TW201538583A - 底部填充材、積層片及半導體裝置之製造方法 - Google Patents

底部填充材、積層片及半導體裝置之製造方法 Download PDF

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Publication number
TW201538583A
TW201538583A TW104107070A TW104107070A TW201538583A TW 201538583 A TW201538583 A TW 201538583A TW 104107070 A TW104107070 A TW 104107070A TW 104107070 A TW104107070 A TW 104107070A TW 201538583 A TW201538583 A TW 201538583A
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Prior art keywords
underfill material
underfill
resin
acid
semiconductor
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TW104107070A
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English (en)
Inventor
Naohide Takamoto
Hiroyuki Hanazono
Akihiro Fukui
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Nitto Denko Corp
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Publication of TW201538583A publication Critical patent/TW201538583A/zh

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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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Abstract

本發明提供一種具有充分之硬化反應性並且即便承受熱歷程黏度變化亦較小而可達成良好之電性連接之底部填充材及具備其之積層片、以及半導體裝置之製造方法。本發明係一種底部填充材，其係加熱處理前於150℃下之熔融黏度為50Pa．s以上且3000Pa．s以下，將上述加熱處理前於150℃下之熔融黏度設為η1，並將於130℃下進行1小時加熱處理後於150℃下之熔融黏度設為η2時，(η2/η1)×100所表示之黏度變化率為500%以下，將DSC測定中自-50℃至300℃為止之升溫過程中之總發熱量設為Qt，並將於175℃下進行2小時加熱後自-50℃至300℃為止之升溫過程中的總發熱量設為Qh時，{(Qt-Qh)/Qt}×100所表示之反應率為90%以上。

Description

底部填充材、積層片及半導體裝置之製造方法
本發明係關於一種底部填充材、積層片及半導體裝置之製造方法。
近年來，更進一步追求半導體裝置及其封裝體之薄型化、小型化。作為實現其之對策，而廣泛利用藉由覆晶接合將半導體晶片等半導體元件安裝於基板上(覆晶連接)而得之覆晶型半導體裝置。覆晶連接係於半導體晶片之電路面與被黏著體之電極形成面對向之狀態下(面朝下)半導體晶片經由形成於其電路面之突起電極而被固定至被黏著體的安裝法。於半導體元件對被黏著體之覆晶安裝中，使設置於半導體元件之焊接凸塊等熔融而將兩者電性連接。
為了保護半導體元件表面或確保半導體元件與基板之間之連接可靠性，覆晶連接後對半導體元件與基板之間之空間進行密封樹脂填充。作為此種密封樹脂，雖然廣泛地使用液狀密封樹脂(底部填充材)，但液狀密封樹脂難以調整注入位置或注入量。因此，業界提出有使用片狀密封樹脂填充半導體元件與基板之間之空間的技術(專利文獻1)。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利第4438973號
根據上述技術，半導體元件與被黏著體之間之空間被填充而獲得良好之連接可靠性。然而，例如於可列舉為半導體裝置製造製程之晶片磊晶圓(CoW)製程、或TSV(Through Silicon Via，矽穿孔)積層製程中，為了實現製程之效率化，推薦如下順序：利用覆晶連接方式將附有底部填充材之多個半導體晶片暫時固定於被黏著體(半導體晶圓或半導體晶片)上，最後進行加熱而一次性全部接合。於該情形時，於步驟之初期接合之半導體晶片與於末期接合之半導體晶片之間產生熱歷程之差。因此，於初期接合之半導體晶片之底部填充材因熱歷程之影響而黏度大幅改變，其結果存在如下情形：於一次性全部接合時，於凸塊等連接構件產生龜裂、或連接構件彼此無法接合，而無法謀求半導體晶片向被黏著體之電性連接。
與此相對，為了減少熱歷程之影響，亦可採用使底部填充材之反應性降低之對策，但若過度地使反應性降低，則為了使硬化反應充分地進行而需要長時間或高溫，而有無法謀求製程效率化之虞。
本發明係鑒於上述問題而成者，目的在於提供一種具有充分之硬化反應性、並且即便承受熱歷程黏度變化亦較小而可達成良好之電性連接的底部填充材及具備其之積層片、以及半導體裝置之製造方法。
本申請案發明者等人潛心研究，結果發現，藉由採用下述構成可達成上述目的，從而完成本發明。
即，本發明係一種底部填充材，其係加熱處理前於150℃下之熔融黏度為50Pa．s以上且3000Pa．s以下，將上述加熱處理前於150℃下之熔融黏度設為η1，且將於130℃下進行1小時加熱處理後於150℃下之熔融黏度設為η2時， (η2/η1)×100所表示之黏度變化率為500%以下，將DSC(Differential Scanning Calorimetry，示差掃描熱量)測定中自-50℃至300℃為止之升溫過程中之總發熱量設為Qt，且將於175℃下進行2小時加熱後自-50℃至300℃為止之升溫過程中之總發熱量設為Qh時，{(Qt-Qh)/Qt}×100所表示之反應率為90%以上。
該底部填充材係加熱處理前於150℃下之熔融黏度(以下，有時簡稱為「熔融黏度」)為50Pa．s以上且3000Pa．s以下。藉由採用上述下限，可防止底部填充材自半導體晶片溢出。另一方面，藉由採用上述上限，而連接構件向底部填充材之進入變得容易，可提高電性連接之確實性。若未達上述下限，則存在底部填充材之溢出量變大而產生周邊要素之污染等之情形。又，若超過上述上限，則有連接構件向底部填充材之進入變得不充分而無法實現電性連接之虞。
又，該底部填充材係130℃下之加熱處理前後於150℃下之黏度變化率(以下，有時簡稱為「黏度變化率」)為500%以下，因此可抑制加熱處理後之過度之黏度上升，即便於加強熱歷程之負荷之製程中亦可達成良好之電性連接。若黏度變化率超過500%，則有凸塊或墊等連接構件中產生應力而導致連接構件之龜裂、或阻礙連接構件彼此之接觸而無法謀求電性連接之虞。
進而，該底部填充材係將DSC測定中自-50℃至300℃為止之升溫過程中之總發熱量設為Qt，且將於175℃下進行2小時加熱後自-50℃至300℃為止之升溫過程中之總發熱量設為Qh時，{(Qt-Qh)/Qt}×100所表示之反應率(以下，有時簡稱為「反應率」)為90%以上。換言之，於175℃下進行2小時加熱硬化時底部填充材之硬化反應之進行度成為90%以上。如上所述，該底部填充材係儘管加熱後之黏度上升得到抑制，但於175℃下進行2小時加熱時底部填充材之硬化反應進行90%以上，因此無需進行高溫或長時間下之硬化處理，可有助於半導 體裝置之製造製程之效率化。若上述反應率未達90%，則與先前相比，因底部填充材之硬化而需要更高溫或更長時間之加熱處理，而製程效率下降。又，有底部填充材於硬化際之硬化反應進行度易變得不充分而耐濕耐熱可靠性下降之虞。
該底部填充材較佳為包含潛伏性硬化促進劑。藉此，可以較高之級別達成底部填充材之因熱歷程引起之黏度上升之抑制與硬化反應性的同時實現。
該底部填充材較佳為包含丙烯酸系樹脂，且相對於上述丙烯酸系樹脂100重量份包含1~2重量份之上述潛伏性硬化促進劑。
因含有丙烯酸系樹脂而被賦予適度之柔軟性，而作業性提高，並且藉由將潛伏性硬化促進劑相對於丙烯酸系樹脂之含量設為特定範圍而抑制意外之黏度上升及硬化反應，從而可獲得良好之電性連接。
於本發明中，亦包括一種積層片，其具備：黏著帶，其具有基材及設置於該基材上之黏著劑層；及該底部填充材，其積層於上述黏著劑層上。
藉由將該底部填充材與黏著帶一體地使用，可謀求半導體晶圓之加工至半導體元件之安裝之製造過程的效率化。
上述黏著帶可為半導體晶圓之背面研削用帶或切晶帶中之任一者。
本發明亦包括一種半導體裝置之製造方法，其係製造具備被黏著體、與該被黏著體電性連接之半導體元件、及填充該被黏著體與該半導體元件之間之空間之底部填充材的半導體裝置者，且該方法包括：準備於上述半導體元件貼合有該底部填充材之附有底部填充材半導體元件之步驟；及利用上述底部填充材填充上述被黏著體與上述半導體元件之間 之空間，並且將上述半導體元件與上述被黏著體電性連接之連接步驟。
該製造方法係使用具有特定之黏度變化率、熔融黏度、及反應率之底部填充材，因此即便於因將複數個半導體元件搭載或積層至被黏著體而底部填充材承受熱歷程之情形時，亦可抑制底部填充材之黏度上升，獲得半導體元件與被黏著體之良好之電性連接。又，由於具備適度之硬化反應性，因此可謀求製程效率之提高。
1‧‧‧切晶帶
1a‧‧‧基材
1b‧‧‧黏著劑層
2‧‧‧底部填充材
3‧‧‧半導體晶圓
3a‧‧‧電路面
3b‧‧‧電路面
4a‧‧‧連接構件(凸塊)
4b‧‧‧背面電極
10‧‧‧積層片
16‧‧‧被黏著體
17‧‧‧導電材
20‧‧‧半導體裝置
31‧‧‧半導體晶片(半導體元件)
32‧‧‧半導體元件(半導體晶片)
40‧‧‧半導體裝置
A‧‧‧積層體
圖1A係表示本發明之一實施形態之半導體裝置之製造步驟的一步驟之剖面示意圖。
圖1B係表示本發明之一實施形態之半導體裝置之製造步驟的一步驟之剖面示意圖。
圖1C係表示本發明之一實施形態之半導體裝置之製造步驟的一步驟之剖面示意圖。
圖1D係表示本發明之一實施形態之半導體裝置之製造步驟的一步驟之剖面示意圖。
圖1E係表示本發明之一實施形態之半導體裝置之製造步驟的一步驟之剖面示意圖。
以下，揭示實施形態，詳細地對本發明進行說明，但本發明並不僅僅限定於該等實施形態。其中，於圖之一部分或全部，省略對說明而言多餘之部分，又，存在為了使說明較為容易而放大或縮小等進行圖示之部分。
<第1實施形態>
以下，以具備切晶帶及積層於該切晶帶上之特定之底部填充材的積層片及使用其之半導體裝置之製造方法為例，對本發明之一實施 形態進行說明。因此，於本實施形態中，使用切晶帶作為黏著帶。以下之說明基本上亦可應用於僅底部填充材之情形。
於本實施形態中，使用於兩面形成有電路之半導體晶圓製造半導體裝置。又，進行切晶帶上之切晶、半導體元件之拾取，最後將半導體元件安裝於被黏著體。
作為本實施形態之代表性步驟，包括：準備步驟，其係準備上述積層片；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積層片之底部填充材貼合；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底部填充材之半導體元件；拾取步驟，其係將附有上述底部填充材之半導體元件自上述積層片剝離；對位步驟，其係使上述半導體元件與上述被黏著體之相對位置對準為彼此之預定連接位置；及連接步驟，其係利用上述底部填充材填充上述被黏著體與上述半導體元件之間之空間，並且經由上述連接構件而將上述半導體元件與上述被黏著體電性連接。
[準備步驟]
(積層片)
於準備步驟中，準備具備切晶帶1及積層於該切晶帶1上之特定之底部填充材2之積層片10(參照圖1A)。
(切晶帶)
切晶帶1具備基材1a、及積層於基材1a上之黏著劑層1b。底部填充材2係積層於黏著劑層1b上。再者，底部填充材2係如圖1A所示，以足以與半導體晶圓3貼合之尺寸設置即可，亦可積層於切晶帶1之整個面。
(基材)
上述基材1a形成積層片10之強度母體。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為紫外線硬化型之情形時，基材1a較佳為對紫外線具有透過性。
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，亦可視需要使用實施過單軸或雙軸延伸處理者。
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、臭氧暴露、火焰暴露、高壓電擊暴露、電離輻射處理等化學或物理處理、利用底塗劑(例如，下述黏著物質)之塗佈處理。
上述基材1a可適當選擇同種或不同種基材而使用，視需要可使用混合數種基材而成者。又，為了對基材1a賦予抗靜電功能，可於上述基材1a上設置由金屬、合金、該等之氧化物等形成之厚度為30~500Å左右之導電性物質之蒸鍍層。亦可藉由於基材中添加抗靜電劑而賦予抗靜電能力。基材1a可為單層或2種以上之複數層。
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)
黏著劑層1b之形成所使用之黏著劑只要為如下者則並無特別限制：於切晶時經由底部填充材牢固地保持半導體晶圓，並且於拾取時可控制附有底部填充材之半導體元件使之可剝離。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諱污染之電子零件之藉由超純水或酒精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為1~30、特別是碳數為4~18之直鏈狀或支鏈狀烷基酯等)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的丙烯酸系聚合物等。再者，所謂(甲基)丙烯酸酯，意指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)均為相同之含義。
為了凝聚力、耐熱性等之改質，上述丙烯酸系聚合物視需要亦可包含可與上述(甲基)丙烯酸烷基酯或環烷基酯共聚合之其他單體成分所對應的單位。作為此種單體成分，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基單體；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)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；2-羥基乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯醯胺、丙烯腈等。該等可共聚合之單體成分可使用1種或2種以上。該等可共聚合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，亦可包含多官能性單體等作為視需要之共聚合用單體成分。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、(甲基)丙烯酸聚酯、(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。多官能性單體之使用量就黏著特性等方面而言，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使單一單體或2種以上單體混合物聚合而獲得。聚合可利用溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等之任一方式進行。就防止對清潔之被黏著體之污染等方面而言，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，上述黏著劑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交聯劑並進行反應之方法。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。通常較佳為相對於上述基 礎聚合物100重量份而調配5重量份左右以下，進而較佳為調配0.1~5重量份。進而，黏著劑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可藉由放射線硬化型黏著劑形成。放射線硬化型黏著劑可藉由照射紫外線等放射線而增大交聯度並容易地降低其黏著力，從而可容易地進行附有底部填充材之半導體晶圓之剝離。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。
放射線硬化型黏著劑可並無特別限制地使用具有碳-碳雙鍵等放射線硬化性官能基且顯示黏著性者。作為放射線硬化型黏著劑，例如可例示於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硬化性單體成分或低聚物成分之添加型放射線硬化性黏著劑。
作為所調配之放射線硬化性單體成分，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，放射線硬化性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，較適當為其重量平均分子量為100~30000左右之範圍者。關於放射線硬化性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地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，作為放射線硬化型黏著劑，除上述說明之添加型放射線硬化性黏著劑以外，可列舉使用於聚合物側鏈或主鏈中或者主鏈末端具 有碳-碳雙鍵者作為基礎聚合物之內在型放射線硬化性黏著劑。內在型放射線硬化性黏著劑無需含有作為低分子成分之低聚物成分等，或不大量含有，故而無低聚物成分等經過一段時間於黏著劑中移動而可形成層結構穩定之黏著劑層，故而較佳。
上述具有碳-碳雙鍵之基礎聚合物可並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。
向上述丙烯酸系聚合物導入碳-碳雙鍵之方法並無特別限制，可採用各種方法，碳-碳雙鍵導入至聚合物側鏈時容易進行分子設計。例如，可列舉如下方法：預先使於丙烯酸系聚合物中具有官能基之單體共聚合後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物維持碳-碳雙鍵之放射線硬化性而直接進行縮合或加成反應。
作為該等官能基之組合之例，可列舉：羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸酯基等。於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，只要為藉由該等官能基之組合而生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則官能基可位於丙烯酸系聚合物與上述化合物之任一側，於上述較佳之組合中，較佳為丙烯酸系聚合物具有羥基且上述化合物具有異氰酸酯基之情形。於該情形時，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、異氰酸2-甲基丙烯醯氧基乙酯、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，可使用將上述例示之含羥基單體或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。
上述內在型放射線硬化性黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(特別是丙烯酸系聚合物)，亦可以不使特性變差之程度 調配上述放射線硬化性單體成分或低聚物成分。放射線硬化性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。
於藉由紫外線等進行硬化之情形時，較佳為使上述放射線硬化型黏著劑中含有光聚合起始劑。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-嗎啉基丙烷-1-酮等苯乙酮系化合物；安息香乙醚、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苄基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-苯基-1,2-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；鹵化酮；醯基氧化膦；醯基磷酸酯等。光聚合起始劑之調配量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，照射放射線時於發生由氧引起之硬化障礙之情形時，較理想為利用一些方法自放射線硬化型黏著劑層1b之表面阻隔氧(空氣)。例如可列舉：利用隔片被覆上述黏著劑層1b之表面之方法、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，就同時實現防止半導體晶圓之研削面缺損、固定保持底部填充材2等觀點而言，較佳為1~50μm左右。較佳為5~40μm，進而較佳為10~30μm。
(底部填充材)
本實施形態中之底部填充材2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的密封用膜。
底部填充材2係加熱處理前於150℃下之熔融黏度為50Pa．s以上且3000Pa．s以下。上述熔融黏度較佳為75Pa．s以上且2,000Pa．s以下，更佳為100Pa．s以上且1,000Pa．s以下。藉由採用上述下限，可防止底部填充材自半導體晶片溢出。另一方面，藉由採用上述上限，連接構件向底部填充材之進入變得容易，可提高電性連接之確實性。
又，底部填充材2係加熱處理前後於150℃下之黏度變化率為500%以下。該黏度變化率較佳為400%以下，更佳為300%以下。黏度變化率之下限較佳為100%，但若考慮底部填充材之硬化性，則亦可為150%以上。藉由將黏度變化率設為上述範圍，可抑制加熱處理後之過度之黏度上升，即便底部填充材經過熱歷程，亦達成良好之電性連接。
進而，於底部填充材2，將DSC測定中自-50℃至300℃為止之升溫過程中之總發熱量設為Qt，並將於175℃下進行2小時加熱後自-50℃至300℃為止之升溫過程中之總發熱量設為Qh時，{(Qt-Qh)/Qt}×100所表示之反應率為90%以上。反應率為90%以上即可，但較佳為92%以上，更佳為95%以上。底部填充材係加熱後之黏度上升得到抑制，且於在175℃下進行2小時加熱時，底部填充材之硬化反應進行90%以上，因此無需進行高溫或長時間下之硬化處理，可有助於半導體裝置之製造製程之效率化。又，可充分地進行底部填充材之硬 化反應，可提高耐濕耐熱可靠性。
作為底部填充材之構成材料，可列舉樹脂成分、潛伏性硬化促進劑、交聯劑、其他有機系添加劑等有機成分(除溶劑以外)、或無機填充劑、其他無機系添加劑等無機成分等。作為樹脂成分，可列舉並用熱塑性樹脂與熱硬化性樹脂所獲得者。又，亦可單獨使用熱塑性樹脂或熱硬化性樹脂。
(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(Polyethylene Terephthalate，聚對苯二甲酸乙二酯)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。該等熱塑性樹脂之中，特佳為離子性雜質較少、耐熱性較高、且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1種或2種以上具有碳數為30以下、特別是碳數為4~18之直鏈或者支鏈之烷基之丙烯酸或甲基丙烯酸之酯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、或二十烷基等。
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：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含羧基單體；順丁烯二酸 酐或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-羥基月桂酯或丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體；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)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；或2-羥基乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯腈等含氰基單體等。
(熱硬化性樹脂)
作為上述熱硬化性樹脂，可列舉：酚系樹脂、胺基樹脂、不飽和聚酯樹脂、環氧樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、或熱硬化性聚醯亞胺樹脂等。該等樹脂可單獨使用或併用2種以上。尤其使半導體元件腐蝕之離子性雜質等之含量較少之環氧樹脂較佳。又，作為環氧樹脂之硬化劑，較佳為酚系樹脂。
上述環氧樹脂只要為通常可用作接著劑組合物者，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、四酚基乙烷型等二官能環氧樹脂或多官能環氧樹脂；或乙內醯脲型、異氰脲酸三縮水甘油酯型或縮水甘油胺型等環氧樹脂。該等可單獨使用或併用2種以上。該等環氧樹脂之中，特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，該等環氧樹脂富於與作為硬化劑之酚系樹脂之反應性且耐熱性等優異。
進而，上述酚系樹脂係作為上述環氧樹脂之硬化劑而發揮作用，例如可列舉：苯酚酚醛清漆樹脂、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 清漆型酚系樹脂、可溶酚醛型酚系樹脂、聚對羥基苯乙烯等聚氧苯乙烯等。該等可單獨使用或併用2種以上。該等酚系樹脂之中，特佳為苯酚酚醛清漆樹脂、苯酚芳烷基樹脂。其原因在於，該等樹脂可使半導體裝置之連接可靠性提高。
關於上述環氧樹脂與酚系樹脂之調配比率，例如較佳為以相對於上述環氧樹脂成分中每1當量環氧基而酚系樹脂中之羥基為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，則無法進行充分之硬化反應，環氧樹脂硬化物之特性容易變差。
再者，於本發明中，特佳為使用環氧樹脂、酚系樹脂及丙烯酸系樹脂之底部填充材。該等樹脂由於離子性雜質較少且耐熱性較高，因此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，環氧樹脂與酚系樹脂之混合量為50~500重量份。
(潛伏性硬化促進劑)
底部填充材較佳為包含硬化促進劑。又，底部填充材較佳為包含潛伏性硬化促進劑。藉由包含潛伏性硬化促進劑作為硬化促進劑，可以更高之級別同時實現加熱處理後之黏度上升之抑制與硬化反應性。所謂潛伏性硬化促進劑，係於某種特定之條件下(溫度等)下發揮硬化促進功能者。
作為潛伏性硬化促進劑，例如可列舉：以微膠囊等保護通常之硬化促進劑而得者、硬化促進劑與各種化合物形成鹽之結構者等。於此種潛伏性硬化促進劑中，例如若超過特定之溫度，則硬化促進劑自微膠囊或鹽釋放至體系中，發揮硬化促進功能。可適當地選擇而使用以使底部填充材發揮目標之黏度變化率、熔融黏度及反應率。
作為潛伏性硬化劑之例，可列舉：胺化合物與環氧化合物之反 應生成物(胺-環氧加成物系)、胺化合物與異氰酸酯化合物、脲化合物之反應生成物(脲型加成物系)。進而，作為潛伏性硬化劑，可較佳地使用不溶於底部填充材之固體粒子、且於加熱成形時解離而發揮硬化促進作用之胺化合物與有機酸之鹽類、於胺化合物或磷化合物加成具有π鍵之化合物而成之具有分子內分極之化合物。
若具體地例示潛伏性硬化劑，則可列舉：1,8-二氮-雙環[5.4.0]十一烯-7、1,5-二氮-雙環[4.3.0]九烯-5、6-二丁基胺基-1,8-二氮-雙環[5.4.0]十一烯-7等環脒化合物與有機酸之鹽；三伸乙胺、二甲苄胺、三乙醇胺、二甲基乙醇胺、三(二甲胺甲基)苯酚等三級胺化合物之衍生物；2-甲咪唑、2-乙基-4-甲咪唑、2-苯咪唑、2-苯基-4-甲咪唑、2-十七基咪唑等咪唑化合物之衍生物；於三丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等有機膦化合物加成順丁烯二酸酐、1,4-苯醌、2,5-甲基苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯甲烷、酚系樹脂等具有π鍵之化合物而成、且具有分子內分極之磷化合物及該等之衍生物；三苯基膦三苯基硼、四苯基鏻四苯基硼酸鹽、2-乙基-4-甲咪唑四苯基硼酸鹽、N-甲基嗎啉四苯基硼酸鹽等苯基硼鹽及該等之衍生物等。該等潛伏性硬化劑可單獨使用1種，亦可組合2種以上。於該等中，較佳為四苯基鏻四苯基硼酸鹽。
作為構成上述鹽之有機酸，並無特別限制，可自通常使用之有機酸適當選擇。作為構成上述鹽之有機酸，大致分為苯酚化合物、脂肪族羧基化合物、芳香族羧基化合物。
作為苯酚化合物，並無特別限制，例如可列舉：使選自苯酚、甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、硫代聯苯酚、胺基苯酚等苯酚類及α-萘酚、β-萘酚、二羥基萘等萘酚類中之至 少1種、與甲醛、苯甲醛、柳醛等具有醛基之化合物於酸性觸媒下縮合或共縮合而獲得之酚醛清漆型酚系樹脂；由選自苯酚類及萘酚類中之至少1種、與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯合成之苯酚-芳烷基樹脂；萘酚-芳烷基樹脂等芳烷基型酚系樹脂；苯酚-酚醛清漆結構與苯酚-芳烷基樹脂無規、嵌段或交替地重複而成之共聚型苯酚-芳烷基樹脂；對二甲苯及/或間二甲苯改性酚系樹脂；三聚氰胺改性酚系樹脂；萜烯改性酚系樹脂；二環戊二烯改性酚系樹脂；環戊二烯改性酚系樹脂；多環芳香環改性酚系樹脂等。
又，作為脂肪族羧基化合物，可列舉：草酸、乳酸、酒石酸、順丁烯二酸、反丁烯二酸、丙二酸、丁二酸、蘋果酸、檸檬酸、烏頭酸、戊二酸、己二酸、甲酸、乙酸、丙酸、丁酸、異丁酸、戊酸、異戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、十五烷基酸、棕櫚酸、珠光子酸、硬脂酸、油酸、亞麻油酸、次亞麻油酸、結核硬脂酸、花生酸、花生油酸、二十碳五烯酸、山萮酸、二十二碳六烯酸、二十四碳酸、蠟酸、褐煤酸、蜜蠟酸、L-抗壞血酸等。
作為芳香族羧基化合物，可列舉：水楊酸、沒食子酸、苯甲酸、鄰苯二甲酸、肉桂酸、苯六甲酸、氧羧酸、丙酮酸等。作為其他有機酸，可列舉胺基酸等。
底部填充材包含潛伏性硬化促進劑之情形時，潛伏性硬化促進劑之含量並無特別限制。潛伏性硬化促進劑之含量相對於上述丙烯酸系樹脂100重量份，較佳為1~2重量份以上，更佳為1.2~1.8重量份。藉由設為上述範圍，可更提高硬化反應性，並且可更有效率地抑制過度之黏度上升。
(交聯劑)
於預先使本實施形態之底部填充材2某種程度交聯之情形時，製作時可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，可使高溫下之接著特性提高且實現耐熱性之改善。
作為上述交聯劑，特別是甲苯二異氰酸酯、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更佳。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，則接著力下降，因此欠佳。另一方面，若少於0.05重量份，則凝聚力不足，因此欠佳。又，亦可與此種聚異氰酸酯化合物一併視需要而包含環氧樹脂等其他多官能性化合物。
(無機填充劑)
又，底部填充材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或提高導熱性、調整儲存模數等。
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、焊料等金屬或合金類；以及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、特別是熔融二氧化矽。
無機填充劑之平均粒徑雖然並無特別限定，但較佳為0.005~10μm之範圍內，更佳為0.01~5μm之範圍內，進而較佳為0.05~2.0μm。若上述無機填充劑之平均粒徑低於0.005μm，則存在容易發生粒子之凝聚而難以形成底部填充材之情形。又，亦成為底部填充材之可撓性降低之原因。另一方面，若上述平均粒徑超過10μm，則容易發生無機粒子嵌入底部填充材與被黏著體之接合部，因此有半導體裝置之連接可靠性下降之虞。又，有因粒子之粗大化而霧度上升之虞。再者，於本發明中，亦可將平均粒徑相互不同之無機填充劑彼此組合而使用。又，平均粒徑係藉由光度式粒度分佈計(HORIBA製造，裝置 名：LA-910)所求出之值。
上述無機填充劑之調配量係相對於樹脂成分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，則存在儲存模數下降而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，則存在底部填充材2之流動性下降不能充分地埋入至基板或半導體元件之凹凸而成為空隙或龜裂之原因的情形。
(其他添加劑)
再者，底部填充材2中除上述無機填充劑以外，視需要亦可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，例如可列舉鋁碳酸鎂類、氫氧化鉍等。該等可單獨使用或併用2種以上。
(底部填充材之其他性狀)
熱硬化前之上述底部填充材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。藉由底部填充材2具有如上所述之吸水率，而水分向底部填充材2之吸收得到抑制，可更有效率地抑制安裝半導體元件31時產生空隙。再者，上述吸水率之下限較佳為較小，較佳為實質上為0重量%，更佳為0重量%。
底部填充材2之厚度(於複數層之情形時為總厚度)並無特別限定，但若考慮底部填充材2之強度或半導體元件31與被黏著體16之間之空間之填充性，則亦可為10μm以上且100μm以下左右。再者，底 部填充材2之厚度係考慮半導體元件31與被黏著體16之間之間隙或連接構件之高度而適當設定即可。
積層片10之底部填充材2較佳為受隔片保護(未圖示)。隔片具有作為保護底部填充材2直至供於實際使用前的保護材之功能。隔片係於將半導體晶圓3貼附至積層片之底部填充材2上時被剝離。作為隔片，亦可使用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塗佈表面而成之塑膠膜或紙等。
(積層片之製造方法)
本實施形態之積層片10例如可藉由分別製作切晶帶1及底部填充材2並於最後將該等貼合而製成。具體而言，可按照如下所述之順序製作。
首先，基材1a可藉由先前公知之製膜方法而製膜。作為該製膜方法，例如可例示壓延製膜法、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、共擠出法、乾式層壓法等。
其次，製備黏著劑層形成用之黏著劑組合物。黏著劑組合物中調配有如黏著劑層一項中說明之樹脂或添加物等。將所製備之黏著劑組合物塗佈於基材1a上形成塗佈膜後，使該塗佈膜於特定條件下乾燥(視需要使其加熱交聯)而形成黏著劑層1b。作為塗佈方法，並無特別限定，例如可列舉：輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如可於乾燥溫度80~150℃、乾燥時間0.5~5分鐘之範圍內進行。又，亦可於隔片上塗佈黏著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成黏著劑層1b。此後，將黏著劑層1b與隔片一併貼合至基材1a上。藉此，可製作具備基材1a及黏著劑層1b之切晶帶1。
底部填充材2例如可以如下所述之方式製作。首先，製備作為底 部填充材2之形成材料之接著劑組合物。如底部填充材之項中說明般，該接著劑組合物中調配有熱塑性成分或環氧樹脂、各種添加劑等。
其次，將所製備之接著劑組合物以成為特定厚度之方式塗佈於基材隔片上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥而形成底部填充材。作為塗佈方法，並無特別限定，例如可列舉：輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如可於乾燥溫度70~160℃、乾燥時間1~5分鐘之範圍內進行。又，亦可於隔片上塗佈接著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成底部填充材。此後，將底部填充材與隔片一併貼合至基材隔片上。
繼而，自切晶帶1及底部填充材2分別剝離隔片，以底部填充材與黏著劑層成為貼合面之方式貼合兩者。貼合例如可藉由壓接而進行。此時，層壓溫度並無特別限定，例如較佳為30~100℃，更佳為40~80℃。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，將底部填充材上之基材隔片剝離而獲得本實施形態之積層片。
[貼合步驟]
於貼合步驟中，如圖1A所示，將具有連接構件4a之電路面3a及具有背面電極4b之電路面3b形成於兩面之半導體晶圓3與上述積層片之底部填充材2貼合。再者，被薄型化成特定厚度之半導體晶圓之強度較弱，因此存在為了補強而經由暫時固定材將半導體晶圓固定至支撐玻璃等支持體之情形(未圖示)。於該情形時，在半導體晶圓與底部填充材之貼合後，亦可更包括連同暫時固定材一併剝離支持體之步驟。將半導體晶圓3中之何電路面與底部填充材2貼合係根據目標之半導體裝置之結構而變更即可。
(半導體晶圓)
半導體晶圓3之電路面3a、3b分別形成有複數個連接構件4a及複數個背面電極4b(參照圖1A)。作為凸塊或導電材等連接構件或背面電極之材質，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-鉍系金屬材等焊料類(合金)、或金系金屬材、銅系金屬材等。連接構件及背面電極之高度亦可根據用途而決定，通常為15~100μm左右。當然，半導體晶圓3中之各個連接構件之高度可相同亦可不同。
半導體晶圓3之兩面之連接構件4a與背面電極4b可電性連接，亦可不連接。兩者之電性連接可列舉被稱為TSV形式之經由通孔之連接等。
於本實施形態之半導體裝置之製造方法中，作為底部填充材之厚度，較佳為形成於半導體晶圓表面之連接構件之高度X(μm)與上述底部填充材之厚度Y(μm)滿足下述關係。
0.5≦Y/X≦2
藉由上述連接構件之高度X(μm)與上述硬化膜之厚度Y(μm)滿足上述關係，可充分地將半導體元件與被黏著體之間之空間填充，並且可防止底部填充材自該空間過量地溢出，可防止底部填充材污染半導體元件等。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，適當地剝離任意地設置於積層片10之底部填充材2上之隔片，並如圖1A所示，使上述半導體晶圓3之形成有連接構件4a之電路面3a與底部填充材2對向，而將上述底部填充材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，較佳為藉由壓接之方法。壓接通常藉由壓接輥等公知之按壓器件負以較佳為0.1~1MPa、更佳為0.3~ 0.7MPa之壓力一面按壓一面進行。此時，亦可一面加熱至40~100℃左右一面壓接。又，為了提高密接性，亦較佳為於減壓下(1~1000Pa)壓接。
[切晶步驟]
於切晶步驟中，基於利用直接光或間接光、紅外線等所求出之切晶位置如圖1B所示對半導體晶圓3及底部填充材2進行切晶，而形成附有經切晶之底部填充材之半導體元件31。藉由經過切晶步驟，將半導體晶圓3切割成特定之尺寸而單片化(小片化)，製造半導體晶片(半導體元件)31。此處所得之半導體晶片31與被切割成該形狀之底部填充材2成為一體。切晶係自半導體晶圓3之與貼合有底部填充材2之電路面3a為相反側之電路面3b側依照常法進行。
於本步驟中，例如可採用利用切晶刀片切入至切晶帶1為止之被稱為全切之切割方式等。作為本步驟中所使用之切晶裝置，並無特別限定，可使用先前公知者。又，半導體晶圓係被切晶帶1以優異之密接性接著固定，因此可抑制晶片缺損或晶片鼓出，並且亦可抑制半導體晶圓之破損。再者，若底部填充材由包含環氧樹脂之樹脂組合物形成，則即便藉由切晶被切割，亦可抑制或防止於該切割面產生底部填充材之底部填充材之糊劑溢出。其結果，可抑制或防止切割面彼此再附著(黏連)，可進一步良好地進行下述拾取。
再者，於切晶步驟後進行切晶帶之擴展之情形時，該擴展可使用先前公知之擴展裝置而進行。擴展裝置具有經由切晶環可將切晶帶向下方按壓之環狀之外圈、及直徑小於外圈且支持切晶帶之內圈。藉由該擴展步驟，於下述拾取步驟中可防止相鄰之半導體晶片彼此接觸而破損。
[拾取步驟]
為了回收接著固定於切晶帶1之半導體晶片31，如圖1C所示，拾 取附有底部填充材2之半導體晶片31，並將半導體晶片31與底部填充材2之積層體A自切晶帶1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：利用針自切晶帶之基材側將各個半導體晶片頂起，並利用拾取裝置拾取被頂起之半導體晶片。再者，所拾取之半導體晶片31與貼合於電路面3a之底部填充材2成為一體而構成積層體A。
於黏著劑層1b為紫外線硬化型之情形時，拾取係於對該黏著劑層1b照射紫外線後進行。藉此，黏著劑層1b對底部填充材2之黏著力下降，半導體晶片31之剝離變得容易。其結果，可不損傷半導體晶片31而將其拾取。照射紫外線時之照射強度、照射時間等條件並無特別限定，只要視需要適當設定即可。又，作為紫外線照射所使用之光源，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、氙氣閃光燈、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31之安裝位置，按照所求得之安裝位置，利用底部填充材2填充被黏著體16與半導體元件31之間之空間，並且經由連接構件4a將半導體元件31與被黏著體16電性連接(參照圖1D)。具體而言，使積層體A之半導體晶片31以半導體晶片31之電路面3a與被黏著體16對向之形態依照常法固定於被黏著體16。例如，使形成於半導體晶片31之凸塊(連接構件)4a與被黏著於被黏著體16之連接墊之接合用導電材17(焊料等)接觸，一面按壓一面使導電材熔融，藉此可確保半導體晶片31與被黏著體16之電性連接，並使半導體晶片31固定於被黏著體16。於半導體晶片31之電路面3a貼附有底部填充材2，因此半導體晶片31與被 黏著體16電性連接，同時半導體晶片31與被黏著體16之間之空間被底部填充材2填充。
又，如圖1E所示，於多段積層半導體元件時，按照目標之段數重複進行於經安裝之半導體元件31上固定其他積層體之半導體元件32的順序即可。亦可藉由熔融將設置於半導體元件31之背面即電路面3b之背面電極4b、與半導體元件32之連接構件4a接合。下段之半導體元件31與上段之半導體元件32之接合處理可1段1段進行，亦可於暫時固定特定段數之半導體元件後一次性全部進行接合處理。後者之順序係一次性地完成加熱處理，因此於效率方面較佳。
通常，作為安裝步驟之暫時固定條件，溫度為100~200℃，加壓為0.5~100N。又，作為安裝步驟之接合條件，溫度為150~300℃，加壓為1~200N。安裝步驟中1段1段之接合處理亦可分為複數次進行。例如，可採用如下順序：於以150℃、20N進行10秒鐘之處理後，以260℃、30N進行10秒鐘之處理。藉由進行複數次接合處理，可高效率地去除連接構件與墊間、及連接構件與背面電極間之樹脂，獲得更良好之金屬間接合。
作為被黏著體16，可使用半導體晶圓、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、玻璃環氧基板等。安裝於1個被黏著體之半導體元件之數量亦無限定，可為1個或複數個之任一者。底部填充材2亦可較佳地應用於在半導體晶圓安裝多個半導體晶片之晶片磊晶圓製程。
再者，於安裝步驟中，使連接構件、背面電極、及導電材之一者熔融或組合該等而使其等熔融，使半導體晶片31之連接構件形成面3a之凸塊4a與被黏著體16之表面之導電材17連接，並且使半導體晶片 31之背面電極4b與半導體晶片32之連接構件4a接合，作為該凸塊4a、背面電極4b、及導電材17之熔融時之溫度，通常為260℃左右(例如250℃~300℃)。本實施形態之積層片藉由利用環氧樹脂等形成底部填充材2，可製成具有亦可耐受該安裝步驟中之高溫之耐熱性者。
[底部填充材硬化步驟]
進行半導體元件31與被黏著體16之間、及視需要進行多段積層而成之半導體元件間之電性連接後，藉由加熱使底部填充材2硬化。藉此，可保護半導體元件31之表面，並且可確保半導體元件31與被黏著體16之間及半導體元件間等之連接可靠性。作為用以使底部填充材硬化之加熱溫度，並無特別限定，為150~250℃左右即可。再者，於藉由安裝步驟中之加熱處理而底部填充材硬化之情形時，本步驟可省略。經由以上之步驟，可獲得具有一段半導體元件31之半導體裝置20或多段積層半導體元件而成之半導體裝置40。
[密封步驟]
其次，為了保護具備經安裝之半導體晶片之半導體裝置20或40整體，亦可進行密封步驟。密封步驟可使用密封樹脂進行。作為此時之密封條件，並無特別限定，通常藉由在175℃下進行60秒鐘~90秒鐘之加熱，而進行密封樹脂之熱硬化，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而使用，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，可列舉上述所例示之環氧樹脂等。又，作為由包含環氧樹脂之樹脂組合物所獲得之密封樹脂，作為樹脂成分，除環氧樹脂以外，亦可包含除環氧樹脂以外之熱硬化性樹脂(酚系樹脂等)或熱塑性樹脂等。再者，酚系樹脂亦可用作環氧樹脂之硬 化劑，作為此種酚系樹脂，可列舉上述所例示之酚系樹脂等。
[半導體裝置]
其次，一面參照圖式一面對使用該積層片所獲得之半導體裝置進行說明(參照圖1D、1E)。本實施形態之半導體裝置40中，半導體元件31與被黏著體16係經由形成於半導體元件31上之凸塊(連接構件)4a及設置於被黏著體16上之導電材17而電性連接。進而，半導體元件31之背面電極4b與半導體元件32之連接構件4a接合，藉此謀求半導體元件31、32間之電性連接。於半導體元件31與被黏著體16之間及半導體元件31、32間，以填充該空間之方式配置有底部填充材2。半導體裝置40可利用採用特定底部填充材2及由光照射獲得之定位的上述製造方法而獲得，因此可於半導體元件31與被黏著體16之間及半導體元件31、32間達成良好之電性連接。因此，半導體元件之表面保護、半導體元件31與被黏著體16之間之空間及半導體元件31、32間之空間之填充、以及半導體元件31與被黏著體16之間及半導體元件31、32間之電性連接分別成為充分之級別，作為半導體裝置40可發揮較高之可靠性。
<第2實施形態>
第1實施形態中使用兩面形成有電路之半導體晶圓，與此相對，本實施形態中使用單面形成有電路之半導體晶圓製造半導體裝置。又，於本實施形態中所使用之半導體晶圓不具有目標厚度之情形時，進行對與半導體晶圓之電路面為相反側之背面進行研削之背面研削步驟。因此，於本實施形態中，使用具備積層於背面研削用帶上之底部填充材的積層片進行半導體晶圓之背面研削，此後進行切晶帶上之切晶、半導體元件之拾取，最後將半導體元件安裝於被黏著體。作為此種背面研削用帶之基材及黏著劑層、以及底部填充材，可使用與第1實施形態相同者。
作為本實施形態之代表性步驟，包括如下步驟：準備步驟，其係準備具備背面研削用帶及積層於該背面研削用帶上之底部填充材的積層片；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積層片之底部填充材貼合；研削步驟，其係對上述半導體晶圓之背面進行研削；固定步驟，其係將半導體晶圓連同上述底部填充材一併自背面研削用帶剝離並將該半導體晶圓貼附至切晶帶；切晶位置決定步驟，其係決定上述半導體晶圓之切晶位置；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底部填充材之半導體元件；拾取步驟，其係將附有上述底部填充材之半導體元件自上述切晶帶剝離；對位步驟，其係使上述半導體元件與上述被黏著體之相對位置對準為彼此之預定連接位置；及連接步驟，其係利用上述底部填充材將上述被黏著體與上述半導體元件之間之空間填充，並且經由上述連接構件而將上述半導體元件與上述被黏著體電性連接。切晶帶可使用第1實施形態之切晶帶，亦可使用公知之市售品等。又，各步驟之條件可較佳地採用公知之條件或與第1實施形態相同之條件。
<第3實施形態>
第1實施形態中使用切晶帶作為積層片之構成構件，但本實施形態中不設置該切晶帶之黏著劑層而單獨使用基材。因此，作為本實施形態之積層片，成為於基材上積層有底部填充材之狀態。本實施形態中，拾取步驟前之紫外線照射因省略黏著劑層而不進行。除該等方面以外經過與第1實施形態相同之步驟，藉此可製造特定之半導體裝置。
<其他實施形態>
於第1實施形態至第3實施形態中，於切晶步驟中採用使用切晶刀片之切晶，亦可採用如下之所謂隱形切晶進行代替：藉由雷射照射於半導體晶圓內部形成改質部分，沿著該改質部分對半導體晶圓進行 分割而進行單片化。
[實施例]
以下，例示性且詳細地對本發明之較佳實施例進行說明。其中，該實施例所記載之材料或調配量等只要無特別限定性記載，則本發明之宗旨並非將該發明之範圍僅限定於上述記載。又，記為份之情況意指重量份。
[實施例1~5及比較例1~4]
(底部填充材之製作)
將以下之成分按照表1所示之比率溶解於甲基乙基酮中，而製備固形物成分濃度為25.4~60.6重量%之接著劑組合物之溶液。
丙烯酸系樹脂：以丙烯酸乙酯-甲基丙烯酸甲酯作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)
環氧樹脂1：商品名「Epikote 1004」，JER股份有限公司製造
環氧樹脂2：商品名「Epikote 828」，JER股份有限公司製造
酚系樹脂：商品名「Milex XLC-4L」，三井化學股份有限公司製造
無機填充劑：球狀二氧化矽(商品名「SO-25R」，Admatechs股份有限公司製造)
潛伏性硬化促進劑：磷系硬化促進劑(商品名「TPP-K」，北興化學股份有限公司製造)
助焊劑：鄰大茴香酸(商品名「o-anisic acid」、東京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(隔片)的經聚矽氧脫模處理之厚度為50μm、由聚對苯二甲酸乙二酯膜形成之脫模處理膜上後，於130℃下乾燥2分鐘，藉此製作厚度為17μm之底部填充 材。
<熔融黏度之測定>
將所製作之底部填充材不經過加熱處理而製成樣品，使用流變計(HAAKE公司製造，RS-1)，利用平行板法進行測定。詳細而言，設為間隙100μm、旋轉平皿直徑20mm、旋轉速度5s-1、升溫速度10℃/分鐘之條件，自80℃升溫，因底部填充材之硬化反應而黏度上升，進行測定直至最終旋轉平皿無法旋轉之溫度(再者，所有實施例及比較例中為200℃以上)。讀取此時於150℃下之熔融黏度。將結果示於表1。
<黏度變化率之測定>
將上述熔融黏度之測定中於150℃下之熔融黏度設為η1。進而，亦對在130℃下進行1小時加熱處理所得之樣品進行相同之順序，讀取此時於150℃下之熔融黏度η2。基於下述式，算出於130℃下進行1小時加熱處理前後之黏度變化率。將結果示於表1。
黏度變化率(%)=(η2/η1)×100
<DSC測定之反應率之測定>
使用熱示差強度測定裝置(TA Instruments公司製造，Q2000)，算出使加熱處理前之底部填充材以10℃/min自-50℃升溫至300℃為止時之總發熱量Qt。另外，於175℃下對加熱處理前之底部填充材進行2小時加熱處理，對該加熱處理後之樣品測定以10℃/min自-50℃升溫至300℃為止時之總發熱量Qh。基於下述式，算出於175℃下進行2小時加熱處理時之反應率。將結果示於表1。
反應率(%)={(Qt-Qh)/Qt}×100
<凸塊接合性之評價>
準備於一面形成有凸塊、於另一面形成有墊之半導體晶片，於80℃下將實施例及比較例中所製作之底部填充材貼合於該半導體晶片 之形成有凸塊之側之面。作為半導體晶片，使用以下之規格者。
(半導體晶片)
尺寸：5mm見方
厚度：0.05mm(50μm)
凸塊之材質：銅柱+Sn-Ag
凸塊尺寸：高度15μm、直徑20μm
凸塊間距：40μm、全陣列
墊：Ni-Au墊
墊之高度：2μm
其次，根據下述熱壓接條件進行積層步驟，於使半導體晶片之凸塊形成面與厚度為200μm之銅板對向之狀態下，將半導體晶片熱壓接於銅板而進行半導體晶片之暫時固定。此後，利用相同之熱壓接條件，將第2段附有底部填充材半導體晶片暫時固定於暫時固定於銅板上之第1段半導體晶片上。重複該順序而積層合計4段之半導體晶片。
(熱壓接條件)
覆晶接合機：商品名「FC-3000W」東麗工程製造
加熱溫度：150℃
荷重：20N
保持時間：2秒
最後，利用下述接合條件，一次性全部地接合4段之半導體晶片，而製作晶片接合體。
(接合條件)
覆晶接合機：商品名「FC-3000W」東麗工程製造
加熱溫度：260℃
荷重：30N
保持時間：10秒
按照以下之順序進行凸塊接合性之評價。於175℃下對晶片接合體進行2小時加熱處理而使底部填充材硬化。其次，對晶片接合體之側面實施切削處理，使第1段至第4段之凸塊接合界面露出。對所露出之接合界面進行截面研削後，使用光學顯微鏡(1000倍)觀察，將凸塊與墊無問題地接合之情形評價為「○」，將於凸塊產生龜裂、或凸塊未接合於墊之情形評價為「×」。將結果示於表1。
<吸濕回流焊評價>
於175℃下對所獲得之晶片接合體進行2小時加熱處理，使底部填充材硬化。將加熱處理後之晶片接合體於85℃ 85%Rh之環境下放置168小時後，進行回流焊試驗。此時之回流焊試驗之條件係根據JEDEC(Joint Electronic Device Engineering Council，電子器件工程聯合會)(J-STD-020C)中所規定之條件而進行。其次，於回流焊後，以包含接合部分之方式切割晶片接合體。使用光學顯微鏡(1000倍)確認切割面，將凸塊與墊無問題地接合之情形評價為「○」，將於凸塊產生有龜裂、或凸塊未接合於墊之情形評價為「×」。將結果示於表1。
根據表1可知，於所有實施例中，凸塊接合性均良好，即便對底部填充材負以熱歷程，亦獲得良好之電性連接。又，實施例之底部填充材係耐濕耐熱可靠性亦良好。另一方面，比較例1、3及4呈凸塊接合性較差之結果。可認為其原因在於：晶片積層時之黏度過高或黏度變化率過高，凸塊中產生應力而產生龜裂、或凸塊未到達墊。於比較例2中，凸塊接合性良好且吻合，但吸濕回流焊試驗後之可靠性下降。可認為該情形係因底部填充材未充分地硬化而引起。再者，於比較例1、3及4中，如上所述般於凸塊接合之階段發生不良，故而無法進行此後之吸濕回流焊試驗本身。
2‧‧‧底部填充材
4a‧‧‧連接構件(凸塊)
4b‧‧‧背面電極
16‧‧‧被黏著體
17‧‧‧導電材
31‧‧‧半導體晶片(半導體元件)
32‧‧‧半導體元件(半導體晶片)
40‧‧‧半導體裝置

Claims (6)

  1. 一種底部填充材，其係加熱處理前於150℃下之熔融黏度為50Pa．s以上且3000Pa．s以下，將上述加熱處理前於150℃下之熔融黏度設為η1，且將於130℃下進行1小時加熱處理後於150℃下之熔融黏度設為η2時，(η2/η1)×100所表示之黏度變化率為500%以下，將DSC測定中自-50℃至300℃為止之升溫過程中之總發熱量設為Qt，且將於175℃下進行2小時加熱後自-50℃至300℃為止之升溫過程中之總發熱量設為Qh時，{(Qt-Qh)/Qt}×100所表示之反應率為90%以上。
  2. 如請求項1之底部填充材，其包含潛伏性硬化促進劑。
  3. 如請求項2之底部填充材，其包含丙烯酸系樹脂，且相對於上述丙烯酸系樹脂100重量份包含1~2重量份之上述潛伏性硬化促進劑。
  4. 一種積層片，其具備：黏著帶，其具有基材及設置於該基材上之黏著劑層；及如請求項1至3中任一項之底部填充材，其積層於上述黏著劑層上。
  5. 如請求項4之積層片，其中上述黏著帶為半導體晶圓之背面研削用帶或切晶帶。
  6. 一種半導體裝置之製造方法，其係具備被黏著體、與該被黏著體電性連接之半導體元件、及將該被黏著體與該半導體元件之間之空間填充之底部填充材的半導體裝置之製造方法，且包括如下步驟：準備步驟，其係準備將如請求項1至3中任一項之底部填充材 貼合於上述半導體元件而成之附有底部填充材半導體元件；及連接步驟，其係利用上述底部填充材將上述被黏著體與上述半導體元件之間之空間填充，並且將上述半導體元件與上述被黏著體電性連接。
TW104107070A 2014-03-07 2015-03-05 底部填充材、積層片及半導體裝置之製造方法 TW201538583A (zh)

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