CN115023771A - 导电性膏和半导体装置 - Google Patents
导电性膏和半导体装置 Download PDFInfo
- Publication number
- CN115023771A CN115023771A CN202180011262.6A CN202180011262A CN115023771A CN 115023771 A CN115023771 A CN 115023771A CN 202180011262 A CN202180011262 A CN 202180011262A CN 115023771 A CN115023771 A CN 115023771A
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- Prior art keywords
- conductive paste
- meth
- acid
- acrylate
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000021588 free fatty acids Nutrition 0.000 claims description 3
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Abstract
一种导电性膏,其含有银粉、脂肪酸和稀释剂。
Description
技术领域
本发明涉及导电性膏和半导体装置。更详细而言,本发明涉及用于将半导体元件粘接、固定在金属框架等支承部件上的作为半导体搭载用芯片粘结膏使用的导电性膏、以及使用该导电性膏制造的半导体装置。
背景技术
通常,半导体装置可通过利用芯片接合材料将半导体芯片等半导体元件粘接到引线框或玻璃环氧配线板等支承部件上而制造。作为这样的芯片接合材料,已知有在粘接剂树脂中分散有导电性填料的树脂膏、和不含粘接剂树脂的烧结类型的银膏。
作为树脂膏,含有丙烯酸酯化合物或甲基丙烯酸酯化合物、环氧树脂和填充材料的(甲基)丙烯酸树脂/环氧树脂混合系膏组合物是公知的(例如,专利文献1)。并且,作为银膏,提出了含有银颗粒和挥发性分散介质的膏状组合物,例如,专利文献2中提出了通过使用将微米级银颗粒和用沸点为130~250℃的具有氨基或羧基的有机物包覆的纳米级银颗粒混合而得到的银膏,来确保银烧结体的耐热性和高致密性的技术。
现有技术文献
专利文献
专利文献1:日本特开2002-179769号公报
专利文献2:日本特开2012-119132号公报
发明内容
发明要解决的技术问题
但是,专利文献1的(甲基)丙烯酸树脂/环氧树脂混合系膏,有时相对于引线框或玻璃环氧配线板等的粘接强度不充分。因此,例如使用该丙烯酸树脂/环氧树脂混合系膏将半导体元件芯片接合在引线框等上来制造半导体装置,在将该半导体装置安装在基板上的状态下对基板进行加热而将该半导体装置接合到基板上时(回流焊接(reflow soldering)时),有时由该膏构成的膏层会剥离。并且,专利文献2的银膏在粘接到由银以外的金属构成的引线框上的情况下,有时空隙会集中在粘接界面的附近,导致粘接强度降低。
本发明是鉴于上述情况而完成的,其目的在于提供一种能够改善相对于引线框等支承部件的密合性,从而能够将半导体元件和支承部件牢固地粘接的导电性膏。
用于解决技术问题的手段
本发明人发现,通过使用特定的添加剂,能够得到相对于支承部件的密合性提高的导电性膏,从而完成了本发明。
根据本发明,提供一种导电性膏,其含有:银粉;脂肪酸;和稀释剂。
并且,根据本发明,提供一种半导体装置,其包括:支承部件;和经由粘接层搭载在所述支承部件上的半导体元件,所述粘接层由所述导电性膏构成。
发明效果
采用本发明,能够提供能够提高相对于支承部件的密合性的导电性膏、以及使用该导电性膏制造的连接可靠性优异的半导体装置。
附图说明
图1是表示本实施方式的电子装置的一个例子的截面图。
图2是表示本实施方式的电子装置的一个例子的截面图。
图3是表示实施例中的芯片剥离强度的测量方法的示意图。
具体实施方式
以下,对本发明的实施方式进行说明。
(导电性膏)
本实施方式的导电性膏是用于形成芯片粘结层的芯片粘结膏,该芯片粘结层用于将半导体元件等电子部件粘接在引线框或配线基板等支承部件上。本实施方式的导电性膏含有作为导电性金属粉的银粉、脂肪酸和稀释剂。本实施方式的导电性膏通过热处理,银粉彼此相互凝聚而形成银颗粒连结结构。这样通过对导电性膏进行加热而得到的芯片粘结层,具有导电性或热导电性,并且相对于支承部件具有高密合性。
本实施方式的导电性膏通过含有脂肪酸,特别是相对于支承部件具有高密合性。其理由尚不清楚,但对支承部件的表面实施的表面处理剂(例如,防渗剂(bleedoutinhibitor)、应力缓和剂等)会发挥作用使得银颗粒连结结构与支承部件表面的密合性降低。但是,在存在脂肪酸的情况下,可以认为该脂肪酸能够作用于表面处理剂,从而缓和密合性的降低。
以下,对本实施方式的导电性膏中所使用的各成分进行说明。
(银粉)
本实施方式的导电性膏中所含有的银粉,通过对导电性膏实施热处理,能够凝聚而形成银颗粒连结结构。也就是说,在对导电性膏进行加热而得到的芯片粘结膏层中,银粉彼此相互凝聚地存在。由此,能够表现出导电性、导热性、与支承部件的密合性。
银粉的形状没有特别限定,例如可以举出球状、片状和鳞片状等。在本实施方式中,银粉更优选含有球状颗粒。由此,能够提高银粉凝聚的均匀性。并且,从降低成本的观点出发,也可以采用银粉含有片状颗粒的方式。此外,从提高成本降低与凝聚均匀的平衡的观点出发,银粉可以含有球状颗粒和片状颗粒两者。
银粉的平均粒径(D50)例如为0.1μm以上10μm以下。通过使银粉的平均粒径为上述下限值以上,能够抑制比表面积的过度增大,抑制由接触热阻导致的导热性的降低。另外,通过使银粉的平均粒径为上述上限值以下,能够提高银粉间的银颗粒连结结构体的形成性。并且,从提高导电性膏的分配性的观点出发,银粉的平均粒径(D50)更优选为0.6μm以上2.7μm以下,特别优选为0.6μm以上2.0μm以下。另外,银粉的平均粒径(D50)例如可以使用市售的激光式粒度分布仪(例如,株式会社岛津制作所(Shimadzu Corporation)制造的SALD-7000等)来测量。
并且,银粉的最大粒径没有特别限定,例如,可以为1μm以上50μm以下,更优选为3μm以上30μm以下,特别优选为4μm以上18μm以下。由此,能够更有效地提高银粉凝聚的均匀性与分配性的平衡。在此,导电性膏的分配性是指将该导电性膏涂敷在支承部件上使用所需要的粘度和固化性等特性。
导电性膏中的银粉的含量相对于导电性膏整体例如为40质量%以上90质量%以下,优选为50质量%以上80质量%以下。通过使导电性膏中的银粉的含量为上述下限值以上,能够有助于提高对导电性膏进行热处理而得到的芯片粘结膏层的导热性和导电性。另一方面,通过使导电性膏中的银粉的含量为上述上限值以下,能够有助于提高得到的导电性膏的分配性(涂敷操作性)、对导电性膏进行热处理而得到的芯片粘结膏层的机械强度等。
本实施方式的导电性膏中使用的银粉,可以含有利用脂肪酸进行了表面处理的银粉。作为在银粉的表面处理中使用的脂肪酸,可以举出己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山嵛酸、棕榈油酸、油酸、芥酸等。从制造容易性和获得容易性的观点出发,优选使用利用硬脂酸或油酸进行了表面处理的银颗粒。作为利用硬脂酸等脂肪酸对银颗粒进行表面处理的方法,例如可以举出将稀释到溶剂中的脂肪酸与银颗粒一起用球磨机等处理后使溶剂干燥的方法等,但是并不限于此。
在使用利用脂肪酸进行了表面处理的银颗粒的情况下,利用脂肪酸进行了表面处理的银颗粒的量相对于所使用的银粉整体例如为0.05质量%以上1质量%以下,优选为0.2质量%以上0.7质量%以下。通过以上述范围内的量使用利用脂肪酸进行了处理的银颗粒,能够提高所得到的导电性膏相对于支承部件的密合性。
本实施方式的导电性膏,除了含有上述的银粉以外,还可以含有其他的导电性金属粉。作为其他的导电性金属粉,可以使用金粉、铂粉、钯粉、铜粉、或镍粉、或它们的合金。在使用其他的导电性金属粉的情况下,其他的导电性金属粉的量相对于上述银颗粒例如为0.05质量%以上1质量%以下,优选为0.2质量%以上0.7质量%以下。通过以上述范围内的量使用其他的导电性金属粉,银颗粒和其他的导电性金属粉能够良好地形成金属颗粒连结结构体。
(脂肪酸)
本实施方式的导电性膏含有脂肪酸。本实施方式的导电性膏在使用时,在被涂敷在支承部件的表面上时,能够表现出相对于支承部件的表面的高密合性和高粘接性。如上所述,可以认为这是由于脂肪酸对存在于支承部件表面的表面处理剂起作用而引起的。
本实施方式的导电性膏中使用的脂肪酸优选为碳原子数4~22的饱和或不饱和的脂肪酸。作为具体例,可以举出:丁酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、山梨酸等饱和脂肪酸;棕榈油酸、油酸、反油酸、异油酸、芥酸、亚油酸、γ-亚麻酸、α-亚麻酸、花生四烯酸等不饱和脂肪酸。其中,从相对于支承部件的密合性的观点出发,优选月桂酸、硬脂酸和油酸。
在本实施方式的导电性膏中,脂肪酸优选以溶解或分散在以下说明的稀释剂中的游离脂肪酸的形态存在。通过脂肪酸作为游离脂肪酸存在,能够进一步提高所得到的导电性膏相对于支承部件的密合性。
导电性膏中的脂肪酸的含量相对于导电性膏整体例如为0.01质量%以上2质量%以下,优选为0.05质量%以上1.5质量%以下。通过使脂肪酸的含量在上述范围内,能够更显著地得到导电性膏相对于支承部件的密合性的效果。
(稀释剂)
考虑到对支承部件的涂敷性和对细部的填充性,本实施方式的导电性膏含有稀释剂,以使导电性膏具有适当的粘度。作为稀释剂,可以使用反应性稀释剂或非反应性溶剂。在此,反应性稀释剂是指能够通过加热处理而固化,促进银颗粒凝聚的聚合性单体,或者在导电性膏中含有作为粘接剂树脂的热固性树脂的情况下,是指具有能够参与与该树脂的交联反应的反应性基团的化合物。非反应性溶剂是指不包含具有聚合性或交联性的反应基团的、能够通过加热处理而挥发的溶剂。
作为用作反应性稀释剂的聚合性单体,例如,可以举出二醇单体、丙烯酸单体、环氧单体、马来酰亚胺单体和酰亚胺单体等。
作为用作聚合性单体的二醇单体,例如,可以举出乙二醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丙醚、乙二醇单异丙醚、乙二醇单正丁醚、乙二醇单异丁醚、乙二醇单己醚、乙二醇单2-乙基己醚、乙二醇单烯丙基醚、乙二醇单苯基醚、乙二醇单苄基醚、二乙二醇、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单正丙醚、二乙二醇单异丙醚、二乙二醇单正丁醚、二乙二醇单异丁醚、二乙二醇单己醚、二乙二醇单2-乙基己醚、二乙二醇单苄基醚、三乙二醇、三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单正丁醚、四乙二醇、四乙二醇单甲醚、四乙二醇单乙醚、四乙二醇单正丁醚、丙二醇、丙二醇单甲醚、丙二醇单乙醚、丙二醇单正丙醚、丙二醇单异丙醚、丙二醇单正丁醚、丙二醇单苯基醚、二丙二醇、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、二丙二醇单正丁醚、三丙二醇、三丙二醇单甲醚、三丙二醇单乙醚、三丙二醇单正丁醚等。这些可以单独使用1种,也可以将2种以上组合使用。
在对导电性膏进行热处理的情况下,从其中所含有的银颗粒彼此凝聚而良好地形成银颗粒连结结构的观点出发,作为二醇单体,优选使用三丙二醇单正丁醚或乙二醇单正丁基乙酸酯。
作为用作聚合性单体的丙烯酸单体,可以使用仅具有1个(甲基)丙烯酰基的单官能丙烯酸单体,或者具有2个以上(甲基)丙烯酰基的多官能丙烯酸单体。
作为单官能丙烯酸单体,例如,可以举出(甲基)丙烯酸2-苯氧乙酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸正月桂酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸异硬脂酯、乙氧基二乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、2-乙基己基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基酚环氧乙烷改性(甲基)丙烯酸酯、苯基苯酚环氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸异莰酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基乙酯季化合物、(甲基)丙烯酸环氧丙酯、季戊二醇(甲基)丙烯酸苯甲酸酯、1,4-环己烷二甲醇单(甲基)丙烯酸酯、(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸2-羟丁酯、(甲基)丙烯酸2-羟基-3-苯氧丙酯、2-(甲基)丙烯酰氧乙基琥珀酸、2-(甲基)丙烯酰氧乙基六氢邻苯二甲酸、2-(甲基)丙烯酰氧乙基邻苯二甲酸、2-(甲基)丙烯酰氧乙基-2-羟乙基邻苯二甲酸和2-(甲基)丙烯酰氧乙基酸性磷酸酯等。作为单官能丙烯酸单体,可以使用上述具体例中的1种或将2种以上组合使用。
作为单官能丙烯酸单体,在上述具体例子中,优选使用甲基丙烯酸2-苯氧基乙酯。由此,能够提高所得到的导电性膏相对于支承部件的密合性。
作为多官能丙烯酸单体,具体而言,可以举出乙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化双酚A二(甲基)丙烯酸酯、己烷-1,6-二醇双(2-(甲基)丙烯酸甲酯)、4,4’-异亚丙基二苯酚二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,6-双((甲基)丙烯酰氧基)-2,2,3,3,4,4,5,5-八氟己烷、1,4-双((甲基)丙烯酰氧基)丁烷、1,6-双((甲基)丙烯酰氧基)己烷、三乙二醇二(甲基)丙烯酸酯、季戊二醇二(甲基)丙烯酸酯、N,N’-二(甲基)丙烯酰基乙二胺、N,N’-(1,2-二羟基乙烯)双(甲基)丙烯酰胺或1,4一双((甲基)丙烯酰基)哌嗪等。
作为用作聚合性单体的环氧单体,可以使用仅具有1个环氧基的单官能环氧单体、或具有2个以上环氧基的多官能环氧单体。
作为单官能环氧单体,可以举出4-叔丁基苯基缩水甘油醚、间,对甲苯基缩水甘油醚、苯基缩水甘油醚、甲苯基缩水甘油醚等。作为单官能环氧单体,可以使用上述具体例中的1种或将2种以上组合使用。
作为多官能环氧单体,可以举出:双酚A、双酚F、联苯酚等双酚化合物或它们的衍生物;氢化双酚A、氢化双酚F、氢化联苯酚、环己烷二醇、环己烷二甲醇、环己烷二乙醇等具有脂环结构的二醇或它们的衍生物;使丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或它们的衍生物等环氧化而得到的2官能的物质;具有三羟基苯基甲烷骨架、氨基苯酚骨架的3官能的物质;使苯酚酚醛清漆树脂、甲酚酚醛清漆树脂、苯酚芳烷基树脂、联苯芳烷基树脂、萘酚芳烷基树脂等环氧化而得到的多官能的物质等。作为多官能环氧单体,可以使用上述具体例中的1种或将2种以上组合使用。
作为用作聚合性单体的马来酰亚胺单体,可以举出聚四亚甲基醚二醇-二(2-马来酰亚胺乙酸酯)等。
作为用作聚合性单体的酰亚胺单体,可以举出均苯四酸二酐等酸酐、4,4’-二氨基二苯醚等二胺等。
在本实施方式中,导电性膏中的聚合性单体的含量相对于导电性膏整体优选为3质量%以上,更优选为4质量%以上。由此,能够更有效地提高导电性膏的涂敷操作性和所得到的粘接层的平坦性。另一方面,导电性膏中的聚合性单体的含量相对于导电性膏整体优选为20质量%以下,更优选为15质量%以下。由此,能够抑制涂敷操作中的滴液的产生等,实现涂敷操作性的提高。并且,还能够提高导电性膏的固化性。
本实施方式的导电性膏也可以含有非反应性溶剂。通过含有非反应性溶剂,能够调整所得到的导电性膏的流动性,提高处理性和操作性。作为非反应性溶剂,可以举出乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚、丙二醇单丁醚、甲基甲氧基丁醇、α-萜品醇、β-萜品醇、己二醇、苄醇、2-苯乙醇、异棕榈醇、异硬脂醇、月桂醇、乙二醇、丙二醇或丙三醇等醇类;丙酮、甲基乙基酮、甲基异丁基酮、环己酮、二丙酮醇(4-羟基-4-甲基-2-戊酮)、2-辛酮、异佛尔酮(3,5,5-三甲基-2-环己烯-1-酮)或二异丁基酮(2,6-二甲基-4-庚酮)等酮类;乙酸乙酯、乙酸丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、乙酰氧基乙烷、丁酸甲酯、己酸甲酯、辛酸甲酯、癸酸甲酯、醋酸甲氧乙酯、乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、1,2-二乙酰氧基乙烷、磷酸三丁酯、磷酸三甲苯酯或磷酸三戊酯等酯类;四氢呋喃、二丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、丙二醇二甲醚、乙氧基乙醚、1,2-双(2-二乙氧基)乙烷或1,2-双(2-甲氧基乙氧基)乙烷等醚类;乙酸2-(2丁氧基乙氧基)乙烷等酯醚类;2-(2-甲氧基乙氧基)乙醇等醚醇类;甲苯、二甲苯、正烷烃、异烷烃、十二基苯、松节油、煤油或轻油等烃类;乙腈或丙腈等腈类;乙酰胺或N,N-二甲基甲酰胺等酰胺类;低分子量的挥发性硅油或挥发性有机改性硅油等。
本实施方式的导电性膏也可以不含有非反应性溶剂。在此,不含有非反应性溶剂是指实质上不含有,是指相对于导电性膏整体的非反应性溶剂的含量为0.1质量%以下的情况。
(热固性树脂)
本实施方式的导电性膏,根据需要,可以含有作为粘接剂树脂的热固性树脂。作为热固性树脂,可以使用选自氰酸酯树脂、环氧树脂、1分子内具有2个以上自由基聚合性的碳-碳双键的树脂、烯丙基树脂和马来酰亚胺树脂中的一种或两种以上。
作为用作热固性树脂的环氧树脂,可以使用所有在1分子内具有2个以上缩水甘油基的单体、低聚物、聚合物,其分子量和分子结构没有特别限定。作为本实施方式中所使用的环氧树脂,例如可以举出联苯型环氧树脂;双酚A型环氧树脂、双酚F型环氧树脂、四甲基双酚F型环氧树脂等双酚型环氧树脂;芪型环氧树脂;苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂等酚醛清漆型环氧树脂;三酚甲烷型环氧树脂、烷基改性三酚甲烷型环氧树脂等多官能环氧树脂;具有亚苯基骨架的苯酚芳烷基型环氧树脂、具有亚联苯基骨架的苯酚芳烷基型环氧树脂等芳烷基型环氧树脂;二羟基萘型环氧树脂、将二羟基萘的二聚体进行缩水甘油基醚化而得到的环氧树脂等萘酚型环氧树脂;三聚异氰酸三环氧丙酯、单烯丙基二缩水甘油基三聚异氰酸酯等含有三嗪核的环氧树脂;二环戊二烯改性苯酚型环氧树脂等桥联环状烃化合物改性苯酚型环氧树脂。并且,作为环氧树脂,例如也可以使用在1分子内含有2个以上的缩水甘油基的化合物中的双酚A、双酚F、联苯酚等双酚化合物或它们的衍生物;氢化双酚A、氢化双酚F、氢化联苯酚、环己烷二醇、环己烷二甲醇、环己烷二乙醇等具有脂环结构的二醇或它们的衍生物;使丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或它们的衍生物等环氧化而得到的2官能的物质;具有三羟基苯基甲烷骨架、氨基苯酚骨架的3官能的物质。作为热固性树脂的环氧树脂,可以含有选自上述例示的树脂中的一种或两种以上。
其中,从提高所得到的导电性膏的涂敷操作性和粘接性的观点出发,更优选含有双酚型环氧树脂,特别优选含有双酚F型环氧树脂。另外,在本实施方式中,从更有效地提高导电性膏的涂敷操作性的观点出发,更优选含有室温(25℃)时为液态的液态环氧树脂。
作为热固性树脂使用的氰酸酯树脂没有特别限定,例如可以含有选自1,3-二氰氧基苯、1,4-二氰氧基苯、1,3,5-三氰氧基苯、1,3-二氰氧基萘、1,4-二氰氧基萘、1,6-二氰氧基萘、1,8-二氰氧基萘、2,6-二氰氧基萘、2,7-二氰氧基萘、1,3,6-三氰氧基萘、4,4,-二氰氧基联苯、双(4-氰氧基苯基)甲烷、双(3,5-二甲基-4-氰氧基苯基)甲烷、2,2-双(4-氰氧基苯基)丙烷、2,2-双(3,5-二溴-4-氰氧基苯基)丙烷、双(4-氰氧基苯基)醚、双(4-氰氧基苯基)硫醚、双(4-氰氧基苯基)砜、三(4-氰氧基苯基)亚磷酸酯、三(4-氰氧基苯基)磷酸酯、通过酚醛清漆树脂与卤化氰的反应得到的氰酸酯类、以及通过将这些多官能氰酸酯树脂的氰酸酯基进行三聚化而形成的具有三嗪环的预聚物中的一种或两种以上。上述预聚物可以通过将上述多官能氰酸酯树脂单体以例如无机酸、路易斯酸等酸、醇钠、叔胺类等碱或碳酸钠等盐类为催化剂进行聚合而得到。
作为用作热固性树脂的1分子内具有2个以上自由基聚合性的碳-碳双键的树脂,例如可以使用分子内具有两个以上(甲基)丙烯酰基的自由基聚合性的丙烯酸树脂。在本实施方式中,作为上述丙烯酸树脂,可以含有分子量为500~10000的聚醚、聚酯、聚碳酸酯或聚(甲基)丙烯酸酯且具有(甲基)丙烯酸基的化合物。另外,作为热固性树脂使用1分子内具有2个以上自由基聚合性的碳-碳双键的树脂时,导热性膏例如可以含有热自由基聚合引发剂等聚合引发剂。
作为热固性树脂使用的烯丙基树脂,可以举出通过使二羧酸、烯丙醇和具有烯丙基的化合物反应而得到的烯丙基酯树脂。在此,作为上述二羧酸,具体而言,可以举出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸等。作为二羧酸,可以使用上述具体例中的1种或将2种以上组合使用。
另外,作为上述具有烯丙基的化合物,具体而言,可以举出具有烯丙基的聚醚、聚酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丁二烯、丁二烯丙烯腈共聚物等。作为具有烯丙基的化合物,可以使用上述具体例中的1种或将2种以上组合使用。作为烯丙基树脂,具体而言,可以使用1,2-环己烷二羧酸双(2-丙烯基)与丙烷-1,2-二醇的聚合物等。
作为热固性树脂使用的马来酰亚胺树脂没有特别限定,例如可以含有选自N,N’-(4,4’-二苯基甲烷)双马来酰亚胺、双(3一乙基-5-甲基-4-马来酰亚胺苯基)甲烷、2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷等双马来酰亚胺树脂如丙烷中的一种或两种以上。
热固性树脂中,作为具有联苯骨架的树脂,可以含有具有联苯骨架的环氧树脂(联苯型环氧树脂)。由此,能够提高导电性膏的金属密合性。
具有联苯骨架环氧树脂,只要是在其分子结构内具有联苯骨架且具有2个以上环氧基的环氧树脂,其结构就没有特别限定,例如,可以举出利用表氯醇对联苯酚或其衍生物进行处理而得到的双官能环氧树脂、具有亚联苯基骨架的苯酚芳烷基型环氧树脂、具有亚联苯基骨架的萘酚芳烷基型环氧树脂等,这些可以单独使用也可以混合使用。其中,尤其是分子内具有2个环氧基的环氧树脂具有优异的耐热性,因此优选。作为这样的环氧树脂,可以举出:联苯型环氧树脂、四甲基联苯型环氧树脂等利用表氯醇对联苯衍生物进行处理而得到的2官能环氧树脂;具有亚联苯基的苯酚芳烷基型环氧树脂中的环氧基为2个(有时表述为苯酚核体数为2)的树脂;具有亚联苯基骨架的萘酚芳烷基型树脂中的环氧基为2个的树脂;等等。
在本实施方式的导电性膏中配合热固性树脂时,热固性树脂的含量的下限值相对于导电性膏整体例如为1质量%以上,优选为3质量%以上,更优选为5质量%以上。由此,能够使导电性膏的处理性良好。并且,能够使导电性膏的粘度为适合使用的程度。另外,热固性树脂的含量的上限值相对于导电性膏整体例如为15质量%以下,优选为12质量%以下,更优选为10质量%以下。由此,能够提高导电性膏的导电性、相对于支承部件的密合性等各种特性的平衡。
(固化剂)
本实施方式的导电性膏可以含有固化剂。由此,能够提高导电性膏的固化性。作为固化剂,例如,可以使用选自脂肪族胺、芳香族胺、双氰胺、二酰肼化合物、酸酐和酚化合物中的一种或两种以上。其中,从提高制造稳定性的观点出发,特别优选含有双氰胺和酚化合物中的至少一种。
作为用作固化剂的二酰肼化合物,可以举出己二酸二酰肼、十二烷酸二酰肼、间苯二甲酸二酰肼、对氧苯甲酸二酰肼等羧酸二酰肼等。并且,作为用作固化剂的酸酐,可以举出邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、十二烯基琥珀酸酐、马来酸酐与聚丁二烯的反应物、马来酸酐与苯乙烯的共聚物等。
作为固化剂使用的酚化合物是1分子内具有2个以上酚性羟基的化合物。更优选1分子内的酚性羟基的数量为2~5,特别优选1分子内的酚性羟基的数量为2个或3个。由此,能够更有效地提高导电性膏的涂敷操作性,并且能够在固化时形成交联结构而使导电性膏的固化物特性优异。上述酚化合物例如可以含有:选自双酚F、双酚A、双酚S、四甲基双酚A、四甲基双酚F、四甲基双酚S、二羟基二苯醚、二羟基二苯基酮、四甲基联苯酚、亚乙基双酚、甲基亚乙基双(甲基苯酚)、亚环己基双酚、联苯酚等双酚类及其衍生物、三(羟基苯基)甲烷、三(羟基苯基)乙烷等3官能的酚类及其衍生物、苯酚酚醛清漆、甲酚酚醛清漆等通过使酚类与甲醛进行反应而得到的化合物中双核体或三核体为主的化合物及其衍生物中的一种或两种以上。其中,更优选含有双酚类,特别优选含有双酚F。
另外,在本实施方式中,作为固化剂的具有联苯骨架的树脂,可以使用具有联苯骨架的酚醛树脂(酚化合物)。由此,能够提高导电性膏的导电性和相对于支承部件的密合性。作为具有联苯骨架的酚醛树脂,只要是在其分子结构内具有联苯骨架且具有2个以上酚基的酚醛树脂,则其结构没有特别限定。
在本实施方式中,导电性膏中的固化剂的含量相对于导热性膏整体优选为0.5质量%以上,更优选为1.0质量%以上。由此,能够更有效地提高导电性膏的固化性。另一方面,导电性膏中固化剂的含量相对于导电性膏整体优选为10质量%以下,更优选为7质量%以下。由此,能够提高使用导电性膏形成的粘接层的低热膨胀性和耐湿性。
(其他成分)
本实施方式的导电性膏,除了上述成分以外,还可以根据需要含有在该领域中通常使用的各种其他成分。作为其他成分,可以举出硅烷偶联剂、固化促进剂、自由基聚合引发剂、低应力剂、无机填料等,但并不限定于此,可以根据期望的性能进行选择。
硅烷偶联剂用于提高导电性膏与支承部件的密合性。作为硅烷偶联剂,例如,可以举出:乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷等乙烯基硅烷;2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷等环氧硅烷;对苯乙烯基三甲氧基硅烷等苯乙烯基硅烷;3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷等甲基丙烯酰基硅烷;甲基丙烯酸3-(三甲氧基硅基)丙酯、3-丙烯酰氧基丙基三甲氧基硅烷等丙烯酸硅烷;N-2-(氨乙基)-3-氨丙基甲基二甲氧基硅烷、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-三乙氧基硅基-N-(1,3-二甲基-亚丁基)丙胺、N-苯基-γ-氨丙基三甲氧基硅烷等氨基硅烷;三聚异氰酸基硅烷;烷基硅烷;3-脲基丙基三烷氧基硅烷等脲基硅烷;3-巯基丙基甲基二甲氧基硅烷、3-巯基丙基三甲氧基硅烷等巯基硅烷;3-异氰酸基丙基三乙氧基硅烷等异氰酸基硅烷等。
固化促进剂用于促进作为聚合性单体使用的环氧单体或作为粘接剂树脂使用的环氧树脂与固化剂的反应。作为固化促进剂,例如可以举出有机膦、四取代鏻化合物、磷酸酯甜菜碱化合物、膦化合物与醌化合物的加成物、鏻化合物与硅烷化合物的加成物等含磷原子的化合物;双氰胺、1,8-二氮杂双环[5.4.0]十一碳烯-7、苄基二甲胺等脒或叔胺;上述脒或上述叔胺的季铵盐等含氮原子的化合物等。
作为自由基聚合引发剂,具体而言,可以使用偶氮化合物、过氧化物等。
作为低应力剂,例如可以使用:硅油、硅橡胶等有机硅化合物;聚丁二烯马来酸酐加成物等聚丁二烯化合物;丙烯腈丁二烯共聚化合物等。
作为无机填料,可以举出:熔融破碎二氧化硅、熔融球状二氧化硅等熔融二氧化硅;结晶二氧化硅、非晶二氧化硅等二氧化硅;二氧化硅;氧化铝;氢氧化铝;氮化硅;以及氮化铝等。
(导电性膏的制备)
导电性膏的制备方法没有特别限定,例如可以通过将上述各成分预混合后,使用三辊机进行混炼,进而进行真空脱泡,从而得到膏状的组合物。此时,通过例如在减压下进行预混合等,适当调整制备条件,能够提高导电性膏的长期操作性。
本实施方式的导电性膏可以根据用途调整粘度。导电性膏的粘度可以通过调整所用的粘接剂树脂的种类、稀释剂的种类、它们的配合量等来控制。本实施方式的导电性膏的粘度的下限值例如为10Pa·s以上,优选为20Pa·s以上,更优选为30Pa·s以上。由此,能够提高导电性膏的操作性。另一方面,导电性膏的粘度的上限值例如为1×103pa·s以下,优选为5×102Pa·s以下,更优选为2×102pa·s以下。由此,能够提高涂敷性。
(用途)
下面对本实施方式的导电性膏的用途进行说明。
本实施方式的导电性膏例如可用于将基板和半导体元件粘接。在此,作为半导体元件,例如,可以举出半导体封装件和LED等。
与以往的膏状粘接剂组合物相比,本实施方式的导电性膏能够提高连接可靠性和外观。由此,能够适合用于将发热量大的半导体元件搭载在基板上的用途。另外,在本实施方式中,LED表示发光二极管(Light Emitting Diode)。
作为使用LED的半导体装置,具体而言,可以举出炮弹型LED、表面安装型(SurfaceMount Device:SMD)LED、COB(Chip On Board:板上芯片封装)、Power LED(电源指示灯)等。
另外,作为上述半导体封装的种类,具体而言,可以举出CMOS图像传感器、中空封装、MAP(Mold Array Package:模塑阵列封装)、QFP(Quad Flat Package:四面扁平封装)、SOP(Small Outline Package:小型封装)、CSP(Chip Size Package:芯片尺寸封装)、QFN(Quad Flat Non-leaded Package:四面扁平无引线封装)、SON(Small Outline Non-leaded Package:小型无引线封装)、BGA(Ball Grid Array:球栅阵列)、LF-BGA(LeadFrame BGA:引线框球栅阵列)、FC-BGA(Flip Chip BGA:覆晶球栅阵列)、MAP-BGA(MoldedArray Process BGA:模塑阵列制程球栅阵列)、eWLB(Embedded Wafer-Level BGA:嵌入式晶圆级球栅阵列)、Fan-In型eWLB(扇入型嵌入式晶圆级球栅阵列)、Fan-Out型eWLB(扇出型嵌入式晶圆级球栅阵列)等种类。
以下,对使用本实施方式的导电性膏的半导体装置的一个例子进行说明。
图1是表示本实施方式的半导体装置的一个例子的截面图。
本实施方式的半导体装置100包括:支承部件30;和半导体元件20,其经由作为导电性膏的固化物的粘接剂层10搭载在支承部件30上。半导体元件20和支承部件30例如经由接合线40等电连接。并且,半导体元件20例如由密封树脂50密封。
在此,粘接剂层10的厚度的下限值例如优选为5μm以上,更优选为10μm以上。由此,能够提高导电性膏的固化物的热容量,提高散热性。另外,粘接剂层10的厚度的上限值例如优选为50μm以下,更优选为30μm以下。由此,导电性膏能够在提高散热性的基础上表现出适当的密合力。
在图1中,支承部件30例如是引线框。此时,半导体元件20经由粘接剂层10搭载在芯片焊盘32或支承部件30上。并且,半导体元件20例如经由接合线40与外引线34(支承部件30)电连接。作为引线框的支承部件30例如由42合金、Cu框架构成。
支承部件30也可以是有机基板或陶瓷基板。作为有机基板,例如优选由环氧树脂、氰酸酯树脂、马来酰亚胺树脂等构成的基板。另外,支承部件30的表面可以由例如银、金等金属包覆。由此,能够提高粘接剂层10与支承部件30的粘接性。
图2是图1的变形例,是表示本实施方式的半导体装置100的一个例子的截面图。在本变形例的半导体装置100中,支承部件30例如为内插板(interposer)。在作为内插板的支承部件30中的与用于搭载半导体元件20的一面相反的一侧的另一面上,例如形成有多个焊球52。在该情况下,半导体装置100经由焊球52与其他配线基板连接。
(半导体装置的制造方法)
下面对本实施方式的半导体装置的制造方法的一个例子进行说明。
首先,在支承部件30上涂敷导电性膏,然后在其上配置半导体元件20。即,支承部件30、膏状粘接剂组合物和半导体元件20依次层叠。作为涂敷导电性膏的方法并无限定,具体而言,可以使用分配法(dispensing)、印刷法、喷墨法等。
接着,通过使导电性膏预固化,然后进行后固化,使导电性膏固化。通过预固化和后固化等热处理,导电性膏中的银颗粒凝聚,在粘接剂层10中形成多个银颗粒彼此的界面消失而得到的导热层。由此,支承部件30和半导体元件20经由粘接剂层10粘接。接着,使用接合线40将半导体元件20和支承部件30电连接。接着,利用密封树脂50将半导体元件20密封。由此,能够制造半导体装置。
以上,对本发明的实施方式进行了说明,但是,这些是本发明的例示,也可以采用上述以外的各种构成。
[实施例]
以下,通过实施例和比较例对本发明进行说明,但本发明并不限定于此。
实施例和比较例中使用的成分如下所示。
(银粉)
·银粉1:利用脂肪酸进行了表面处理的银粉,株式会社德力本店(TOKURIKIHONTEN CO.,LTD.)制造,TKR-88,片状,平均粒径(D50)为3μm
(脂肪酸)
·脂肪酸1:油酸,关东化学株式会社(KANTO CHEMICAL CO.,INC.)制造
(稀释剂)
·稀释剂1:单官能丙烯酸单体((甲基)丙烯酸单体2:甲基丙烯酸2-苯氧乙酯),共荣社化学株式会社(KYOEISHA CHEMICAL Co.,LTD.)制造,Light Ester PO
·稀释剂2:2官能丙烯酸单体(聚乙二醇二甲基丙烯酸酯),共荣社化学株式会社制造,Light Ester 1,6Hx
(低应力剂)
·低应力剂1:丙烯酸树脂,东亚合成株式会社(TOAGOSEI CO.,LTD.)制造,UG4035
·低应力剂2:烯丙基树脂,关东化学株式会社制造,SBM8C03
(自由基聚合引发剂)
·自由基聚合引发剂1:过氧化物,化药阿克苏株式会社(Kayaku AkzoCorporation)制造,Perkadox BC
(实施例1~实施例5、比较例1)
<清漆状树脂组合物的制作>
首先,在常温下,用三辊研磨机混炼表1的“清漆组成”中记载的配合量的成分,由此制作出清漆状混合物。接着,以表1的“膏组成”中记载的配合量使用所得到的清漆状混合物,混合银粉,在常温下,用三辊研磨机进行混炼,由此得到膏状的组合物(导电性膏)。
对各实施例和各比较例的导电性膏,对以下项目进行测量,对导电性膏的粘接强度(芯片剪切强度)进行评价。
<吸湿后的芯片剪切强度(长度2mm×宽度2mm×厚度350μm的硅芯片)>
固化条件:将上述得到的导电性膏涂敷在铜框架上,并在其上安装长度2mm×宽度2mm的硅芯片,使厚度为20μm。之后,在氮气气氛下在175℃升温30分钟,放置5小时(1小时固化和塑封后烘焙(Post Mold Curing)),从而得到试验片。
吸湿条件:将得到的试验片在温度120℃、相对湿度100%的环境中放置24小时,将取出的样品通过260℃的回流工序3次。
芯片剪切强度的测量条件:将吸湿处理后的试验片在260℃的板上放置20秒钟,在该状态下利用接合试验器(DAGE 4000P型)测量芯片剥离强度。图3是表示芯片剥离强度的测量方法的示意图。硅芯片220经由导电性膏210粘接在利用防渗剂进行了表面处理的铜框架200上。将治具230按压在硅芯片220的侧面,在测量速度50μm/秒、测量高度50μm的条件下,测量作为沿着图3所示的箭头方向施加力时的最大应力的芯片剪切强度,将其作为粘接强度。将芯片剪切强度和其标准偏差的值示于表1。芯片剪切强度的单位为“N”。芯片剪切强度的值越大,表示硅芯片与铜框架粘接得越牢固。
另外,通过目视确认在芯片剪切强度的测量试验中破坏了的导电性膏固化物的破坏模式。当在铜框与导电性膏固化物的界面剥离的情况下,确认为“LF破坏”,在芯片粘结膏固化物自身产生了龟裂的情况下,确认为“凝聚破坏”,在观察到这两种剥离的情况下,确认为“凝聚破坏/LF破坏”,将结果示于表1。
<芯片剪切强度(长度5mm×宽度5mm×厚度350μm的硅芯片)>
固化条件:将上述得到的导电性膏涂敷在铜框架上,并在其上安装5mm×5mm的硅芯片,使厚度为20μm。之后,在氮气气氛下在175℃升温30分钟,放置5小时(1小时固化和塑封后烘焙),从而得到试验片。
芯片剪切强度的测量条件:与上述“吸湿后的芯片剪切强度(长度2mm×宽度2mm的硅芯片)”中记载的“芯片剪切强度的测量条件”同样地测量芯片剪切强度。将芯片剪切强度和其标准偏差的测量结果示于表1。
<吸湿后的芯片剪切强度(长度5mm×宽度5mm×厚度350μm的硅芯片)>
固化条件:将上述得到的导电性膏涂敷在铜框架上,并在其上安装5mm×5mm的硅芯片,使厚度为20μm。之后,在氮气气氛下在175℃升温30分钟,放置5小时(1小时固化和塑封后烘焙),从而得到试验片。
吸湿条件:将得到的试验片在温度120℃、相对湿度100%的环境中放置24小时,将取出的样品通过260℃的回流工序3次。
芯片剪切强度的测量条件:与上述“吸湿后的芯片剪切强度(长度2mm×宽度2mm的硅芯片)”中记载的“芯片剪切强度的测量条件”同样地测量芯片剪切强度。将芯片剪切强度和其标准偏差的测量结果示于表1。
<可靠性(封装剥离试验)>
将上述得到的导电性膏涂敷在铜框架上,并在其上安装长度8mm×宽度8mm的厚度为200μm的硅芯片,使厚度为20μm。之后,在氮气气氛下在175℃升温30分钟,放置1小时,从而得到试验片。之后,使用环氧树脂模塑化合物进行密封,得到封装件。之后,在175℃进行4小时的塑封后烘焙,得到封装结构物。该封装结构物的长度为14mm,宽度为14mm,厚度为0.8mm。之后,将得到的封装结构物分别在以下的环境下各投入9个。
环境1:温度85℃,相对湿度85%,72小时
环境2:温度85℃,相对湿度85%,168小时
环境3:温度120℃,相对湿度100%,24小时
取出在各环境中暴露了规定时间的封装结构物,接着,使其通过260℃的回流工序3次。之后,确认该封装结构物中有无硅芯片从铜框架的剥离。将观察到剥离的封装结构物的个数示于表1。另外,可靠性的评价仅对实施例2、实施例4和比较例1实施。对实施例1、实施例3和实施例5,未实施(表示为“-”)。
将实施例的导电性膏作为密封材料使用的封装件,在吸湿处理、之后的回流处理后,密封材料不会从硅芯片剥离,能够适合用作半导体装置用的密封材料。
本申请以2020年1月28日申请的日本申请特愿2020-011504号为基础要求优先权,将其全部公开内容援用于此。
Claims (10)
1.一种导电性膏,其特征在于,含有:
银粉;
脂肪酸;和
稀释剂。
2.根据权利要求1所述的导电性膏,其特征在于:
所述脂肪酸为溶解或分散在所述稀释剂中的游离脂肪酸。
3.根据权利要求1或2所述的导电性膏,其特征在于:
所述脂肪酸为碳原子数4~22的饱和或不饱和的脂肪酸。
4.根据权利要求1至3中任一项所述的导电性膏,其特征在于:
所述脂肪酸的量相对于该导电性膏整体为0.01质量%以上2质量%以下。
5.根据权利要求1至4中任一项所述的导电性膏,其特征在于:
所述稀释剂含有选自二醇单体、丙烯酸单体、环氧单体、马来酰亚胺单体和酰亚胺单体中的至少一种聚合性单体。
6.根据权利要求1至5中任一项所述的导电性膏,其特征在于:
所述银粉的量相对于该导电性膏整体为40质量%以上90质量%以下。
7.根据权利要求1至6中任一项所述的导电性膏,其特征在于:
还含有热固性树脂。
8.根据权利要求1至7中任一项所述的导电性膏,其特征在于:
还含有固化剂。
9.根据权利要求1至8中任一项所述的导电性膏,其特征在于:
所述银粉含有利用脂肪酸进行了表面处理的银粉。
10.一种半导体装置,其特征在于,包括:
支承部件;和
经由粘接层搭载在所述支承部件上的半导体元件,
所述粘接层由权利要求1至9中任一项所述的导电性膏构成。
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