由多价基团分隔的马来酰亚胺官能团、衣康酰亚胺官能团、或NA酰亚胺官能团,每个单价基团或多价基团具有足够的长度和支化以使马来酰亚胺、衣康酰亚胺或NA酰亚胺的化合物分别为液体。
24.一种采用粘合剂连接权利要求1、2或3的制造制品到载体衬底的方法,该方法的步骤包括:
a.提供权利要求1、2或3的制造制品;
b.提供载体衬底;
c.联接权利要求1、2或3的制造制品与载体衬底以形成组件,其中权利要求1、2或3的制造制品和载体衬底由预施涂的模片连接粘合剂材料分隔;和
d.曝露预施涂的模片连接粘合剂材料于足以固化预施涂的模片连接粘合剂材料的温度。
25.权利要求24的方法,其中载体衬底是芯模片。
26.权利要求24的方法,其中载体衬底是预施涂的模片连接芯模片。
27.权利要求24的方法,其中载体衬底是电路板。
28.一种半导体芯片,包括:
硅衬底;
半导体层;
至少两个导体层,在其至少两个之间是包括一种或多种含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物的间层电介质。
29.一种半导体芯片,包括:
硅衬底;
半导体层;
至少两个导体层,在其至少两个之间是包括一种或多种含苯并噁嗪的化合物的间层电介质。
30.一种组装半导体器件的方法,该方法的步骤包括:
提供含有相对表面的半导体芯片,其中一个用于粘合到载体衬底和其另一个含有用于在其间建立电互连的电互连,其中在其一个粘合表面上布置预施涂数量的模片连接粘合剂材料,该粘合剂材料包括一种或多种含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物或一种或多种含苯并噁嗪的化合物;
提供载体衬底,该载体衬底含有用于粘合半导体芯片的表面部分和用于与半导体芯片建立电互连的另一个表面部分;和
配合半导体芯片的预施涂模片连接粘合剂材料涂敷的粘合表面与载体衬底的粘合表面,以形成半导体器件组件和曝露半导体器件组件于足以固化预施涂的模片连接组合物的条件,因此将半导体芯片粘合到载体衬底;和
在半导体芯片和载体衬底之间建立电互连。
31.制品,包括:
(a)含有表面的载体衬底,该表面具有以预定图案布置的电接触和在载体衬底的一部分表面上作为层布置的B阶段模片连接粘合剂材料,和其中在B阶段之前,模片连接粘合剂材料包括:
(i)一种或多种以液体形式与热塑性弹性体结合的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物。
32.制品,包括:
(a)含有表面的载体衬底,该表面具有以预定图案布置的电接触和在载体衬底的一部分表面上作为层布置的预施涂的模片连接粘合剂材料,和其中预施涂的模片连接粘合剂材料包括:
(i)一种或多种非必要地与热塑性弹性体结合的含马来酰亚胺、衣康酰胺或NA酰亚胺的化合物。
33.制品,包括:
(a)含有表面的载体衬底,该表面具有以预定图案布置的电接触和在载体衬底的一部分表面上作为层布置的预施涂的模片连接粘合剂材料,和其中预施涂的模片连接粘合剂材料包括:
(i)一种或多种非必要地与热塑性弹性体结合的含苯并噁嗪的化合物。
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-
2003
- 2003-06-17 CN CNA2008101733589A patent/CN101488480A/zh active Pending
- 2003-06-17 AU AU2003276729A patent/AU2003276729A1/en not_active Abandoned
- 2003-06-17 KR KR1020107024075A patent/KR101136719B1/ko not_active IP Right Cessation
- 2003-06-17 JP JP2004514137A patent/JP2005532678A/ja active Pending
- 2003-06-17 WO PCT/US2003/019052 patent/WO2003107427A1/en active Application Filing
- 2003-06-17 CN CNB038140942A patent/CN100449776C/zh not_active Expired - Fee Related
- 2003-06-17 KR KR1020047020440A patent/KR101164671B1/ko not_active IP Right Cessation
- 2003-06-17 US US10/502,976 patent/US7312534B2/en not_active Expired - Fee Related
-
2007
- 2007-06-05 US US11/758,089 patent/US7550825B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
WO2003107427A1 (en) | 2003-12-24 |
KR101136719B1 (ko) | 2012-04-20 |
US7550825B2 (en) | 2009-06-23 |
KR20050010933A (ko) | 2005-01-28 |
US20050008832A1 (en) | 2005-01-13 |
JP2005532678A (ja) | 2005-10-27 |
AU2003276729A1 (en) | 2003-12-31 |
KR20100121552A (ko) | 2010-11-17 |
CN1663048A (zh) | 2005-08-31 |
US20070278683A1 (en) | 2007-12-06 |
KR101164671B1 (ko) | 2012-07-11 |
CN100449776C (zh) | 2009-01-07 |
US7312534B2 (en) | 2007-12-25 |
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