TWI700749B - 加熱接合用片材、以及附切晶帶加熱接合用片材 - Google Patents

加熱接合用片材、以及附切晶帶加熱接合用片材 Download PDF

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TWI700749B
TWI700749B TW105131684A TW105131684A TWI700749B TW I700749 B TWI700749 B TW I700749B TW 105131684 A TW105131684 A TW 105131684A TW 105131684 A TW105131684 A TW 105131684A TW I700749 B TWI700749 B TW I700749B
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heating
bonding
aforementioned
layer
sheet
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TW105131684A
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TW201717291A (zh
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菅生悠樹
鎌倉菜穗
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日商日東電工股份有限公司
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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Abstract

本發明提供一種加熱接合用片材，其可抑制貼附時之溢出或覆蓋到貼附對象物表面，且燒結後可得到強固的燒結層。

一種加熱接合用片材，其具有藉由加熱所形成燒結層之層；前述層係大氣環境下，以昇溫速度10℃/分之條件，從23℃至500℃藉由差動型示差熱天秤進行分析時，在500℃之重量減少量(%)減去在300℃之重量減少量(%)之值，在-1%~0%之範圍內。

Description

加熱接合用片材、以及附切晶帶加熱接合用片材
本發明係關於一種加熱接合用片材，以及附切晶帶之加熱接合用片材。
半導體裝置之製造中，將半導體元件接著在金屬導線架等被黏物之方法(所謂的晶片接合法)，從過去的金-矽共晶開始、發展到藉由焊接、樹脂膏之方法。現今，有使用導電性之樹脂膏之方法。
近年，進行電力控制或供給的電力半導體裝置的普及日漸顯著。電力半導體裝置因電流隨時在流通，發熱量大。因此，使用在電力半導體裝置的接著劑被期望具有高散熱性和低電阻。
電力半導體裝置要求低損失之高速作動。過去，電力半導體裝置使用IGBT(絕緣閘雙極電晶體，Insulated Gate Bipolar Transistor)或MOSFET(金氧半場效應電晶體，Metal-Oxide-Semiconductor Field-Effect Transistor)等的使用Si的半導體。近年，使用SiC或GaN等的半導體也被開發，可預想以後之擴大發展。
使用SiC或GaN的半導體，有能隙大、絕緣破壞電場高等特徵，可低損失、高速作動、且高溫作動。高溫作動，是在熱環境嚴苛 的汽車或小型電力變換機等之優勢所在。用在熱環境嚴苛用途的半導體裝置，預計係在250℃左右的高溫作動，習知的接合‧接著材料之焊接和導電性接著劑上會有熱特性、信賴性的問題產生。因此，過去曾提案含有燒結金屬粒子的膏狀材料(例如參照專利文獻1)。含有燒結金屬粒子的膏狀材料裡，係含有奈米‧微米尺寸的金屬粒子，這些金屬粒子在奈米尺寸效果下會以比較一般的熔點更低的溫度，進行熔解，並進行粒子間的燒結。
【先前技術文獻】 【專利文獻】
【專利文獻1】日本特開2014-111800號公報
然而，含有燒結金屬粒子的膏狀材料，因屬於膏狀，在半導體晶片黏晶時會發生溢出或，覆蓋到晶片表面上的情況發生。因此，可能會產生傾斜，造成半導體裝置製造的產量降低或性能的偏差。特別是，使用高電壓的時候，晶片傾斜使接合距離不均，造成裝置的特性變差。
此外，進行燒結時，若多數的有機成分仍然殘存，則燒結沒有進展，而無法成為強固的燒結層之問題存在。
本發明有鑑於前述問題點，其目的在於提供一種可抑制貼附時之溢出或覆蓋到貼附對象物表面，且燒結後可得到強固的燒結層之加熱 接合用片材，及具有該加熱接合用片材之附切晶帶之加熱接合用片材。
本案發明人等，檢討關於能解決前述傳統的問題點之加熱接合用片材，以及具有該加熱用片材的附切晶帶的加熱接合用片材。其結果，發現藉由採用下述的構成，可抑制貼附時之溢出或覆蓋到貼附對象物表面，且燒結後可得到強固的燒結層，從而完成本發明。
亦即，本發明之加熱接合用片材，具有藉由加熱形成燒結層之層；前述層係大氣環境下，以昇溫速度10℃/分之條件，從23℃至500℃藉由差動型示差熱天秤進行分析時，在500℃之重量減少量(%)減去在300℃之重量減少量(%)之值，在-1%~0%之範圍內。
根據前述構成，並非膏狀，而為片材狀，因此可抑制貼附時之溢出或覆蓋到貼附對象物表面。
此外，具有藉由加熱形成燒結層之層；前述層係大氣環境下，以昇溫速度10℃/分之條件，從23℃至500℃藉由差動型示差熱天秤進行分析時，在500℃之重量減少量(%)減去在300℃之重量減少量(%)之值(以下，稱作「差值」)，在-1%~0%之範圍內。因前述差值在-1%~0%之範圍內，300℃之時間點，可認為大部分的有機成分於前述層內已不存在。換言之，在燒結步驟(加熱接合步驟)之早期階段，可認為大部分的有機成分於前述層內已不存在。其結果，加熱前述層得到之燒結層係形成為強固者。
此外，本發明之加熱接合用片材係具有藉由加熱形成燒結層之層；前述層係藉由下述加熱條件A加熱後之燃燒-紅外吸收法之碳量為0%~1．6%之範圍內；
<加熱條件A>
前述層，在10MPa之加壓下，從80℃至300℃以昇溫速度1．5℃/秒昇溫後，在300℃維持2．5分鐘。
根據前述構成，並非膏狀，而為片材狀，因此可抑制貼附時之溢出或覆蓋到貼附對象物表面。
此外，具有藉由加熱形成燒結層之層；前述層，藉由下述加熱條件A加熱後之燃燒-紅外吸收法之碳量為0%~1．6%之範圍內。上述加熱條件A係假定前述層藉由加熱而形成燒結層之條件所規定之加熱條件。因前述碳量為0%~1．6%之範圍內，燒結步驟(加熱接合步驟)之後，可認為大部分的有機成分於前述層內已不存在。其結果，加熱前述層得到之燒結層係形成為強固者。
前述構成中，前述層含有在23℃為固態之熱分解性黏合劑為佳。
若前述層含有在23℃為固態之熱分解性黏合劑，則加熱接合步驟前，容易維持片材形狀。此外，加熱接合步驟時容易熱分解。
前述構成中，前述層含有金屬微粒子；前述金屬微粒子選自銀、銅、氧化銀、氧化銅所成群中之至少1種為佳。
若含有金屬微粒子；前述金屬微粒子選自銀、銅、氧化銀、 氧化銅所成群中之至少1種，則可更適合加熱接合。
此外，本發明之附切晶帶之加熱接合用片材，其特徵係其具有切晶帶，及積層於前述切晶帶上前述加熱接合用片材。
前述附切晶帶之加熱接合用片材中，因與切晶帶一體成形，故能省略與切晶帶貼合的步驟。此外，因具備前述加熱接合用片材，故能抑制貼附時之溢出或覆蓋到貼附對象物表面。此外，因具有前述層之加熱接合用片材，加熱前述層得到之燒結層係形成為強固者。
1‧‧‧基材
2‧‧‧黏著劑層
3、3’‧‧‧加熱接合用片材
4‧‧‧半導體晶圓
5‧‧‧半導體晶片
6‧‧‧被黏物
7‧‧‧焊接導線
8‧‧‧密封樹脂
10、12‧‧‧附有切晶帶之加熱接合用片材
11‧‧‧切晶帶
30‧‧‧附有兩面隔板之加熱接合用片材
31‧‧‧藉由加熱形成燒結層之層
32‧‧‧第1隔板
34‧‧‧第2隔板
【圖1】表示本發明之一實施型態中，附切晶帶之加熱接合用片材之斷面模式圖。
【圖2】表示本發明之其他實施型態中，附切晶帶之加熱接合用片材之斷面模式圖。
【圖3】表示附有兩面隔板之加熱接合用片材之斷面模式圖。
【圖4】用於說明本實施型態之半導體裝置之一製造方法之斷面模式圖。
【圖5】關於實施例1之加熱接合用片材，表示進行示差熱天秤之分析時之溫度及重量減少量(%)之關係之圖表。
(附切晶帶之加熱接合用片材)
關於本發明之一實施型態中之加熱接合用片材，及附切晶帶之加熱接合用片材，在以下進行說明。本實施型態中的加熱接合用片材，可列舉如下述說明之附切晶帶之加熱接合用片材中，其係沒有貼上切晶帶的狀態。因此，以下說明附切晶帶之加熱接合用片材，並就加熱用接合片材在其中加以說明。圖1係表示本發明之一實施型態的附切晶帶之加熱接合用片材之斷面模式圖。圖2係表示本發明之另一實施型態的其他附切晶帶之加熱接合片材之斷面模式圖。
如圖1所示，附切晶帶之加熱接合用片材10係具有在切晶帶11上積層加熱接合用片材3之構成。切晶帶11係在基材1上積層黏著劑層2所構成，而加熱接合用片材3設置於該黏著劑層2上。又，本發明之附切晶帶之加熱接合用片材，如圖2所示附切晶帶之加熱接合用片材12，亦可以僅在加工黏貼部分上形成加熱接合用片材3’之構成。
(加熱接合用片材)
加熱接合用片材3、3’係片材狀。因並非膏狀，而為片材狀，可抑制貼附時之溢出或覆蓋到貼附對象物表面。
本實施型態之加熱接合用片材3、3’，藉由加熱形成燒結層之層31所構成。本實施型態，說明加熱接合用片材為藉由加熱形成燒結層之層為1層之情形，但本發明並不限定於此例。本發明中，藉由加熱形成燒結層之層，亦可為複數積層藉由加熱形成燒結層之層之構成。
此外，本實施型態，說明加熱接合用片材為藉由加熱形成燒結層之層 所構成之情形，但本發明並不限定於此例。本發明之加熱接合用片材亦可為2層以上。例如，藉由加熱形成燒結層之層，及其他層(藉由加熱不成為燒結層之層)所積成之構成亦可。
亦即，本發明之加熱接合用片材，只要具有藉由加熱形成燒結層之層即可，其構成並無特別限定。
(藉由加熱形成燒結層之層)
藉由加熱形成燒結層之層31(以下，稱做「層31」)，大氣環境下，在昇溫速度10℃/分之條件，，從23℃至500℃藉由差動型示差熱天秤進行分析時，在500℃之重量減少量(%)減去在300℃之重量減少量(%)之值(差值)，在-1%~0%之範圍內為佳。前述差值在-0．8%~0%之範圍內為更佳，在-0．5%~0%之範圍內為特佳。若前述差值為-1%~0%之範圍內，則300℃之時間點，可認為大部分的有機成分於前述層內已不存在。換言之，在燒結步驟(加熱接合步驟)之早期階段，可認為大部分的有機成分於前述層內已不存在。其結果，加熱層31得到之燒結層係形成為強固者。
前述差值，可藉由以下控制：金屬微粒子之種類、含有量、平均粒徑，熱分解黏合劑之種類、含有量，低沸點黏合劑之種類、含有量，藉由加熱形成燒結層時之加熱條件(例如，溫度、時間、昇温速度等)，形成燒結層時之環境氣體(大氣環境、氮氣、或還原氣體等)。
前述差值更詳細的求得方法係根據實施例所記載之方法。
層31，藉由下述加熱條件A加熱後之燃燒-紅外吸收法之碳量為0%~1．6%之範圍內為佳。前述碳量在0%~1．3%之範圍 內為更佳，在0%~1%之範圍內為特佳。上述加熱條件A係假定前述層藉由加熱而形成燒結層之條件所規定之加熱條件。
前述碳量，可藉由以下控制：金屬微粒子之種類、含有量、平均粒徑；熱分解黏合劑之種類、含有量，低沸點黏合劑之種類、含有量；藉由加熱形成燒結層時之加熱條件(例如，溫度、時間、昇温速度等)，形成燒結層時之環境氣體(大氣環境、氮氣、或還原氣體等)。
<加熱條件A>
前述層，在10MPa之加壓下，從80℃至300℃以昇溫速度1．5℃/秒昇溫後，在300℃維持2．5分鐘。
若前述碳量為0%~1．6%之範圍內，則燒結步驟(加熱接合步驟)之後，可認為大部分的有機成分於前述層內已不存在。其結果，加熱前述層得到之燒結層係形成為強固者。
層31，藉由下述拉伸試驗方法所得之拉伸彈性率為10MPa~3000MPa、12MPa~2900MPa為佳，15MPa~2500M更佳。
拉伸試驗方法：(1)準備厚度200μm、寬10mm、長40mm的加熱接合用片材(拉伸試驗用加熱接合用片材)，作為試驗材料，(2)在夾具間距離為10mm、拉伸速度為50mm/分、23℃的條件下進行拉伸試驗，(3)以所得的應力-應變曲線圖之直線部分之斜率作為拉伸彈性率。
若層31之前述拉伸彈性率為10MPa以上，則能抑制黏 晶時加熱接合用片材之構成材料的溢出或覆蓋到晶片表面上。此外，若前述拉伸彈性率係3000MPa以下，則例如在切割時能固定半導體晶圓。
層31，相對於層31全體而含有金屬微粒子在60~98重量%的範圍內為佳。前述金屬微粒子的含有量，在65~97重量%的範圍內為更佳，在70~95重量%範圍內特佳。若前述金屬微粒子含量在60~98重量%範圍內，則能燒結金屬微粒子，或使其熔融而接合兩個物(例如，半導體晶片及導線架)。
前述金屬微粒子，可列舉為燒結性金屬粒子。
前述燒結性金屬粒子，適合使用金屬微粒子的凝集體。金屬微粒子可列舉由金屬所成之微粒子等。前述金屬可列舉為金、銀、銅、氧化銀、氧化銅等。其中，較佳係選自銀、銅、氧化銀、氧化銅所成群中至少一種。如前述金屬微粒子係選自銀、銅、氧化銀、氧化銅所成群中至少一種時，可更適合地進行加熱接合。
前述燒結性金屬粒子之平均粒徑較佳係0．0005μm以上，更佳係0．001μm以上。平均粒徑之下限，可例示為0．01μm、0．05μm、0．1μm。另一方面，燒結性金屬粒子之平均粒徑較佳係以30μm以下，更佳係25μm以下。平均粒徑之上限，可例示為20μm、15μm、10μm、5μm。
前述燒結性金屬粒子之平均粒徑由以下方法測量。亦即，前述燒結性金屬粒子用SEM(掃描式電子顯微鏡)觀察，測量平均粒徑。又，SEM觀察中，例如，燒結性金屬粒子為微米尺寸時，用5000倍觀察；亞微米尺寸時，用50000倍觀察；奈米尺寸時，用300000倍觀 察為佳。
前述燒結性金屬粒子之形狀無特別限定，例如，球狀、棒狀、鱗片狀、不定形。
層31，含有低沸點黏合劑為佳。前述低沸點黏合劑，用於使前述金屬微粒子之處理變得容易。此外，前述低沸點黏合劑，亦用於調整任意之機械物性。具體而言，使前述金屬微粒子分散於前述低沸點黏合劑，可作為含有金屬微粒子之糊膏使用。
前述低沸點黏合劑，在23℃為液狀。本說明書中，「液狀」係包含半液狀。具體而言，藉由動態黏彈性測定裝置(流變儀)黏度測定在23℃之黏度為100，000Pa‧s以下。
黏度測定之條件，如同下述。
流變儀：Thermo SCIENTFIC公司製MER III
治具：平行板20mmφ、間距100μm、剪斷速度1/秒)
前述低沸點黏合劑之具體例，可列舉例如，戊醇、己醇、庚醇、辛醇、1-癸醇、乙二醇、二甘醇、丙二醇、丁二醇、α-松油醇、1,6-己二醇、異莰基環己醇(MTPH)等之一價及多價醇類、乙二醇丁醚、乙二醇苯醚、二甘醇甲醚、二甘醇乙醚、二甘醇丁醚、二甘醇異丁醚、二甘醇己醚、三甘醇甲醚、二甘醇二甲醚、二甘醇二乙醚、二甘醇二丁醚、二甘醇丁甲醚、二甘醇異丙甲醚、三甘醇二甲醚、三甘醇丁甲醚、丙二醇丙醚、二丙二醇甲醚、二丙二醇乙醚、二丙二醇丙醚、二丙二醇丁醚、二丙二醇二甲醚、三丙二醇甲醚、三丙二醇二甲醚等醚類、乙二醇乙醚乙酸酯、乙二醇丁醚乙酸酯、二甘醇乙醚乙酸酯、二甘醇丁醚乙酸酯、二丙二 醇甲基醚乙酸酯(D PMA)等。亦可將此等之2種以上併用。其中，將沸點相異之2種類併用為佳。若使用沸點相異之2種類，則於片材形狀之維持方面優異。
層31，含有在23℃為固體之熱分解性黏合劑為佳。若含有前述熱分解性黏合劑，則加熱接合步驟前，容易維持片材形狀。此外，加熱接合步驟時容易熱分解。
本說明書中，「固體」係具體而言藉由前述流變儀黏度測定在23℃之黏度為大於100，000Pa‧s。
本說明書中所謂「熱分解性黏合劑」，係指加熱接合步驟中可使其熱分解之黏合劑。前述熱分解性黏合劑，在加熱接合步驟後，於燒結層(加熱後之層31)，幾乎不殘留在加熱接合用片材者為佳。前述熱分解性黏合劑，可列舉例如，即使含在層31，大氣環境下，以昇溫速度10℃/分之條件，從23℃昇溫到400℃後以能量分散型X射線分析所得之碳濃度為15重量%以下之材料。例如，作為熱分解黏合劑，如採用更容易熱分解之材料時，即使相對含有量較多，可在加熱接合步驟後，幾乎不殘留於燒結層(加熱後之層31)。
前述熱分解性黏合劑，可列舉聚碳酸酯、丙烯酸樹脂、乙基纖維素、聚乙烯醇等。此等材料可單獨、或混合2種以上使用。其中，從高熱分解性之觀點而言，聚碳酸酯為佳。
前述聚碳酸酯樹脂，若能在加熱接合步驟中使其熱分解者即可，並無特別限定，可列舉為主鏈的碳酸酯基(-O-CO-O-)間不含芳香族化合物(例如，苯環等)，由脂肪族鏈構成的脂肪族聚碳酸酯，或主鏈 的碳酸酯基(-O-CO-O-)間含芳香族化合物的芳香族聚碳酸酯。其中，以脂肪族聚碳酸酯為佳。
前述脂肪族聚碳酸酯，可列舉為聚乙烯碳酸酯、聚丙烯碳酸酯等。其中，以形成片材的塗漆製造中對有機溶劑的溶解性的觀點而言，以聚乙烯碳酸酯為佳。
前述芳香族聚碳酸酯，可列舉主鏈含雙酚A構造者等。
前述聚碳酸酯樹脂的重量平均分子量在10，000~1，000，000的範圍內較合適。又，重量平均分子量是藉由GPC(凝膠滲透層析儀)測量，由聚苯乙烯換算而得之數值。
前述丙烯酸樹脂，在加熱接合步驟可使其熱分解的範圍中，可列舉為碳數30以下，尤其具有碳數4~18的直鏈或者分枝的烷基的丙烯酸，或甲基丙烯酸的酯之1種或2種以上作為成分之聚合物(丙烯酸共聚物)等。前述烷基可列舉例如，甲基、乙基、丙基、異丙基、n-丁基、t-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、十二烷基、十三烷基、十四烷基、硬脂基、十八烷基，或月桂基等。
此外，作為形成聚合物(丙烯酸共聚物)之其他單體，無特別限定，可列舉例如丙烯酸、甲基丙烯酸、丙烯酸羧乙酯、丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸、或巴豆酸等含有羧基的單體，馬來酸酐或衣康酸酐等酸酐單體，(甲基)丙烯酸2-羥乙基、(甲基)丙烯酸2-羥丙基、(甲基)丙烯酸4-羥丁基、(甲基)丙烯酸6-羥己基、(甲基)丙烯酸8-羥辛基、(甲基)丙烯酸10-羥癸基、(甲基)丙烯酸12-羥十二烷基或(4-羥 甲基環己基)-丙烯酸甲酯等含有羥基的單體、苯乙烯磺酸、丙烯磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、丙磺酸(甲基)丙烯酸酯或(甲基)丙烯醯氧基萘磺酸等含有磺酸基之單體，或2-羥乙基丙烯醯基磷酸酯等含有磷酸基之單體。
丙烯酸樹脂之中，較佳係重量平均分子量為1萬~100萬者，更佳係3萬~70萬者。若在上述數值範圍內時，則加熱接合步驟前的接著性，以及加熱接合步驟時的熱分解性優良。又，重量平均分子量是藉由GPC(凝膠滲透層析儀)測量，由聚苯乙烯換算而得之數值。
此外，丙烯酸樹脂中，在200℃~400℃熱分解之丙烯酸樹脂為佳。
又，層31，除前述成分以外，例如，可適當含有可塑劑等。
加熱接合用片材3、3’，可用一般方法製造。例如，製造含有形成層31之前述各成分的塗漆，以塗漆在基材隔板上塗佈成所定厚度，形成塗佈膜後，乾燥該塗佈膜，即可製造加熱接合用片材3、3’。
作為塗漆所使用的溶劑雖無特別限定，惟較佳係能使前述各成分均一溶解、混練或分散的有機溶劑或醇類溶劑。前述有機溶劑，可列舉例如，為二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮、丙酮、甲乙酮、環己酮等酮系溶劑、甲苯、二甲苯等。又，前述醇類溶劑，可列舉為乙二醇、二甘醇、1，2-丙二醇、1，3-丙二醇、1，2-丁二醇、1，3-丁二醇、1，4-丁二醇、2-丁烯-1，4-二醇、1，2，6-己三醇、丙三醇、辛二醇、2-甲基-2，4-戊二醇、松油醇。
塗佈方法無特別限定。作為溶劑塗工方法，可列舉例如，薄 膜塗佈機、凹版塗佈機、滾輪式塗佈機、反向式塗佈機、刮刀式塗佈機、管刮刀塗佈機、網版印刷等。其中，以塗佈厚度之均一性較高之觀點，較佳係薄膜塗佈機。又，塗佈膜的乾燥條件無特別限定，例如，可以乾燥溫度70~160℃、乾燥時間1~5分鐘進行。又，塗佈膜乾燥後根據所使用的溶劑種類，會有溶劑無全部氣化而殘留於塗膜中之情形。
層31含有前述低沸點黏合劑時，因應前述乾燥條件，前述低沸點黏合劑之一部份有揮發之情形。因此，因應前述乾燥條件，改變構成層31之各成分之比例。例如，即使同樣之塗漆所形成之層31，乾燥溫度越高，或乾燥時間越長，佔層31全體之金屬微粒子之含有量、或熱分解性黏合劑之含有量越多。因此，使層31中之金屬微粒子或熱分解性黏合劑之含有量形成所需的量，設定前述乾燥條件為佳。
基材隔板，可使用藉由聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或氟系剥離劑、長鏈烷基丙烯酸酯系剝離劑等之剝離劑進行表面塗佈的塑膠薄膜或紙張等。
加熱接合用片材3、3’的製造方法，例如，前述各成分以攪拌器混合，所得之混合物加壓成形製造加熱接合用片材3、3’的方法等亦為合適。攪拌器可列舉為行星攪拌器等。
加熱接合用片材3、3’，在加熱前23℃之厚度，較佳係5~100μm，更佳係10~80μm。在23℃之厚度為5μm以上時，更能抑制溢出。另一方面，100μm以下時，更能抑制加熱接合時之傾斜。
(切晶帶)
切晶帶11係在基材1上積層黏著劑層2所構成者。
基材1係附切晶帶之加熱接合用片材10、12之強度母體，較佳係具有紫外線透過性者。基材1，可列舉例如，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、隨機共聚合聚丙烯、嵌段共聚合聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴，乙烯-醋酸乙烯共聚合物、離子鍵聚合物樹脂、乙烯-(甲基)丙烯酸共聚合物、乙烯-(甲基)丙烯酸酯(隨機、交替)共聚合物、乙烯-丁烯共聚合物、乙烯-己烯共聚合物、聚胺酯、聚乙烯對苯二甲酯、聚乙烯萘二甲酯等的聚酯，聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚二苯硫醚、芳綸(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素樹脂、矽酮樹脂、金屬(箔)、紙等。
又，基材1之材料，可列舉為前述樹脂之交聯等之聚合物。前述塑膠薄膜，可不做延伸處理，亦可視需要進行一軸或二軸之延伸處理。如藉由延伸處理等賦予熱伸縮性之樹脂片材，在切割後該基材1可藉由熱收縮使黏著劑層2與加熱接合用片材3、3’之接著面積降低，可達到使半導體晶片之回收容易化的目的。
基材1之表面，為提高與鄰接層之密著性、保持性等，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、離子化放射線處理等化學性或物理性處理，利用底塗劑(例如，下述黏著物質)所進行之塗佈處理。
基材1之厚度並無特別的限制，可適當地決定，一般為5~200μm左右。
用於黏著劑層2之形成的黏著劑並無特別限制，例如，可使用丙烯酸系黏著劑、橡膠系黏著劑等的一般感壓性接著劑。前述感壓性接著劑，如基於以半導體晶圓或玻璃等怕污染的電子零件之超純水或酒精等有機溶劑之清淨洗淨性等觀點而言，較佳係以丙烯酸系聚合物為基礎聚合物之丙烯酸黏著劑。
作為前述丙烯酸系聚合物，可列舉例如，(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、s-丁酯、t-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、十一酯、十二酯、十三酯、十四酯、十六酯、十八酯、二十酯等烷基之碳數1~30，尤其是碳數4~18的直鏈狀或分枝鏈狀之烷基酯等)，以及(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使用之丙烯酸系聚合物等。又，(甲基)丙烯酸酯即係指丙烯酸酯及/或甲基丙烯酸酯，本發明中之(甲基)，皆為同樣意義。
前述丙烯酸系聚合物，以凝集力、耐熱性等的改良為目的，可視需要含有與前述(甲基)丙烯酸烷酯或環烷酯共聚合之其他單體成分之對應單位。此種單體成分，可列舉例如，丙烯酸、甲基丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、衣康酸、馬來酸、富馬酸、丁烯酸等含羧基之單體；馬來酸酐、衣康酸酐等酸酐單體；(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、(4-羥基甲基環己基)甲基(甲基)丙烯酸酯等含羥基之單體；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、磺酸丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基之單體；丙烯醯胺、丙烯腈等。此等可共聚合之單體成分可使用1種或2種以上。此整可共聚合之單體之使用量在全部單體成分之40重量%以下為佳。
進一步，為使前述丙烯酸系聚合物進行交聯，可視需要包含多官能性單體等作為共聚合用單體成分。此種多官能性單體，可列舉例如，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、胺基甲酸(甲基)丙烯酸酯等。此等多官能性單體亦可使用1種或2種以上。從黏著特性等之觀點而言，多官能性單體之使用量在全部單體成分之30重量%以下為佳。
前述丙烯酸系聚合物，可藉由使單一單體或2種以上之單體混合物進行聚合而得。聚合亦可以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任一方式進行。以防止對潔淨之被黏物之污染等之觀點而言，以低分子量物質之含量較小為佳。以此點而言，丙烯酸系聚合物之數量平均分子量較佳係10萬以上，更較佳係20萬~300萬左右，特佳係30萬~100萬左右。
此外，由於前述黏著劑中，作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，因此可適宜地採用外部交聯劑。作為外部交聯方 法之具體手段，可列舉添加聚異氰酸酯化合物、環氧化合物、氮丙環化合物、三聚氰胺系交聯劑等所謂交聯劑使其反應之方法。使用外部交聯劑時，其使用量係根據與該應交聯之基礎聚合物之平衡，進一步，可根據作為黏著劑之使用用途來適當決定。一般而言，對於前述基礎聚合物100重量份，以約5重量份以下，進一步以0．1~5重量份配合為佳。進一步，黏著劑視需要，除前述成分外，亦可使用過去習知的各種黏著賦予劑、抗老化劑等之添加劑。
黏著劑層2能以放射線硬化型黏著劑形成。放射線硬化型黏著劑，藉由紫外線等放射線的照射增大交聯程度，從而可容易地使其黏著力降低，藉由僅在圖2所示黏著劑層2之加工黏貼部分之對應部分2a照射放射線，能使與其他部分2b之黏著力造成差異。
此外，藉由使圖2所示之加熱接合用片材3’同時與放射線硬化型之黏著劑層2硬化，可容易地形成黏著力明顯降低之前述部分2a。由於在硬化、黏著力降低之前述部分2a貼附加熱接合用片材3’，在黏著劑層2之前述部分2a與加熱接合用片材3’之界面，具有在撿拾時容易剝離的性質。另一方面，未照射放射線之部分具有足夠的黏著力，而形成前述部分2b。又，對黏著劑層之放射線照射，亦可在切割後撿拾前進行。
如同前述，圖1所示附切晶帶之加熱接合用片材10之黏著劑層2中，由未硬化之放射線硬化型黏著劑所形成的前述部分2b係與加熱接合用片材3黏著，能確保切割時之保持力。此種放射線硬化型黏著劑能將用以固定晶片狀加工品(半導體晶片等)於基板等被黏物之加熱接合 用片材3，在接著‧剝離的平衡良好情形下進行支撐，圖2所示附切晶帶之加熱接合用片材11之黏著劑層2中，前述部分2b能固定晶片環。
放射線硬化型黏著劑係具有碳-碳雙鍵等放射線硬化性之官能基，且可使用表現黏著性之物質，無特別限制。放射線硬化型黏著劑，可例示如，在前述丙烯酸系黏著劑、橡膠系黏著劑等一般感壓性黏著劑上，配合放射線硬化性之單體成分或低聚物成分之添加型放射線硬化型黏著劑。
配合放射線硬化性之單體成分，可列舉例如，為胺基甲酸酯低聚物、胺基甲酸(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基四(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，其分子量係100~30000左右之範圍者為適當。放射線硬化性之單體成分或低聚物成分之配合量，可因應前述黏著劑層之種類、黏著劑層之黏著力之可降低量，做適當的決定。一般而言，對於構成黏著劑之丙烯酸系聚合物等的基礎聚合物100重量份，例如為5~500重量份、較佳為40~150重量份左右。
此外，放射線硬化型黏著劑，可列舉除前述說明之添加型放射線硬化型黏著劑外，基礎聚合物還可列舉使用內在型之放射線硬化型黏著劑，其係在聚合物側鏈或主鏈中間或主鏈末端具有碳-碳雙鍵者。內在型放射線硬化型黏著劑，因不需含有低分子成分之低聚物或含量不多，故 低聚物成分不會隨時間經過在黏著劑中移動，能形成安定層構造之黏著劑層而較佳。
前述具有碳-碳雙鍵之基礎聚合物，可使用具有碳-碳雙鍵且具有黏著性者，並無特別限制。作為此種基礎聚合物，基本骨架係以丙烯酸系聚合物者為佳。作為丙烯酸系聚合物之基本骨架，可列舉前述例示之丙烯酸系聚合物。
前述對丙烯酸系聚合物之碳-碳雙鍵之導入法無特別限制，可採用各種方法，以分子設計之觀點，係以碳-碳雙鍵導入聚合物側鏈為容易。可列舉例如，事先，在丙烯酸系聚合物單體中共聚合具有官能基之單體後，將可與此官能基反應之官能基以及具有碳-碳雙鍵之化合物，在維持碳-碳雙鍵之放射線硬化性狀態下使其縮合或加成反應之方法。
此等官能基之組合之例，可列舉羧酸基及環氧基、羧酸基和氮丙環基、羥基及異氰酸酯基等。此等官能基之組合中，從追蹤反應之容易度而言，係以羥基和異氰酸酯基之組合較適合。此外，根據此等官能基之組合，若是生成前述具有碳-碳雙鍵之丙烯酸系聚合物之組合時，官能基在丙烯酸系聚合物和前述化合物之任一側皆可；而前述較佳之組合，丙烯酸系聚合物具有羥基，前述化合物具有異氰酸酯基之情形則為合適。此種情形，具有碳-碳雙鍵之異氰酸酯化合物，可列舉例如，甲基丙烯醯異氰酸酯、2-甲基丙烯醯氧乙基異氰酸酯、m-異丙烯-α、α-二甲基芐基異氰酸酯等。此外，作為丙烯酸系聚合物，前述例示之含有羥基之單體或2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二甘醇單乙烯醚之醚系化合物等用於共聚合之物。
前述內在型之放射線硬化型黏著劑，可單獨使用前述含有碳-碳雙鍵之基礎聚合物(尤其係丙烯酸系聚合物)，也可在不惡化其特性的程度配合前述放射線硬化性之單體成分或低聚物成分等。放射線硬化性之低聚物成分等，對於通常基礎聚合物100重量份係30重量份之範圍內，較佳則係0~10重量份之範圍。
前述放射線硬化型黏著劑，藉由紫外線等使其硬化時含有光聚合引發劑。作為光聚合引發劑，可列舉例如，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-羥基環己苯酮等之α-酮系化合物；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)-苯基〕-2-嗎啉丙烷-1等苯乙酮系化合物；苯偶姻乙醚、苯偶姻異丙醚、茴香偶姻甲醚等之苯偶姻乙醚系化合物；芐基二甲基縮酮等之縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯甲酮-1，1-丙二酮-2-(o-乙氧羰基)肟等之光活性肟系化合物；二苯甲酮、苯甲醯安息香酸、3，3’-二甲基-4-甲氧基二苯甲酮等之二苯甲酮系化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2，4-二甲基噻噸酮、噻噸酮、異丙基噻噸酮、2，4-二氯噻噸酮、2，4-二乙基噻噸酮、2，4-二異丙基噻噸酮等之噻噸酮系化合物；樟腦醌；鹵化酮；醯基氧化磷；醯基磷酸酯等。光聚合引發劑之配合量，相對於構成黏著劑之丙烯酸系聚合物等之基礎聚合物100重量比，例如為0．05~20重量比左右。
又，放射線硬化型黏著劑，可列舉例如，特開昭60-19 6956号公報所揭露，有2個以上不飽和鍵之加成聚合化合物，含有具有環氧基之烷氧基矽烷等光聚合性化合物，和羰基化合物、有機硫磺化合物、過氧化物、胺、鎓鹽系化合物等之光聚合引發劑之橡膠系黏著劑或丙烯酸系黏著劑等。
前述放射線硬化型之黏著劑層2中，可視需要，含有藉由放射線照射來著色之化合物。藉由放射線照射，藉由使黏著劑層2含有著色之化合物，可使僅被放射線照射之部分著色。亦即，可使圖1所示加工黏貼部分3a之對應部分2a著色。因此，能以目視直接判斷黏著劑層2是否被放射線照射過，加工黏貼部分3a容易被識別，加工之黏貼更為容易。又，用光感測器等檢測半導體晶片時，其檢測精度提高，半導體之撿取時不會發生錯誤操作。藉由放射線著色之化合物，在放射線照射前為無色或淡色，藉由放射線照射成為有色之化合物，可列舉例如無色染料等。藉由放射線著色之化合物之使用比例，可適當設定。
黏著劑層2之厚度，雖無特別限定，但從晶片切斷面之缺陷防止或加熱接合用片材3、3’之固定保持之兼顧性等觀點而言，係以1~50μm左右為佳。較佳為2~30μm，更佳為5~25μm。
本實施例型態之切晶帶11，例如，能以如下製作。
首先，基材1，可由過去習知的製膜方法來製膜。該製膜方法，可例示如壓延(calendaring)製膜法、在有機溶劑中之鑄膜(casting)法、在密閉系統之吹膜擠出法、T模擠出法、共擠出法、乾式層壓法等。
接著，基材1上形成塗佈黏著劑組成物溶液之塗佈膜後，該塗佈膜在所定條件下乾燥(視需求加熱交聯)，形成黏著劑層2。塗佈方法無 特別限定，可列舉例如，滾輪塗工、網版塗工、凹版塗工等。又，乾燥條件，例如可在乾燥溫度80~150℃、乾燥時間0．5~5分之間之範圍內進行。又，在隔板上塗佈黏著劑組成物形成塗佈膜後，在前述乾燥條件下乾燥塗佈膜而形成黏著劑層2亦可。之後，在基材1上將隔板與黏著劑層2一起貼合。藉此，製作切晶帶11。
附切晶帶之加熱接合用片材10、12，可用一般方法製造。例如，將切晶帶11之黏著劑層2與加熱接合用片材3貼合，可製造附切晶帶之加熱接合用片材10。
附切晶帶之加熱接合用片材10，以隔板覆蓋加熱接合用片材3者為佳。可列舉例如，貼合切晶帶11及加熱接合用片材3後，剝離於加熱接合用片材3積層之前述基材隔板，於剝離前述基材隔板後之附切晶帶之加熱接合用片材10之加熱接合用片材3之露出面，貼附隔板之方法。亦即，貼合切晶帶11、加熱接合用片材3，及前述隔板之順序積層之形態為佳。
上述實施型態，說明關於切晶帶及加熱接合用片材所積層之附切晶帶之加熱接合用片材。然而，本發明之加熱接合用片材，亦可提供不貼合切晶帶之狀態。
加熱接合用片材，不貼合切晶帶之形態之情形，夾於2片之隔板形成附有兩面隔板之加熱接合用片材為佳。亦即，第1隔板、加熱接合用片材、及第2隔板之順序所積層而形成附有兩面隔板之加熱接合用片材為佳。
圖3，表示附有兩面隔板之加熱接合用片材之一實施型態之斷面模式圖。
圖3所示之附有兩面隔板之加熱接合用片材30，具有第1隔板3 2、加熱接合用片材3、及第2隔板34之順序所積層之構成。第1隔板32、及第2隔板34，可使用與前述基材隔板相同之物。
又，加熱接合用片材，形成不貼合切晶帶之形態時，僅加熱接合用片材之一側之面積層隔板之形態亦可。
(半導體裝置之製造方法)
本實施型態中之半導體裝置之製造方法包含：準備前述加熱接合用片材之步驟，及介由前述加熱接合用片材，使半導體晶片在被黏物上加熱接合之加熱接合步驟(以下，亦稱為第1實施型態)。
此外，本實施型態中半導體裝置之製造方法包含：準備前述所記載之附切晶帶之加熱接合用片材之步驟，及將前述附切晶帶之加熱接合用片材與半導體晶圓之背面貼合之貼合步驟，及將前述半導體晶圓與前述加熱接合用片材一起切割，形成晶片狀之半導體晶片之切晶步驟，及將前述半導體晶片，從前述附切晶帶之加熱接合用片材，與前述加熱接合用片材一起撿拾之撿拾步驟，及介由前述加熱接合用片材，將前述半導體晶片於被黏物上進行加熱接合之加熱接合步驟(以下，亦稱為第2實施型態)。
第1實施型態中半導體裝置之製造方法，相對於第2之實施型態中半導體裝置之製造方法，其使用附切晶帶之加熱接合用片材，係在第1實施型態中半導體裝置之製造方法中，於以單體使用加熱接合用片材之部分不 同，而其他部分相同。第1之實施型態中半導體裝置之製造方法中，準備加熱接合用片材後，若將其與切晶帶進行貼合步驟，其後，可與第2實施型態中半導體裝置之製造方法相同地進行。因此，以下針對第2實施型態中半導體裝置之製造方法加以說明。
本實施型態中半導體裝置之製造方法中，首先，準備附切晶帶之加熱接合用片材10、12(準備步驟)。附切晶帶之加熱接合用片材10、12，可在加熱接合用片材3、3’上任意設置之隔板上適宜地剝離，如以下使用。以下，一邊參照圖3使用附切晶帶之加熱接合用片材10之情形為例，加以說明。
首先，附切晶帶之加熱接合用片材10中加熱接合用片材3之半導體晶圓黏貼部分3a上，壓接半導體晶圓4，將此保持接著並固定(貼合步驟)。本步驟，是用壓著滾輪等之按壓方法一邊按壓一邊進行。裝載時之黏貼溫度並無特別限定，例如在23~90℃之範圍內為佳。
半導體晶圓4，於一側之面形成電極墊，於其他的面(以下，稱作背面)之最表面形成銀薄膜為佳。前述銀薄膜之厚度，可列舉例如，10nm~1000nm。此外，於半導體晶圓4與前述銀薄膜之間，進一步，亦可形成鈦薄膜。前述鈦薄膜之厚度，可例舉例如，10nm~1000nm。若形成前述銀薄膜，則後述之加熱接合步驟中，半導體晶片5與加熱接合用片材3可強固地加熱接合。此外，若形成前述鈦薄膜則電極之信賴性提升。前述銀薄膜、及前述鈦薄膜，例如，可藉由氣相沉積形成。
接著，進行半導體晶圓4之切割(切晶步驟)。藉此，切斷 並單片化半導體晶圓4成所定之尺寸，從而製造半導體晶片5。切晶方法雖無特別限定，例如可從半導體晶圓4之迴路面側，按照普通方法進行。此外，本步驟，例如可採用附切晶帶之加熱接合用片材10，以進行切割之稱作全切之切斷方式。本步驟所用的切晶裝置並無特別限定，可使用過去習知之物。此外，由於半導體晶圓4，藉由切晶帶之加熱接合用片材10接著固定，故可抑制晶片缺陷或晶片飛散的同時，亦可抑制半導體晶圓4的破損。
接著，為剝離在附切晶帶之加熱接合用片材10上接著固定之半導體晶片5，進行半導體晶片5之撿拾(撿拾步驟)。撿拾之方法無特別限定，可採用過去各種習知的方法。可列舉例如將個別半導體晶片5從附切晶帶之加熱接合用片材10側藉由針突起，再將突起之半導體晶片5經由撿拾裝置撿拾之方法等。
作為撿拾條件，以防止破片之觀點，針的突起速度在5~100mm/秒為佳，在5~10mm/秒更佳。
此處之撿拾，係黏著劑層2為紫外線硬化型之情形，其係在該黏著劑層2照射紫外線後進行。藉此，對於黏著劑層2之加熱接合用片材3之黏著力降低，使半導體晶片5之剝離變得容易。其結果，可在撿拾半導體晶片5時不使其受損。紫外線照射時之照射強度、照射時間等之條件並無特別限定，可視需要適當設定。此外，紫外線照射所使用之光源，可使用習知之物。此外，黏著劑層事先照射紫外線使其硬化，貼合此硬化之黏著劑層與加熱接合用片材時，並不需紫外線照射。
接著，撿拾之半導體晶片5，介由加熱接合用片材3，而黏 晶(加熱接合)於被黏物6(加熱接合步驟)。被黏物6，可列舉有導線架、TAB薄膜、基板或另外製作之半導體晶片等。被黏物6，例如，可為容易變形之變形型被黏物，亦可為不易變形之非變形型被黏物(半導體晶圓等)。
前述導線架，可列舉Cu導線架、42Alloy導線架等之金屬導線架。又，前述基板，可使用過去習知之物。可列舉例如玻璃環氧基、BT(雙馬來醯亞胺-三嗪)、聚醯亞胺等構成之有機基板。其中，若使用金屬導線架，可藉由加熱接合與金屬微粒子一體化。又，前述基板係在陶瓷板等之絕緣基板上，例如積層銅電路基板之絕緣電路基板。若使用絕緣電路基板，例如，可製造進行電力的控制或供給之電力半導體裝置。
前述加熱接合步驟，藉由加熱燒結金屬微粒子的同時，可視需要熱分解熱分解性黏合劑。此外，揮發藉由乾燥步驟無法完全揮發所殘留之低沸點黏合劑。加熱溫度為，以180~400℃為佳、190~370℃較佳、在200~350℃進行更佳。此外，加熱時間，以0．3~300分為佳、0．5~240分較佳、在1~180分進行更佳。又加熱接合，亦可在加壓條件下進行。加壓條件，以1~500kg/cm2的範圍內為佳、5~400kg/cm2的範圍內更佳。在加壓下之加熱接合，例如，可以如倒裝焊接機之加熱與加壓可同時進行之裝置來進行。此外，平行平板加壓亦可。
接著，可視需要，如圖4所示，在被黏物6之端子部(內引線)之前端與半導體晶片5上之電極墊(無圖示)以焊接導線7做電氣連接(導線焊接步驟)。前述焊接導線7，例如，可使用金線、鋁線或銅線等。 進行導線焊接時之溫度，在23~300℃，較佳係在23~250℃之範圍內進行。此外，其加熱時間為數秒~數分內進行。結線為在前述溫度範圍內之加熱狀態下，藉由超音波之振動能量與藉由施加電壓之壓接能量之併用下進行。
接著，可視需要，如圖4所示，藉由密封樹脂8密封半導體晶片5(密封步驟)。本步驟係為保護在被黏物6所搭載之半導體晶片5或焊接導線7而進行。本步驟可藉由密封用樹脂在模具成型來進行。密封樹脂8，例如使用環氧樹脂。樹脂密封時之加熱溫度，通常在175℃、60~90秒之間進行，但本發明並無限定於此，例如可在165~185℃、數分內處理。藉此，使密封樹脂8硬化。又，本密封步驟，亦可採用在片材狀之密封用片材嵌入半導體晶片5之方法(例如，參照特開2013-7028号公報)。此外，除了藉由模具之密封樹脂之成型以外，在箱型容器流入矽酮凝膠之凝膠密封型亦可。
接著，可視需要進行加熱，使在前述密封步驟硬化不足之密封樹脂8完全硬化(後硬化步驟)。本步驟中之加熱溫度，因密封樹脂之種類而異，例如在165~185℃之範圍內，加熱時間為0．5~8小時左右。
又，本發明之加熱接合用片材、及附切晶帶之加熱接合用片材，亦可適合於積層有複數半導體晶片且立體實裝之情形。此時，可於半導體晶片間積層加熱接合片材及隔離層，亦可不積層隔離層，而僅在半導體晶片間積層加熱接合用片材，可視製造條件或用途等作適當變更。
此外，本發明之加熱接合用片材，及附切晶帶之加熱接合用片材，不 限定於上述例示之用途，可利用2者於加熱接合。
【實施例】
以下，關於本發明所使用之實施例做詳細的說明，但本發明在不超過其主旨之情況下，並不限於以下之實施例。
關於實施例使用成分加以說明。
金屬微粒子混合膏A：適當調整含在應用奈米粒子研究所製的ANP-1(奈米尺寸的銀微粒子分散於低沸點黏合劑的膏)之低沸點黏合劑之量。
熱分解性黏合劑A(聚碳酸丙烯酯樹脂)：Empower公司製之QPAC40、在23℃固態
熱分解性黏合劑B(丙烯酸樹脂)：藤倉化成公司製之MM-2002-1、在23℃固態
有機溶劑A：甲乙酮(MEK)
〔加熱接合用片材之製作〕
依據表1所記載之配合比，將表1所記載之各成分及溶劑放入混合攪拌器(KEYENCE製HM-500)之攪拌槽中，攪拌模式以3分鐘攪拌‧混合。
所得到之塗漆，在離型處理薄膜(三菱樹脂(株)製的MRA50)上塗佈‧乾燥。藉此之實施例及比較例，得到厚度40μm之加熱接合片材。
〔重量減少量之測定〕
對實施例及比較例之加熱接合用片材切取約10mg，大氣環境下， 以昇溫速度10℃/分之條件，從23℃至500℃藉由差動型示差熱天秤進行分析。分析係使用理學電機(股份有限公司)製之差動型示差熱天秤TG-DTA TG8120。在23℃之重量減少量為0%。又，此分析，當重量比起在23℃之重量為減少時，值為負值。讀取在500℃之值(重量減少量(%))及300℃之值(重量減少量(%))，算出500℃之值減去300℃之值所得之值。
圖5，關於實施例1之加熱接合用片材，表示藉由示差熱天秤之分析進行時之溫度及重量減少量(%)之關係之圖表。如圖5所示，實施例1，在500℃之值(重量減少量(%))為-5．8%。此外，300℃之值(重量減少量(%))為-5．5%。因此，500℃之值減去300℃之值所得之值，如下，為-0．3%。
〔-5．8(%)〕-〔-5．5(%)〕=〔-0．3(%)〕
對其他實施例、及比較例亦相同地算出。
算出之結果，500℃之值減去300℃之值所得之值，在-1%~0%之範圍內時為○、不在-1%~0%之範圍內時為×做評價。結果如表1所示。
〔燃燒-紅外吸收法之殘碳量之測定〕
實施例及比較例之加熱接合用片材夾於矽晶圓，以下述條件接合。藉此，得到具有燒結層之評價用樣品。接合係使用燒結裝置(伯東公司製，HTM-3000)。
<接合條件>
在10MPa之加壓(平板加壓)下，從80℃至300℃以昇溫速 度1．5℃/秒昇溫後，在300℃維持2．5分鐘。然後，空氣冷卻至170℃，然後，水冷至80℃。又，水冷係加壓板內附設之水冷式冷卻板之物。
接著，評價用樣品之燒結層中之碳量，使用碳分析裝置(堀場製作所公司製，EMIA-110)測定。具體而言，首先，在爐中，以1350℃燃燒評價用樣品之燒結層。此時，使用助燃劑。然後，燃燒產生之CO及CO2藉由紅外線檢出器檢出並換算成碳量。0%~1．6%之情形為○、大於1．6%之情形為×做評價。結果如表1所示。
〔信賴性試驗後之剩餘接合面積率〕
準備於背面依序形成Ti層(厚度50nm)及Ag層(厚度100nm)之矽晶片(矽晶片之厚度350μm、縱5mm、橫5mm)。於準備之矽晶片之Ag層面個別貼合實施例、及比較例之加熱接合用片材。
貼合之條件係溫度70℃、壓力0．3MPa、速度10mm/秒。
準備以Ag層(厚度5μm)覆蓋全體之銅板(銅板之厚度3mm)。準備之銅板上，以下述條件接合附有矽晶片之加熱接合用片材。藉此，得到評價用樣品。接合係使用燒結裝置(伯東公司製、HTM-3000)。
<接合條件>
10MPa之加壓(平板加壓)下，從80℃至300℃以昇溫速度1．5℃/秒昇溫後，在300維持2．5分鐘。然後，空氣冷卻至170℃，然後，水冷至80℃。又，水冷係藉由加壓板內附設之水冷式冷卻板。
接著，評價用樣品放入冷熱衝擊試驗機(ESPEC公司製之TSE-103ES)，給予100循環-40℃~200℃之冷熱衝擊。又，此時，在-40℃及200℃個別維持15分鐘。
100循環後，使用超音波影像裝置〔SAT〕(日立建機Finetech製
Figure 105131684-A0202-12-0032-7
FineSAT II)，確認矽晶片與銅板於燒結層接合之部分，進行攝影。使用傳感器(探測器)，PQ-50-13：WD〔頻率50MHz〕。
求得於得到的像中接合而剩餘部分之面積(剩餘面積)，算出相對於全體面積之剩餘面積之比例(剩餘接合面積率)。此外，剩餘接合面積率在50%以上時為○、低於50%時為×做評價。結果表1所示。又，藉由超音波影像裝置之像，可見矽晶片與基板剝離之部分為白，接合而剩餘之部分為灰。
Figure 105131684-A0202-12-0032-1
比較例1係熱分解性黏合劑，使用熱分解性比聚碳酸酯低的 丙烯酸樹脂。此外，熱分解性黏合劑之含有量比起實施例多。進一步，片材形成時之乾燥條件，比起實施例2、實施例3為較緩和的條件。因此，比起實施例2、實施例3，低沸點黏合劑殘存較多。根據以上之理由，比較例1，比起實施例，可認為在燒結後，熱分解性黏合劑或低沸點黏合劑亦大多殘存於片材內。其結果，比較例1之燒結層，可認為變得較脆弱。
1‧‧‧基材
2‧‧‧黏著劑層
3、3’‧‧‧加熱接合用片材
4‧‧‧半導體晶圓
10‧‧‧附有切晶帶之加熱接合用片材
11‧‧‧切晶帶
31‧‧‧藉由加熱形成燒結層之層

Claims (4)

  1. 一種加熱接合用片材，其特徵係其具有藉由加熱形成燒結層之層；前述層係大氣環境下，以昇溫速度10℃/分之條件，從23℃至500℃藉由差動型示差熱天秤進行分析時，在500℃之重量減少量(%)減去在300℃之重量減少量(%)之值，在-1%~0%之範圍內；前述層含有在23℃為固態之熱分解性黏合劑。
  2. 一種加熱接合用片材，其特徵係其具有藉由加熱形成燒結層之層；前述層係藉由下述加熱條件A加熱後之燃燒-紅外吸收法之碳量為0%~1．6%之範圍內；<加熱條件A>前述層，在10MPa之加壓下，從80℃至300℃以昇溫速度1．5℃/秒昇溫後，在300℃維持2．5分鐘；前述層含有在23℃為固態之熱分解性黏合劑。
  3. 如申請專利範圍第1項所記載之加熱接合用片材，其中，前述層含有金屬微粒子；前述金屬微粒子選自銀、銅、氧化銀、氧化銅所成群中之至少1種。
  4. 一種附切晶帶之加熱接合用片材，其特徵係其具有切晶帶，及積層於前述切晶帶上如申請專利範圍第1至3項中任一項所記載之加熱接合用片材。
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