CN102057475B - 半导体装置的制造方法以及半导体装置 - Google Patents

半导体装置的制造方法以及半导体装置 Download PDF

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CN102057475B
CN102057475B CN2009801207336A CN200980120733A CN102057475B CN 102057475 B CN102057475 B CN 102057475B CN 2009801207336 A CN2009801207336 A CN 2009801207336A CN 200980120733 A CN200980120733 A CN 200980120733A CN 102057475 B CN102057475 B CN 102057475B
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semiconductor device
thermosetting resin
manufacture method
paste compositions
cooling rate
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CN102057475A (zh
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桂山悟
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract

本发明提供一种半导体装置的制造方法，其特征在于，具有：涂布工序，在基板或半导体元件的至少一方涂布具有焊剂活性的膏状热固性树脂组合物；接合工序，将所述基板和所述半导体元件介由所述膏状热固性树脂组合物进行电接合；固化工序，加热所述膏状热固性树脂组合物从而进行固化；冷却工序，在所述固化工序之后，以10(℃/小时)以上且50(℃/小时)以下的冷却速度进行冷却。

Description

半导体装置的制造方法以及半导体装置
技术领域
本发明涉及半导体装置的制造方法以及半导体装置。
背景技术
近年来，伴随着电脑、手机的小型化、薄型化、高性能化，半导体封装也日益多样化，尤其是为了提高电信号的传送速度而将半导体元件利用焊锡凸块等的凸块进行面连接的组装方法日益多样化。作为这种组装方法，研究过为了进一步提高电信号的传送而用金属凸块进行垂直连接的方法。
另一方面，半导体元件布线设计的窄节距化也在发展，而为了维持其特性，半导体元件的结构也呈复杂化，进而半导体元件自身变得越来越脆弱。
另外，从如今的环境问题的倾向出发凸块所使用的金属本身也受无铅化等活动的影响，该凸块的保护也已变得不易。
因此，对于该凸块连接所使用的密封材料(底部填充材料)的特性要求也变得日益严格，以同时能够保护凸块和保护芯片为必须条件。为了保护凸块，优选的是底部填充材料具有高弹性率，而为了保护芯片(降低芯片的翘曲)，优选的是底部填充材料具有低弹性率。即，关于凸块保护和芯片保护，对底部填充材料要求相反的特性。为了解决这种课题，进行过实现底部填充材料物性平衡的研究(例如，参考专利文献1以及2)。
但是，现状是由于半导体封装的复杂化、大小的限制等，仅靠底部填充材料的物性平衡，则对半导体装置的高性能化也有限，所以不得不进行结构本身的再设计，甚至是为了实现高可靠性还要采取延迟无铅化的方法。
专利文献1：日本特开平07-335791号公报
专利文献2：日本特开平10-204259号公报
发明内容
本发明提供一种半导体装置的制造方法，其能够保护凸块的同时，又能够通过降低翘曲的产生而保护半导体元件。
通过下述(1)～(18)中所述的本发明来实现这种目的。
(1)一种半导体装置的制造方法，具有：
涂布工序，在基板或半导体元件的至少一方涂布具有焊剂活性的膏状热固性树脂组合物，
接合工序，将所述基板和所述半导体元件介由所述膏状热固性树脂组合物进行电接合，
固化工序，加热所述膏状热固性树脂组合物从而进行固化，
冷却工序，在所述固化工序之后，以10(℃/小时)以上且50(℃/小时)以下的冷却速度进行冷却。
(2)如(1)所述的半导体装置的制造方法，其中，在所述固化工序中，所述膏状热固性树脂组合物的固化温度为Tc(℃)时，
所述冷却工序是在Tc(℃)以下且(Tc-90)(℃)以上的温度范围，以所述冷却速度进行冷却。
(3)如(2)所述的半导体装置的制造方法，其中，所述固化温度(Tc)为150(℃)时，
所述冷却工序是在150℃以下且60℃以上的温度范围，以所述冷却速度进行冷却。
(4)如(2)所述的半导体装置的制造方法，其中，在小于(Tc-90)(℃)的温度范围内，以60(℃/小时)以上且120(℃/小时)以下的冷却速度进行冷却。
(5)如(1)所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度(Tg)以下的区域的、所述基板的厚度方向线膨胀系数(α1)为20ppm以下。
(6)如(1)所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度(Tg)以下的区域的、所述基板的厚度方向线膨胀系数(α1)为5ppm以上。
(7)如(1)所述的半导体装置的制造方法，其中，所述固化工序后的所述膏状热固性树脂组合物的固化物的玻璃转移温度为50℃以上且150℃以下。
(8)如(2)所述的半导体装置的制造方法，其中，所述固化工序后的所述膏状热固性树脂组合物的固化物的玻璃转移温度为50℃以上且150℃以下。
(9)如(8)所述的半导体装置的制造方法，其中，所述冷却工序是在Tc(℃)以下且(所述膏状热固性树脂组合物的固化物的所述玻璃转移温度-20)(℃)以上的温度范围，以所述冷却速度进行冷却。
(10)如(1)所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度(Tg)以下的区域的、所述固化工序后的所述膏状热固性树脂组合物的固化物的线膨胀系数为5ppm/℃以上且60ppm/℃以下。
(11)如(1)所述的半导体装置的制造方法，其中，所述冷却工序中，所述冷却速度为25(℃/小时)以下。
(12)如(1)所述的半导体装置的制造方法，其中，使用具有第一导电部的所述基板和具有第二导电部的所述半导体元件，
所述接合工序是以在用所述膏状热固性树脂组合物进行覆盖的状态下使所述第一导电部与所述第二导电部进行焊锡连接的方式将所述基板与所述半导体元件电接合。
(13)如(12)所述的半导体装置的制造方法，其中，所述第一导电部以及所述第二导电部的至少一方为焊锡凸块。
(14)如(1)所述的半导体装置的制造方法，其中，所述膏状热固性树脂组合物含有热固性树脂和焊剂活性剂。
(15)如(14)所述的半导体装置的制造方法，其中，所述热固性树脂的含量为所述膏状热固性树脂组合物整体的5重量％以上且70重量％以下。
(16)如(14)所述的半导体装置的制造方法，其中，所述焊剂活性剂的含量为所述膏状热固性树脂组合物整体的0.1重量％以上且50重量％以下。
(17)如(14)所述的半导体装置的制造方法，其中，所述焊剂活性剂在分子中具有羧基以及酚型羟基。
(18)一种半导体装置，是通过(1)至(17)中任一项所述的半导体装置的制造方法制得。
根据本发明，可提供一种半导体装置的制造方法，其能够保护凸块的同时，又能够通过减少翘曲的发生而保护芯片。
附图说明
将通过下述优选实施方式以及与其相应的下述附图，进一步明确上述目的、其他目的、特征以及优点。
图1是表示半导体装置的制造方法的一例的剖面图。
图2是表示半导体装置的制造方法的一例的剖面图。
图3是表示半导体装置的制造方法的一例的剖面图。
图4是表示半导体装置的制造方法的一例的剖面图。
图5是表示半导体装置的制造方法的一例的剖面图。
具体实施方式
下面对本发明的半导体装置的制造方法进行详细说明。
本发明的半导体装置的制造方法，其特征在于，具有涂布工序，是在基板或半导体元件的至少一方涂布具有焊剂活性的膏状热固性树脂组合物；接合工序，是将所述基板和所述半导体元件介由所述膏状热固性树脂组合物进行电接合；固化工序，是加热所述膏状热固性树脂组合物从而进行固化；冷却工序，是在所述固化工序之后，以10(℃/小时)以上且50(℃/小时)以下的冷却速度进行冷却(以下，有时也将(℃/小时)表示为(℃/h))。
图1至5是示意表示本发明的半导体装置的制造方法的剖面图。
以下，说明本发明的半导体装置的制造方法。
首先，如图1所示，准备基板1(电路基板)。在基板1的一侧(图1中的上侧)形成有布线图案11，设置有电极垫部12。另外，在基板1的另一侧(图1中的下侧)，设置有导体层13用于可在以后形成电路图案。
在25℃以上且玻璃转移温度(Tg)以下的区域的、基板1的厚度方向热膨胀系数无特别限制，但优选的是20ppm以下，特别优选的是5～18ppm(以下，“～”在没有特别说明的情况下，表示包括上限值和下限值)。通过使其在该范围内，可抑制由于与芯片的线膨胀系数差而产生的应力，提高翘曲。
为了得到这种基板1，可采用在构成基板1的树脂组合物中多配合无机填充材料的方法，使构成基板1的材料具有高弹性率的方法等。
(涂布工序)
接着，以覆盖这种基板1的电极垫部12的方式，涂布具有焊剂活性的膏状热固性树脂组合物21(图2、图3)。作为涂布装置无特别限制，例如可使用图2所示的注射器2。
具有焊剂活性的膏状热固性树脂组合物21的涂布量无特别限制，例如，如图3所示，至少覆盖电极垫部12(连接部分)的涂布量即可。
作为该具有焊剂活性的膏状热固性树脂组合物21，例如可举出含有热固性树脂和焊剂活性剂的树脂组合物。
作为所述热固性树脂，例如可使用环氧树脂、氰酸酯树脂、双马来酰亚胺树脂、聚氨酯树脂、聚丁二烯树脂、硅树脂、酚醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯树脂、醇酸树脂等至今所知的热固性树脂。更加优选的是环氧树脂。基于半导体元件的密封目的，优选杂质尤其是离子性杂质少的树脂。
作为所述环氧树脂具体可列举双酚A型环氧树脂、双酚F型环氧树脂、双酚AD型环氧树脂、双酚E型环氧树脂等双酚型环氧树脂；线型苯酚醛清漆型环氧树脂、线型甲酚醛清漆型环氧树脂等线型酚醛清漆型环氧树脂；N，N-二(缩水甘油基)苯胺、N，N-二(缩水甘油基)甲苯胺、二氨基二苯基甲烷型缩水甘油胺、氨基苯酚型缩水甘油胺等芳香族缩水甘油胺型环氧树脂；对苯二酚型环氧树脂；联苯芳烷基型环氧树脂等联苯型环氧树脂；二苯乙烯型环氧树脂；三苯酚基甲烷型环氧树脂；三苯酚基丙烷型环氧树脂；烷基改性三苯酚基甲烷型环氧树脂；含有三嗪核的环氧树脂；二环戊二烯改性苯酚型环氧树脂；萘酚型环氧树脂；萘型环氧树脂；具有亚苯基和/或亚联苯基骨架的苯酚芳烷基型环氧树脂、具有亚苯基和/或亚联苯基骨架的萘酚芳烷基型环氧树脂等芳烷基型环氧树脂等的环氧树脂；乙烯基环己烯二氧化物、二环戊二烯氧化物、脂环族双环氧己二酸酯等脂环式环氧化物等的脂肪族环氧树脂；含溴环氧树脂等。
所述热固性树脂(环氧树脂)的含量无特别限制，优选为膏状热固性树脂组合物21整体的5～70重量％，特别优选为10～50重量％。若含量在所述范围内，则玻璃转移温度、弹性率等热及机械特性特别优异。
所述焊剂活性剂是指具有还原金属表面的氧化膜，使金属表面暴露这样的作用(焊剂作用)的物质。
作为所述焊剂活性剂，例如可举出酚系化合物、酸或酸酐系化合物、胺系化合物、酰胺系化合物等咪唑类、活性松脂等。
作为所述酚系化合物，例如可举出四甲基双酚A、邻苯二酚、间苯二酚、对苯二酚、二甲苯酚、双酚A、双酚F、双酚AP、双酚S、双酚Z、二甲基双酚A、二甲基双酚F、四甲基双酚A、四甲基双酚F、双酚、四甲基双酚、二羟基苯基醚、二羟基二苯甲酮、邻羟基苯酚、间羟基苯酚、对羟基苯酚、酚醛清漆树脂或邻甲酚醛清漆树脂的多酚类、三羟基苯基甲烷等三苯酚类、具有萘骨架的酚类等。
作为所述酸或酸酐类化合物，例如可举出甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、十七烷酸、硬脂酸、油酸、亚油酸、亚麻酸、花生四烯酸、二十二碳六烯酸、二十碳五烯酸、草酸、丙二酸、琥珀酸、苯甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、水杨酸、没食子酸、苯六甲酸、肉桂酸、丙酮酸、乳酸、苹果酸、枸橼酸、富马酸、马来酸、乌头酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、氨基酸、硝基羧酸、松香酸、邻苯二甲酸酐、偏苯三酸酐、均苯四酸酐、马来酸酐、二苯甲酮四羧酸酐、乙二醇双偏苯三酸酯、氯茵酸酐、四溴邻苯二甲酸酐、四氢化邻苯二甲酸酐、甲基四氢化邻苯二甲酸酐、纳丁酸酐甲酯、六氢化邻苯二甲酸酐、甲基六氢化邻苯二甲酸酐、十二烷基琥珀酸酐、聚己二酸酐、聚壬二酸酐、聚癸二酸酐、聚(乙基十八烷二酸)酐、聚(苯基十六烷二酸)酐、甲基纳迪克酸酐、三烷基四氢化邻苯二甲酸酐、甲基环己烯二羧酸酐等。
另外，也可以是具有酚型羟基和羧基两者的化合物。具体而言，可列举2，3-二羟基苯甲酸、2，4-二羟基苯甲酸、2，5-二羟基苯甲酸、2，6-二羟基苯甲酸、3，4-二羟基苯甲酸、没食子酸、1，4-二羟基-2-萘甲酸、3，5-二羟基-2-萘甲酸、3，7-二羟基-2-萘甲酸、酚酞、双酚酸等。
作为所述胺系化合物，例如可举出乙二胺、1，3-二氨基丙烷、1，4-二氨基丁烷、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、二亚丙基二胺、二乙基氨基丙基胺、三(甲基氨基)己烷、二甲基氨基丙基胺、二乙基氨基丙基胺、甲基亚氨基双丙基胺、六亚甲基二胺、二氨基二苯基甲烷、二氨基二苯基砜、异佛尔酮二胺、
Figure BPA00001266017400071
烷二胺、异佛尔酮二胺、二(4-氨基-3-甲基环己基)甲烷(ピス(4-アミノ-3-メチルジンクロヘキシル)メタン)、二氨基环己基甲烷(ジアミノジンクロヘキシルメタン)、N-氨基乙基哌嗪、3，9-双(3-氨基丙基)2，4，8，10-四氧杂螺(5，5)十一碳烷、2，5-二甲基六亚甲基二胺、三甲基六亚甲基二胺、亚氨基双丙基胺、双(六亚甲基)三胺、间苯二甲胺、间苯二胺、二氨基二乙基苯基甲烷、聚醚二胺等。
作为所述酰胺系化合物，例如可举出由氰基胍、亚麻酸的二聚物与乙二胺合成的聚酰胺树脂等。
作为所述咪唑类，可列举2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基-4，5-二羟基甲基咪唑、2-苯基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑等。
这些不仅可作为焊剂活性剂使用，而且，与环氧树脂发生交联反应的物质还可以做为固化剂使用。
所述焊剂活性剂的含量，无特别限制，优选的是膏状热固性树脂组合物21整体的0.1～50重量％，特别优选的是1～40重量％。若含量在所述范围内，则焊剂活性优异，尤其是作为固化剂使用时，除玻璃转移温度、弹性率等热及机械特性优异以外，固化性也优异。
在该焊剂活性剂中，优选具有氧化还原作用的同时，还可用于与环氧树脂等热固性树脂的固化反应、并参加交联的化合物(具有焊剂活性的固化剂)。由此，可以不需要焊剂清洗，并且提高长久可靠性。
作为该具有焊剂活性的固化剂，例如可举出酚化合物、酸酐、咪唑类、具有酚型羟基和羧基两者的化合物等。
具有焊剂活性的膏状热固性树脂组合物21中，除了含有上述热固性树脂、焊剂活性剂以外，还可含有固化剂、填料、偶联剂等填充剂。
作为所述填料，例如可举出滑石、烧成粘土、未烧成粘土、云母、玻璃等硅酸盐；氧化钛、氧化铝、熔融二氧化硅(熔融球状二氧化硅、熔融破碎二氧化硅)、合成二氧化硅、结晶二氧化硅等二氧化硅粉末等氧化物；碳酸钙、碳酸镁、水滑石等碳酸盐；氢氧化铝、氢氧化镁、氢氧化钙等氢氧化物；硫酸钡、硫酸钙、亚硫酸钙等硫酸盐或亚硫酸盐；硼酸锌、偏硼酸钡、硼酸铝、硼酸钙、硼酸钠等硼酸盐；氮化铝、氮化硼、氮化硅等氮化物等无机填充剂。另外，也可使用有机填充剂。其中，从能够提高液状密封树脂组合物的耐热性、耐湿性、强度等的可靠性出发，优选熔融二氧化硅、结晶二氧化硅、合成二氧化硅粉末。所述填充剂的形状，无特别限制，从粘度·流动特性的观点出发，优选的是形状为球状。
所述填料的含量，无特别限制，优选的是膏状热固性树脂组合物21整体的20～90重量％，特别优选的是30～85重量％。如果含量小于所述下限值时，则有时会降低使低线膨胀化和低吸水率化等的可靠性提高的效果，如果超过所述上限值时，则有时会出现热固性树脂组合物的粘度增加，操作性降低，以及凸块连接性降低。
作为所述偶联剂，例如可举出乙烯基三氯硅烷、乙烯基三甲氧基甲硅烷、乙烯基三乙氧基硅烷、乙烯基三-(β-甲氧基乙氧基)硅烷、β-(3，4-环氧环己基)乙基三甲氧基硅烷、γ-丙烯酰氧基丙基甲基二甲氧基硅烷、γ-丙烯酰氧基丙基三甲氧基硅烷、γ-丙烯酰氧基丙基甲基二乙氧基硅烷、γ-丙烯酰氧基丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、γ-甲基丙烯酰氧基丙基三乙氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基甲基二乙氧基硅烷、γ-环氧丙氧基丙基三乙氧基硅烷、对苯乙烯基三甲氧基硅烷、N-β(氨基乙基)γ-氨基丙基甲基二甲氧基硅烷、N-β(氨基乙基)γ-氨基丙基三甲氧基硅烷、N-β(氨基乙基)γ-氨基丙基三乙氧基硅烷、γ-氨基丙基三乙氧基硅烷、γ-苯基-γ-氨基丙基三甲氧基硅烷等，可单独使用或混合使用。这些偶联剂中，优选胺末端型硅烷偶联剂。由此，可提高流动性和密合力。
所述偶联剂的含量，无特别限制，优选的是膏状热固性树脂组合物21整体的0.1～20重量％，特别优选的是0.3～10重量％。如果含量小于所述下限值时，密合力和流动性可能降低，如果超过所述上限值时，挥发空隙性(揮発ボイド性)可能降低。
(接合工序)
接着，用倒装式焊接器32，将半导体元件3搭载在基板1上。这时，以半导体元件3的焊锡凸块31(第一导电部)与基板1的电极垫部12(第二导电部)相抵接的方式，一边进行定位，一边进行搭载(图4)。在搭载时，一边熔融焊锡凸块31，一边与电极垫部12电连接。这时，由于膏状热固性树脂组合物21具有焊剂活性，因此，可一边去除焊锡凸块31表面的氧化膜，一边进行焊锡连接(图5)。换言之，在本接合工序中，以在用膏状热固性树脂组合物21进行覆盖的状态下使焊锡凸块31与电极垫部12进行焊锡连接的方式将基板1与半导体元件3电接合。
对其连接条件无特别限制，优选的是将倒装式焊接器32的设定温度设定为焊锡凸块31所使用的焊锡材料熔点的+10℃～100℃，加热1～30秒。这时，更优选的是仅从半导体元件3侧进行加热。由此，可减少对基板的热压，减少由与芯片的线膨胀系数差而产生的翘曲，进而可抑制来自基板的挥发性空隙(揮発性ボイド)。
其中，在本实施方式中，第一导电部以及第二导电部各自并不限于焊锡凸块31以及电极垫部12，至少一方为焊锡凸块即可，也可以同时为焊锡凸块。
(固化工序)
接着，加热膏状热固性树脂组合物21，使其固化。由此，可将焊锡凸块31与电极垫部12之间密封，提高连接可靠性。作为加热固化膏状热固性树脂组合物21的装置无特别限制，例如，可使用烘炉。
加热条件与所使用的热固性树脂相关，无特别限制，优选的是100～200℃×30～180分钟，特别优选的是120～170℃×60～150分钟。例如，作为加热温度，可以是膏状热固性树脂组合物21的固化物的玻璃转移温度以上的温度。
对于固化工序后的具有焊剂活性的膏状热固性树脂组合物21的固化物的玻璃转移温度，无特别限制，优选20℃～300℃，特别优选50℃～150℃。通过使玻璃转移温度在所述下限值以上，能够更有效地保护凸块。另外，通过在所述上限值以下，能够有效抑制在基板1和半导体元件3接合后形成的、由具有焊剂活性的膏状热固性树脂组合物21构成的焊脚的裂缝。
对于固化工序后的具有焊剂活性的膏状热固性树脂组合物21的固化物的、在25℃以上玻璃转移温度以下区域的平均线膨胀系数(α1)，无特别限制，优选5ppm/℃～60ppm/℃，特别优选15ppm/℃～40ppm/℃。通过使玻璃转移温度在所述范围内，可使具有焊剂活性的膏状热固性树脂组合物21的固化物的玻璃转移温度以下的平均线膨胀系数接近于凸块(焊锡凸块31)的线膨胀系数。因此，可有效地抑制凸块裂缝。
固化工序后的具有焊剂活性的膏状热固性树脂组合物21的固化物的玻璃转移温度以及线膨胀系数可通过以下方法进行测定。
将具有焊剂活性的膏状热固性树脂组合物21，在150℃固化3小时，制作4mm×4mm×10mm大小的样品。接着，使用TMA装置(SII公司制造)，以压缩负荷：10g，升温速度：10℃/分钟，测定温度范围：-100℃～300℃，算出玻璃转移温度及玻璃转移温度以下区域的平均线膨胀系数。
(冷却工序)
接着，在所述固化工序后，以10～50℃/h的冷却速度进行冷却。作为冷却方法，例如可举出继续使用在固化工序中使用的烘炉，设定该烘炉的冷却速度条件的方法。冷却速度，可以是恒定速度，也可以是可变速度。作为算出冷却速度方法，例如，通过将从固化工序刚刚完成后的环境中的温度减去冷却工序结束后的温度而得到的温度差，除以冷却时间从而得到。其中，温度，例如表示烘炉环境中的温度。
如此，通过以10～50℃/h的冷却速度(第一冷却速度)进行冷却，尤其是以恒定的冷却速度进行冷却，能够缓和冷却中的应力，减少翘曲。
以往的半导体装置的制造工序的一例中，如专利文献2所示，不进行冷却工序，在回流炉中实施焊接后，将半导体元件与布线基板之间的热固性树脂加热至120℃，使其固化，得到半导体装置。这样地，从生产率的观点考虑，固化后立即取出半导体装置，暴露于室温中。因此，半导体装置急速冷却，至少以100℃/h以上的冷却速度进行冷却。如此，作为粘弹性体的热固性树脂中，在内部和外部产生热分布，产生残留应力。换言之，产生由于急速冷却而引起的构成部件的热收缩，进而，由各构成部件的线膨胀系数的差而产生较大的应力。如此，在以往的半导体装置的制造工序中，由于因急速冷却而产生的应力而引起翘曲。
相对于此，在本发明的半导体装置的制造工序中，如上所述地进行冷却工序。进而，在固化工序之后，接着，以10～50℃/h的冷却速度进行冷却，使热收缩的方式变得缓慢，进而可缓和由构成部件的线膨胀系数的差引起的应力。因此，本发明中，可通过缓和冷却中的应力从而减少翘曲。
冷却速度(第一冷却速度)的下限值优选为15℃/h以上，更加优选为20℃/h以上。另外，冷却速度(第一冷却速度)的上限值优选为40℃/h以下，更加优选为30℃/h以下。通过使冷却速度在所述下限值以上，可进一步抑制翘曲的产生。另外，使冷却速度在所述上限值以下，可进一步抑制翘曲的产生。
本冷却工序中，控制冷却速度的温度范围(以下，有时称为控制范围)无特别限制，将固化工序中的膏状热固性树脂组合物21的固化温度设为Tc(℃)时，可以是Tc(℃)～(Tc-90)(℃)的温度范围。优选的是在该温度范围以所述第一冷却速度进行冷却。这是因为控制范围内的应力产生更加显著，所以通过控制温度范围从而翘曲产生的抑制效果特别优异。
所述第一冷却速度的控制范围，更具体而言，将固化温度(Tc)设为150(℃)时，则可以是150～60(℃)的温度范围，更优选的是可设为150～80(℃)的温度范围。优选的是在该温度范围以第一冷却速度进行冷却。尤其是，控制范围可以是Tc(℃)以下且(膏状热固性树脂组合物21的固化物的玻璃转移温度-20)(℃)以上的温度范围，具体而言，可以是150～(膏状热固性树脂组合物21的固化物的玻璃转移温度(Tg)-20)(℃)的温度范围。优选的是在该温度范围以所述第一冷却速度进行冷却。控制范围在该温度范围内时，翘曲的抑制尤其优异。
另外，将所述控制范围以外的冷却速度作为第二冷却速度。在该冷却速度的控制范围以外(尤其是在低温侧的范围以外，例如，小于(Tc-90)(℃)的温度范围)中，无特别限制，优选的是将第二冷却速度设为60～120℃/h，特别优选的是40～100℃/h。由此，缓和应力的效果与良好的生产率的平衡优异。
上述工序中，经过连接母板用焊锡凸块的形成和部件搭载等工序，可得到半导体装置。如此得到的半导体装置在保护凸块的同时，通过减少翘曲的产生从而可保护半导体元件。
实施例
以下，结合实施例及比较例，详细说明本发明，但本发明不限于此。
(实施例1)
1.膏状热固性树脂组合物的制备
称量70.9重量％的作为热固性树脂的双酚F型环氧树脂(大日本油墨化学工业(株)制，EXA-830LVP，环氧当量161)、21.3重量％的作为固化剂的线型酚醛清漆(住友DUREZ(株)制，商品编号PR-51470，软化点110℃)、7.1重量％的作为焊剂活性剂的酚酞(东京化成工业(株)制(熔点235℃))、和0.7重量％的作为固化促进剂的2-苯基-4-甲基咪唑(四国化成工业(株)制，2P4MZ)，使用3个辊进行分散混炼，真空下进行脱气处理，得到膏状热固性树脂组合物。
2.半导体装置的制造
将上述膏状热固性树脂组合物，涂布在形成有电路图案的电路基板上(作为芯材，SUMITOMO BAKELITE(株)公司制，商品编号ELC-4785GS，热膨胀系数(Tg以下)XY方向：11ppm，Z方向：16ppm)，接着，用倒装式焊接器将具有焊锡凸块的半导体元件(大小：纵15×横15×厚度0.725mm)在260℃，加热10秒钟进行搭载。接着，使用烘炉，在150℃，加热120分钟，固化膏状热固性树脂组合物。
接着，设定烘炉的冷却速度条件，在150～60℃的温度范围以25℃/h的冷却速度进行冷却后，以60℃/h左右进行冷却直到30℃附近，得到半导体装置。其中，温度表示烘炉环境中的温度。
(实施例2)
在半导体装置的制造工序中，除了使冷却速度成为如下之外，与实施例1同样地进行操作。
将150～60℃范围的冷却速度设为15℃/h。
(实施例3)
在半导体装置的制造工序中，除了使冷却范围成为如下之外，与实施例1同样地进行操作。
150～80℃范围的冷却速度与实施例1相同，小于80℃～30℃时，以1℃/分钟进行冷却。
(实施例4)
除了作为膏状热固性树脂组合物使用以下物质以外，与实施例1同样地进行操作。
称量76.3重量％的作为热固性树脂的双酚F型环氧树脂(大日本油墨化学工业(株)制，EXA-830LVP，环氧当量161)、22.9重量％的作为具有焊剂活性的固化剂的2，5-二羟基苯甲酸(东京化成工业制(熔点200～205℃))、0.8重量％的作为固化促进剂的2-苯基-4-甲基咪唑(四国化成工业(株)制)，使用3个辊进行分散混炼，真空下进行脱气处理，得到膏状热固性树脂组合物。
(实施例5)
在半导体装置的制造方法中，除了将膏状热固性树脂组合物不涂布在基板上，而涂布在半导体元件上以外，与实施例1同样地进行操作。
(实施例6)
除了作为基板使用以下物质以外，与实施例1同样地进行操作。
作为基板，使用芯材为BT(Mitsubishi Gas Chemical Company制，商品编号CCL-HL832HS，热膨胀系数(Tg以下)XY方向：15ppm，Z方向：55ppm)的物质。
(比较例1)
在半导体装置的制造工序中，除了将冷却速度设为如下之外，与实施例1同样地进行操作。
将150～60℃范围的冷却速度设为5℃/h。
(比较例2)
半导体装置的制造工序中，将下述膏状热固性树脂组合物注入到预先将半导体元件搭载在基板上而成的半导体装置中，得到半导体封装。
膏状热固性树脂组合物通过称量79.4重量％的作为热固性树脂的双酚F型环氧树脂(大日本油墨化学工业(株)制，EXA-830LVP，环氧当量161)、19.8重量％的作为固化剂的线型酚醛清漆、和0.8重量％的作为固化促进剂的2-苯基-4-甲基咪唑(四国化成工业(株)制)，使用3个辊进行分散混炼，真空下进行脱气处理而得到。
另外，固化工序后，以保持固化温度的状态，在烘炉中将半导体装置保持规定时间后，立即取出半导体装置，暴露在室温中，评价该半导体装置的翘曲。这时，固化温度为150℃，室温为25℃，冷却时间为30分钟左右，因此，考虑以约250℃/h以上的冷却速度进行冷却。评价半导体装置的结果为通过目视可确认翘曲的产生。
对于各实施例及比较例中得到的半导体装置，进行以下评价。同时表示评价项目与内容。将得到的结果示于表1。
1.半导体装置的翘曲
评价得到的半导体装置的翘曲与后述的耐回流试验后的半导体装置的翘曲。各符号如下所示。
◎：翘曲量为80μm以下。
○：翘曲量为超过80μm且100μm以下。
△：翘曲量为超过100μm且120μm以下。
×：翘曲量为超过120μm。
2.可靠性
通过评价以JEDEC级别3，260℃峰值SMT回流(3次)的条件进行耐回流试验后的、半导体装置的剥离性及连接性，进行可靠性评价。应予说明，评价以n＝20进行。各符号如下所示。
剥离性
◎：全部无剥离。
○：剥离产生率小于5％。
△：剥离产生率为5％以上且小于10％。
×：剥离产生率为10％以上。
连接性
◎：连接率为100％。
○：连接率为小于100％(8/10以上)且95％以上(2/10以下)。
△：连接率为超过80％且小于95％。
×：连接率为80％以下。
3.操作性
将比较例2的操作工时作为基准(100)，评价操作性。各符号如下所示。
◎：操作工时为50以上且75以下。
○：操作工时为超过75且95以下。
△：操作工时为超过95且105以下。
×：操作工时为超过105且150以下。
4.膏状热固性树脂组合物的固化物的玻璃转移温度以及线膨胀系数
将实施例中得到的膏状热固性树脂组合物在150℃固化3小时，制作4mm×4mm×10mm大小的样品。接着，使用TMA装置(SII公司制)，以压缩负荷：10g，升温速度：10℃/分钟，测定温度范围：-100℃～300℃，算出玻璃转移温度及玻璃转移温度以下区域的平均线膨胀系数。
(表1)
Figure BPA00001266017400171
从表1可知，实施例1～6中得到的半导体装置在制造后及耐回流试验后的两方面，翘曲小。
另外，实施例1～6的可靠性也优异。由此，表明可以保护焊锡凸块。
另外，实施例1～6的操作性也优异。

Claims (16)

1.一种半导体装置的制造方法，具有：
涂布工序，在基板或半导体元件的至少一方涂布具有焊剂活性的膏状热固性树脂组合物，
接合工序，将所述基板和所述半导体元件介由所述膏状热固性树脂组合物进行电接合，
固化工序，加热所述膏状热固性树脂组合物从而进行固化，
冷却工序，在所述固化工序之后，以10℃/小时以上且50℃/小时以下的冷却速度进行冷却，
其中，在所述固化工序中，所述膏状热固性树脂组合物的固化温度为Tc℃时，
所述冷却工序是在Tc℃以下且(Tc-90)℃以上的温度范围，以所述冷却速度进行冷却。
2.如权利要求1所述的半导体装置的制造方法，其中，所述固化温度Tc为150℃时，
所述冷却工序是在150℃以下且60℃以上的温度范围，以所述冷却速度进行冷却。
3.如权利要求1所述的半导体装置的制造方法，其中，在小于(Tc-90)℃的温度范围内，以60℃/小时以上且120℃/小时以下的冷却速度进行冷却。
4.如权利要求1所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度Tg以下的区域的、所述基板的厚度方向线膨胀系数α1为20ppm以下。
5.如权利要求1所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度Tg以下的区域的、所述基板的厚度方向线膨胀系数α1为5ppm以上。
6.如权利要求1所述的半导体装置的制造方法，其中，所述固化工序后的所述膏状热固性树脂组合物的固化物的玻璃转移温度为50℃以上且150℃以下。
7.如权利要求6所述的半导体装置的制造方法，其中，所述冷却工序是在Tc℃以下且(所述膏状热固性树脂组合物的固化物的所述玻璃转移温度-20)℃以上的温度范围，以所述冷却速度进行冷却。
8.如权利要求1所述的半导体装置的制造方法，其中，在25℃以上且玻璃转移温度Tg以下的区域的、所述固化工序后的所述膏状热固性树脂组合物的固化物的线膨胀系数为5ppm/℃以上且60ppm/℃以下。
9.如权利要求1所述的半导体装置的制造方法，其中，所述冷却工序中，所述冷却速度为25℃/小时以下。
10.如权利要求1所述的半导体装置的制造方法，其中，使用具有第一导电部的所述基板和具有第二导电部的所述半导体元件，
所述接合工序是以在用所述膏状热固性树脂组合物进行覆盖的状态下使所述第一导电部与所述第二导电部进行焊锡连接的方式将所述基板与所述半导体元件电接合。
11.如权利要求10所述的半导体装置的制造方法，其中，所述第一导电部以及所述第二导电部的至少一方为焊锡凸块。
12.如权利要求1所述的半导体装置的制造方法，其中，所述膏状热固性树脂组合物含有热固性树脂和焊剂活性剂。
13.如权利要求12所述的半导体装置的制造方法，其中，所述热固性树脂的含量为所述膏状热固性树脂组合物整体的5重量％以上且70重量％以下。
14.如权利要求12所述的半导体装置的制造方法，其中，所述焊剂活性剂的含量为所述膏状热固性树脂组合物整体的0.1重量％以上且50重量％以下。
15.如权利要求12所述的半导体装置的制造方法，其中，所述焊剂活性剂在分子中具有羧基以及酚型羟基。
16.一种半导体装置，是通过权利要求1～15中任一项所述的半导体装置的制造方法制得。
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