TWI725131B - 半導體感測器晶片安裝用接著劑及半導體感測器 - Google Patents

半導體感測器晶片安裝用接著劑及半導體感測器 Download PDF

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TWI725131B
TWI725131B TW106108074A TW106108074A TWI725131B TW I725131 B TWI725131 B TW I725131B TW 106108074 A TW106108074 A TW 106108074A TW 106108074 A TW106108074 A TW 106108074A TW I725131 B TWI725131 B TW I725131B
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adhesive
semiconductor sensor
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spacers
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TW106108074A
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TW201800546A (zh
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上田沙織
山田恭幸
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日商積水化學工業股份有限公司
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Abstract

本發明提供一種可降低雜訊之感知且提高耐熱性及耐冷熱循環特性之半導體感測器晶片安裝用接著劑。 本發明之半導體感測器晶片安裝用接著劑係用於半導體感測器晶片之安裝的接著劑，包含聚矽氧樹脂與間隔件，上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下，上述間隔件之壓縮回復率為20%以下，且上述間隔件之平均粒徑為10 μm以上且200 μm以下。

Description

半導體感測器晶片安裝用接著劑及半導體感測器
本發明係關於一種用於半導體感測器晶片之安裝之半導體感測器晶片安裝用接著劑。又，本發明係關於一種使用上述接著劑之半導體感測器。
近年來，為了應對高輸出化等，對將半導體裝置接著於基板之接著劑要求耐熱性，提出有使用聚矽氧樹脂之接著劑。又，半導體裝置之中，尤其是壓力感測器除要求耐熱性以外，亦要求將感測器晶片水平地接著於基板之性能，因此將間隔件用於使用聚矽氧樹脂之接著劑。使用此種接著劑之感測器裝置例如揭示於專利文獻1中。 於專利文獻1中揭示有一種感測器裝置，其具備：第1接著劑，其由聚矽氧系樹脂形成，且將封裝體與電路晶片之間之距離保持為固定；及第2接著劑，其由聚矽氧系樹脂形成，且將封裝體與電路晶片接著。上述第1接著劑發揮作為間隔件之功能。 於專利文獻2中揭示有於3軸加速度感測器中使用混練有球形間隔件之矽橡膠系樹脂作為接著劑。上述球形間隔件係硬質塑膠。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2011-174803號公報 [專利文獻2]日本專利特開2007-322160號公報
[發明所欲解決之問題] 專利文獻1所記載之接著劑存在耐熱性較低之情況。進而，專利文獻1所記載之接著劑存在因熱衝擊而產生龜裂及剝離之情況，存在耐冷熱循環特性較低之情況。 專利文獻2所記載之接著劑存在由於球形間隔件為硬質塑膠，故而接著劑間之應力傳遞過於靈敏而感知到雜訊級別之振動或壓力等之情形。 本發明之目的在於提供一種可降低雜訊之感知且可提高耐熱性及耐冷熱循環特性之半導體感測器晶片安裝用接著劑。又，本發明之目的亦在於提供一種使用上述接著劑之半導體感測器。 [解決問題之技術手段] 根據本發明之較廣之態樣，提供一種半導體感測器晶片安裝用接著劑(以下，有時記載為接著劑)，其係用於半導體感測器晶片之安裝之接著劑，包含聚矽氧樹脂與間隔件，上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下，上述間隔件之壓縮回復率為20%以下，且上述間隔件之平均粒徑為10 μm以上且200 μm以下。 於本發明之接著劑之某一特定之態樣中，於將上述間隔件以150℃加熱1000小時時，加熱後之間隔件之10%壓縮彈性模數相對於加熱前之間隔件之10%壓縮彈性模數之比為0.95以上且1.05以下。 於本發明之接著劑之某一特定之態樣中，於上述接著劑中所包含之上述間隔件中，不存在平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件，或於上述間隔件之總個數100%中，平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件係以0.1%以下之個數存在。 於本發明之接著劑之某一特定之態樣中，上述間隔件係聚矽氧間隔件。 於本發明之接著劑之某一特定之態樣中，上述間隔件係具有異𦯉基之(甲基)丙烯酸系化合物之聚合物。 根據本發明之較廣之態樣，提供一種半導體感測器，其具備第1構件、作為第2構件之半導體感測器晶片、及將上述第1構件與上述第2構件接著之接著層，且上述接著層係上述半導體感測器晶片安裝用接著劑之硬化物。 [發明之效果] 本發明之半導體感測器晶片安裝用接著劑包含聚矽氧樹脂與間隔件，上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下，上述間隔件之壓縮回復率為20%以下，且上述間隔件之平均粒徑為10 μm以上且200 μm以下，因此可降低雜訊之感知，且可提高耐熱性及耐冷熱循環特性。
以下，對本發明之詳細內容進行說明。 [半導體感測器晶片安裝用接著劑] 本發明之半導體感測器晶片安裝用接著劑(以下，有時記載為接著劑)係用於半導體感測器晶片之安裝之接著劑。本發明之接著劑包含聚矽氧樹脂與間隔件。 上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下。上述間隔件之壓縮回復率為20%以下。上述間隔件之平均粒徑為10 μm以上且200 μm以下。 於本發明中，由於具備上述構成，因此可降低雜訊之感知，且可提高耐熱性。又，就耐熱性而言，可提高高溫下之接著強度。進而，於本發明中，由於具備上述構成，因此亦可提高耐冷熱循環特性。於本發明中，可提高耐熱性與耐冷熱循環特性之兩者而非僅其中一者。 上述10%壓縮彈性模數係將間隔件壓縮10%時之壓縮彈性模數。就充分地降低雜訊之感知之觀點而言，上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下。就進一步降低雜訊之感知之觀點而言，上述間隔件之10%壓縮彈性模數較佳為500 N/mm2 以下，更佳為100 N/mm2 以下。 上述間隔件之10%壓縮彈性模數能夠以如下方式進行測定。 使用微小壓縮試驗機，利用圓柱(直徑50 μm、金剛石製)之平滑壓頭端面於在25℃下施加60秒最大試驗負載20 mN之條件下對間隔件進行壓縮。測定此時之負載值(N)及壓縮位移(mm)。可根據所獲得之測定值並藉由下述式求出上述壓縮彈性模數。作為上述微小壓縮試驗機，例如使用Fischer公司製造之「Fischerscope H-100」等。 10%壓縮彈性模數(N/mm2 )＝(3/21/2 )・F・S-3/2 ・R-1/2 F：間隔件壓縮變形10%時之負載值(N) S：間隔件壓縮變形10%時之壓縮位移(mm) R：間隔件之半徑(mm) 就充分地提高間隙控制效果之觀點而言，上述間隔件之壓縮回復率為20%以下。就進一步提高間隙控制效果之觀點而言，上述間隔件之壓縮回復率較佳為15%以下，更佳為10%以下。上述間隔件之壓縮回復率之下限並無特別限定，通常為1%以上。 上述間隔件之壓縮回復率能夠以如下方式進行測定。 將間隔件散佈於試樣台上。針對經散佈之1個間隔件，使用微小壓縮試驗機沿間隔件之中心方向施加負載(反轉負載值)直至間隔件壓縮變形30%。其後，進行卸載直至成為原點用負載值(0.40 mN)。測定其間之負載-壓縮位移，並可根據下述式求出壓縮回復率。再者，負載速度係設為0.33 mN/秒。作為上述微小壓縮試驗機，例如使用Fischer公司製造之「Fischerscope H-100」等。 壓縮回復率(%)＝[(L1－L2)/L1]×100 L1：自施加負載時之原點用負載值至達到反轉負載值之壓縮位移 L2：自解除負載時之反轉負載值至達到原點用負載值之卸載位移 上述間隔件之平均粒徑為10 μm以上且200 μm以下。就進一步提高間隙控制效果之觀點而言，上述間隔件之平均粒徑較佳為20 μm以上，更佳為30 μm以上，且較佳為150 μm以下，更佳為110 μm以下，進而較佳為100 μm以下。 上述平均粒徑係藉由利用掃描式電子顯微鏡對間隔件進行觀察，並對所觀察之圖像中之任意選擇之50個各間隔件之最大直徑進行算術平均而求出。 就進一步提高間隙控制效果之觀點而言，上述間隔件之含量於上述接著劑100重量%中，較佳為0.1重量%以上，更佳為1重量%以上，且較佳為10重量%以下，更佳為5重量%以下。 就進一步提高耐熱性從而進一步抑制經時之熱劣化之觀點而言，於將上述間隔件以150℃加熱1000小時時，加熱後之間隔件之10%壓縮彈性模數相對於加熱前之間隔件之10%壓縮彈性模數之比(加熱後之10%壓縮彈性模數/加熱前之10%壓縮彈性模數)較佳為0.95以上，更佳為0.98以上，且較佳為1.05以下，更佳為1.02以下。 就進一步提高間隙控制效果之觀點而言，較佳為於上述接著劑中所包含之上述間隔件中不存在平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件。又，於存在平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件之情形時，就進一步提高間隙控制效果之觀點而言，於上述接著劑中所包含之上述間隔件中，於上述間隔件之總個數100%中，平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件較佳為以0.1%以下之個數存在，更佳為以0.05%以下之個數存在。 就進一步降低雜訊之感知且進一步提高耐熱性之觀點而言，上述間隔件較佳為聚矽氧樹脂，較佳為聚矽氧間隔件。上述間隔件較佳為聚矽氧粒子。 上述間隔件較佳為不包含鉑觸媒或包含100 ppm以下之鉑觸媒。於使用鉑觸媒之情形時，鉑觸媒之含量越少越佳。若鉑觸媒之含量較多，則有可靠性降低之傾向。鉑觸媒之含量更佳為80 ppm以下，進一步較佳為60 ppm以下，進而較佳為50 ppm以下，更進一步較佳為40 ppm以下，尤佳為30 ppm以下，尤其更佳為20 ppm以下，最佳為10 ppm以下。 一般，聚矽氧粒子多數情況下係藉由使用鉑觸媒使單體聚合而獲得。於此種聚矽氧粒子中，即便經洗淨，內部亦包含鉑觸媒，且鉑觸媒之含量超過100 ppm。相對於此，於不使用鉑觸媒而獲得之聚矽氧粒子中，通常不包含鉑觸媒。 上述聚矽氧粒子之材料較佳為有機聚矽氧烷，更佳為烷氧化矽烷。有機聚矽氧烷及烷氧化矽烷可分別僅使用1種，亦可將2種以上併用。 就進一步降低雜訊之感知而製成進一步柔軟之構造之觀點而言，上述烷氧化矽烷較佳為包含下述式(1A)所表示之烷氧化矽烷A或下述式(1B)所表示之烷氧化矽烷B。上述烷氧化矽烷可包含下述式(1A)所表示之烷氧化矽烷A，亦可包含下述式(1B)所表示之烷氧化矽烷B。 Si(R1)n (OR2)4-n ・・・(1A) 上述式(1A)中，R1表示氫原子、苯基或碳數1～30之烷基，R2表示碳數1～6之烷基，n表示0～2之整數。於n為2時，複數個R1可相同，亦可不同。複數個R2可相同，亦可不同。 於上述式(1A)中之上述R1為碳數1～30之烷基之情形時，作為R1之具體例，可列舉：甲基、乙基、丙基、異丙基、異丁基、正己基、環己基、正辛基、及正癸基等。該烷基之碳數較佳為10以下，更佳為6以下。再者，烷基包含環烷基。 作為上述R2之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、及異丁基等。 作為上述烷氧化矽烷A之具體例，可列舉：四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、異丙基三甲氧基矽烷、異丁基三甲氧基矽烷、環己基三甲氧基矽烷、正己基三甲氧基矽烷、正辛基三乙氧基矽烷、正癸基三甲氧基矽烷、苯基三甲氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷及二異丙基二甲氧基矽烷、及二苯基二甲氧基矽烷等。亦可使用該等以外之烷氧化矽烷。 Si(R1)n (OR2)4-n ・・・(1B) 上述式(1B)中，R1表示氫原子、苯基、碳數1～30之烷基、或具有聚合性雙鍵之碳數1～30之有機基，R2表示碳數1～6之烷基，n表示0～2之整數。於n為2時，複數個R1可相同，亦可不同。複數個R2可相同，亦可不同。但至少1個R1為具有聚合性雙鍵之碳數1～30之有機基。至少1個R1較佳為乙烯基、苯乙烯基或(甲基)丙烯醯氧基，更佳為乙烯基或(甲基)丙烯醯氧基，進而較佳為乙烯基。 於上述式(1B)中之上述R1為碳數1～30之烷基之情形時，作為R1之具體例，可列舉：甲基、乙基、丙基、異丙基、異丁基、正己基、環己基、正辛基、及正癸基等。該烷基之碳數較佳為10以下，更佳為6以下。再者，烷基包含環烷基。 作為上述聚合性雙鍵，可列舉碳-碳雙鍵。於上述R1為具有聚合性雙鍵之碳數1～30之有機基之情形時，作為R1之具體例，可列舉：乙烯基、苯乙烯基、烯丙基、異丙烯基、及3-(甲基)丙烯醯氧基烷基等。作為上述苯乙烯基，可列舉：對苯乙烯基、鄰苯乙烯基、及間苯乙烯基。作為上述(甲基)丙烯醯氧基烷基，可列舉：(甲基)丙烯醯氧基甲基、(甲基)丙烯醯氧基乙基及(甲基)丙烯醯氧基丙基等。上述具有聚合性雙鍵之碳數1～30之有機基之碳數較佳為2以上，且較佳為30以下，更佳為10以下。上述「(甲基)丙烯醯氧基」之用語表示丙烯醯氧基與甲基丙烯醯氧基。 作為上述R2之具體例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、及異丁基等。 就進一步降低雜訊之感知而獲得具有進一步柔軟之構造之間隔件之觀點而言，上述烷氧化矽烷較佳為包含二烷氧基矽烷。 就進一步降低雜訊之感知而製成進一步柔軟之構造之觀點而言，上述烷氧化矽烷之水解縮合物較佳為於烷氧化矽烷100重量%中包含單烷氧基矽烷0重量%(未使用)以上且20重量%以下、二烷氧基矽烷70重量%以上且99.9重量%以下、及三烷氧基矽烷與四烷氧基矽烷合計0.1重量%以上且30重量%以下的烷氧化矽烷之水解縮合物，更佳為於烷氧化矽烷100重量%中包含單烷氧基矽烷0重量%(未使用)以上且15重量%以下、二烷氧基矽烷75重量%以上且99重量%以下、及三烷氧基矽烷與四烷氧基矽烷合計1重量%以上且25重量%以下的烷氧化矽烷之水解縮合物。 就進一步容易地調整粒徑之觀點而言，上述烷氧化矽烷較佳為包含具有聚合性官能基之烷氧化矽烷，更佳為包含具有聚合性雙鍵之烷氧化矽烷。作為具有聚合性雙鍵之烷氧化矽烷之具體例，可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二甲氧基甲基乙烯基矽烷、二甲氧基乙基乙烯基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基乙基乙烯基矽烷、乙基甲基二乙烯基矽烷、甲基乙烯基二甲氧基矽烷、乙基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、乙基乙烯基二乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、及3-丙烯醯氧基丙基三甲氧基矽烷等。又，可使用環狀矽氧烷，亦可使用改性(反應性)聚矽氧油等。作為環狀矽氧烷之具體例，可列舉十甲基環五矽氧烷等。作為改性聚矽氧油，可列舉單末端改性聚矽氧油、兩末端聚矽氧油、及側鏈型聚矽氧油等。 作為上述聚矽氧粒子之具體之製造方法，有如下方法等，即：於將上述烷氧化矽烷預先縮合而獲得低聚物後，利用懸浮聚合法、分散聚合法、微小乳液聚合法或乳化聚合法等進行聚合反應而製作基材粒子。 就進一步降低雜訊之感知且進一步提高耐熱性之觀點而言，上述間隔件較佳為包含具有乙烯性不飽和基之聚合性單體之聚合物。 作為上述具有乙烯性不飽和基之聚合性單體，可列舉非交聯性之單體與交聯性之單體。 作為上述非交聯性之單體，例如，作為乙烯系化合物，可列舉：苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯系單體；甲基乙烯醚、乙基乙烯醚、丙基乙烯醚、1,4-丁二醇二乙烯醚、環己烷二甲醇二乙烯醚、二乙二醇二乙烯醚等乙烯醚化合物；乙酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等酸乙烯酯化合物；氯乙烯、氟乙烯等含鹵素之單體；作為(甲基)丙烯酸系化合物，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異𦯉酯等(甲基)丙烯酸烷基酯化合物；(甲基)丙烯酸2-羥基乙酯、甘油(甲基)丙烯酸酯、聚氧乙烯(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯等含氧原子之(甲基)丙烯酸酯化合物；(甲基)丙烯腈等含腈之單體；(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸五氟乙酯等含鹵素之(甲基)丙烯酸酯化合物；作為α-烯烴化合物，可列舉：二異丁烯、異丁烯、Linealene、乙烯、丙烯等烯烴化合物；作為共軛二烯化合物，可列舉：異戊二烯、丁二烯等。 作為上述交聯性之單體，例如，作為乙烯系化合物，可列舉：二乙烯苯、1,4-二乙烯氧基丁烷、二乙烯碸等乙烯系單體；作為(甲基)丙烯酸系化合物，可列舉：四羥甲基甲烷四(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)四亞甲基二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯化合物；作為烯丙基化合物，可列舉：(異)氰尿酸三烯丙酯、偏苯三甲酸三烯丙酯、鄰苯二甲酸二烯丙酯、二烯丙基丙烯醯胺、二烯丙醚；作為聚矽氧化合物，可列舉：四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、異丙基三甲氧基矽烷、異丁基三甲氧基矽烷、環己基三甲氧基矽烷、正己基三甲氧基矽烷、正辛基三乙氧基矽烷、正癸基三甲氧基矽烷、苯基三甲氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二異丙基二甲氧基矽烷、三甲氧基矽烷基苯乙烯、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、1,3-二乙烯基四甲基二矽氧烷、甲基苯基二甲氧基矽烷、二苯基二甲氧基矽烷等烷氧化矽烷化合物；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二甲氧基甲基乙烯基矽烷、二甲氧基乙基乙烯基矽烷、二乙氧基甲基乙烯基矽烷、二乙氧基乙基乙烯基矽烷、乙基甲基二乙烯基矽烷、甲基乙烯基二甲氧基矽烷、乙基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、乙基乙烯基二乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等含聚合性雙鍵之烷氧化矽烷；十甲基環五矽氧烷等環狀矽氧烷；單末端改性聚矽氧油、兩末端聚矽氧油、側鏈型聚矽氧油等改性(反應性)聚矽氧油；(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐等含羧基之單體等。 「(甲基)丙烯酸酯」之用語表示丙烯酸酯與甲基丙烯酸酯。「(甲基)丙烯酸系」之用語表示丙烯酸系與甲基丙烯酸系。 就進一步降低雜訊之感知且進一步提高耐熱性之觀點而言，上述間隔件較佳為(甲基)丙烯酸系化合物之聚合物，更佳為具有異𦯉基之(甲基)丙烯酸系化合物之聚合物。作為上述具有異𦯉基之(甲基)丙烯酸系化合物，例如可列舉(甲基)丙烯酸異𦯉酯、二(甲基)丙烯酸異𦯉酯等。 上述接著劑包含上述間隔件與聚矽氧樹脂。上述間隔件較佳為分散於聚矽氧樹脂中而以接著劑使用。上述聚矽氧樹脂較佳為具有流動性。上述聚矽氧樹脂較佳為糊狀。上述糊狀包含液狀。 上述接著劑可為將主劑及硬化劑等預先混合而成之一液型，亦可為主劑與硬化劑分開之二液型。上述接著劑可為縮合硬化型，亦可為加成硬化型。上述接著劑可使用鉑等觸媒進行硬化，亦可藉由加熱或濕氣進行硬化。 上述聚矽氧樹脂並無特別限定。上述聚矽氧樹脂可為有機聚矽氧烷化合物，該有機聚矽氧烷可於末端具有羥基，亦可於末端具有乙烯基。上述聚矽氧樹脂亦可為具有甲基二甲氧基矽烷基之聚環氧丙烷。 上述接著劑除上述聚矽氧樹脂及上述間隔件以外，亦可包含乙烯系樹脂、熱塑性樹脂、硬化性樹脂、熱塑性嵌段共聚物、彈性體及溶劑等。該等成分可僅使用1種，亦可將2種以上併用。 作為上述乙烯系樹脂，例如可列舉：乙酸乙烯酯樹脂、丙烯酸系樹脂及苯乙烯樹脂等。作為上述熱塑性樹脂，例如可列舉：聚烯烴樹脂、乙烯-乙酸乙烯酯共聚物及聚醯胺樹脂等。作為上述硬化性樹脂，例如可列舉：環氧樹脂、胺基甲酸酯樹脂、聚醯亞胺樹脂及不飽和聚酯樹脂等。再者，上述硬化性樹脂亦可為常溫硬化型樹脂、熱硬化型樹脂、光硬化型樹脂或濕氣硬化型樹脂。上述硬化性樹脂亦可與硬化劑併用。作為上述熱塑性嵌段共聚物，例如可列舉：苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物之氫化物、及苯乙烯-異戊二烯-苯乙烯嵌段共聚物之氫化物等。作為上述彈性體，例如可列舉：苯乙烯-丁二烯共聚橡膠、及丙烯腈-苯乙烯嵌段共聚橡膠等。 作為上述溶劑，可列舉水及有機溶劑等。就可容易地去除之方面而言，較佳為有機溶劑。作為上述有機溶劑，可列舉：乙醇等醇化合物；丙酮、甲基乙基酮、環己酮等酮化合物；甲苯、二甲苯、四甲基苯等芳香族烴化合物；溶纖素、甲基溶纖素、丁基溶纖素、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二乙醚、三丙二醇單甲醚等二醇醚化合物；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纖素乙酸酯、丁基溶纖素乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙酸酯、碳酸丙二酯等酯化合物；辛烷、癸烷等脂肪族烴化合物；以及石油醚、石腦油等石油系溶劑等。 上述接著劑除上述間隔件及上述聚矽氧樹脂以外，例如亦可包含填充劑、增量劑、軟化劑、塑化劑、聚合觸媒、硬化觸媒、著色劑、抗氧化劑、熱穩定劑、光穩定劑、紫外線吸收劑、潤滑劑、抗靜電劑及難燃劑等各種添加劑。 使上述間隔件分散於上述聚矽氧樹脂中之方法可使用先前公知之分散方法，並無特別限定。作為使上述間隔件分散於上述聚矽氧樹脂中之方法，例如可列舉：於將上述間隔件添加至上述聚矽氧樹脂中後，利用行星式混合機等進行混練而使之分散之方法；於使用均質機等使上述間隔件均勻地分散於水或有機溶劑中後，添加至上述聚矽氧樹脂中，並利用行星式混合機等進行混練而使之分散之方法；以及於利用水或有機溶劑等將上述聚矽氧樹脂稀釋後，添加上述間隔件，並利用行星式混合機等進行混練而使之分散之方法等。 就進一步緩和外部衝擊從而進一步防止龜裂及剝離之觀點而言，上述聚矽氧樹脂之含量於上述接著劑100重量%中，較佳為70重量%以上，更佳為80重量%以上，且較佳為99重量%以下，更佳為95重量%以下。 [半導體感測器] 本發明之半導體感測器具備第1構件、作為第2構件之半導體感測器晶片、及將第1、第2構件接著之接著層。於本發明之半導體感測器中，上述接著層係藉由上述接著劑之硬化物而形成。 圖1係表示使用本發明之半導體感測器晶片安裝用接著劑之半導體感測器之一例的剖視圖。 圖1所示之半導體感測器1具備第1構件3、作為第2構件4之半導體感測器晶片、及將第1構件3與第2構件4接著之接著層5。接著層5係包含間隔件2與聚矽氧樹脂之接著劑之硬化物。 於第1構件3與第2構件4之間存在間隔件2，且第1構件3與第2構件4係以固定之間隔(間隙)水平地接著。 上述半導體感測器之製造方法並無特別限定。作為半導體感測器之製造方法之一例，可列舉於第1構件與第2構件之間配置上述接著劑而獲得積層體後，對該積層體進行加熱及加壓之方法等。 作為上述第1構件，具體而言，可列舉：半導體晶片、電容器及二極體等電子零件；以及印刷基板、可撓性印刷基板、玻璃環氧基板及玻璃基板等電路基板等電子零件等。上述第1構件較佳為電子零件。上述接著劑較佳為用以將電子零件接著之接著劑。 上述半導體感測器晶片較佳為壓力感測器。 上述第1構件亦可於表面具有第1電極。上述第2構件亦可於表面具有第2電極。作為設置於上述構件之電極，可列舉金電極、鎳電極、錫電極、鋁電極、銅電極、銀電極、鈦電極、鉬電極及鎢電極等金屬電極。於上述構件為可撓性印刷基板之情形時，上述電極較佳為金電極、鎳電極、鈦電極、錫電極或銅電極。於上述構件為玻璃基板之情形時，上述電極較佳為鋁電極、鈦電極、銅電極、鉬電極或鎢電極。再者，於上述電極為鋁電極之情形時，可為僅由鋁形成之電極，亦可為於金屬氧化物層之表面積層有鋁層之電極。作為上述金屬氧化物層之材料，可列舉摻雜有三價金屬元素之氧化銦及摻雜有三價金屬元素之氧化鋅等。作為上述三價金屬元素，可列舉Sn、Al及Ga等。 以下，列舉實施例及比較例對本發明具體地進行說明。本發明並不僅限定於以下之實施例。 (間隔件1之製作) 聚矽氧低聚物之製作： 向設置於溫浴槽內之100 ml之可分離式燒瓶中添加1,3-二乙烯基四甲基二矽氧烷1重量份與0.5重量%對甲苯磺酸水溶液20重量份。於40℃下攪拌1小時後，添加碳酸氫鈉0.05重量份。其後，添加二甲氧基甲基苯基矽烷10重量份、二甲基二甲氧基矽烷49重量份、三甲基甲氧基矽烷0.6重量份、及甲基三甲氧基矽烷3.6重量份，並進行1小時攪拌。其後，添加10重量%氫氧化鉀水溶液1.9重量份，升溫至85℃，一面利用抽吸器進行減壓，一面攪拌10小時進行反應。反應結束後，恢復至常壓並冷卻至40℃，添加乙酸0.2重量份，並於分液漏斗內靜置12小時以上。提取兩層分離後之下層，並利用蒸發器進行精製，藉此獲得聚矽氧低聚物。 聚矽氧粒子之製作： 準備使2-乙基過氧化己酸第三丁酯(聚合起始劑，日油公司製造之「PERBUTYL O」)0.5重量份溶解於所獲得之聚矽氧低聚物30重量份中而成之溶解液A。又，將月桂基硫酸三乙醇胺鹽之40重量%水溶液(乳化劑)0.8重量份、聚乙烯醇(聚合度：約2000，皂化度：86.5～89莫耳%，日本合成化學公司製造之「Gohsenol GH-20」)之5重量%水溶液80重量份與離子交換水150重量份進行混合而準備水溶液B。於向設置於溫浴槽中之可分離式燒瓶中添加上述溶解液A後，添加上述水溶液B。其後，藉由使用白砂多孔玻璃(SPG，Shirasu Porous Glass)膜(細孔平均徑約20 μm)進行乳化。其後，升溫至85℃並進行9小時聚合。藉由離心分離將聚合後之粒子全部用水洗淨後，進行分級操作而獲得聚矽氧粒子。 間隔件1之製作： 向設置於溫浴槽內之500 ml之可分離式燒瓶中添加所獲得之聚矽氧粒子6.5重量份、十六烷基三甲基溴化銨0.6重量份、蒸餾水240重量份、及甲醇120重量份。於40℃下攪拌1小時後，添加二乙烯苯3.0重量份與苯乙烯0.5重量份，升溫至75℃並進行0.5小時攪拌。其後，添加2,2'-偶氮雙(異丁酸)二甲酯0.4重量份並攪拌8小時進行反應。藉由離心分離將聚合後之粒子全部用水洗淨而獲得間隔件1。關於所獲得之間隔件1，平均粒徑為20.5 μm，粒徑之CV(coefficient of variation，變異係數)值為3.5%。 (間隔件2之製作) 使用兩末端為丙烯醯基之聚矽氧油(信越化學工業公司製造之「X-22-2445」)代替聚矽氧低聚物，除此以外，以與間隔件1之製作相同之方式獲得間隔件2。於所獲得之間隔件2中，平均粒徑為20.3 μm，粒徑之CV值為3.6%。 (間隔件3之製作) 將乙二醇二甲基丙烯酸酯100 g、丙烯酸異𦯉酯800 g、甲基丙烯酸環己酯100 g、過氧化苯甲醯35 g進行混合，並使其等均勻地溶解而獲得單體混合液。製作1重量%聚乙烯醇水溶液5 kg並添加至反應釜中。向該反應釜之中進而添加上述單體混合液，並藉由攪拌2～4小時而以單體混合液之液滴成為特定之粒徑之方式調整粒徑。此後，於90℃之氮氣環境下進行9小時反應，獲得間隔件3。利用熱水將所獲得之間隔件3洗淨數次後進行分級操作。關於所獲得之間隔件3，平均粒徑為20.1 μm，粒徑之CV值為3.1%。 (間隔件A) 市售之20 μm之二氧化矽粒子「Micropearl SI」(積水化學工業公司製造) (間隔件B之製作) 將四羥甲基甲烷500 g、二乙烯苯500 g及過氧化苯甲醯20 g進行混合，使其等均勻地溶解而獲得單體混合液。製作1重量%聚乙烯醇水溶液5 kg，並添加至反應釜中。向該反應釜之中進而添加上述單體混合液，並藉由攪拌2～4小時而以單體混合液之液滴成為特定之粒徑之方式調整粒徑。此後，於85℃之氮氣環境下進行10小時反應，獲得間隔件B。於利用熱水將所獲得之間隔件B洗淨數次後進行分級操作。關於所獲得之間隔件B，平均粒徑為19.8 μm，粒徑之CV值為3.5%。 (間隔件C之製作) 將聚四亞甲基二醇二丙烯酸酯970 g、四羥甲基甲烷四丙烯酸酯30 g、及過氧化苯甲醯39 g進行混合，使其等均勻地溶解而獲得單體混合液。製作1重量%聚乙烯醇水溶液5 kg，並添加至反應釜中。向該反應釜之中進而添加上述單體混合液，並藉由攪拌2～4小時而以單體混合液之液滴成為特定之粒徑之方式調整粒徑。此後，於85℃之氮氣環境下進行9小時反應，獲得間隔件C。於利用熱水將所獲得之間隔件C洗淨數次後進行分級操作。關於所獲得之間隔件C，平均粒徑為20.1 μm，粒徑之CV值為3.2%。 (實施例1) (聚矽氧接著劑之製備) 向單一成分之加熱硬化型聚矽氧接著劑TSE322(邁圖高新材料公司製造)中以所獲得之接著劑中之含量成為2重量%之方式添加間隔件1作為間隙控制粒子，並利用行星式攪拌機進行攪拌，使之均勻地分散而製備聚矽氧接著劑。 (壓力感測器構造體之製作) 將上述聚矽氧接著劑填充至注射器中，並使用分配器以厚度成為20 μm之方式塗佈於印刷基板上後，將壓力感測器晶片配置於塗佈之接著劑上，以150℃加熱10分鐘進行硬化、接著而獲得壓力感測器構造體。 (實施例2) 於製備聚矽氧接著劑時，使用間隔件2代替間隔件1，除此以外，以與實施例1相同之方式獲得壓力感測器構造體。 (實施例3) 於製備聚矽氧接著劑時，使用間隔件3代替間隔件1，除此以外，以與實施例1相同之方式獲得壓力感測器構造體。 (比較例1) 於製備聚矽氧接著劑時，使用間隔件A代替間隔件1，除此以外，以與實施例1相同之方式獲得壓力感測器構造體。 (比較例2) 於製備聚矽氧接著劑時，使用間隔件B代替間隔件1，除此以外，以與實施例1相同之方式獲得壓力感測器構造體。 (比較例3) 於製備聚矽氧接著劑時，使用間隔件C代替間隔件1，除此以外，以與實施例1相同之方式獲得壓力感測器構造體。 (評價) (1)10%壓縮彈性模數 使用Fischer公司製造之「Fischerscope H-100」並利用上述方法測定間隔件之10%壓縮彈性模數。 (2)平均粒徑 藉由利用掃描式電子顯微鏡對間隔件進行觀察，並對所觀察之圖像中之任意選擇之50個各間隔件之最大粒徑進行算術平均而求出。 (3)壓縮回復率 使用Fischer公司製造之「Fischerscope H-100」並利用上述方法測定間隔件之壓縮回復率。 (4)熱經時變化 使用Fischer公司製造之「Fischerscope H-100」，測定將間隔件以150℃於大氣中加熱1000小時後之10%壓縮彈性模數。根據以下之基準對間隔件之熱經時變化進行判定。 [熱經時變化之判定基準] ○：加熱後之10%壓縮彈性模數相對於加熱前之10%壓縮彈性模數之比為0.95以上且1.05以下 △：加熱後之10%壓縮彈性模數相對於加熱前之10%壓縮彈性模數之比為0.9以上且未達0.95或大於1.05且為1.10以下 ×：加熱後之10%壓縮彈性模數相對於加熱前之10%壓縮彈性模數之比未達0.9或大於1.10 (5)耐熱性：連接強度 測定所獲得之壓力感測器構造體之260℃下之剪切強度。根據剪切強度判定耐熱性：連接強度。 [耐熱性：連接強度之判定基準] ○○：剪切強度為150 N/cm2 以上 ○：剪切強度為100 N/cm2 以上且未達150 N/cm2 ×：剪切強度未達100 N/cm2 (6)耐冷熱循環特性 使用所獲得之壓力感測器構造體並使用液槽式熱衝擊試驗機(ESPEC公司製造之「TSB-51」)實施將於-40℃下保持5分鐘後升溫至120℃，並於120℃下保持5分鐘後降溫至-40℃之過程設為1個循環的冷熱循環試驗。於500個循環後取出樣品。 利用立體顯微鏡(Nikon公司製造之「SMZ-10」)對樣品進行觀察。觀察接著層是否產生龜裂或接著層是否自基板剝離。根據下述基準對耐冷熱循環特性進行判定。 [耐冷熱循環特性之判定基準] ○○：接著層未產生龜裂且接著層未自基板剝離 ○：接著層產生輕微龜裂或接著層略微自基板剝離 ×：接著層產生較大之龜裂或接著層大幅自基板剝離 將結果示於下述表1。 [表1]
Figure 106108074-A0304-0001
 再者，於實施例1～3中確認到，接著劑所包含之間隔件之10%壓縮彈性模數為2000 N/mm2 以下，間隔件相對柔軟，因此於壓力感測器構造體中可降低雜訊之感知。
1‧‧‧半導體感測器2‧‧‧間隔件3‧‧‧第1構件4‧‧‧第2構件(半導體感測器晶片)5‧‧‧接著層
圖1係表示使用本發明之半導體感測器晶片安裝用接著劑之半導體感測器之一例的剖視圖。
1‧‧‧半導體感測器
2‧‧‧間隔件
3‧‧‧第1構件
4‧‧‧第2構件(半導體感測器晶片)
5‧‧‧接著層

Claims (6)

  1. 一種半導體感測器晶片安裝用接著劑，其係用於半導體感測器晶片之安裝的接著劑，且 包含聚矽氧樹脂與間隔件， 上述間隔件之10%壓縮彈性模數為10 N/mm2 以上且2000 N/mm2 以下， 上述間隔件之壓縮回復率為20%以下，且 上述間隔件之平均粒徑為10 μm以上且200 μm以下。
  2. 如請求項1之半導體感測器晶片安裝用接著劑，其中於將上述間隔件以150℃加熱1000小時時，加熱後之間隔件之10%壓縮彈性模數相對於加熱前之間隔件之10%壓縮彈性模數之比為0.95以上且1.05以下。
  3. 如請求項1或2之半導體感測器晶片安裝用接著劑，其中於上述接著劑中所包含之上述間隔件中，不存在平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件，或於上述間隔件之總個數100%中，平均粒徑相對於上述間隔件之平均粒徑為1.5倍以上之間隔件係以0.1%以下之個數存在。
  4. 如請求項1或2之半導體感測器晶片安裝用接著劑，其中上述間隔件係聚矽氧間隔件。
  5. 如請求項1或2之半導體感測器晶片安裝用接著劑，其中上述間隔件係具有異𦯉基之(甲基)丙烯酸系化合物之聚合物。
  6. 一種半導體感測器，其包括： 第1構件、 作為第2構件之半導體感測器晶片、及 將上述第1構件與上述第2構件接著之接著層，且 上述接著層係如請求項1至5中任一項之半導體感測器晶片安裝用接著劑之硬化物。
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TWI751142B (zh) 2022-01-01
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