TWI442483B - 自圓角化的晶片附著膏 - Google Patents

自圓角化的晶片附著膏 Download PDF

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TWI442483B
TWI442483B TW097147928A TW97147928A TWI442483B TW I442483 B TWI442483 B TW I442483B TW 097147928 A TW097147928 A TW 097147928A TW 97147928 A TW97147928 A TW 97147928A TW I442483 B TWI442483 B TW I442483B
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Taiwan
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wafer
filler
yield stress
acrylate
self
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TW097147928A
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TW200937537A (en
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Minghai Wang
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Henkel Ag & Co Kgaa
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Description

自圓角化的晶片附著膏
本發明係關於一種組合物；更詳而言之，本發明係關於一種包含樹脂和填料的組合物。
 發明背景
微電子裝置包含上百萬個由各類基片支撐的電路元件。這些元件包含半導體矽晶片(晶粒)。這些元件與基片之間的電連接是在晶片上的電端子和基片上相應的電端子之間形成的。製造這些連接的一種方法是使用膏狀晶片附著黏合劑將半導體晶片與基片黏合，並用金屬線將晶片上的端子與基片上的端子連接。
在這種晶片附著過程中，使用足夠程度的壓力和/或熱，使晶片與晶片附著黏合劑接觸，以使黏合劑於晶片下蔓延並完全覆蓋基片。期望的是，黏合劑進一步在晶片周邊形成圓角(fillet)，即突起的邊緣或脊。
當使用薄晶片時以及當進行晶片堆疊時，在分配晶片附著黏合劑中出現問題。傳統的膏狀晶片附著黏合材料不適合這些應用，因為這些晶片附著黏合材料不易在期望的邊緣形成圓角，並且可能容易溢出至半導體封裝件的擁擠有效區內，以致污染相鄰的晶片和電互連件(interconnect)，或溢出至晶片上面，這將影響後續的引線接合製程。另外，在不施加壓力的情況下，難以使黏合劑的流動和接合達到恰當的程度。在對薄晶片施加壓力時，晶片可能破裂、或傾斜、或捲曲。
優選的是，應用一種晶片附著材料：其具有合適的流變性能，以致在沒有施加或僅施加最小的壓力和/或熱的情況下，自動地流動並充滿要黏合的區域，並且在區域周邊精確且均一地形成圓角，而沒有黏合劑擴散到周邊區域。
 發明概述
本發明者已經發現一種組合物，其在25℃(周圍環境溫度)下可以自動地流動(自動流動(auto-flow))並形成圓角(自圓角化(self-fillet))，屈服應力的範圍在1.8Pa至10Pa(18達因/平方釐米(dynes/cm2 )至100達因/平方釐米)。此種組合物可以通過使用合適選擇的填料設計，而不管與組合物中使用的樹脂系統為何。因此，本發明是一種包含樹脂和填料的組合物，其特徵在於，該組合物具有範圍在1.8Pa至10Pa的屈服應力，因此在25℃下自動流動並形成圓角。對本說明書和申請專利範圍而言，屈服應力是組合物從黏彈性固體變成剪切稀化液體的數值，其係通過在“發明詳述”中揭露的方案測定。
 發明詳述
自動流動是指晶片附著黏合劑一旦被放置到兩個基片之間並與這些基片相接觸時，將在室溫、不需要施加過多壓力的情況下開始流動，並覆蓋兩個基片之間的區域。基片可以是指半導體晶片的基片或半導體晶片本身，例如，兩個或多個晶片以堆疊幾何形狀佈置時所發生的情況。當使用半導體基片和半導體晶片的組合時，自圓角化是指晶片附著黏合劑的自動流動會在基片上晶片的周邊停止並凝固，以形成圍繞晶片四周的圓角，而不會溢流至晶片之上或擴散到除了與此晶片緊鄰的區域以外的基片上其他區域。圓角是突起的邊緣或脊，可以具有彎曲的內角。在兩個或多個晶片以堆疊幾何形狀佈置的情況下，當基片是另一個晶片時，圓角可能是不期望的。通過對輕微壓力的調整，和或在屈服應力的範圍之內對屈服應力進行調整，對於這種幾何佈置，圓角可以避免，儘管所述膏能夠如所述進行自圓角化。
屈服應力值是在25℃時於壓力下從包括樹脂和填料的組合物所產生的流變學曲線確定的。方案如下，使用Rheometer公司的AR2000EX：首先對組合物進行剪切，直到它從黏彈性固體變成液體；達到平衡；將剪切應力從0.1Pa施加至200Pa，然後將應力從200Pa降低至0.1Pa。每步的持續時間通常為2分鐘至10分鐘。對於每一組合物，通過下述步驟確定每步的實際持續時間：以每步持續時間2分鐘運行該方案；再以10分鐘運行該方案。如果10分鐘時屈服應力的測定值與2分鐘時相同，則2分鐘被用作每步的持續時間。如果不相同，則10分鐘時的屈服應力被作為精確的屈服應力值。由實施者決定，對每一步，可以以不同持續時間進行多輪該方案，直到結果不發生變化，然後對每一步選出產生一致性屈服應力值的最短持續時間。記錄剪切應力施加(從0.1Pa至200Pa)的緩升曲線係模擬晶片附著黏合劑的分配過程；晶片附著黏合劑通常用注射器分配，並且注射器活塞的壓力在黏合劑上施加剪切應力。記錄剪切應力降低(從200Pa至0.1Pa)的緩降曲線係模擬晶片與黏合劑接觸的晶片附著過程。本發明者發現，緩降曲線更準確地預測了發生自動流動和自圓角化的屈服應力。
驅動自動流動和自圓角化的力主要來自黏合劑膏與晶片之間的能量相互作用。當此驅動力小於黏合劑的屈服應力時，自動流動和自圓角化將不會發生。此驅動力取決於半導體封裝的設計，其影響參數如晶片厚度、接合線厚度、黏合劑膏密度、晶片和基片的表面能以及黏合劑、晶片和基片的介面能。在目前的封裝設計中，通常的驅動力值約為10Pa；因此，當晶片附著黏合劑的屈服應力小於10Pa時，黏合劑膏將自動流動。如果屈服應力太小而不能抵抗黏合劑膏和晶片之間的能量相互作用，則將發生“溢流(overflow)”，並且，儘管黏合劑也自圓角化，但此自圓角化不會發生在晶片的周邊。這通常發生在屈服應力小於約1.8Pa時。
對於填充的樹脂系統，屈服應力將取決於填料顆粒和樹脂之間相互作用的性質。因此，為了設計滿足上述具有適合屈服應力的流變性能的組合物，填料是關鍵組分。通常，在相同的填料量下，相較於更大粒徑的填料，更小粒徑的填料產生更高的屈服應力值，並且，更高的填料量產生更高的屈服應力。
通過適當選擇在組合物中使用的、對於獲得從1.8Pa至10Pa範圍的屈服應力有效的填料數量、尺寸和形狀，獲得自動流動和自圓角化。填料的形狀可以是顆粒或片或二者的結合。填料可以是從納米級到幾毫米之間的任何尺寸。對填料的量加以改變，以提供有效範圍內的屈服應力，獲得自動流動和自圓角化。在本說明書中的揭露內容中，測定填料的精確級別的實驗方法在本領域技術人員的專業知識內，而無需過多的實驗方法。
例示性的絕緣填料包括二氧化矽(包括火成二氧化矽和其他類型的二氧化矽)、碳化矽、氮化硼、金剛石、氧化鋁、氫氧化鋁、蛭石、雲母、鈣矽石、碳酸鈣、二氧化鈦、沙子、玻璃、硫酸鋇、鋯、炭黑、有機填料以及鹵化乙烯聚合物，例如四氟乙烯、三氟乙烯、1,1-二氟乙烯、氟乙烯、1,1-二氯乙烯、氯乙烯以及這些的組合。
在一個實施方式中，填料是絕緣的，特別地是二氧化矽填料。火成二氧化矽顯示出比球形二氧化矽高得多的屈服應力。在各種實施方式中，球形二氧化矽和火成二氧化矽的組合被使用，並且是調節流變性能至所需屈服應力範圍的有效方法。
例示性的電或熱傳導填料包括炭黑和石墨；金、銀、銅、鉑、鈀、鎳、鋁、以及這些金屬相互之間或與其他金屬的合金、其他金屬合金、以及鍍金屬顆粒；鍍有金屬，特別是金、銀、銅、鉑、鈀、鎳、鋁以及這些金屬相互之間的合金的玻璃、有機聚合物、或球形二氧化矽、或類似物。
適合的樹脂是熱固性或熱塑性聚合物。在各種實施方式中，這些聚合物選自環氧化物、馬來醯亞胺(包括雙馬來醯亞胺)、丙烯酸酯和甲基丙烯酸酯、以及氰酸酯、乙烯醚、硫醇-烯、包含連接於芳香環且與芳香環中之非飽和部分共軛的碳碳雙鍵的樹脂(如衍生自肉桂基和苯乙烯基起始化合物的化合物)、延胡索酸酯和馬來酸酯。在各種其他實施方式中，這些聚合物包括聚醯胺、苯氧基化合物、苯並噁嗪、聚苯並噁嗪、聚醚碸、聚醯亞胺、矽氧烷化烯烴、聚烯烴、聚酯、聚苯乙烯、聚碳酸酯、聚丙烯、聚氯乙烯、聚異丁烯、聚丙烯腈、聚乙酸乙烯酯、聚(2-乙烯基吡啶)、順-1,4-聚異戊二烯、3,4-聚氯丁二烯、乙烯基共聚物、聚環氧乙烷、聚乙二醇、聚甲醛、聚乙醛、聚(β-丙內酯)、聚(10-癸酸酯)、聚對苯二酸乙二酯、聚己內醯胺、聚(11-十一醯胺)、聚(間亞苯基-對苯二醯胺)、聚(四亞甲基-間苯磺醯胺)、聚酯聚芳酯、聚苯醚、聚苯硫醚、聚碸、聚醚酮、聚醚醯亞胺、氟化聚醯亞胺、聚醯亞胺矽氧烷、聚異吲哚並喹唑啉二酮、聚硫醚醯亞胺、聚苯基喹喔啉、聚喹喔酮、醯亞胺-芳基醚苯基喹喔啉共聚物、聚喹喔啉、聚苯並咪唑、聚苯並噁唑、聚降冰片烯、聚芳醚、聚矽烷、聚對二甲苯基、苯並環丁烯、羥基-苯並噁唑共聚物以及聚亞芳基矽氧烷(poly(silarylene siloxane))。
適合的環氧樹脂包括雙酚、萘和脂肪族類型的環氧化物。可購買到的材料包括來自Dainippon Ink ＆ Chemicals,Inc.的雙酚型環氧樹脂(Epiclon 830LVP、830CRP、835LV、850CRP)；來自Dainippon Ink ＆ Chemicals,Inc.的萘型環氧樹脂(Epiclon HP4032)；來自Ciba Specialty Chemicals的脂肪族環氧樹脂(Araldite CY179、184、192、175、179)，來自Dow Corporation的脂肪族環氧樹脂(Epoxy 1234、249、206)和來自Daicel Chemical Industries,Ltd.的脂肪族環氧樹脂(EHPE-3150)。其他適合的環氧樹脂包括脂環族的環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、環氧酚醛清漆樹脂、聯苯型環氧樹脂、萘型環氧樹脂和二環戊二烯苯酚型環氧樹脂。
適合的馬來醯亞胺樹脂包括具有通式結構的那些，其中n為1至3，X1 為脂肪族或芳香族基團。例示性的X1 實體包括：聚丁二烯、聚碳酸酯、聚氨酯、聚醚、聚酯、簡單烴以及包含如羰基、羧基、醯胘、氨基甲酸酯、脲、酯或醚官能團的簡單烴。這些類型的樹脂可以購買到，並且可以從例如Dainipp on Ink and Chemical,Inc.獲得。
另外的通合的馬來醯亞胺樹脂包括但不僅限於，固體芳香雙馬來醯亞胺(BMI)樹脂，特別是具有結構的那些，其中Q為芳香基團。具有芳香Q橋聯基團的雙馬來醯亞胺樹脂是可以購買到的，並且可以例如從Sartomer(美國)或HOS-Technic GmbH(奧地利)獲得。
其他的適合的馬來醯亞胺樹脂包括其中C36 代表具有36個碳原子的直鏈或支鏈烴鏈(包含或不包含環部分)；
適合的丙烯酸酯和甲基丙烯酸酯樹脂包括具有通式結構那些，其中n是1至6，R1 是-H或-CH3 ，X2 是芳香基團或脂肪族基團。例示性的X2 實體包括聚丁二稀、聚碳酸酯、聚氨酯、聚醚、聚酯、簡單烴以及包含如羰基、羧基、醯胺、氨基甲酸酯、脲、酯或醚官能團的簡單烴。可以購買到的材料包括：可以從Kyoeisha Chemical Co.,LTD購買到的(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷酯、(甲基)丙烯酸烷酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸正十八烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸異冰片酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、全氟辛基乙基(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、壬基苯酚聚丙氧基(甲基)丙烯酸酯、和聚戊氧基四氫糠基(甲基)丙烯酸酯；可以從Sartomer Company,Inc獲取的聚丁二烯氨基甲酸乙酯二甲基丙烯酸酯(CN302、NTX6513)和聚丁二烯二甲基丙烯酸酯(CN301、NTX6039、PRO6270)；聚碳酸酯氨基甲酸乙酯二丙烯酸酯(ArtResin UN9200A)，可以從Negami Chemical Industries Co.,LTD獲取；丙烯酸化脂肪族氨基甲酸乙酯低聚物(Ebecryl 230、264、265、270、284、4830、4833、4834、4835、4866、4881、4883、8402、8800-20R、8803、8804)，可以從Radcure Specialities,Inc獲取；聚酯丙烯酸酯低聚物(Ebecryl 657、770、810、830、1657、1810、1830)，可以從Radcure Specialities,Inc.獲取；以及環氧丙烯酸酯樹脂(CN104、111、112、115、116、117、118、119、120、124、136)，可以從Sartomer Company,Inc.獲取。在一個實施方式中，丙烯酸樹脂選自：丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸十二烷酯、甲基丙烯酸十二烷酯、具有丙烯酸酯官能度的聚丁二烯和具有甲基丙烯酸酯官能度的聚丁二烯。
可以購買到的氰酸酯材料包括：可以從Huntsman LLC購買到的AroCy L-10、AroCy XU366、AroCy XU371、AroCy XU378、XU71787.02L和XU 71787.07L；可以從Lonza Group Limited購買到的Primaset PT30、Primaset PT30 S75、Primaset PT60、Primaset PT60S、Primaset BADCY、Primaset DA230S、Primaset MethylCy和Primaset LECY；可以從Oakwood Products,Inc.購買到的2-烯丙基苯酚氰酸酯、4-甲氧基苯酚氰酸酯、2,2-二(4-氰氧基苯酚)-1,1,1,3,3,3-六氟丙烷、雙酚A氰酸酯、2-烯丙基雙酚A氰酸酯、4-苯基苯酚氰酸酯、1,1,1-三(4-氰氧基苯基)乙烷、4-枯基苯酚氰酸酯、1,1-二(4-氰氧基苯基)乙烷、2,2,3,4,4,5,5,6,6,7,7-十二氟-辛二醇二氰酸酯和4,4’-雙酚氰酸酯。
適合的乙烯醚樹脂是含有乙烯醚官能團的任何樹脂，並且包括：聚丁二烯、聚碳酸酯、聚氨酯、聚醚、聚酯、簡單烴以及包含如羰基、羧基、醯胺、氨基甲酸酯、脲、酯或醚官能團的簡單烴。可以購買到的樹脂包括可以得自International Speciality Products(ISP)的環己烷二甲醇二乙烯醚、十二烷基乙烯醚、環己基乙烯醚、2-乙基己基乙烯醚、雙丙甘醇二乙烯醚、己二醇二乙烯醚、十八烷基乙烯醚和丁二醇二乙烯醚；可以得自Sigma-Aldrich,Inc的Vectomer 4010、4020、4030、4040、4051、4210、4220、4230、4060、5015。
熱固性或熱塑性聚合物反應物的固化劑可以是自由基引發劑或離子型引發劑(陽離子型或陰離子型)，這取決於是選擇自由基固化樹脂還是離子固化樹脂。固化劑以有效量存在。對自由基固化劑，有效量通常是有機化合物(除了任何填料)的0.1至10重量百分比，但是可以高達30重量百分比。對離子型固化劑或引發劑，有效量通常是有機化合物(除了任何填料)的0.1至10重量百分比，但是可以高達30重量百分比。固化劑的例子包括：咪唑、三級胺、有機金屬鹽、胺鹽和改性的咪唑化合物、無機金屬鹽、苯酚類、酸酐和其他這樣的化合物。
在某些情況下，可能會希望使用多於一種類型的固化劑，例如，陽離子型和自由基引發劑，在這種情況下自由基固化和離子型固化樹脂都可以用在組合物中。這樣的組合物會允許，例如，固化過程通過使用紫外線輻射進行陽離子引發而開始，並在其後的處理步驟中通過應用熱進行自由基引發而完成。
在某些系統中除了固化劑之外，可以使用固化促進劑以優化固化速率。固化促進劑包括但不僅限於：環烷酸金屬鹽、乙醯丙酮金屬(螯合物)、辛酸金屬鹽、乙酸金屬鹽、金屬鹵化物、金屬咪唑錯合物、金屬胺錯合物、三苯基膦、烷基取代的咪唑、咪唑鎓鹽和硼酸鎓鹽。
實施例
在每一實施例中，製備配製物，以含有樹脂和硬化劑(RH)，其中硬化劑是固化劑。然後，這些以各種載入程度載入填料。每一配製物均在Brookfield黏度計上使用CP51轉子，在每分鐘五轉(5RPM)下測定黏度，並使用來自TA company的流變儀AR 2000ex測定屈服應力。通過測定0.5RPM時黏度/5RPM時黏度的比值，確定觸變指數。屈服應力使用在“發明詳述”中描述的方案進行測定。也使用在作為測試載體的玻璃片上的10mm×10mm、0.175mm厚的玻璃晶片，測定每一配製物的自動流動和自圓角化。用手進行晶片附著。對於目前的工業目的而言，長度超過0.15mm的圓角被認為溢流。在某些樣品中，圓角在1.8Pa的屈服應力以下形成，但是這些圓角的長度超過0.15mm。
實施例1：丙烯酸樹脂和填料載入的影響
在此實施例中，測定填料裝載程度和填料類型對包含丙烯酸樹脂、硬化劑和二氧化矽填料的組合物的影響。使用的材料的成分和數量以及測試的結果揭露在表中。
注：二氧化矽SE-15(National Starch＆Chemical,粒徑<20μm)
二氧化矽SE-1050(Admatechs CO，粒徑<2μm)
火成二氧化矽TS720(Cabbt)
實施例2：雙馬來醯亞胺樹脂和填料類型及比率的影響
在此實施例中，測定填料載入程度和填料類型對包含雙馬來醯亞胺樹脂、硬化劑和二氧化矽填料的組合物的影響。使用的材料和量以及測試的結果揭露在表中。
雙馬來醯亞胺1具有結構：其中C36 表示具有36個碳原子的直鏈或支鏈烴鏈(包含或不包含環)。
注：二氧化矽SE-15(National Starch＆Chemical，粒徑<20μm)
二氧化矽SE-1050(Admatechs CO，粒徑<2μm)
火成二氧化矽TS720(Cabot)
實施例3：環氧樹脂和填料裝載的影響
在此實施例中，測定填料載入程度和填料類型對包含環氧樹脂、硬化劑和二氧化矽填料的組合物的影響。使用的材料的成分和量以及測試的結果揭露在表中。
二氧化矽SE-1050(Admatechs CO,粒徑<2μm)
火成二氧化矽TS720(Cabot)
實施例4：銀填料
在此實施例中，使用銀作為填料，與二氧化矽具有相同屈服應力。
實施例5：在晶片接合機對自圓角化材料進行評價
目前通常使用的晶片包括但不僅限於：玻璃、具有或不具有鈍化層(例如氮化硼、聚醯亞胺)的矽；目前通常使用的基片包括但不僅限於：玻璃晶片、矽晶片、BGA、A42、CU、AG以及PPF。這些材料對於本領域技術人員是已知的。在此實施例中，對實施例1、2和3的樣品，在商業化晶片接合機SWISSLINE 9022(來自ALPHASEM)上，使用10×10mm、厚度為0.1mm的矽晶片，以PBGA為基片以及改良的雪花狀分配圖案，進行評估。結果在下表中列出，並與使用玻璃晶片和玻璃片基片進行手動晶片附著所獲得的結果相一致。

Claims (1)

  1. 一種用於選擇晶片附著黏合劑之方法，該黏合劑當被放置到兩個基片之間時會自動地流動並形成圓角，該方法包括：提供一包含樹脂和填料的晶片附著黏合劑；對該晶片附著黏合劑施加一初始剪切應力直到它從黏彈性固體變成液體，在25℃下持續2至10分鐘；平衡該晶片，在25℃下持續2至10分鐘；對該晶片附著黏合劑施加剪切應力從0.1Pa施加至200Pa，在25℃下持續2至10分鐘，然後將應力從200Pa降低至0.1Pa，在25℃下持續2至10分鐘，以獲得一屈服應力之流變曲線；從該屈服應力之流變曲線測量屈服應力值；及選擇具有的屈服應力的範圍是1.8Pa至10Pa的晶片附著黏合劑。
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