TW201444934A - 熱固性樹脂組合物及半導體裝置之製造方法 - Google Patents

熱固性樹脂組合物及半導體裝置之製造方法 Download PDF

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Publication number
TW201444934A
TW201444934A TW103114076A TW103114076A TW201444934A TW 201444934 A TW201444934 A TW 201444934A TW 103114076 A TW103114076 A TW 103114076A TW 103114076 A TW103114076 A TW 103114076A TW 201444934 A TW201444934 A TW 201444934A
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Taiwan
Prior art keywords
resin composition
thermosetting resin
semiconductor device
semiconductor
semiconductor wafer
Prior art date
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TW103114076A
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English (en)
Inventor
Kosuke Morita
Naohide Takamoto
Hiroyuki Hanazono
Akihiro Fukui
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Nitto Denko Corp
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Publication of TW201444934A publication Critical patent/TW201444934A/zh

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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
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Abstract

本發明提供一種藉由緩和半導體元件與被黏著體之熱響應行為之差異而確保構件之材質之可利用性，並且可製造連接可靠性較高之半導體裝置的熱固性樹脂組合物及使用其之半導體裝置之製造方法。本發明係一種半導體裝置製造用之熱固性樹脂組合物，其包含環氧樹脂、及羥基當量為200 g/eq以上之酚醛清漆型酚樹脂。上述酚醛清漆型酚樹脂較佳為包含下述結構式所表示之結構。□(式中，n為0~12之整數)

Description

熱固性樹脂組合物及半導體裝置之製造方法
本發明係關於一種熱固性樹脂組合物及半導體裝置之製造方法。
近年來，對電子機器之小型、薄型化帶來之高密度安裝之要求急遽增加。因此，半導體封裝中，適於高密度安裝之表面安裝型代替先前之插件型而成為主流。該表面安裝型係將引線直接焊接於印刷基板等。作為加熱方法，藉由紅外線回焊或汽相回焊、浸焊等將封裝體整體加熱而安裝。
於表面安裝後，為了確保半導體元件表面之保護或半導體元件與基板之間之連接可靠性，而向半導體元件與基板之間之空間填充底填充材。作為此種底填充材，考慮到配置之容易性或調節填充程度之容易性而提出使用片狀之底填充材代替液狀者而填充半導體元件與基板之間之空間的技術(專利文獻1)。
通常，作為使用片狀之底填充材之製程，採用如下順序：將片狀之底填充材貼附於半導體元件後，一面將半導體元件連接而安裝於基板等被黏著體，一面以與半導體元件成為一體之片狀之底填充材將基板等被黏著體與半導體元件之間之空間填充。於該製程中，被黏著體與半導體元件之間之空間之填充較為容易。
[先前技術文獻] [專利文獻]
專利文獻1：日本專利第4438973號
且說，對於半導體裝置之小型化、薄型化，雖只要使半導體元件之厚度變薄即可，但隨著半導體元件之薄型化推進，被黏著體對半導體元件之熱響應行為之影響(翹曲或膨脹等)變大。此種情況起因於，通常基板等被黏著體之熱膨脹係數大於半導體元件之值。尤其是於連接半導體元件與被黏著體之焊錫凸塊等連接構件中，由半導體元件及被黏著體之熱響應行為之不同所引起之應力容易集中，視情況會有於接合部產生斷裂之情形。對此，亦可以使半導體元件與被黏著體之熱響應性行為匹配之方式選擇兩者之材質等，但可選擇之材質之餘地受到限制。
本發明之目的在於提供一種藉由緩和半導體元件與被黏著體之熱響應行為之差異而確保構件之材質之可利用性，並且可製造連接可靠性較高之半導體裝置的熱固性樹脂組合物及使用其之半導體裝置之製造方法。
本案發明者等人進行了銳意研究，結果發現，藉由採用下述構成而可達成上述目的，從而完成本發明。
本發明係一種半導體裝置製造用之熱固性樹脂組合物，其包含：環氧樹脂、及羥基當量為200g/eq以上之酚醛清漆型酚樹脂。
該熱固性樹脂組合物包含環氧樹脂，並且包含羥基當量為200g/eq以上之酚醛清漆型酚樹脂(以下，亦稱為「特定酚樹脂」)，因此，可確保熱固後之固化物(以下，亦簡稱為「固化物」)之剛性，並 且可抑制兩樹脂間之過度之交聯而發揮適度之柔軟性。藉此，可緩和半導體元件與被黏著體之熱響應行為之差異，從而可獲得接合部之斷裂得到抑制之連接可靠性較高之半導體裝置。又，藉由使用該熱固性樹脂組合物而可緩和半導體元件與被黏著體之熱響應行為之差異，因此可對半導體元件或被黏著體之材質賦予選擇之餘地。
該熱固性樹脂組合物係作為半導體元件密封用而較佳。
該熱固性樹脂組合物較佳為上述酚醛清漆型酚樹脂包含下述結構式所表示之結構。
(式中，n為0~12之整數)
藉由使用具有上述特定結構之酚醛清漆型酚樹脂，可以更高水準達成固化物之剛性與柔軟性之平衡，從而可進一步提高半導體裝置之可靠性。
該熱固性樹脂組合物較佳為包含平均粒徑為10nm以上且1000nm以下之無機填充劑。藉由該熱固性樹脂組合物含有無機填充劑，可降低固化物之熱膨脹率，抑制由固化物本身所引起之熱響應行為之影響，而可進一步提高半導體裝置之可靠性。又，藉由將無機填充劑之平均粒徑設為上述範圍而該熱固性樹脂組合物可獲得良好之透明性，其結果為，可容易地進行晶圓之切晶位置或半導體元件向被黏著體之安裝位置之對準。
該熱固性樹脂組合物於175℃下熱處理1小時後之熱膨脹係數α較 佳為10ppm/K以上且200ppm/K以下。藉由將固化物之熱膨脹係數α設為上述範圍，可抑制由固化物本身所引起之熱響應行為，其結果為，可進一步提高半導體裝置之可靠性。
該熱固性樹脂組合物於175℃下熱處理1小時後之儲存彈性模數E'較佳為100MPa以上且10000MPa以下。藉此，固化物可獲得適度之剛性，促進熱響應行為之差異之吸收或分散而可進一步提高半導體裝置之可靠性。
該熱固性樹脂組合物較佳為片狀。藉此，操作性變得良好，並且向半導體元件與被黏著體之間之空間之配置變得容易，從而可提高半導體裝置之製造效率。
本發明中亦包含一種半導體裝置之製造方法，其包括：固定步驟，其係將半導體元件經由該熱固性樹脂組合物固定於被黏著體；及固化步驟，其係使上述熱固性樹脂組合物固化。
藉由使用該熱固性樹脂組合物製造半導體裝置，可緩和半導體元件、該熱固性樹脂組合物之固化物、被黏著體三者間之熱響應行為之差異，從而可效率良好地製造優異之可靠性之半導體裝置。
1‧‧‧背面研削用膠帶
1a‧‧‧基材
1b‧‧‧黏著劑層
2‧‧‧熱固性樹脂組合物
3‧‧‧半導體晶圓
3a‧‧‧電路面
3b‧‧‧背面
4‧‧‧連接構件
5‧‧‧半導體晶片(半導體元件)
10‧‧‧密封片材
11‧‧‧切晶膠帶
11a‧‧‧基材
11b‧‧‧黏著劑層
16‧‧‧被黏著體
17‧‧‧導電材
20‧‧‧半導體裝置
41‧‧‧切晶膠帶
41a‧‧‧基材
41b‧‧‧黏著劑層
42‧‧‧熱固性樹脂組合物
43‧‧‧半導體晶圓
44‧‧‧連接構件
45‧‧‧半導體元件
60‧‧‧半導體裝置
66‧‧‧被黏著體
圖1係表示具有本發明之一實施形態之熱固性樹脂組合物之密封片材的剖面模式圖。
圖2A係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖2B係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖2C係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖2D係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖2E係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖2F係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖3A係表示本發明之其他實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖3B係表示本發明之其他實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖3C係表示本發明之其他實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
圖3D係表示本發明之其他實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。
以下，針對本發明之一實施形態，以片狀之熱固性樹脂組合物與背面研削用膠帶成為一體之密封片材及使用其之半導體裝置之製造方法為例進行說明。以下之說明基本上亦可適用於熱固性樹脂組合物單獨之情形。
<密封片材>
如圖1所示，密封片材10具備背面研削用膠帶1、及積層於背面研削用膠帶1上之片狀之熱固性樹脂組合物2。再者，如圖1所示，熱固性樹脂組合物2亦可不積層於背面研削用膠帶1之整個表面，只要以對於與半導體晶圓3(參照圖2A)之貼合而言充分之尺寸設置即可。
[熱固性樹脂組合物]
本實施形態中之熱固性樹脂組合物2為片狀，可較佳地用作填充 經表面安裝(例如覆晶安裝等)之半導體元件與被黏著體之間之空間之密封用膜、或者用以將半導體元件固定於被黏著體之接著膜。
熱固性樹脂組合物2包含環氧樹脂、及羥基當量為200g/eq以上之酚醛清漆型酚樹脂，視需要亦可包含熱固促進觸媒、助焊劑、交聯劑、無機填充劑等。
(環氧樹脂)
環氧樹脂只要為通常用作熱固性樹脂者則並無特別限定，例如可使用雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、茀型、苯酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥基苯基甲烷型、四酚基乙烷型等之二官能環氧樹脂或多官能環氧樹脂、或者乙內醯脲型、異氰尿酸三縮水甘油酯型或縮水甘油胺型等之環氧樹脂。該等可單獨使用或併用2種以上。該等環氧樹脂中尤佳為酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥基苯基甲烷型樹脂或四酚基乙烷型環氧樹脂。其原因在於，該等環氧樹脂富有與作為固化劑之酚樹脂之反應性，且耐熱性等優異。
(羥基當量為200g/eq以上之酚醛清漆型酚樹脂)
熱固性樹脂組合物2中所含之酚醛清漆型酚樹脂係作為環氧樹脂之固化劑發揮作用者，只要其羥基當量為200g/eq以上則並無特別限定。具有此種羥基當量之酚醛清漆型酚樹脂可藉由依據常規方法使酚類與可與該酚類進行縮合反應之具有適度分子鏈長之化合物(例如，醛類、雙(烷氧基甲基)聯苯類等)反應而獲得。又，市售之羥基當量為200g/eq以上之酚醛清漆型酚樹脂亦可較佳地使用，例如可列舉新日鐵化學製造之「SN-495」或明和化成製造之「MEH-7851H」等。再者，羥基當量之上限並無特別限定，但若考慮熱固性樹脂組合物之固化性或其固化物之剛性等，則較佳為250g/eq以下。
其中，較佳為酚醛清漆型酚樹脂包含下述結構式所表示之結 構。
(式中，n為0~12之整數)
藉由使用具有上述特定結構之酚醛清漆型酚樹脂，可以更高水準達成固化物之剛性與柔軟性之平衡，從而可進一步提高半導體裝置之可靠性。再者，上述式中之n只要為0~12之整數即可，但較佳為0~8之整數。
(其他樹脂)
熱固性樹脂組合物2除上述環氧樹脂及特定酚樹脂以外，亦可包含該等以外之熱固性樹脂或熱塑性樹脂。
(其他熱固性樹脂)
作為其他熱固性樹脂，可列舉胺基樹脂、不飽和聚酯樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、或熱固性聚醯亞胺樹脂等。該等樹脂可單獨使用或併用2種以上。
除上述特定之酚醛清漆型酚樹脂以外，作為酚樹脂，只要無損本發明之效果則可併用苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚樹脂、可溶酚醛型酚樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等酚樹脂之1種或2種以上。
關於上述環氧樹脂與上述特定酚樹脂之調配比率，例如較佳為以相對於上述環氧樹脂成分中之環氧基每1當量而特定酚樹脂中之羥 基成為0.5~2.0當量之方式進行調配。更佳為0.8~1.2當量。即，其原因在於，若兩者之調配比率偏離上述範圍，則無法進行充分之固化反應，該熱固性樹脂組合物之固化物之特性容易劣化。
(熱塑性樹脂)
作為上述熱塑性樹脂，可列舉天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、6-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET或PBT(polybutylene terephthalate，聚對苯二甲酸丁二酯)等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、或氟樹脂等。該等熱塑性樹脂可單獨使用或併用2種以上。該等熱塑性樹脂中，尤佳為離子性雜質較少且耐熱性較高而可確保半導體元件之可靠性的丙烯酸系樹脂。
作為上述丙烯酸系樹脂，並無特別限定，可列舉以具有碳數30以下、尤其是碳數4~18之直鏈或支鏈之烷基的丙烯酸或甲基丙烯酸之酯之1種或2種以上作為成分的聚合物等。作為上述烷基，例如可列舉甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。
又，作為形成上述聚合物之其他單體，並無特別限定，例如可列舉：如丙烯腈之類的含氰基之單體；如丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸或丁烯酸等之類的含羧基之單體；如順丁烯二酸酐或伊康酸酐等之類的酸酐單體；如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8- 羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或丙烯酸(4-羥基甲基環己基)甲酯等之類的含羥基之單體；如苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺基丙酯或(甲基)丙烯醯氧基萘磺酸等之類的含磺酸基之單體；或如丙烯醯基磷酸2-羥基乙酯等之類的含磷酸基之單體。
再者，於本實施形態中，尤佳為使用環氧樹脂、特定酚樹脂及丙烯酸系樹脂之熱固性樹脂組合物。該等樹脂之離子性雜質較少且耐熱性較高，故而可確保半導體元件之可靠性。關於該情形時之調配比，相對於丙烯酸系樹脂成分100重量份，環氧樹脂與特定酚樹脂之混合量為10~200重量份。
(熱固促進觸媒)
作為環氧樹脂與特定酚樹脂之熱固促進觸媒，並無特別限制，可自公知之熱固促進觸媒中適當選擇使用。熱固促進觸媒可單獨使用或組合使用2種以上。作為熱固促進觸媒，例如可使用胺系固化促進劑、磷系固化促進劑、咪唑系固化促進劑、硼系固化促進劑、磷-硼系固化促進劑等。熱固促進觸媒之添加量相對於環氧樹脂與特定酚樹脂之合計100重量份較佳為0.1~5重量份。
(助焊劑)
為了去除焊錫凸塊表面之氧化膜而使半導體元件之安裝變得容易，亦可於熱固性樹脂組合物2中添加助焊劑。作為助焊劑，並無特別限定，可使用先前公知之具有助焊作用之化合物，例如可列舉：雙酚酸、己二酸、乙醯水楊酸、苯甲酸、二苯乙醇酸、壬二酸、苄基苯甲酸、丙二酸、2,2-雙(羥甲基)丙酸、水楊酸、鄰甲氧基苯甲酸、間羥基苯甲酸、丁二酸、2,6-二甲氧基甲基對甲酚、苯甲酸醯肼、碳醯肼、丙二酸二醯肼、丁二酸二醯肼、戊二酸二醯肼、水楊酸醯肼、亞 胺基二乙酸二醯肼、伊康酸二醯肼、檸檬酸三醯肼、硫代碳醯肼、二苯甲酮腙、4,4'-氧基雙苯磺醯肼及己二酸二醯肼等。助焊劑之添加量只要為發揮上述助焊作用之程度即可，通常相對於熱固性樹脂組合物中所含之樹脂成分100重量份為0.1~20重量份左右。
(交聯劑)
於使本實施形態之熱固性樹脂組合物2預先以某種程度進行交聯之情形時，可於製作時預先添加與聚合物之分子鏈末端之官能基等反應之多官能性化合物作為交聯劑。藉此，可提高高溫下之接著特性而實現耐熱性之改善。
作為上述交聯劑，尤其更佳為甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、對苯二異氰酸酯、1,5-萘二異氰酸酯、多元醇與二異氰酸酯之加成物等聚異氰酸酯化合物。作為交聯劑之添加量，相對於上述聚合物100重量份，通常較佳為設為0.05~7重量份。若交聯劑之量多於7重量份，則接著力降低，故而欠佳。另一方面，若少於0.05重量份，則凝聚力不足，故而欠佳。又，亦可包含此種聚異氰酸酯化合物，並且視需要一併包含環氧樹脂等其他多官能性化合物。
(無機填充劑)
又，於熱固性樹脂組合物2中可適當調配無機填充劑。無機填充劑之調配可賦予導電性及提高熱導性、調節儲存彈性模數等。
作為上述無機填充劑，例如可列舉：二氧化矽、黏土、石膏、碳酸鈣、硫酸鋇、氧化鋁、氧化鈹、碳化矽、氮化矽等陶瓷類、鋁、銅、銀、金、鎳、鉻、鉛、錫、鋅、鈀、焊錫等金屬、或合金類、其他包含碳等之各種無機粉末。該等可單獨使用或併用2種以上。其中，可較佳地使用二氧化矽、尤其是熔融二氧化矽。
無機填充劑之平均粒徑並無特別限定，較佳為10nm以上且1000nm以下之範圍內，更佳為20nm以上且200nm以下之範圍內，進而較 佳為30nm以上且100nm以下之範圍內。若無機填充劑之平均粒徑未達10nm，則會成為熱固性樹脂組合物之可撓性降低之原因。另一方面，若上述平均粒徑超過1000nm，則熱固性樹脂組合物之透明性降低，並且相對於熱固性樹脂組合物密封之間隙而言粒徑較大而成為密封性降低之主要原因。再者，於本實施形態中，亦可將平均粒徑互不相同之無機填充劑彼此組合使用。又，平均粒徑係藉由光度式之粒度分佈計(HORIBA製造，裝置名：LA-910)求出之值。
上述無機填充劑之調配量係相對於有機樹脂成分100重量份較佳為10~400重量份，更佳為50~250重量份。若無機填充劑之調配量未達10重量份，則有儲存彈性模數降低而使封裝體之應力可靠性嚴重受損之情形。另一方面，若超過400重量份，則有熱固性樹脂組合物2之流動性降低而無法充分埋入至基板或半導體元件之凹凸從而成為空隙或龜裂之原因之情形。
(其他添加劑)
再者，於熱固性樹脂組合物2中，除上述無機填充劑以外，亦可視需要適當調配其他添加劑。作為其他添加劑，例如可列舉阻燃劑、矽烷偶合劑或離子捕捉劑等。作為上述阻燃劑，例如可列舉三氧化銻、五氧化銻、溴化環氧樹脂等。該等可單獨使用或併用2種以上。作為上述矽烷偶合劑，例如可列舉β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等。該等化合物可單獨使用或併用2種以上。作為上述離子捕捉劑，例如可列舉水滑石類、氫氧化鉍等。該等可單獨使用或併用2種以上。
於本實施形態中，熱固性樹脂組合物2亦可視需要著色。對於熱固性樹脂組合物2，藉由著色而呈現之顏色並無特別限制，例如較佳為黑色、藍色、紅色、綠色等。著色時，可自顏料、染料等公知之著 色劑中適當選擇使用。
(熱固性樹脂組合物之物性)
熱固前之熱固性樹脂組合物之霧度較佳為70%以下，更佳為50%以下，進而較佳為30%以下。藉由使該熱固性樹脂組合物之霧度降低而提高透明性，可更容易地進行切晶或安裝時之半導體元件之對準。各熱固性樹脂組合物之霧度係使用霧度計HM-150(村上色彩技術研究所製造)測定。測定係依據JIS K 7136進行。
將該熱固性樹脂組合物於175℃下熱處理1小時後之固化物之熱膨脹係數α並無特別限定，但較佳為10ppm/K以上且200ppm/K以下，更佳為10ppm/K以上且100ppm/K以下，進而較佳為10ppm/K以上且50ppm/K以下。藉由將固化物之熱膨脹係數α設為上述範圍，可抑制由固化物本身所引起之熱響應行為，其結果為，可進一步提高半導體裝置之可靠性。
將該熱固性樹脂組合物於175℃下熱處理1小時後之固化物之儲存彈性模數E'並無特別限定，較佳為100MPa以上且10000MPa以下，更佳為500MPa以上且7000MPa以下，進而較佳為1000MPa以上且5000MPa以下。藉此，固化物可獲得適度之剛性，促進熱響應行為之差異之吸收或分散而可進一步提高半導體裝置之可靠性。
將上述熱固性樹脂組合物於175℃下熱固處理1小時後之玻璃轉移溫度(Tg)較佳為100~180℃，更佳為130~170℃。藉由將熱固後之熱固性樹脂組合物之玻璃轉移溫度設為上述範圍，可抑制熱循環可靠性試驗之溫度範圍內之急遽之物性變化，從而可期待可靠性之進一步提高。
於本實施形態中，熱固前之上述熱固性樹脂組合物2於100~200℃下之最低熔融黏度較佳為100Pa．s以上且20000Pa．s以下，更佳為1000Pa．s以上且10000Pa．s以下。藉由將最低熔融黏度設為上述範 圍，可使連接構件4(參照圖2A)容易進入熱固性樹脂組合物2。又，可防止半導體元件5之電性連接時之空隙之產生、及熱固性樹脂組合物2自半導體元件5與被黏著體6之間之空間之溢出(參照圖2E)。再者，最低熔融黏度之測定係使用流變計(HAAKE公司製造，RS-1)並藉由平行板法測定所得之值。更詳細而言，於間隙100μm、旋轉板直徑20mm、旋轉速度10s-1、升溫速度10℃/分鐘之條件下，於60℃至200℃之範圍內測定熔融黏度，將此時所獲得之於100℃至200℃之範圍內之熔融黏度之最低值設為最低熔融黏度。
又，熱固前之上述熱固性樹脂組合物2於23℃下之黏度較佳為0.01MPa．s以上且100MPa．s以下，更佳為0.1MPa．s以上且10MPa．s以下。藉由熱固前之熱固性樹脂組合物具有上述範圍之黏度，可提高切晶時之半導體晶圓3(參照圖2C)之保持性或作業時之操作性。再者，黏度之測定可依據最低熔融黏度之測定法進行。
進而，熱固前之上述熱固性樹脂組合物2於溫度23℃、濕度70%之條件下之吸水率較佳為1重量%以下，更佳為0.5重量%以下。藉由熱固性樹脂組合物2具有如上所述之吸水率，可抑制水分向熱固性樹脂組合物2之吸收，從而可更有效率地抑制半導體元件5之安裝時之空隙之產生。再者，上述吸水率之下限越小越佳，較佳為實質上為0重量%，更佳為0重量%。
熱固性樹脂組合物2之厚度(複層之情形時為總厚)並無特別限定，但若考慮熱固性樹脂組合物2之強度或半導體元件5與被黏著體6之間之空間之填充性，則亦可為10μm以上且100μm以下左右。再者，熱固性樹脂組合物2之厚度可考慮半導體元件5與被黏著體6之間之間隙或連接構件之高度而適當設定。
密封片材10之熱固性樹脂組合物2較佳為由分隔件所保護(未圖示)。分隔件具有作為供實用之前保護熱固性樹脂組合物2之保護材之 功能。分隔件係於在密封片材之熱固性樹脂組合物2上貼合半導體晶圓3時被剝離。作為分隔件，亦可使用藉由聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或氟系剝離劑、丙烯酸長鏈烷基酯系剝離劑等剝離劑進行表面塗佈而成之塑膠膜或紙等。
[背面研削用膠帶]
背面研削用膠帶1具備基材1a、及積層於基材1a上之黏著劑層1b。再者，熱固性樹脂組合物2係積層於黏著劑層1b上。
(基材)
上述基材1a係成為密封片材10之強度母體者。例如可列舉：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯、聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧樹脂、金屬(箔)、紙等。於黏著劑層1b為紫外線固化型之情形時，基材1a較佳為對紫外線具有透過性者。
又，作為基材1a之材料，可列舉上述樹脂之交聯體等聚合物。上述塑膠膜可未經延伸而使用，視需要亦可使用實施有單軸或雙軸之延伸處理者。
為了提高與鄰接之層之密接性、保持性等，基材1a之表面可實施慣用之表面處理，例如鉻酸處理、臭氧曝露、火焰曝露、高壓電擊曝露、離子化放射線處理等化學或物理處理、利用底塗劑(例如黏著物質)之塗佈處理。
上述基材1a可適當選擇使用同種或異種者，視需要可使用摻合有數種者。又，為了對基材1a賦予抗靜電能力，可於上述基材1a上設置包含金屬、合金、該等之氧化物等之厚度為30~500Å左右之導電性物質之蒸鍍層。基材1a可為單層或2種以上之複層。
基材1a之厚度可適當決定，通常為5μm以上且200μm以下左右，較佳為35μm以上且120μm以下。
再者，基材1a中亦可於無損本發明之效果等之範圍內包含各種添加劑(例如著色劑、填充劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、阻燃劑等)。
(黏著劑層)
用於形成黏著劑層1b之黏著劑只要為於切晶時能夠經由熱固性樹脂組合物牢固地保持半導體晶圓或半導體晶片、於拾取時能夠可剝離地控制附有熱固性樹脂組合物之半導體晶片者則並無特別限制。例如可使用丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性接著劑。作為上述感壓性接著劑，就半導體晶圓或玻璃等忌避污染之電子零件的利用超純水或醇等有機溶劑之清潔洗淨性等方面而言，較佳為以丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑。
作為上述丙烯酸系聚合物，可列舉使用丙烯酸酯作為主單體成分者。作為上述丙烯酸酯，例如可列舉：使用(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數1~30、尤其是碳數4~18之直鏈狀或支鏈狀之烷基酯等)及(甲基)丙烯酸環烷基酯(例如，環戊酯、環己酯等)之1種或2種以上作為單體成分之丙烯酸系聚合物等。再者，所謂(甲基)丙烯酸酯，係指丙烯酸酯及/或甲基 丙烯酸酯，本發明之(甲基)全部為相同之含義。
以凝聚力、耐熱性等之改質為目的，上述丙烯酸系聚合物亦可視需要包含對應於可與上述(甲基)丙烯酸烷基酯或環烷基酯共聚合之其他單體成分的單元。作為此種單體成分，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基之單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等含羥基之單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺基丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體；丙烯醯基磷酸2-羥基乙酯等含磷酸基之單體；丙烯醯胺、丙烯腈等。該等可共聚之單體成分可使用1種或2種以上。該等可共聚之單體之使用量較佳為全部單體成分之40重量%以下。
進而，上述丙烯酸系聚合物為了進行交聯，亦可視需要包含多官能性單體等作為共聚合用單體成分。作為此種多官能性單體，例如可列舉己二醇二(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、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。該等多官能性單體亦可使用1種或2種以上。就黏著特性等方面而言，多官能性單體之使用量較佳為全部單體成分之30重量%以下。
上述丙烯酸系聚合物可藉由將單一單體或2種以上之單體之混合 物供於聚合而獲得。聚合以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任一種方式進行均可。就防止污染清潔之被黏著體等方面而言，較佳為低分子量物質之含量較少。就該方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，進而較佳為40萬~300萬左右。
又，為了提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，於上述黏著劑中亦可適當採用外部交聯劑。作為外部交聯方法之具體方法，可列舉添加聚異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂之交聯劑使之反應的方法。於使用外部交聯劑之情形時，其使用量可根據與應交聯之基礎聚合物之平衡，進而根據作為黏著劑之使用用途而適當決定。通常相對於上述基礎聚合物100重量份，較佳為調配約5重量份以下，進而較佳為調配0.1~5重量份。進而，於黏著劑中，視需要除上述成分以外，亦可使用先前公知之各種黏著賦予劑、抗老化劑等添加劑。
黏著劑層1b可藉由放射線固化型黏著劑而形成。放射線固化型黏著劑可藉由紫外線等放射線之照射而使交聯度增大從而可容易地降低其黏著力，可容易地進行拾取。作為放射線，可列舉X射線、紫外線、電子束、α射線、β射線、中子射線等。
放射線固化型黏著劑可無特別限制地使用具有碳-碳雙鍵等放射線固化性之官能基且顯示黏著性者。作為放射線固化型黏著劑，例如可例示：上述丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配有放射線固化性之單體成分或低聚物成分的添加型之放射線固化性黏著劑。
作為所調配之放射線固化性之單體成分，例如可列舉：胺基甲酸酯低聚物、(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸 酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，放射線固化性之低聚物成分可列舉胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，其重量平均分子量為100~30000左右之範圍者較為適當。放射線固化性之單體成分或低聚物成分之調配量可根據上述黏著劑層之種類，適當決定可降低黏著劑層之黏著力之量。通常，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為5~500重量份，較佳為40~150重量份左右。
又，作為放射線固化型黏著劑，除上述說明之添加型之放射線固化性黏著劑外，亦可列舉使用在聚合物側鏈或主鏈中或主鏈末端具有碳-碳雙鍵者作為基礎聚合物的內在型之放射線固化性黏著劑。內在型之放射線固化性黏著劑無須含有作為低分子成分之低聚物成分等或者大多數不含，故而低聚物成分等不會經時性地於黏著劑中移動，可形成穩定之層結構之黏著劑層，故而較佳。
上述具有碳-碳雙鍵之基礎聚合物可無特別限制地使用具有碳-碳雙鍵且具有黏著性者。作為此種基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架者。作為丙烯酸系聚合物之基本骨架，可列舉上述例示之丙烯酸系聚合物。
碳-碳雙鍵向上述丙烯酸系聚合物之導入法並無特別限制，可採用各種方法，但分子設計較為容易的是將碳-碳雙鍵導入至聚合物側鏈。例如可列舉如下方法：預先使具有官能基之單體共聚合成丙烯酸系聚合物後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物於維持碳-碳雙鍵之放射線固化性之狀態下進行縮合或加成反應。
作為該等官能基之組合之例，可列舉羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。該等官能基之組合中，就追蹤反應之容易性而言，較佳為羥基與異氰酸酯基之組合。又，根據該等官 能基之組合，只要為如生成上述具有碳-碳雙鍵之丙烯酸系聚合物般之組合，則官能基亦可位於丙烯酸系聚合物與上述化合物之任一側，但於上述較佳之組合中，較佳為丙烯酸系聚合物具有羥基、上述化合物具有異氰酸酯基之情形。該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可列舉甲基丙烯醯基異氰酸酯、2-甲基丙烯醯氧基乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用使上述例示之含羥基之單體或2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚之醚系化合物等共聚合而成者。
上述內在型之放射線固化性黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(尤其是丙烯酸系聚合物)，亦可於不使特性惡化之程度上調配上述放射線固化性之單體成分或低聚物成分。放射線固化性之低聚物成分等通常相對於基礎聚合物100重量份為30重量份之範圍內，較佳為0~10重量份之範圍。
上述放射線固化型黏著劑中，於藉由紫外線等使之固化之情形時，較佳為含有光聚合起始劑。作為光聚合起始劑，例如可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-啉基丙烷-1等苯乙酮系化合物；安息香乙醚、安息香異丙醚、茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；9-氧硫、2-氯-9-氧硫、2-甲基-9-氧硫、2,4-二甲基-9-氧硫、異丙基-9-氧硫、2,4-二氯-9-氧硫、2,4-二乙基-9-氧 硫、2,4-二異丙基-9-氧硫等9-氧硫系化合物；樟腦醌；鹵代酮；醯基膦氧化物；醯基膦酸酯等。光聚合起始劑之調配量係相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份例如為0.05~20重量份左右。
再者，於照射放射線時由氧氣引起固化阻礙之情形時，較理想為利用某些方法自放射線固化型之黏著劑層1b之表面阻斷氧氣(空氣)。例如可列舉：將上述黏著劑層1b之表面以隔片被覆之方法、或於氮氣環境中進行紫外線等放射線之照射之方法等。
再者，黏著劑層1b中亦可於無損本發明之效果等之範圍內包含各種添加劑(例如，著色劑、增黏劑、增量劑、填充劑、黏著賦予劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、交聯劑等)。
黏著劑層1b之厚度並無特別限定，就防止晶片切斷面之缺損、保持熱固性樹脂組合物2之固定之兼具性等觀點而言，較佳為1~50μm左右。較佳為2~30μm，進而較佳為5~25μm。
(密封片材之製造方法)
本實施形態之密封片材10例如可藉由分別預先製作背面研削用膠帶1及熱固性樹脂組合物2，最後將該等貼合而製作。具體而言，可依據如下順序進行製作。
首先，基材1a可藉由先前公知之製膜方法進行製膜。作為該製膜方法，例如可例示軋光機製膜法、有機溶劑中之流延法、密閉系統中之吹脹擠出法、T型模頭擠出法、共擠壓法、乾式層壓法等。
其次，製備黏著劑層形成用之黏著劑組合物。於黏著劑組合物中調配如黏著劑層之項中說明般之樹脂或添加物等。將製備而成之黏著劑組合物塗佈於基材1a上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥(視需要使之加熱交聯)，形成黏著劑層1b。作為塗佈方法，並無特別限定，例如可列舉輥式塗佈、網版塗佈、凹版塗佈等。又，作 為乾燥條件，例如於乾燥溫度80~150℃、乾燥時間0.5~5分鐘之範圍內進行。又，亦可於分隔件上塗佈黏著劑組合物而形成塗佈膜，其後於上述乾燥條件下使塗佈膜乾燥而形成黏著劑層1b。其後，將黏著劑層1b與分隔件一併貼合於基材1a上。藉此，製作具備基材1a及黏著劑層1b之背面研削用膠帶1。
片狀之熱固性樹脂組合物2例如以如下方式製作。首先，調配作為熱固性樹脂組合物2之形成材料之環氧樹脂及特定酚樹脂，視需要調配熱塑性成分或各種添加劑等，使之適當溶解或分散於溶劑(例如，甲基乙基酮、乙酸乙酯等)中而製備塗佈液。
其次，以成為特定厚度之方式將所製備之塗佈液塗佈於基材分隔件上而形成塗佈膜，其後使該塗佈膜於特定條件下乾燥，形成片狀之熱固性樹脂組合物。作為塗佈方法，並無特別限定，例如可列舉輥式塗佈、網版塗佈、凹版塗佈等。又，作為乾燥條件，例如於乾燥溫度70~160℃、乾燥時間1~5分鐘之範圍內進行。又，亦可於分隔件上塗佈塗佈液而形成塗佈膜，其後於上述乾燥條件下使塗佈膜乾燥而形成片狀之熱固性樹脂組合物。其後，將熱固性樹脂組合物與分隔件一併貼合於基材分隔件上。
繼而，分別自背面研削用膠帶1及熱固性樹脂組合物2剝離分隔件，以熱固性樹脂組合物與黏著劑層成為貼合面之方式將兩者貼合。貼合例如可藉由壓接進行。此時，層壓溫度並無特別限定，例如較佳為30~50℃，更佳為35~45℃。又，線壓並無特別限定，例如較佳為0.98~196N/cm，更佳為9.8~98N/cm。其次，將熱固性樹脂組合物上之基材分隔件剝離，獲得本實施形態之密封片材。
<半導體裝置之製造方法>
其次，對利用上述密封片材之半導體裝置之製造方法之一實施形態進行說明。本實施形態之半導體裝置之製造方法包括：固定步 驟，其係將半導體元件經由上述熱固性樹脂組合物固定於被黏著體；及固化步驟，其係使上述熱固性樹脂組合物固化。然而，於本實施形態中，上述熱固性樹脂組合物係積層於背面研削用膠帶上而形成密封片材，又，於固定半導體元件時，將被黏著體與半導體元件電性連接。因此，更詳細而言，本實施形態之半導體裝置之製造方法包括：貼合步驟，其係將半導體晶圓之形成有連接構件之電路面與上述密封片材之熱固性樹脂組合物貼合；研削步驟，其係對上述半導體晶圓之背面進行研削；晶圓固定步驟，其係將半導體晶圓與上述熱固性樹脂組合物一併自背面研削用膠帶剝離，並將該半導體晶圓貼附於切晶膠帶；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述熱固性樹脂組合物之半導體元件；及拾取步驟，其係將附有上述熱固性樹脂組合物之半導體元件自上述切晶膠帶剝離；連接步驟，其係一面將上述被黏著體與上述半導體元件之間之空間以上述熱固性樹脂組合物填充一面經由上述連接構件將上述半導體元件與上述被黏著體電性連接；及固化步驟，其係使上述熱固性樹脂組合物固化。
[貼合步驟]
於貼合步驟中，將半導體晶圓3之形成有連接構件4之電路面3a與上述密封片材10之熱固性樹脂組合物2貼合(參照圖2A)。
(半導體晶圓)
於半導體晶圓3之電路面3a形成有複數個連接構件4(參照圖2A)。作為凸塊或導電材等連接構件之材質，並無特別限定，例如可列舉錫-鉛系金屬材、錫-銀系金屬材、錫-銀-銅系金屬材、錫-鋅系金屬材、錫-鋅-鉍系金屬材等焊錫類(合金)、或金系金屬材、銅系金屬材等。連接構件之高度亦視用途而定，通常為15~100μm左右。當然，半導體晶圓3中之各連接構件之高度可相同亦可不同。
於本實施形態之半導體裝置之製造方法中，作為熱固性樹脂組 合物之厚度，較佳為形成於半導體晶圓表面之連接構件之高度X(μm)與上述熱固性樹脂組合物之厚度Y(μm)滿足下述關係。
0.5≦Y/X≦2
藉由使上述連接構件之高度X(μm)與上述固化膜之厚度Y(μm)滿足上述關係，可充分填充半導體元件與被黏著體之間之空間，並且可防止熱固性樹脂組合物自該空間之過剩之溢出，從而可防止由熱固性樹脂組合物引起之半導體元件之污染等。再者，於各連接構件之高度不同之情形時，以最高之連接構件之高度為基準。
(貼合)
首先，將任意地設置於密封片材10之熱固性樹脂組合物2上之分隔件適當剝離，如圖2A所示，使上述半導體晶圓3之形成有連接構件4之電路面3a與熱固性樹脂組合物2對向，將上述熱固性樹脂組合物2與上述半導體晶圓3貼合(安裝)。
貼合之方法並無特別限定，較佳為利用壓接之方法。壓接通常利用壓接輥等公知之擠壓機構，一面負載較佳為0.1~1MPa、更佳為0.3~0.7MPa之壓力按壓一面進行。此時，亦可一面加熱至40~100℃左右一面進行壓接。又，為了提高密接性，亦可於減壓下(1~1000Pa)進行壓接。
[研削步驟]
於研削步驟中，對上述半導體晶圓3之與電路面3a相反側之面(即，背面)3b進行研削(參照圖2B)。作為用於半導體晶圓3之背面研削之薄型加工機，並無特別限定，例如可例示研削機(背面研磨機)、研磨墊等。又，亦可以蝕刻等化學方法進行背面研削。背面研削係進行至半導體晶圓成為所需之厚度(例如，700~25μm)為止。
[晶圓固定步驟]
研削步驟後，於貼附有熱固性樹脂組合物2之狀態下將半導體晶 圓3自背面研削用膠帶1剝離，並將半導體晶圓3與切晶膠帶11貼合(參照圖2C)。此時，以半導體晶圓3之背面3b與切晶膠帶11之黏著劑層11b對向之方式貼合。因此，貼合於半導體晶圓3之電路面3a之熱固性樹脂組合物2成為露出之狀態。再者，切晶膠帶11具有於基材11a上積層有黏著劑層11b之構造。作為基材11a及黏著劑層11b，可使用上述背面研削用膠帶1之基材1a及黏著劑層1b之項中所示之成分及製法而較佳地製作。又，市售之切晶膠帶亦可較佳地使用。
將半導體晶圓3自背面研削用膠帶1剝離時，於黏著劑層1b具有放射線固化性之情形時，藉由對黏著劑層1b照射放射線使黏著劑層1b固化，而可容易地進行剝離。放射線之照射量只要考慮所使用之放射線之種類或黏著劑層之固化度等而適當設定即可。
[切晶步驟]
於切晶步驟中，基於藉由直接光或間接光、紅外線等而求出之切晶位置，如圖2D所示對半導體晶圓3及熱固性樹脂組合物2進行切晶，而形成切晶所得之附有熱固性樹脂組合物之半導體元件5。藉由根據無機填充劑之平均粒徑等適當調整熱固性樹脂組合物2之透明性，可容易地決定切晶位置。藉由經過切晶步驟，將半導體晶圓3切斷為特定之尺寸而單片化(小片化)，從而製造半導體晶片(半導體元件)5。此處所獲得之半導體晶片5係與切斷為相同形狀之熱固性樹脂組合物2成為一體。切晶係自半導體晶圓3之貼合有熱固性樹脂組合物2之電路面3a依據常規方法進行。
於本步驟中，例如可採用切入至切晶膠帶11為止之被稱為全切之切斷方式等。作為本步驟中使用之切晶裝置，並無特別限定，可使用先前公知者。又，半導體晶圓係藉由切晶膠帶11以優異之密接性接著固定，因此可抑制晶片缺損或晶片飛散，並且亦可抑制半導體晶圓之破損。再者，若熱固性樹脂組合物係藉由包含環氧樹脂之樹脂組合物 所形成，則即便藉由切晶進行切斷，亦可抑制或防止在其切斷面中產生熱固性樹脂組合物之糊劑溢出。其結果為，可抑制或防止切斷面彼此再附著(黏連)，可更良好地進行下述拾取。
再者，於繼切晶步驟進行切晶膠帶之延伸之情形時，該延伸可使用先前公知之延伸裝置進行。延伸裝置具有可經由切晶環將切晶膠帶向下方按下之環狀之外環、及直徑小於外環且支持切晶膠帶之內環。藉由該延伸步驟，於下述拾取步驟中，可防止鄰接之半導體晶片彼此接觸而破損。
[拾取步驟]
為了將接著固定於切晶膠帶11之半導體晶片5回收，如圖2E所示，進行附有熱固性樹脂組合物2之半導體晶片5之拾取，將半導體晶片5與熱固性樹脂組合物2之積層體A自切晶膠帶11剝離。
作為拾取之方法，並無特別限定，可採用先前公知之各種方法。例如可列舉如下方法等：利用針將各半導體晶片自切晶膠帶之基材側頂出，藉由拾取裝置將被頂出之半導體晶片拾取。再者，被拾取之半導體晶片5係與貼合於電路面3a之熱固性樹脂組合物2成為一體而構成積層體A。
此處關於拾取，於切晶膠帶11之黏著劑層11b為紫外線固化型之情形時，於對該黏著劑層11b照射紫外線後進行。藉此，黏著劑層11b對半導體晶片5之黏著力降低，半導體晶片5之剝離變得容易。其結果為，可不使半導體晶片5損傷而進行拾取。紫外線照射時之照射強度、照射時間等條件並無特別限定，視需要適當設定即可。又，作為紫外線照射中使用之光源，例如可使用低壓水銀燈、低壓高輸出燈、中壓水銀燈、無電極水銀燈、氙閃光燈、準分子燈、紫外LED(Light Emitting Diode，發光二極體)等。
[安裝步驟]
於安裝步驟中，藉由直接光或間接光、紅外線等預先求出半導體元件5之安裝位置，並根據所求出之安裝位置，一面將被黏著體16與半導體元件5之間之空間以熱固性樹脂組合物2填充一面經由連接構件4將半導體元件5與被黏著體16電性連接(參照圖2F)。藉由無機填充劑之平均粒徑等適當調整熱固性樹脂組合物2之透明性，藉此可容易地決定安裝位置。具體而言，於半導體晶片5之電路面3a與被黏著體16對向之形態下，依據常規方法使積層體A之半導體晶片5固定於被黏著體16。例如，藉由一面使形成於半導體晶片5之凸塊(連接構件)4與被黏著於被黏著體16之連接焊墊之接合用之導電材17(焊錫等)接觸並擠壓一面使導電材熔融，而可確保半導體晶片5與被黏著體16之電性連接，從而可使半導體晶片5固定於被黏著體16。於半導體晶片5之電路面3a貼附有熱固性樹脂組合物2，因此於半導體晶片5與被黏著體16之電性連接之同時，半導體晶片5與被黏著體16之間之空間被熱固性樹脂組合物2所填充。
通常，安裝步驟中之加熱條件為100~300℃，加壓條件為0.5~500N。又，亦可以多階段進行安裝步驟中之熱壓接處理。例如，可採用於以150℃、100N處理10秒後以300℃、100~200N處理10秒的順序。藉由以多階段進行熱壓接處理，而可高效率地去除連接構件與焊墊間之樹脂，從而可獲得更良好之金屬間接合。
作為被黏著體16，可使用導線架或電路基板(配線電路基板等)等各種基板、其他半導體元件。作為基板之材質，並無特別限定，可列舉陶瓷基板、或塑膠基板。作為塑膠基板，例如可列舉環氧基板、雙順丁烯二醯亞胺三基板、聚醯亞胺基板、環氧玻璃基板等。
再者，於安裝步驟中，使連接構件及導電材之一者或兩者熔融，使半導體晶片5之連接構件形成面3a之凸塊4與被黏著體16之表面之導電材17連接，作為該凸塊4及導電材17之熔融時之溫度，通常成 為260℃左右(例如，250℃~300℃)。本實施形態之密封片材藉由利用環氧樹脂等形成熱固性樹脂組合物2，從而可成為具有亦能夠經受該安裝步驟中之高溫之耐熱性者。
[熱固性樹脂組合物固化步驟]
於進行半導體元件5與被黏著體16之電性連接後，藉由加熱使熱固性樹脂組合物2固化。藉此，可保護半導體元件5之表面，並且可將半導體元件5與被黏著體16之間之空間密封而確保半導體裝置之連接可靠性。作為用於熱固性樹脂組合物之固化之加熱溫度，並無特別限定，只要於150~200℃下進行10~120分鐘即可。再者，於藉由安裝步驟中之加熱處理而使熱固性樹脂組合物固化之情形時，可省略本步驟。
[後密封步驟]
其次，為了保護安裝而成之具備半導體晶片5之半導體裝置20整體，亦可進行後密封步驟。後密封步驟係使用密封樹脂進行。作為此時之密封條件，並無特別限定，通常藉由於175℃下進行60秒~90秒之加熱而進行密封樹脂之熱固，但本發明並不限定於此，例如可於165℃~185℃下固化數分鐘。
作為上述密封樹脂，只要為具有絕緣性之樹脂(絕緣樹脂)，則並無特別限制，可自公知之密封樹脂等密封材中適當選擇使用，但更佳為具有彈性之絕緣樹脂。作為密封樹脂，例如可列舉包含環氧樹脂之樹脂組合物等。作為環氧樹脂，可列舉上述例示之環氧樹脂等。又，作為基於包含環氧樹脂之樹脂組合物之密封樹脂，除環氧樹脂以外，亦可包含除環氧樹脂以外之熱固性樹脂(酚樹脂等)、或熱塑性樹脂等作為樹脂成分。再者，酚樹脂亦可用作環氧樹脂之固化劑，作為此種酚樹脂，可列舉上述例示之酚樹脂等。
[半導體裝置]
其次，一面參照圖式，一面對使用該密封片材所獲得之半導體裝置進行說明(參照圖2F)。於本實施形態之半導體裝置20中，半導體元件5與被黏著體16經由形成於半導體元件5上之凸塊(連接構件)4及設置於被黏著體16上之導電材17而電性連接。又，於半導體元件5與被黏著體16之間，以填充該空間之方式配置有熱固性樹脂組合物2。半導體裝置20可利用採用特定之熱固性樹脂組合物2之上述製造方法獲得，因此半導體元件5之表面保護、半導體元件5與被黏著體16之間之空間之填充、及半導體元件5與被黏著體16之間之電性連接分別成為充分之水準，作為半導體裝置20而可發揮較高之可靠性。
<第2實施形態>
於第1實施形態中使用單面形成有電路之半導體晶圓，相對於此，於本實施形態中使用兩面形成有電路之半導體晶圓製造半導體裝置。又，本實施形態中使用之半導體晶圓具有目標厚度，因此省略研削步驟。因此，作為第2實施形態中之密封片材，使用具備切晶膠帶及積層於該切晶膠帶上之熱固性樹脂組合物之密封片材。作為第2實施形態中之代表性步驟，可列舉如下步驟：準備步驟，其係準備上述密封片材；貼合步驟，其係將於兩面形成有具有連接構件之電路面之半導體晶圓與上述密封片材之熱固性樹脂組合物貼合；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述熱固性樹脂組合物之半導體元件；拾取步驟，其係將附有上述熱固性樹脂組合物之半導體元件自上述密封片材剝離。其後，進行安裝步驟以後之步驟而製造半導體裝置。
[準備步驟]
於準備步驟中，準備具備切晶膠帶41及積層於該切晶膠帶41上之熱固性樹脂組合物42之密封片材(參照圖3A)。切晶膠帶41具備基材41a、及積層於基材41a上之黏著劑層41b。再者，熱固性樹脂組合物 42係積層於黏著劑層41b上。作為此種切晶膠帶41之基材41a及黏著劑層41b、以及熱固性樹脂組合物42，可使用與第1實施形態相同者。
[貼合步驟]
於貼合步驟中，如圖3A所示，將於兩面形成有具有連接構件44之電路面之半導體晶圓43與上述密封片材之熱固性樹脂組合物42貼合。再者，薄型化為特定厚度之半導體晶圓之強度較弱，故而有為了補強而將半導體晶圓經由暫時固定材固定於支持玻璃等支持體之情形(未圖示)。該情形時，亦可於半導體晶圓與熱固性樹脂組合物之貼合後，包括將支持體與暫時固定材一併剝離之步驟。將半導體晶圓43之哪一電路面與熱固性樹脂組合物42貼合只要根據目標之半導體裝置之構造變更即可。
作為半導體晶圓43，除於兩面形成有具有連接構件44之電路面且具有特定厚度之方面外，與第1實施形態之半導體晶圓相同。半導體晶圓43之兩面之連接構件44彼此可電性連接，亦可不連接。連接構件44彼此之電性連接可列舉被稱為TSV(Through Silicon Via，矽穿孔)形式之利用經由通孔之連接的連接等。作為貼合條件，可較佳地採用第1實施形態中之貼合條件。
[切晶步驟]
於切晶步驟中，對上述半導體晶圓43及熱固性樹脂組合物42進行切晶而形成附有上述熱固性樹脂組合物之半導體元件45(參照圖3B)。作為切晶條件，可較佳地採用第1實施形態中之各條件。再者，切晶係對半導體晶圓43之露出之電路面進行，因此容易檢測出切晶位置。
[拾取步驟]
於拾取步驟中，將附有上述熱固性樹脂組合物42之半導體元件45自上述切晶膠帶41剝離(圖3C)。作為拾取條件，可較佳地採用第1 實施形態中之各條件。
[安裝步驟]
於安裝步驟中，一面將被黏著體66與半導體元件45之間之空間以熱固性樹脂組合物42填充一面經由連接構件44將半導體元件45與被黏著體66電性連接(參照圖3D)。安裝步驟中之條件可較佳地採用第1實施形態中之各條件。藉此，可製造本實施形態之半導體裝置60。
以後，亦可與第1實施形態同樣地，視需要進行熱固性樹脂組合物固化步驟及密封步驟。
<第3實施形態>
於第1實施形態中使用背面研削用膠帶作為密封片材之構成構件，但於本實施形態中不設置該背面研削用膠帶之黏著劑層而使用單獨之基材。因此，作為本實施形態之密封片材，成為於基材上積層有熱固性樹脂組合物之狀態。於本實施形態中研削步驟可任意地進行，但拾取步驟前之紫外線照射因黏著劑層之省略而未進行。若除去該等方面，則可藉由經過與第1實施形態同樣之步驟而製造特定之半導體裝置。
[實施例]
以下，以例示之方式詳細地說明本發明之較佳實施例。然而，本實施例中記載之材料或調配量等只要無特別限定性之記載，則並非旨在將本發明之範圍僅限定於該等。又，記為份時，意指重量份。
[實施例1~4及比較例1~4]
(密封片材之製作)
將以下成分以表1所示之比率溶解於甲基乙基酮中，製備固形物成分濃度成為23.6~60.6重量%之接著劑組合物之溶液。
彈性體1：以丙烯酸乙酯-甲基丙烯酸甲酯為主成分之丙烯酸酯系聚合物(商品名「PARACRON W-197CM」，根上工業股份有限公司製 造)
彈性體2：以丙烯酸丁酯-丙烯腈為主成分之丙烯酸酯系聚合物(商品名「SG-28GM」，Nagase ChemteX股份有限公司製造)
環氧樹脂1：商品名「Epikote 828」，JER股份有限公司製造
環氧樹脂2：商品名「Epikote 1004」，JER股份有限公司製造
酚樹脂1：商品名「MEH-7851M」，明和化成股份有限公司製造
酚樹脂2：商品名「MEH-7851-3H」，明和化成股份有限公司製造
酚樹脂3：商品名「P-200」，荒川化學股份有限公司製造
酚樹脂4：商品名「DPP-M」，日本石油化學(股)製造
無機填充劑1：球狀二氧化矽(商品名「YC100C-MLC」，Admatechs股份有限公司製造)
無機填充劑2：球狀二氧化矽(商品名「SO-25R」，Admatechs股份有限公司製造)
有機酸：鄰茴香酸(商品名「Ortho-Anisic Acid」，東京化成股份有限公司製造)
固化劑：咪唑觸媒(商品名「2PHZ-PW」，四國化成股份有限公司製造)
將該接著劑組合物之溶液塗佈於作為剝離襯墊(分隔件)的經聚矽氧脫模處理之厚度為50μm之包含聚對苯二甲酸乙二酯膜之脫模處理膜上後，於130℃下乾燥2分鐘，藉此製作厚度45μm之熱固性樹脂組合物。
使用手壓輥將上述熱固性樹脂組合物貼合於背面研磨膠帶(商品名「UB-2154」，日東電工股份有限公司製造)之黏著劑層上，製作密封片材。
(熱膨脹率α之測定)
熱膨脹率α係首先將所製作之熱固性樹脂組合物於175℃下熱固處理1小時後，使用熱機械測定裝置(TA Instruments公司製造：型號Q-400EM)進行測定。具體而言，將測定試樣之尺寸設為長度15mm×寬度5mm×厚度200μm，將測定試樣設置於上述裝置之膜拉伸測定用治具後，置於-50~300℃之溫度區域、且拉伸荷重2g、升溫速度10℃/min之條件下，由20℃~60℃下之膨脹率算出熱膨脹係數α。將結果示於表1。
(儲存彈性模數E'之測定)
儲存彈性模數之測定係將所製作之熱固性樹脂組合物於175℃下熱固處理1小時後，使用固體黏彈性測定裝置(Rheometric Scientific公司製造：型號：RSA-III)進行測定。即，藉由如下方式而獲得：將樣品尺寸設為長度40mm×寬度10mm×厚度200μm，將測定試樣設置於膜拉伸測定用治具，於頻率1Hz、升溫速度10℃/min之條件下測定-50~300℃之溫度區域內之拉伸儲存彈性模數及損失彈性模數，並讀取25℃下之儲存彈性模數(E')。將結果示於表1。
(玻璃轉移溫度之測定)
熱固性樹脂組合物之玻璃轉移溫度之測定方法如下所述。首先，使熱固性樹脂組合物於175℃下藉由1小時之加熱處理而熱固，其後以截切刀切取為厚度200μm、長度40mm(測定長度)、寬度10mm之短條狀，使用固體黏彈性測定裝置(RSAIII，Rheometric Scientific(股)製造)，測定-50~300℃下之儲存彈性模數及損失彈性模數。測定條件係設為頻率1Hz、升溫速度10℃/min。進而，藉由算出tanδ(G"(損失彈性模數)/G'(儲存彈性模數))之值而獲得玻璃轉移溫度。將結果示於表1。
(半導體裝置之製作)
準備單面形成有凸塊之單面附凸塊矽晶圓，將所製作之密封片 材以熱固性樹脂組合物作為貼合面而貼合於該單面附凸塊矽晶圓之形成有凸塊之側之面。作為單面附凸塊矽晶圓，使用以下者。又，貼合條件如下所述。熱固性樹脂組合物之厚度Y(=45μm)相對於連接構件之高度X(=45μm)之比(Y/X)為1。
<單面附凸塊矽晶圓>
矽晶圓之直徑：8英吋
矽晶圓之厚度：0.7mm(700μm)
凸塊之高度：45μm
凸塊之間距：50μm
凸塊之材質：焊錫
<貼合條件>
貼附裝置：商品名「DSA840-WS」，日東精機股份有限公司製造
貼附速度：5mm/min
貼附壓力：0.25MPa
貼附時之載置台溫度：80℃
貼附時之減壓度：150Pa
依據上述順序將單面附凸塊矽晶圓與密封片材貼合後，於下述條件下研削矽晶圓之背面。
<研削條件>
研削裝置：商品名「DFG-8560」，DISCO公司製造
半導體晶圓：自厚度0.7mm(700μm)背面研削至0.2mm(200μm)
於背面研削後，將矽晶圓與熱固性樹脂組合物一併自背面研磨膠帶剝離，將矽晶圓貼合並固定於切晶膠帶(DU-300，日東電工(股)製造)之黏著劑層上。此時，矽晶圓之背面與黏著劑層貼合，且貼合於矽晶圓之電路面之熱固性樹脂組合物露出。
其次，於下述條件下進行半導體晶圓之切晶。切晶係以成為7.3 mm見方之晶片尺寸之方式全切。
<切晶條件>
切晶裝置：商品名「DFD-6361」DISCO公司製造
切晶環：「2-8-1」(DISCO公司製造)
切晶速度：30mm/sec
切晶刀片：
Z1：DISCO公司製造之「203O-SE 27HCDD」
Z2：DISCO公司製造之「203O-SE 27HCBB」
切晶刀片轉數：
Z1：40,000rpm
Z2：45,000rpm
切割方式：分步切割
晶圓晶片尺寸：7.3mm見方
其次，自各密封片材之基材側以利用針之頂出方式拾取熱固性樹脂組合物與單面附凸塊半導體晶片之積層體。拾取條件如下所述。
<拾取條件>
拾取裝置：商品名「SPA-300」新川股份有限公司製造
針根數：9根
針頂出量：500μm(0.5mm)
針頂出速度：20mm/秒
拾取時間：1秒
延伸量：3mm
最後，藉由下述熱壓接條件，於使半導體晶片之凸塊形成面與BGA(Ball Grid Array，球柵陣列)基板對向之狀態下將半導體晶片熱壓接於BGA基板而進行半導體晶片之安裝。藉此，獲得BGA基板上安裝有半導體晶片之半導體裝置。再者，於本步驟中，進行繼熱壓接條 件1後藉由熱壓接條件2進行熱壓接之兩階段之處理。
<熱壓接條件1>
拾取裝置：商品名「FCB-3」Panasonic製造
加熱溫度：150℃
荷重：98N
保持時間：10秒
<熱壓接條件2>
拾取裝置：商品名「FCB-3」Panasonic製造
加熱溫度：260℃
荷重：98N
保持時間：10秒
(半導體裝置之可靠性之評價)
將實施例及比較例之半導體裝置製作各10個樣品，將於-55℃~125℃下以30分鐘循環1次之熱循環重複500個循環後，將半導體裝置以包埋用環氧樹脂包埋。其次，將半導體裝置以焊錫接合部露出之方式於與基板垂直之方向上切斷，並對露出之焊錫接合部之剖面進行研磨。其後，藉由光學顯微鏡(倍率：1000倍)對經研磨之焊錫接合部之剖面進行觀察，將焊錫接合部未斷裂之情形評價為「○」，將焊錫接合部即便1個樣品斷裂之情形評價為「×」。將結果示於表1。
由表1可知，於實施例1~4之半導體裝置中，焊錫接合部之斷裂之產生得到抑制。另一方面，於比較例1~4之半導體裝置中焊錫接合部斷裂。根據以上可知，藉由使用包含環氧樹脂、及羥基當量為200g/eq以上之酚醛清漆型酚樹脂之熱固性樹脂組合物，可製造焊錫接合部之斷裂得到抑制之高可靠性之半導體裝置。
2‧‧‧熱固性樹脂組合物
4‧‧‧連接構件
5‧‧‧半導體晶片(半導體元件)
16‧‧‧被黏著體
17‧‧‧導電材
20‧‧‧半導體裝置

Claims (8)

  1. 一種半導體裝置製造用之熱固性樹脂組合物，其包含：環氧樹脂、及羥基當量為200g/eq以上之酚醛清漆型酚樹脂。
  2. 如請求項1之熱固性樹脂組合物，其為半導體元件密封用。
  3. 如請求項1之熱固性樹脂組合物，其中上述酚醛清漆型酚樹脂包含下述結構式所表示之結構， (式中，n為0~12之整數)。
  4. 如請求項1之熱固性樹脂組合物，其包含平均粒徑為10nm以上且1000nm以下之無機填充劑。
  5. 如請求項1之熱固性樹脂組合物，其於175℃下熱處理1小時後之熱膨脹係數α為10ppm/K以上且200ppm/K以下。
  6. 如請求項1之熱固性樹脂組合物，其於175℃下熱處理1小時後之儲存彈性模數E'為100MPa以上且10000MPa以下。
  7. 如請求項1之熱固性樹脂組合物，其為片狀。
  8. 一種半導體裝置之製造方法，其包括：固定步驟，其係將半導體元件經由如請求項1至7中任一項之熱固性樹脂組合物固定於被黏著體；及固化步驟，其係使上述熱固性樹脂組合物固化。
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