CN102205470B - 填充组合物、包括其的半导体装置及该半导体装置的制法 - Google Patents

填充组合物、包括其的半导体装置及该半导体装置的制法 Download PDF

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CN102205470B
CN102205470B CN201010546515.3A CN201010546515A CN102205470B CN 102205470 B CN102205470 B CN 102205470B CN 201010546515 A CN201010546515 A CN 201010546515A CN 102205470 B CN102205470 B CN 102205470B
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particle
filled compositions
volume
acid
reducing agent
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CN102205470A (zh
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严龙成
文钟太
崔光成
裵贤哲
李宗津
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Electronics and Telecommunications Research Institute ETRI
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Abstract

本发明提供填充组合物、包括其的半导体装置及该半导体装置的制法。所述填充组合物包含:包括Cu和/或Ag的第一颗粒;使第一颗粒电连接的第二颗粒;以及所述第一和第二颗粒分散于其中的包含高分子化合物、硬化剂以及还原剂的树脂,其中所述硬化剂包括胺和/或酸酐,且所述还原剂包括羧基。

Description

填充组合物、包括其的半导体装置及该半导体装置的制法
技术领域
本文公开的本发明涉及填充组合物、包括其的半导体装置、以及制造该半导体装置的方法,且更具体地,涉及通过设置在基板之间而使所述基板电连接的填充组合物、包括该填充组合物的半导体装置以及制造该半导体装置的方法。
背景技术
通常,在半导体装置的制造过程中,通过设置在多个基板之间而使所述基板电连接的导电图案是通过使用典型地包含银颗粒和树脂的组合物而形成的。仅包含银颗粒和树脂的组合物的电阻由于树脂中的氧化物或其它外界条件而增加。因此,如果形成由所述组合物制成的导电图案以通过设置在基板之间而使所述基板电连接,则所述导电图案的电阻变高,使得可出现电连接方面的缺陷。
发明内容
本发明提供具有低电阻的填充组合物。
本发明还提供包括该填充组合物的半导体装置。
本发明还提供制造该半导体装置的方法。
本发明的各实施方式提供填充组合物,其包含:包括Cu和/或Ag的第一颗粒;使所述第一颗粒电连接的第二颗粒;以及所述第一和第二颗粒分散于其中的包含高分子化合物、硬化剂以及还原剂的树脂,其中所述硬化剂包括胺和/或酸酐,且所述还原剂包括羧基。
在一些实施方式中,所述第一颗粒可占所述组合物的约5体积%~约40体积%;且所述第二颗粒可占所述组合物的约5体积%~约40体积%。
在另一些实施方式中,所述第一和第二颗粒可占所述组合物的约30体积%~约50体积%。
在另外一些实施方式中,所述第二颗粒可为选自Sn、Bi、In、Ag、Pb、Cu、以及它们的合金的至少一种。
在另外一些实施方式中,所述第二颗粒可为选自如下的至少一种:60Sn/40Bi、52In/48Sn、97In/3Ag、57Bi/42Sn/1Ag、58Bi/42Sn、52Bi/32Pb/16Sn以及96.5Sn/3Ag/0.5Cu。
在另外一些实施方式中,所述高分子化合物可包括选自如下的至少一种单体:双酚A的二缩水甘油醚(DBEBA)、四缩水甘油基4,4’-二氨基二苯基甲烷(TGDDM)、其中
Figure BSA00000362859500022
异氰酸酯以及双马来酰亚胺。
在进一步实施方式中,所述硬化剂可具有为所述高分子化合物的约0.4至约1.2的当量。
在更进一步的实施方式中,所述硬化剂可为选自如下的至少一种:间苯二胺(MPDA)、二氨基二苯基甲烷(DDM)、二氨基二苯基砜(DDS)、甲基纳迪克酸酐(MNA)、十二碳烯基琥珀酸酐(DDSA)、马来酸酐(MA)、琥珀酸酐(SA)、甲基四氢邻苯二甲酸酐(MTHPA)、六氢邻苯二甲酸酐(HHPA)、四氢邻苯二甲酸酐(THPA)以及均苯四甲酸二酐(PMDA)。
在甚至进一步的实施方式中,所述还原剂可以相对于树脂重量为小于约10份/100份树脂(phr)的量添加。
在还进一步的实施方式中,所述还原剂可为选自如下的至少一种:戊二酸、苹果酸、壬二酸、松香酸、己二酸、抗坏血酸、丙烯酸和柠檬酸。
在还进一步的实施方式中,所述第一颗粒的直径为约1μm~30μm,且所述第二颗粒的直径为约5nm~100μm。
在还进一步的实施方式中,所述填充组合物可进一步包含催化剂和消泡剂。
在还进一步的实施方式中,所述催化剂可以相对于树脂重量为小于30份/100份树脂(phr)的量添加。
在还进一步的实施方式中,所述催化剂可为选自如下的至少一种:苄基二甲基胺(BDMA)、三氟化硼单乙基胺络合物(BF3-MEA)、二甲基氨基甲基苯酚(DMP)以及二甲基苯胺(DMBA)。
在还进一步的实施方式中,所述消泡剂可为选自如下的至少一种:丙烯酸酯低聚物、聚乙二醇、甘油酯、聚丙二醇、二甲基硅氧烷、二甲基硅油、磷酸三丁酯以及聚二甲基硅氧烷。
在本发明的另外的实施方式中,半导体装置包括:形成有第一导电图案的第一基板;形成有设置成面向所述第一导电图案的第二导电图案的第二基板;以及使第一和第二导电图案电连接的连接图案,其中该连接图案包括填充组合物,所述填充组合物包含包括Cu或Ag的颗粒、焊剂粉、以及所述包括Cu或Ag的颗粒和所述焊剂粉分散于其中的包含高分子化合物、硬化剂和还原剂的树脂;所述硬化剂包括胺和/或酸酐;且所述还原剂包括羧基。
在一些实施方式中,所述焊剂粉可为选自Sn、Bi、In、Ag、Pb、Cu、以及它们的合金的至少一种,并且使Cu颗粒电连接。
在另外一些实施方式中,所述Cu颗粒可占所述填充组合物的约5体积%~约40体积%;且所述焊剂粉可占所述填充组合物的约5体积%~约40体积%。
在本发明另一些实施方式中,制造半导体装置的方法包括:制备形成有导电图案的第一基板;在所述第一基板上形成预连接图案;制备形成有第二导电图案的第二基板;安置所述第二基板以使所述第二导电图案接触所述预连接图案;以及通过向所述预连接图案施加热量而形成使所述第一和第二导电图案电连接的连接图案,其中所述预连接图案包括填充组合物,所述填充组合物包含包括Cu或Ag的颗粒、焊剂粉、以及所述包括Cu或Ag的颗粒和所述焊剂粉分散于其中的包含高分子化合物、硬化剂和还原剂的树脂;所述硬化剂包括胺和/或酸酐;且所述还原剂包括羧基。
在一些实施方式中,连接图案的形成可包括:经由向所述预连接图案施加热量,通过所述还原剂除去所述预连接图案中的氧化物;以及通过焊剂粉球的延伸而使所述Cu颗粒电连接。
附图说明
包括附图以提供对本发明的进一步理解,附图引入本说明书中并且构成本说明书的一部分。附图说明了本发明的示例性实施方式,并与说明书一起用于解释本发明的原理。在附图中:
图1是说明根据本发明实施方式的填充组合物的图;
图2A~2E是说明根据本发明实施方式的半导体装置的制造方法的截面图;以及
图3是说明实施例1~3以及比较例的填充组合物的接触电阻值的图。
具体实施方式
以下,将参考附图详细说明本发明的优选实施方式。然而,本发明可体现为不同形式,并且不应解释为限于本文中所阐述的实施方式。相反,提供这些实施方式使得该公开内容彻底和完整,并且向本领域技术人员全面传达本发明的范围。
附图中,为了说明的清楚起见,放大了层和区域的尺寸。还应理解,当一个层(或膜)被称为“在”另一层或基板“上”时,其可直接在所述另一层或基板上,或者还可存在中间层。还应理解,当一个层被称为“在”另一层“之下”时,其可直接在所述另一层之下,并且还可存在一个或多个中间层。此外,还应理解,当一个层被称为“在”两个层“之间”时,其可为所述两个层之间唯一的层,或者还可存在一个或多个中间层。相同的附图标记始终表示相同的元件。
此外,将使用作为本发明的理想的示例性视图的截面图对实施方式进行具体的描述。因此,示例性视图的形状可根据制造技术和/或容许误差而变化。因此,本发明的实施方式不限于示例性视图中所示的具体形状,而是可包括可根据制造方法而产生的其它形状。图中示例的区域具有通常的性质,并且用于图示半导体封装区域的具体形状。因此,这不应解释为限制本发明的范围。例如,图示为矩形的蚀刻区域可能具有圆形或曲线特征。而且,虽然例如第一和第二的术语用于描述本发明各个实施方式中的各种部件、组分、区域、层和/或部分,但是部件、组分、区域、层和/或部分不受这些术语限制。
在以下说明中,技术术语仅用于解释具体实施方式,而不限制本发明。单数形式的术语可包括复数形式,除非相反地指出。
以下,将结合附图说明本发明的示例性实施方式。
(填充组合物)
图1是说明根据本发明实施方式的填充组合物的图。
参考图1,填充组合物100可包含:第一颗粒104,第二颗粒102,以及包含硬化剂和还原剂的树脂110。
第一颗粒104可包括铜和/或银。如果颗粒104包括铜和银两者,则其不是化合物形式,而是混合物形式。第一颗粒104可具有片状结构。第一颗粒104的尺寸可为约1μm~约30μm。例如,如果第一颗粒有许多,则填充组合物100可包含分别具有显著不同直径的第一颗粒104。另外,第一颗粒104可占填充组合物总体积的约5体积%~约40体积%。
第二颗粒102可为包括金属的焊剂球。根据本发明的一些实施方式,第二颗粒102可为选自Sn、Bi、In、Ag、Pb、Cu、以及它们的合金的至少一种。例如,第二颗粒102可为选自60Sn/40Bi、52In/48Sn、97In/3Ag、57Bi/42Sn/1Ag、58Bi/42Sn、52Bi/32Pb/16Sn以及96.5Sn/3Ag/0.5Cu的至少一种。
第二颗粒102的直径可为约5nm~约50μm。例如,如果第二颗粒有许多,则填充组合物100可包含分别具有显著不同直径的第二颗粒102。而且,第二颗粒102可占填充组合物总体积的约5体积%~约40体积%。
根据本发明的实施方式,第一颗粒104和第二颗粒102两者的总体积可占填充组合物总体积的约30体积%~约50体积%。
树脂110可包含高分子化合物、硬化剂和还原剂。
所述高分子化合物可包括选自如下的至少一种单体:双酚A的二缩水甘油醚(DBEBA)、四缩水甘油基4,4’-二氨基二苯基甲烷(TGDDM)、其中
Figure BSA00000362859500051
异氰酸酯以及双马来酰亚胺。
所述硬化剂可包括胺和/或酸酐。根据本发明的一些实施方式,所述硬化剂可为选自如下的至少一种:间苯二胺(MPDA)、二氨基二苯基甲烷(DDM)、二氨基二苯基砜(DDS)、甲基纳迪克酸酐(MNA)、十二碳烯基琥珀酸酐(DDSA)、马来酸酐(MA)、琥珀酸酐(SA)、甲基四氢邻苯二甲酸酐(MTHPA)、六氢邻苯二甲酸酐(HHPA)、四氢邻苯二甲酸酐(THPA)以及均苯四甲酸二酐(PMDA)。
所述硬化剂可为约0.4当量~约1.2当量。即,所述硬化剂的官能团与单体的官能团的当量比可为约0.4~约1.2。
根据本发明的一些实施方式,如果所述硬化剂包括酸酐,则第二颗粒102可作为填充组合物100的固化催化剂。
所述还原剂可用于从填充组合物100中除去氧化物。而且,所述还原剂的重量可根据树脂110的还原性质和反应性质变化。根据本发明的实施方式,所添加的还原剂可相对于树脂110为少于约10份/100份树脂(phr)。单位phr表示每100份树脂重量所添加的材料的重量。例如,如果还原剂以相对于树脂110的重量为约10phr的量添加且树脂110的重量约为100g,则还原剂的重量约为10g。
所述还原剂可包括羧基(-COOH)材料。根据本发明的实施方式,所述还原剂可为选自戊二酸、苹果酸、壬二酸、松香酸、己二酸、抗坏血酸、丙烯酸和柠檬酸的至少一种。
由于所述还原剂具有从填充组合物100中除去氧化物的功能,所以当向填充组合物100施加热量时,可改善第一颗粒104和第二颗粒102之间的润湿性质。因此,除了由填充组合物100中的导电材料引起的物理接触之外,还由于改善的润湿性质,填充组合物100可具有优异的电导率。
根据本发明的一些实施方式,填充组合物100可进一步包含催化剂和消泡剂。
根据催化剂的重量,在向填充组合物100施加热量之后,催化剂决定了使第一颗粒104和第二颗粒102硬化所需的时间。根据本发明的一些实施方式,所添加的催化剂可少于树脂110的重量的约30phr。
所述催化剂可为选自苄基二甲基胺(BDMA)、三氟化硼单乙基胺络合物(BF3-MEA)、二甲基氨基甲基苯酚(DMP)以及二甲基苯胺(DMBA)的至少一种。
所述消泡剂可为选自丙烯酸酯低聚物、聚乙二醇、甘油酯、聚丙二醇、二甲基硅氧烷、二甲基硅油、磷酸三丁酯以及聚二甲基硅氧烷的至少一种。
(制造半导体装置的方法)
图2A~2E是说明根据本发明实施方式的半导体装置的制造方法的截面图。根据本发明的实施方式,半导体装置可包括由图1中所示的填充组合物形成的连接图案。
参考图2A,可制备包括第一导电图案202的第一基板200。
第一基板200可为包括半导体芯片的基板。第一导电图案202可电连接到半导体芯片。
根据本发明的实施方式,第一导电图案202可形成在第一基板200上。在这种情况下,第一导电图案202可具有从第一基板200凸出的结构。
根据本发明的另一实施方式,第一导电图案202形成在第一基板200中,使得可仅暴露第一导电图案202的顶表面。在这种情况下,第一导电图案202的顶表面以及第一基板200的顶表面可处于基本上相同的水平上。
参考图2B,可形成电连接到第一导电图案202的预连接图案100。更详细地,可使预连接图案100的一侧形成为与第一导电图案202和第一基板200接触。
预连接图案100可包括图1的填充组合物100。简单来讲,填充组合物100可包括铜和银的颗粒104、焊剂粉102、由高分子化合物、硬化剂和还原剂形成的树脂110。根据本发明实施方式的填充组合物100的包括铜和银的颗粒104以及焊剂粉102可分别对应于图1的第一颗粒和第二颗粒。
参考图2C,可制备包括第二导电图案206的第二基板204。
第二基板204可为电路基板。电路基板的一个实例包括印刷电路板(PCB),其中铜箔的电路图案在由增强玻璃纤维或环氧树脂形成的芯材的一侧。电路图案可包括用于提供用于与第一基板200交换数据的电信号路径的图案、用于为第一基板200或接地输送功率的图案以及用于连接到外部端子的图案。根据一个实施方式,第二导电图案206可形成在第二基板204上。根据本发明的另一实施方式,第二导电图案206可形成在第二基板204中。
参考图2D,安置第二基板204以使第二导电图案206接触预连接图案100。
这样,第一导电图案202设置为接触预连接图案100的一侧,并且第二导电图案206可设置为接触预连接图案100的另一侧。
参考图2E,通过加热图2D的预连接图案100,可形成使第一导电图案202和第二导电图案206电连接的连接图案210。
根据本发明的实施方式,如果加热预连接图案100,则填充结构中的焊剂球212熔融,由此可使包括铜或银的颗粒104电连接。例如,如果焊剂球212包括58Sn/42Bi,则焊剂球212的熔融温度可为约150℃。因此,当在超过约150℃的温度下加热预连接图案100时,焊剂球212熔融并因此可使包括铜或银的颗粒104电连接。
根据另一实施方式,可通过物理挤压第二基板204并且同时进行以上加热工艺而形成连接图案210。
而且,当加热预连接图案100时,填充结构中的还原剂可除去预连接图案100中的氧化物。因此,可改善包括铜或银的颗粒104和焊剂球212之间的润湿性质,使得焊剂球212可更有效地电连接至包括铜或银的颗粒104。此外,由于连接图案210中的氧化物被除去,可改善热特性。
(组合物实施例)
通过混合基于环氧的双酚A二缩水甘油醚(DGEBA)和铜颗粒、58Sn/42Bi、硬化剂、催化剂和还原剂而制造用于氧化物除去功能和固化反应的填充组合物。
更详细地,通过将10体积%(基于含有铜颗粒的最终填充组合物)的58Sn/42Bi与100重量%的树脂(包括20重量%的苹果酸以及DGEBA、相对于环氧具有0.8当量比的DDS)、0.5重量%的BF3MEA混合而形成初始的填充组合物。这里,58Sn/42Bi的直径约为10μm。
在实施例1中,通过向所述初始的填充组合物中添加20体积%(基于含有铜颗粒的最终填充组合物)的铜颗粒而制备组合物。在实施例2中,通过向所述初始的填充组合物中添加25体积%的铜颗粒而制备组合物。在实施例3中,通过向所述初始的填充组合物中添加27体积%的铜颗粒而制备组合物。这里,各铜颗粒具有约3μm的直径。
在比较例中,制备包括树脂和约2μm~约10μm的银颗粒的填充组合物。银部分(piece)占填充组合物的约30体积%,和树脂占填充组合物的约70体积%。
使实施例1~3以及比较例的各填充组合物介于包括第一导电图案的第一基板和包括第二导电图案的第二基板之间,然后将其在约70℃/min的加热条件下加热到约160℃。1分钟后,测量电接触电阻。
图3是说明实施例1~3以及比较例的填充组合物的电阻值的图,其中X轴表示填充组合物,且Y轴表示电阻值。单位是毫欧姆(mΩ)。
参考图3,根据比较例,包括银颗粒的填充组合物的电阻值小于实施例1~3的填充组合物的电阻值。
而且,在实施例1~3中,随着填充组合物中铜颗粒的含量增加,接触电阻值降低。具体地,实施例1的填充组合物具有约488mΩ的电阻值,实施例2的填充组合物具有约286mΩ的电阻值,且实施例3的填充组合物具有约45mΩ的电阻值。
根据本发明的实施方式,通过将包括铜而不是包括银的填充组合物应用到半导体装置,可以提高成本效益。另外,通过在填充组合物中使用还原剂除去氧化物,可改善第一和第二颗粒中的润湿性质,使得可改善半导体装置的导热和导电特性。
应认为以上公开的主题是说明性的而非限制性的,且所附权利要求旨在涵盖所有落入本发明的真实精神和范围内的改进、增强和其它实施方式。因此,在法律允许的最大程度上,本发明的范围应由所附权利要求及其等同物的最宽泛的可容许的解释来确定,且不应受以上具体描述的束缚或限制。

Claims (17)

1.填充组合物,包含:
包括Cu和/或Ag的第一颗粒;
使所述第一颗粒电连接的第二颗粒;以及
所述第一和第二颗粒分散于其中的包含高分子化合物、硬化剂以及还原剂的树脂,
其中所述硬化剂包括胺和/或酸酐,且所述还原剂包括羧基,
所述填充组合物还包含催化剂和消泡剂,其中所述催化剂以相对于所述树脂重量为小于30份/100份树脂(phr)的量添加,和其中所述催化剂为选自如下的至少一种:苄基二甲基胺(BDMA)、三氟化硼单乙基胺络合物(BF3-MEA)、二甲基氨基甲基苯酚(DMP)以及二甲基苯胺(DMBA)。
2.权利要求1的填充组合物,其中:
所述第一颗粒占所述组合物的5体积%~40体积%;且
所述第二颗粒占所述组合物的5体积%~40体积%。
3.权利要求1的填充组合物,其中所述第一和第二颗粒占所述组合物的30体积%~50体积%。
4.权利要求1的填充组合物,其中所述第二颗粒为选自如下的至少一种:Sn、Bi、In、Ag、Pb、Cu、及它们的合金。
5.权利要求1的填充组合物,其中所述第二颗粒为选自如下的至少一种:60Sn/40Bi、52In/48Sn、97In/3Ag、57Bi/42Sn/1Ag、58Bi/42Sn、52Bi/32Pb/16Sn以及96.5Sn/3Ag/0.5Cu。
6.权利要求1的填充组合物,其中所述高分子化合物包括选自如下的至少一种单体:双酚A的二缩水甘油醚、四缩水甘油基4,4'-二氨基二苯基甲烷(TGDDM)、其中
Figure FSB0000120199760000011
Figure FSB0000120199760000012
(triDDM)、异氰酸酯以及双马来酰亚胺。
7.权利要求1的填充组合物,其中所述硬化剂具有为所述高分子化合物的0.4~1.2的当量。
8.权利要求1的填充组合物,其中所述硬化剂为选自如下的至少一种:间苯二胺(MPDA)、二氨基二苯基甲烷(DDM)、二氨基二苯基砜(DDS)、甲基纳迪克酸酐(MNA)、十二碳烯基琥珀酸酐(DDSA)、马来酸酐(MA)、琥珀酸酐(SA)、甲基四氢邻苯二甲酸酐(MTHPA)、六氢邻苯二甲酸酐(HHPA)、四氢邻苯二甲酸酐(THPA)以及均苯四甲酸二酐(PMDA)。
9.权利要求1的填充组合物,其中所述还原剂以相对于所述树脂重量为小于10份/100份树脂(phr)的量添加。
10.权利要求1的填充组合物,其中所述还原剂为选自如下的至少一种:戊二酸、苹果酸、壬二酸、松香酸、己二酸、抗坏血酸、丙烯酸和柠檬酸。
11.权利要求1的填充组合物,其中所述第一颗粒的直径为1μm~30μm,且所述第二颗粒的直径为5nm~100μm。
12.权利要求1的填充组合物,其中所述消泡剂为选自如下的至少一种:丙烯酸酯低聚物、聚乙二醇、甘油酯、聚丙二醇、二甲基硅氧烷、二甲基硅油、磷酸三丁酯以及聚二甲基硅氧烷。
13.半导体装置,包括:
形成有第一导电图案的第一基板;
形成有设置成面向所述第一导电图案的第二导电图案的第二基板;以及
使所述第一和第二导电图案电连接的连接图案,
其中所述连接图案包括填充组合物,所述填充组合物包含包括Cu或Ag的颗粒、焊剂粉、以及所述包括Cu或Ag的颗粒和所述焊剂粉分散于其中的包含高分子化合物、硬化剂和还原剂的树脂;所述硬化剂包括胺和/或酸酐;且所述还原剂包括羧基,
所述填充组合物还包含催化剂和消泡剂,其中所述催化剂以相对于所述树脂重量为小于30份/100份树脂(phr)的量添加,和其中所述催化剂为选自如下的至少一种:苄基二甲基胺(BDMA)、三氟化硼单乙基胺络合物(BF3-MEA)、二甲基氨基甲基苯酚(DMP)以及二甲基苯胺(DMBA)。
14.权利要求13的半导体装置,其中所述焊剂粉为选自Sn、Bi、In、Ag、Pb、Cu、及它们的合金的至少一种,并且使Cu颗粒电连接。
15.权利要求13的半导体装置,其中:
所述Cu颗粒占所述填充组合物的5体积%~40体积%;且
所述焊剂粉占所述填充组合物的5体积%~40体积%。
16.制造半导体装置的方法,该方法包括:
制备形成有导电图案的第一基板;
在所述第一基板上形成预连接图案;
制备形成有第二导电图案的第二基板;
安置所述第二基板以使所述第二导电图案接触所述预连接图案;和
通过向所述预连接图案施加热量而形成使所述第一和第二导电图案电连接的连接图案,
其中所述预连接图案包括填充组合物,所述填充组合物包含包括Cu或Ag的颗粒、焊剂粉、以及所述包括Cu或Ag的颗粒和所述焊剂粉分散于其中的包含高分子化合物、硬化剂和还原剂的树脂;所述硬化剂包括胺和/或酸酐;且所述还原剂包括羧基,
所述填充组合物还包含催化剂和消泡剂,其中所述催化剂以相对于所述树脂重量为小于30份/100份树脂(phr)的量添加,和其中所述催化剂为选自如下的至少一种:苄基二甲基胺(BDMA)、三氟化硼单乙基胺络合物(BF3-MEA)、二甲基氨基甲基苯酚(DMP)以及二甲基苯胺(DMBA)。
17.权利要求16的方法,其中连接图案的形成包括:
经由向所述预连接图案施加热量,通过所述还原剂除去所述预连接图案中的氧化物;以及
通过焊剂粉球的延伸使Cu颗粒电连接。
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