CN102834907A - 半导体芯片接合用粘接材料、半导体芯片接合用粘接膜、半导体装置的制造方法及半导体装置 - Google Patents
半导体芯片接合用粘接材料、半导体芯片接合用粘接膜、半导体装置的制造方法及半导体装置 Download PDFInfo
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- CN102834907A CN102834907A CN2011800185924A CN201180018592A CN102834907A CN 102834907 A CN102834907 A CN 102834907A CN 2011800185924 A CN2011800185924 A CN 2011800185924A CN 201180018592 A CN201180018592 A CN 201180018592A CN 102834907 A CN102834907 A CN 102834907A
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明的目的在于提供可控制圆角形状不成为凸状且可制造可靠性高的半导体装置的半导体芯片接合用粘接材料。本发明为一种半导体芯片接合用粘接材料,其中,用粘弹性测定装置测得的25℃剪切弹性模量Gr为1×106Pa以上,用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min为5×101Pa·s以下,在140℃的温度、1rad的变形量、1Hz的频率下测得的复数粘度η*(1Hz)是在140℃的温度、1rad的变形量、10Hz的频率下测得的复数粘度η*(10Hz)的0.5~4.5倍。
Description
技术领域
本发明涉及可控制圆角形状不成为凸状且可制造可靠性高的半导体装置的半导体芯片接合用粘接材料。另外,本发明还涉及由该半导体芯片接合用粘接材料形成的半导体芯片接合用粘接膜、使用了该半导体芯片接合用粘接材料或该半导体芯片接合用粘接膜的半导体装置的制造方法、以及通过该半导体装置的制造方法得到的半导体装置。
背景技术
近年来,为了应对日益进步的半导体装置的小型化、高集成化,而多采用使用了具有由软纤料等形成的连接端子(凸出)的半导体芯片的倒装式安装。
在倒装式安装中,通常采用在借助凸出将具有多个凸出的半导体芯片连接于其它的半导体芯片或基板后,填充底层填料的方法。在这种填充底层填料的方法中,在底层填料固化收缩时,或者在回焊试验或冷热循环试验时,例如往往因半导体芯片与基板之间的线膨胀系数之差,而导致应力集中于底层填料的界面等,产生裂缝。
因此,为了抑制裂缝的产生,例如在专利文献1中记载了:在具备半导体元件、搭载该半导体元件的基板、和将形成于上述半导体元件的电路形成面密封的密封树脂的半导体装置中,设置将半导体元件外周侧面覆盖的侧面覆盖部。这种将半导体元件外周侧面覆盖的侧面覆盖部通常被称为圆角。
进而,在专利文献1中记载的半导体装置中,为更可靠地抑制裂缝的产生,而提出了将距侧面覆盖部的电路形成面的高度设为规定范围。
另外,在专利文献2中记载了:在电路基板与半导体芯片之间注入密封树脂、并且将密封树脂供给至半导体芯片的外周侧部来形成圆角部而成的特定倒装式半导体组件。在专利文献2中记载的倒装式半导体组件中,圆角部具有表面形成为从半导体芯片的外周侧部的上缘开始朝向基板而延伸至外部的倾斜面的结构。
进而,在专利文献2中记载了:通过在半导体芯片的外周侧部的上缘附近倾斜面与半导体芯片的外周侧部所形成的倾斜角为50度以下,从而可抑制或减少因应力集中造成的裂缝的产生,可抑制半导体芯片破损。
但是,在现有的方法中,问题在于形成圆角的工序繁杂、或者通过圆角的形成也无法充分地抑制裂缝的产生。
另一方面,近年来,随着推进半导体芯片的小型化,凸出间的间距也变得越来越窄,另外与之相伴的是半导体芯片间、或半导体芯片与基板之间的间隙也变得越来越窄,所以问题还在于无法填充底层填料,或者在于填充需要长时间、或在填充时容易卷入空气而容易产生空隙。
因此,例如提出了如下的先涂布型安装方法,即,利用粘接剂或粘接膜,将粘接剂层形成于具有多个凸出的晶片上的形成有凸出的面,然后将晶片连同粘接剂层进行切割而制成各个半导体芯片,借助凸出将它们结合于其它的半导体芯片或基板的方法,因而需要的是亦可适用于这种先涂布型安装方法、并且可充分抑制裂缝的产生的新型粘接剂或粘接膜。
专利文献
专利文献1:日本特开2000-40775号公报
专利文献2:国际公开第08/018557号小册子
发明内容
发明所要解决的课题
本发明的目的在于,提供可控制圆角形状不成为凸状且可制造可靠性高的半导体装置的半导体芯片接合用粘接材料。另外,本发明的目的还在于,提供由该半导体芯片接合用粘接材料形成的半导体芯片接合用粘接膜、使用了该半导体芯片接合用粘接材料或该半导体芯片接合用粘接膜的半导体装置的制造方法、以及通过该半导体装置的制造方法得到的半导体装置。
解决课题的手段
本发明为一种半导体芯片接合用粘接材料,其中,用粘弹性测定装置测得的25℃剪切弹性模量Gr为1×106Pa以上,用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min为5×101Pa·s以下,在140℃的温度、1rad的变形量、1Hz的频率下测得的复数粘度η*(1Hz)是在140℃的温度、1rad的变形量、10Hz的频率下测得的复数粘度η*(10Hz)的0.5~4.5倍。
以下对本发明进行详细叙述。
通常,使用粘接剂或粘接膜而将预先形成有粘接剂层的半导体芯片与其它的半导体芯片或基板结合时,若要形成圆角,则该圆角的剖面图的形状容易形成为如图2所示的凸状。而且,就凸状圆角而言,半导体芯片的侧壁与圆角所形成的角度容易达到70°以上。本发明人等发现:对于此类凸状圆角而言,应力集中于凸部,容易发生半导体芯片的剥离或破裂,另一方面,通过形成如图1所示的非凸状圆角,从而可抑制应力的集中,可制造可靠性高的半导体装置。
即,本发明人等发现通过将半导体芯片接合用粘接材料的25℃剪切弹性模量和粘度特性设为规定范围,从而可形成非凸状圆角,由此可制造可靠性高的半导体装置,从而完成了本发明。
在本说明书中,凸状圆角是指在观察圆角的剖面时,在端部具有如图2所示的倒U字形的突出部的圆角。另一方面,非凸状圆角是指在观察圆角的剖面时,在端部不具有如图2所示的倒U字形的凸出部的圆角。
需说明的是,图1和图2是表示使用半导体芯片接合用粘接材料3,介助凸出4将半导体芯片2结合于基板1上的状态的一例的剖面图。图1表示形成非凸状圆角的状态,图2表示形成凸状圆角的状态。
如图3所示,上述非凸状优选为半导体芯片的侧壁与圆角所形成的角度θ不足70°。
对于本发明的半导体芯片接合用粘接材料而言,用粘弹性测定装置测得的25℃剪切弹性模量Gr的下限为1×106Pa。若上述用粘弹性测定装置测得的25℃剪切弹性模量Gr不足1×106Pa,则得到的半导体芯片接合用粘接材料容易产生折缝,例如在切割时会产生切削碎屑附着于半导体芯片接合用粘接材料等不良状况。
上述用粘弹性测定装置测得的25℃剪切弹性模量Gr的优选下限为3×106Pa,更优选的下限为5×106Pa。
上述用粘弹性测定装置测得的25℃剪切弹性模量Gr的上限没有特殊限定,但优选上限为1×108Pa。若上述用粘弹性测定装置测得的25℃剪切弹性模量Gr超过1×108Pa,则在切割时半导体芯片接合用粘接材料的一部分往往会剥落飞散。
上述用粘弹性测定装置测得的25℃剪切弹性模量Gr的更优选的上限为5×107Pa。
在本说明书中,用粘弹性测定装置测得的25℃剪切弹性模量Gr是指使本发明的半导体芯片接合用粘接材料形成膜状而测得的值。上述用粘弹性测定装置测定25℃剪切弹性模量Gr的方法没有特殊限定,例如可列举出使用动态粘弹性测定装置DVA-200(IT计测器公司制)等粘弹性测定装置,对厚600μm、宽6mm、长10mm的膜进行剪切测定的方法等。
本发明的半导体芯片接合用粘接材料用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min的上限为5×101Pa·s。若上述用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min超过5×101Pa·s,则在结合时,软纤料容易被半导体芯片接合用粘接材料冲走,得不到稳定的导通。
上述用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min的优选上限为4.5×101Pa·s,更优选的上限为4×101Pa·s,进一步优选的上限为3.0×101Pa·s。
上述用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min的下限没有特殊限定,但优选下限为5×10-1Pa·s。若上述用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min不足5×10-1Pa·s,则在结合时咬入而得的空隙往往残留于粘接剂层。
上述用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min的更优选的下限为1Pa·s。
在本说明书中,用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min是指使本发明的半导体芯片接合用粘接材料形成膜状而测得的值。上述用流变仪测定直到软纤料熔点为止的最低复数粘度η*min的方法没有特殊限定,例如可列举出使用STRESSTECH(REOLOGICA公司制)等通常的流变仪,在600μm的样品厚度、变形控制(1rad)、10Hz的频率、20℃/min的升温速度、60℃至300℃的测定温度范围下进行测定的方法等。
需说明的是,上述软纤料熔点例如为230~320℃范围的温度。
本发明的半导体芯片接合用粘接材料在140℃的温度、1rad的变形量、1Hz的频率下测得的复数粘度η*(1Hz)是在140℃的温度、1rad的变形量、10Hz的频率下测得的复数粘度η*(10Hz)的0.5~4.5倍。通过具有这样的复数粘度之比,从而本发明的半导体芯片接合用粘接材料可通过结合时的加热而借助于自重来形成非凸状圆角,可提高得到的半导体装置的可靠性,另外即使应用于切割等其它的工序也不会产生不良状况。
若上述复数粘度η*(1Hz)不足上述复数粘度η*(10Hz)的0.5倍,则在结合时半导体芯片接合用粘接材料的流动性降低,例如产生妨碍凸出的接触等不良状况。若上述复数粘度η*(1Hz)超过上述复数粘度η*(10Hz)的4.5倍,则无法形成非凸状圆角,若半导体芯片的侧壁与圆角所形成的角度达到70°以上,则应力集中于凸部,得到的半导体装置的可靠性降低。
对于本发明的半导体芯片接合用粘接材料而言,优选上述复数粘度η*(1Hz)是上述复数粘度η*(10Hz)的0.7倍以上,更优选是0.9倍以上,进一步优选是1.0倍以上,另外优选是4.3倍以下,更优选是4.0倍以下。
在本说明书中,复数粘度η*(1Hz)和上述复数粘度η*(10Hz)是指使本发明的半导体芯片接合用粘接材料形成膜状而测得的值。上述测定复数粘度η*(1Hz)和上述复数粘度η*(10Hz)的方法没有特殊限定,例如可列举出使用STRESSTECH(REOLOGICA公司制)等通常的粘度测定装置,在600μm的样品厚度、变形控制(1rad)、1Hz或10Hz的频率、140℃的温度下进行测定的方法等。
对于本发明的半导体芯片接合用粘接材料而言,实现上述范围的剪切弹性模量和粘度特性的方法没有特殊限定,例如优选通过适当地配合环氧化合物、具有能够与该环氧化合物反应的官能团的高分子化合物(以下也简称为具有能够反应的官能团的高分子化合物)、以及根据需要配合其它的添加成分,从而调整剪切弹性模量和粘度特性的方法。
其中,优选通过控制环氧化合物的种类和配合量以及具有能够反应的官能团的高分子化合物的分子量和配合量,从而将半导体芯片接合用粘接材料中的各成分的相互作用或分子链的聚合度降低至极限。另外,当添加无机填充材料等非溶解性成分时,优选通过提高相对于环氧化合物等的亲和性,或控制无机填充材料的粒径和配合量,从而抑制半导体芯片接合用粘接材料中的凝集等网状结构的形成。
上述环氧化合物没有特殊限定,例如可列举出软化点为150℃以下的环氧树脂、常温下为液体或结晶性固体的环氧树脂等。这些环氧化合物可单独使用或将两种以上合用。
作为上述软化点为150℃以下的环氧树脂,例如可列举出苯酚酚醛环氧树脂、双酚A酚醛环氧树脂、甲酚酚醛环氧树脂、二环戊二烯苯酚酚醛型环氧树脂、联苯苯酚酚醛环氧树脂等。其中,优选二环戊二烯苯酚酚醛型环氧树脂。
作为上述在常温下为液体或结晶性固体的环氧树脂,例如可列举出双酚A型、双酚F型、双酚AD型、双酚S型等双酚型环氧树脂,二环戊二烯型环氧树脂,间苯二酚型环氧树脂,联苯型环氧树脂,蒽型环氧树脂,萘型环氧树脂,芴型环氧树脂等。其中,优选为蒽型环氧树脂。
通过含有上述具有能够反应的官能团的高分子化合物,从而本发明的半导体芯片接合用粘接材料的固化物具有韧性,可展现出优异的耐冲击性。
上述具有能够反应的官能团的高分子化合物没有特殊限定,例如可列举出具有氨基、氨基甲酸乙酯基、酰亚胺基、羟基、羧基、环氧基等的高分子化合物等。其中,优选为具有环氧基的高分子化合物。
通过含有上述具有环氧基的高分子化合物,从而得到的半导体芯片接合用粘接材料的固化物展现出优异的韧性。即,所得的半导体芯片接合用粘接材料的固化物因兼具源于上述环氧化合物的优异的机械强度、耐热性和耐湿性以及源于上述具有环氧基的高分子化合物的优异的韧性,从而可展现出高的接合可靠性和连接可靠性。
上述具有环氧基的高分子化合物若为末端和/或侧链(侧位)具有环氧基的高分子化合物,则没有特殊限定,例如可列举出含环氧基的丙烯酸橡胶、含环氧基的丁二烯橡胶、双酚型高分子量环氧树脂、含环氧基的苯氧基树脂、含环氧基的丙烯酸树脂、含环氧基的聚氨酯树脂、含环氧基的聚酯树脂等。其中,从含有大量环氧基,得到的半导体芯片接合用粘接材料的固化物可展现出优异的机械强度、耐热性、韧性等出发,优选为含环氧基的丙烯酸树脂。这些具有环氧基的高分子化合物可单独使用或将两种以上合用。
当使用上述具有环氧基的高分子化合物,特别是含环氧基的丙烯酸树脂时,该具有环氧基的高分子化合物的重均分子量的优选上限为20万。优选下限为1万。若上述重均分子量不足1万,则使用半导体芯片接合用粘接材料造膜时的造膜性不足,作为膜而往往无法保持形状。若上述重均分子量超过20万,则在得到的半导体芯片接合用粘接材料中往往无法达成上述范围的剪切弹性模量和复数粘度之比。
另外,若上述重均分子量不足1万,则由于在得到的半导体芯片接合用粘接材料中存在大量低分子量化合物,所以在结合时往往易产生空隙。
上述具有环氧基的高分子化合物的重均分子量的更优选的上限为15万,进一步优选的上限为10万,更进一步优选的上限为5万,特别优选的上限为2万。
上述具有环氧基的高分子化合物可单独使用或将具有不同重均分子量的两种以上合用。例如可将重均分子量为5万以下的高分子化合物与重均分子量超过5万的高分子化合物合用。在这种情况下,上述重均分子量超过5万的高分子化合物的含量在上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份中所占的优选上限为20重量份。若上述重均分子量超过5万的高分子化合物的含量超过20重量份,则在得到的半导体芯片接合用粘接材料中上述最低复数粘度和复数粘度之比往往变得过大。
当使用上述具有环氧基的高分子化合物,特别是含环氧基的丙烯酸树脂时,该具有环氧基的高分子化合物的环氧当量的优选下限为200,优选上限为1000。若上述环氧当量不足200,则得到的半导体芯片接合用粘接材料的固化物往往变硬、变脆。若上述环氧当量超过1000,则得到的半导体芯片接合用粘接材料的固化物的机械强度、耐热性等往往变得不足。
上述具有能够反应的官能团的高分子化合物的含量没有特殊限定,但相对于100重量份的上述环氧化合物的优选下限为1重量份,优选上限为500重量份。若上述具有能够反应的官能团的高分子化合物的含量不足1重量份,则得到的半导体芯片接合用粘接材料的固化物在发生由热导致的变形时往往韧性变得不足,接合可靠性变差。若上述具有能够反应的官能团的高分子化合物的含量超过500重量份,则在得到的半导体芯片接合用粘接材料中上述复数粘度之比往往变得过大,另外固化物的耐热性往往降低。
从达成上述范围的复数粘度之比的观点出发,上述具有能够反应的官能团的高分子化合物的含量相对于100重量份的上述环氧化合物的更优选上限为400重量份。
本发明的半导体芯片接合用粘接材料优选含有固化剂。
上述固化剂没有特殊限定,例如可列举出胺系固化剂、酸酐固化剂、酚系固化剂等。其中,优选酸酐固化剂。
上述酸酐固化剂没有特殊限定,但优选为2官能的酸酐固化剂。上述2官能的酸酐固化剂没有特殊限定,例如可列举出邻苯二甲酸衍生物的酸酐、马来酸酐等。
另外,作为上述固化剂,可使用3官能以上的酸酐固化剂粒子。上述3官能以上的酸酐固化剂粒子没有特殊限定,例如可列举出由偏苯三酸酐等3官能的酸酐形成的粒子,由均苯四酸酐、二苯甲酮四羧酸酐、甲基环己烯四羧酸酐、聚壬二酸酐等4官能以上的酸酐形成的粒子等。
上述3官能以上的酸酐固化剂粒子的平均粒径没有特殊限定,但优选下限为0.1μm,优选上限为5μm。若上述3官能以上的酸酐固化剂粒子的平均粒径不足0.1μm,则往往发生固化剂粒子的凝集,半导体芯片接合用粘接材料增稠,而无法形成凸状圆角。若上述3官能以上的酸酐固化剂粒子的平均粒径超过5μm,则在得到的半导体芯片接合用粘接材料中往往在固化时固化剂粒子无法充分扩散,导致固化不良。
当本发明的半导体芯片接合用粘接材料含有上述固化剂时,上述固化剂的含量没有特殊限定,但相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为5重量份,优选上限为150重量份。若上述固化剂的含量不足5重量份,则得到的半导体芯片接合用粘接材料往往没有充分固化。若上述固化剂的含量超过150重量份,则得到的半导体芯片接合用粘接材料的连接可靠性往往降低。
上述固化剂的含量相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的更优选下限为10重量份,更优选上限为140重量份。
另外,当上述固化剂含有上述2官能的酸酐固化剂和上述3官能以上的酸酐固化剂粒子时,它们的配合比没有特殊限定,但用上述3官能以上的酸酐固化剂粒子的含量(重量)除以上述2官能的酸酐固化剂的含量(重量)得到的值[=(3官能以上的酸酐固化剂粒子的含量)/(2官能的酸酐固化剂的含量)]的优选下限为0.1,优选上限为10。若上述值不足0.1未満,则往往无法充分获得添加上述3官能以上的酸酐固化剂粒子的效果。若上述值超过10,则得到的半导体芯片接合用粘接材料的固化物往往变脆,无法得到充分的粘接可靠性。上述值的更优选下限为0.2,更优选上限为8。
本发明的半导体芯片接合用粘接材料可含有固化促进剂。
上述固化促进剂没有特殊限定,但优选为咪唑化合物。由于上述咪唑化合物与上述环氧化合物的反应性高,所以通过含有上述咪唑化合物,而提高得到的半导体芯片接合用粘接材料的速固化性。
上述咪唑化合物没有特殊限定,例如可列举出将咪唑的1位用氰基乙基保护而得的1-氰基乙基-2-苯基咪唑,用异氰脲酸保护碱性而得的咪唑化合物(商品名“2MA-OK”,四国化成工业公司制),2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪(商品名“2MZ-A”,四国化成工业公司制),2-苯基-4-甲基-5-羟甲基咪唑(商品名“2P4MHZ”,四国化成工业公司制),FUJICURE 7000(富士化成工业)等。这些咪唑化合物可单独使用或将两种以上合用。
当本发明的半导体芯片接合用粘接材料含有上述固化促进剂时,上述固化促进剂的含量没有特殊限定,但相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为0.3重量份,优选上限为8重量份。若上述固化促进剂的含量不足0.3重量份,则得到的半导体芯片接合用粘接材料往往没有充分固化。若上述固化促进剂的含量超过8重量份,则在得到的半导体芯片接合用粘接材料中,往往由于未反应的固化促进剂在粘接界面渗出而导致接合可靠性降低。
本发明的半导体芯片接合用粘接材料可含有无机填充材料。
通过含有上述无机填充材料,从而可降低得到的半导体芯片接合用粘接材料的固化物的线膨胀率,可良好地防止向所接合的半导体芯片的应力的产生和软纤料等导通部分的裂缝的产生。
上述无机填充材料没有特殊限定,例如可列举出热解法二氧化硅、胶态二氧化硅等二氧化硅,氧化铝,氮化铝,氮化硼,氮化硅,玻璃粉,玻璃料等。
上述无机填充材料优选在表面具有含有碳数为1~10的烃的基团。
通过上述无机填充材料在表面具有上述含碳数为1~10的烃的基因,从而在得到的半导体芯片接合用粘接材料中,即使上述无机填充材料的配合量增加,也可降低最低复数粘度的上升。另外,达成上述范围的复数粘度之比也变得容易。进而,通过在半导体芯片接合用粘接材料中配合表面具有上述含有碳数为1~10的烃的基团的无机填充材料,从而可进一步提高得到的半导体装置的可靠性。
需说明的是,即使是表面不具有上述含有碳数为1~10的烃的基团的无机填充材料,若可通过调整配合量或调整与其它的成分的配合比而达成上述范围的最低复数粘度和复数粘度之比,则也可使用。
上述含有碳数为1~10的烃的基团没有特殊限定,但优选为己基、甲基、苯基等。上述含有碳数为1~10的烃的基团例如可通过使用骨架中具有上述含有碳数为1~10的烃的基团的硅烷偶联剂等偶联剂来对上述无机填充材料实施表面处理而导入。
当使用粒子状无机填充材料作为上述无机填充材料时,平均粒径的优选下限为1nm,优选上限为5μm。若上述粒子状无机填充材料的平均粒径不足1nm,则在得到的半导体芯片接合用粘接材料中往往易发生上述无机填充材料的凝集,无法达成上述范围的复数粘度之比,得到容易形成凸状圆角的半导体芯片接合用粘接材料。若上述粒子状无机填充材料的平均粒径超过5μm,则在使用得到的半导体芯片接合用粘接材料进行压接时,往往在电极间咬入上述无机填充材料。
上述粒子状无机填充材料的平均粒径的更优选下限为5nm,更优选上限为3μm,特别优选下限为10nm,特别优选上限为1μm。
在本说明书中,平均粒径是指用激光衍射/散射式粒径分布测定装置测得的%累积直径为50%的粒径。
当本发明的半导体芯片接合用粘接材料含有表面具有上述含有碳数为1~10的烃的基团的无机填充材料时,上述无机填充材料的含量没有特殊限定,但相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为5重量份,优选上限为500重量份。若上述无机填充材料的含量不足5重量份,则往往基本上无法获得添加上述无机填充材料的效果。若上述无机填充材料的含量超过500重量份,则虽然得到半导体芯片接合用粘接材料的固化物的线膨胀率降低,但同时剪切弹性模量上升,往往无法形成非凸状圆角。由此,往往使得容易产生向所接合的半导体芯片的应力和软纤料等导通部分的裂缝。
表面具有上述含有碳数为1~10的烃的基团的无机填充材料的含量相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为10重量份,优选上限为400重量份,进一步优选的下限为15重量份,进一步优选的上限为300重量份。
另外,当本发明的半导体芯片接合用粘接材料含有表面不具有上述含有碳数为1~10的烃的基团的无机填充材料时,上述无机填充材料的含量没有特殊限定,但相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为5重量份,优选上限为200重量份。
另外,当本发明的半导体芯片接合用粘接材料含有上述平均粒径为10nm以下的无机填充材料时,上述无机填充材料的含量没有特殊限定,但无论有无表面处理,相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份,均优选为50重量份以下。
本发明的半导体芯片接合用粘接材料可在不损害本发明的效果的范围内含有稀释剂。
上述稀释剂没有特殊限定,但优选为在半导体芯片接合用粘接材料的加热固化时混入到固化物中的反应性稀释剂。其中,为了不使得到的半导体芯片接合用粘接材料的粘接可靠性恶化,而更优选为1分子中具有2个以上官能团的反应性稀释剂。
作为上述1分子中具有2个以上官能团的反应性稀释剂,例如可列举出脂族型环氧树脂、环氧乙烷改性环氧树脂、环氧丙烷改性环氧树脂、环己烷型环氧树脂、二环戊二烯型环氧树脂、苯酚型环氧树脂等。
当本发明的半导体芯片接合用粘接材料含有上述稀释剂时,上述稀释剂的含量没有特殊限定,但相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的优选下限为1重量份,优选上限为300重量份。若上述稀释剂的含量不足1重量份,则往往基本上无法得到添加上述稀释剂的效果。若上述稀释剂的含量超过300重量份,则由于得到的半导体芯片接合用粘接材料的固化物变硬变脆,所以粘接可靠性往往变差。
上述稀释剂的含量相对于上述环氧化合物与上述具有能够反应的官能团的高分子化合物的合计100重量份的更优选下限为5重量份,更优选上限为200重量份。
本发明的半导体芯片接合用粘接材料可根据需要含有无机离子交换剂。在上述无机离子交换剂中,作为市售品,例如可列举出IXE系列(东亚合成公司制)等。当本发明的半导体芯片接合用粘接材料含有上述无机离子交换剂时,上述无机离子交换剂的含量没有特殊限定,但在本发明的半导体芯片接合用粘接材料中的优选下限为1重量%,优选上限为10重量%。
本发明的半导体芯片接合用粘接材料进而可根据需要含有防渗剂、硅烷偶联剂、咪唑硅烷偶联剂等粘接性赋予剂,增稠剂等添加剂。
制造本发明的半导体芯片接合用粘接材料的方法没有特殊限定,例如可列举出配合规定量的上述环氧化合物、上述具有能够反应的官能团的高分子化合物、上述固化剂、上述无机填充材料等进行混合的方法等。
上述混合的方法没有特殊限定,例如可列举出使用均质分散机、万能搅拌机、班拍里混炼机、捏合机等进行混合的方法等。
本发明的半导体芯片接合用粘接材料的用途没有特殊限定,例如可在将晶片或半导体芯片安装于其它的晶片、其它的半导体芯片或基板时使用。其中,本发明的半导体芯片接合用粘接材料优选用于倒装式安装,与在电极接合后填充底层填料的倒装式安装相比,更优选用于预先将粘接剂层搭载于晶片、半导体芯片或基板的倒装式安装。
本发明的半导体芯片接合用粘接材料由于可控制圆角形状不成为凸状,所以通过使用本发明的半导体芯片接合用粘接材料,从而可制造可靠性高的半导体装置。
使用了本发明的半导体芯片接合用粘接材料的半导体装置的制造方法没有特殊限定,例如可列举出在本发明的半导体芯片接合用粘接材料中添加溶剂,将由此制备而得的粘接剂溶液涂布于晶片,将上述溶剂干燥而成膜的方法等。这样的半导体装置的制造方法也是本发明之一。
作为上述溶剂,例如可列举出丙二醇甲醚乙酸酯等具有120~250℃左右的沸点的中沸点溶剂或高沸点溶剂等。将在本发明的半导体芯片接合用粘接材料中添加溶剂制备而得的粘接剂溶液涂布于晶片的方法没有特殊限定,例如可列举出旋涂、丝网印刷等。
另外,作为使用了本发明的半导体芯片接合用粘接材料的半导体装置的制造方法,当本发明的半导体芯片接合用粘接材料不含有溶剂时,例如可列举出将本发明的半导体芯片接合用粘接材料涂布于晶片,通过B阶化剂或曝光而成膜的方法等。
由本发明的半导体芯片接合用粘接材料形成的半导体芯片接合用粘接膜也是本发明之一。
本发明的半导体芯片接合用粘接膜的厚度没有特殊限定,但优选下限为2μm,优选上限为500μm。若上述厚度不足2μm,则往往会因异物的混入而无法得到平滑的膜。若上述厚度超过500μm,则在得到的半导体芯片接合用粘接膜中往往易残留溶剂,在压接时和固化时产生气泡。
制造本发明的半导体芯片接合用粘接膜的方法没有特殊限定,例如可列举出配合规定量的上述环氧化合物、上述具有能够反应的官能团的高分子化合物、上述固化剂、上述无机填充材料、溶剂等进行混合,在制备粘接剂溶液后成膜的方法等。
上述混合的方法没有特殊限定,例如可列举出使用均质分散机、万能搅拌机、班拍里混炼机、捏合机等进行混合的方法等。上述成膜的方法没有特殊限定,例如可列举出作为溶剂而使用甲乙酮等低沸点溶剂,在使用模式涂布机、棒式涂布机、凹版涂布机、狭缝涂布机等将上述粘接剂溶液涂装于间隔件上后,通过加热等干燥溶剂的方法等。
本发明的半导体芯片接合用粘接膜的用途没有特殊限定,例如可在将晶片或半导体芯片安装于其它的晶片、其它的半导体芯片或基板时使用。其中,本发明的半导体芯片接合用粘接膜优选用于倒装式安装,与在电极接合后填充底层填料的倒装式安装相比,更优选用于预先将粘接剂层搭载于晶片、半导体芯片或基板的倒装式安装。
由于本发明的半导体芯片接合用粘接膜可控制圆角形状不成为凸状,所以通过使用本发明的半导体芯片接合用粘接膜,从而可制造可靠性高的半导体装置。
使用了本发明的半导体芯片接合用粘接膜的半导体装置的制造方法没有特殊限定,例如可列举出将本发明的半导体芯片接合用粘接膜通过层压供给至晶片或半导体芯片的方法,对照半导体芯片的芯片尺寸,将本发明的半导体芯片接合用粘接膜裁断,供给至其它的半导体芯片或基板的方法等。这样的半导体装置的制造方法也是本发明之一。
一种半导体装置也是本发明之一,其是通过本发明的半导体装置的制造方法得到的半导体装置,介助粘接剂层将半导体芯片与其它的半导体芯片或基板结合,形成沿上述半导体芯片的侧壁向上爬的圆角,上述半导体芯片的侧壁与上述圆角所形成的角度不足70°。
若上述半导体芯片的侧壁与上述圆角所形成的角度为70°以上,则应力集中于凸部,半导体装置的可靠性降低。
发明的效果
根据本发明,可提供可控制圆角形状不成为凸状且可制造可靠性高的半导体装置的半导体芯片接合用粘接材料。另外,根据本发明,可提供由该半导体芯片接合用粘接材料形成的半导体芯片接合用粘接膜、使用了该半导体芯片接合用粘接材料或该半导体芯片接合用粘接膜的半导体装置的制造方法、以及通过该半导体装置的制造方法得到的半导体装置。
附图说明
图1是表示使用本发明的半导体芯片接合用粘接材料将半导体芯片结合于基板上,形成非凸状圆角的状态的一例的剖面图。
图2是表示使用现有的半导体芯片接合用粘接材料将半导体芯片结合于基板上,形成凸状圆角的状态的一例的剖面图。
图3是表示使用本发明的半导体芯片接合用粘接材料将半导体芯片结合于基板上,形成半导体芯片的侧壁与圆角所形成的角度θ不足70°的圆角的状态的一例的剖面图。
具体实施方式
以下列举实施例对本发明的实施方式进行更详细的说明,但本发明并不仅限定于这些实施例。
(实施例1~31和比较例1~18)
根据表1~5的组成,使用均质分散机将如下所示的各种材料搅拌混合,制备粘接剂溶液。通过涂布器将粘接剂溶液涂装于经脱模处理的PET膜(日文为ペツトフイルム)上,将溶剂干燥,得到100μm厚的半导体芯片接合用粘接膜。
(1)环氧化合物
·联苯型环氧树脂(商品名“YX-4000”,Japan Epoxy Resins Co.,Ltd.制)
·双酚A型环氧树脂(商品名“1004AF”,Japan Epoxy Resins Co.,Ltd.制)
·二环戊二烯型环氧树脂(商品名“HP-7200HH”,DIC公司制)
·二环戊二烯型环氧树脂(商品名“EP-4088S”,Adeka Corporation制)
(2)具有能够反应的官能团的高分子化合物
·含缩水甘油基的丙烯酸树脂(重均分子量20万,商品名“G-2050M”,日油公司制)、
·含缩水甘油基的丙烯酸树脂(重均分子量2万,商品名“G-0250SP”,日油公司制)
·含缩水甘油基的丙烯酸树脂(重均分子量8千,商品名“G-0130S”,日油公司制)
·含缩水甘油基的丙烯酸化合物(重均分子量10万,商品名“G-1010S”,日油公司制)
(3)固化剂
·三烷基四氢邻苯二甲酸酐(商品名“YH-306”,JER公司制)
(4)固化促进剂
·2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪异氰脲酸加成盐(商品名“2MA-OK”,四国化成工业公司制)
(5)无机填充材料
·表面苯基处理无机填充剂(二氧化硅)(商品名“SE-1050-SPT”,Admatechs Co.,Ltd.制,平均粒径300nm)
·表面苯基处理无机填充剂(二氧化硅)(商品名“SE-2050-SPJ”,Admatechs Co.,Ltd.制,平均粒径500nm)
·表面苯基处理无机填充剂(二氧化硅)(商品名“SS-01”,TokuyamaCorporation制,平均粒径100nm)
·表面苯基处理无机填充剂(二氧化硅)(商品名“YA050-MJF”,Admatechs Co.,Ltd.制,平均粒径50nm)
·表面无处理无机填充剂(二氧化硅)(商品名“SE-1050”,AdmatechsCo.,Ltd.制,平均粒径300nm)
·表面无处理无机填充剂(二氧化硅)(商品名“SE-2050”,AdmatechsCo.,Ltd.制,平均粒径500nm)
·表面无处理无机填充剂(二氧化硅)(商品名“QS-40”,TokuyamaCorporation制,平均粒径7nm)
·表面具有CH3-Si-O-基的二氧化硅粒子(商品名“MT-10”,Tokuyama Corporation制,平均粒径15nm)
·表面具有CH3-Si-O-基的二氧化硅粒子(商品名“SE-2050-STJ”,Admatechs Co.,Ltd.制,平均粒径500nm)
·表面具有CH3-Si-O-基的二氧化硅粒子(商品名“SE-1050-STT”,Admatechs Co.,Ltd.制,平均粒径300nm)
·表面六甲基二硅氮烷处理无机填充剂(二氧化硅)(商品名“HM-20L”,Tokuyama Corporation制,平均粒径12nm)
·表面硅酮油处理无机填充剂(二氧化硅)(商品名“PM-20L”,TokuyamaCorporation制,平均粒径12nm)
·表面环氧基硅烷处理无机填充剂(二氧化硅)(商品名“SE-1050-SET”,Admatechs Co.,Ltd.制,平均粒径300nm)
·表面甲基丙烯酸处理无机填充剂(二氧化硅)(商品名“SE-1050-SMT”,Admatechs Co.,Ltd.制,平均粒径300nm)
(6)其它
硅烷偶联剂(商品名“KBM-573”,信越化学工业公司制)
溶剂甲乙酮(MEK,和光纯药工业公司制)
<评价>
针对在实施例和比较例中得到的半导体芯片接合用粘接膜进行以下评价。将结果示于表1~5中。
(1)25℃剪切弹性模量Gr的测定
针对得到的半导体芯片接合用粘接膜,通过使用动态粘弹性测定装置(DVA-200,IT计测器公司制),从-20℃至80℃为止对厚600μm、宽6mm、长10mm的半导体芯片接合用粘接剂膜进行剪切测定,从而求出25℃剪切弹性模量Gr(MPa)。
(2)直到软纤料熔点为止的最低复数粘度η*min的测定
针对得到的半导体芯片接合用粘接膜,使用流变仪(STRESSTECH,REOLOGICA公司制),在600μm的样品厚度、变形控制(1rad)、10Hz的频率、20℃/min的升温速度、60℃至300℃的测定温度范围下进行测定,将在测定过程中复数粘度降低最多的值作为直到软纤料熔点为止的最低复数粘度η*min(Pa·s)。
(3){复数粘度η*(1Hz)}/{复数粘度η*(10Hz)}的测定
针对得到的半导体芯片接合用粘接膜,通过使用STRESSTECH(REOLOGICA公司制),在600μm的样品厚度、变形控制(1rad)、1Hz或10Hz的频率、140℃的温度下进行测定,从而求出{复数粘度η*(1Hz)}/{复数粘度η*(10Hz)}的值。
(4)圆角的剖面形状
将得到的半导体芯片接合用粘接膜层压于以150μm的间隔在芯片整面形成有3136个软纤料球(高85μm)的全阵列TEG芯片(10mm×10mm×厚725μm)后,对照芯片尺寸,将半导体芯片接合用粘接膜裁断,得到带有树脂的TEG芯片。接着,在120℃的Stage温度、140℃的Head温度20秒、280℃5秒、100N的顶端压力下,将带有树脂的TEG芯片倒装式结合于经以与得到的带有树脂的TEG芯片的软纤料形成雏菊链的方式布线而得的带有软纤料预涂层的玻璃环氧TEG基板。然后,在190℃下进行30分钟的二次硬化(后固化),得到层叠体。
将得到的层叠体用冷树脂埋入后,直至芯片区域的中央附近的部分为止进行剖面研磨,测定TEG芯片的侧壁与圆角所形成的角度(圆角角度)。
(5)回焊试验
针对在上述(4)中得到的层叠体,预先测定导通电阻值(以下计为初期电阻),在60℃、60%RH下吸湿40小时,通过峰温度为260℃的回焊炉3次而进行回焊试验,然后再次测定导通电阻值。将回焊试验后的导通电阻值距初期电阻值变化了10%以上的情况计为不良,制作8个层叠体,评价不良个数。
(6)冷热循环试验1
针对在上述(5)中进行过回焊试验的层叠体,进行-55~125℃(30分钟/1次循环)下1000次循环的冷热循环试验,然后测定导通电阻值。将冷热循环试验后的导通电阻值距初期电阻值变化了10%以上的情况计为不良,制作8个层叠体,评价不良个数。
当不良个数为0个时计为○,为1个时计为△,为2个以上时计为×。
(7)冷热循环试验2
针对在上述(5)中进行过回焊试验的层叠体,进行-55~125℃(30分钟/1次循环)下3000次循环的冷热循环试验,然后测定导通电阻值。将冷热循环试验后的传导电阻值距初期电阻值变化了10%以上的情况计为不良,制作8个层叠体,评价不良个数。
当不良个数为2个以下时计为◎,为3~4个时计为○,为5~6个时计为△,为7个以上时计为×。
[表1]
[表2]
[表3]
[表4]
[表5]
产业上的可利用性
根据本发明,能够提供可控制圆角形状不成为凸状且可制造可靠性高的半导体装置的半导体芯片接合用粘接材料。另外,根据本发明,可提供由该半导体芯片接合用粘接材料形成的半导体芯片接合用粘接膜、使用了该半导体芯片接合用粘接材料或该半导体芯片接合用粘接膜的半导体装置的制造方法、以及通过该半导体装置的制造方法得到的半导体装置。
符号说明
1、基板
2、半导体芯片
3、半导体芯片接合用粘接材料
4、凸出
Claims (9)
1.一种半导体芯片接合用粘接材料,其特征在于,用粘弹性测定装置测得的25℃剪切弹性模量Gr为1×106Pa以上,用流变仪测得的直到软纤料熔点为止的最低复数粘度η*min为5×101Pa·s以下,在140℃的温度、1rad的变形量、1Hz的频率下测得的复数粘度η*(1Hz)是在140℃的温度、1rad的变形量、10Hz的频率下测得的复数粘度η*(10Hz)的0.5~4.5倍。
2.根据权利要求1所述的半导体芯片接合用粘接材料,其特征在于,含有环氧化合物、和具有能够与所述环氧化合物反应的官能团的高分子化合物,所述具有能够与环氧化合物反应的官能团的高分子化合物的重均分子量为5万以下。
3.根据权利要求1或2所述的半导体芯片接合用粘接材料,其特征在于,用于预先将粘接剂层搭载于晶片、半导体芯片或基板的倒装式安装。
4.一种半导体装置的制造方法,其特征在于,是使用了权利要求1、2或3所述的半导体芯片接合用粘接材料的半导体装置的制造方法,其中,
在权利要求1、2或3所述的半导体芯片接合用粘接材料中添加溶剂,将由此制备而得的粘接剂溶液涂布于晶片,将所述溶剂干燥而成膜。
5.根据权利要求4所述的半导体装置的制造方法,其特征在于,将在权利要求1、2或3所述的半导体芯片接合用粘接材料中添加溶剂,将由此制备而得的的粘接剂溶液通过旋涂或丝网印刷涂布于晶片。
6.一种半导体芯片接合用粘接膜,其特征在于,由权利要求1、2或3所述的半导体芯片接合用粘接材料形成。
7.一种半导体装置的制造方法,其特征在于,是使用了权利要求6所述的半导体芯片接合用粘接膜的半导体装置的制造方法,其中,
将权利要求6所述的半导体芯片接合用粘接膜通过层压供给至晶片或半导体芯片。
8.一种半导体装置的制造方法,其特征在于,是使用了权利要求6所述的半导体芯片接合用粘接膜的半导体装置的制造方法,其中,
对照半导体芯片的芯片尺寸,将权利要求6所述的半导体芯片接合用粘接膜裁断,供给至其它的半导体芯片或基板。
9.一种半导体装置,其特征在于,是通过权利要求4、5、7或8所述的半导体装置的制造方法而得的半导体装置,其中,
借助粘接剂层将半导体芯片与其它的半导体芯片或基板结合,
形成沿所述半导体芯片的侧壁向上爬的圆角,
所述半导体芯片的侧壁与所述圆角所形成的角度不足70°。
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CN111566787A (zh) * | 2018-01-17 | 2020-08-21 | 思美定株式会社 | 安装体 |
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