TW201400576A - 用於半導體裝置之黏合劑膜 - Google Patents

用於半導體裝置之黏合劑膜 Download PDF

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Publication number
TW201400576A
TW201400576A TW100139122A TW100139122A TW201400576A TW 201400576 A TW201400576 A TW 201400576A TW 100139122 A TW100139122 A TW 100139122A TW 100139122 A TW100139122 A TW 100139122A TW 201400576 A TW201400576 A TW 201400576A
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Taiwan
Prior art keywords
film
adhesive
adhesive film
base film
pressure
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TW100139122A
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English (en)
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TWI541312B (zh
Inventor
Dong-Seon Uh
Gyu-Seok Song
Min-Kyu Hwang
Ki-Tae Song
Dae-Ho Seo
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Cheil Ind Inc
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Publication of TW201400576A publication Critical patent/TW201400576A/zh
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Publication of TWI541312B publication Critical patent/TWI541312B/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C—CHEMISTRY; METALLURGY
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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Abstract

本發明提供了一種用於半導體裝置的黏合劑膜，所述黏合劑膜包括在0℃至5℃下具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數的基膜。所述黏合劑膜在低溫儲存較長時間後具有優異的捲繞形狀穩定性，從而在以後的半導體封裝工藝中不會導致傾斜現象並降低缺陷。

Description

用於半導體裝置之黏合劑膜 發明領域
本發明涉及一種用於半導體裝置的黏合劑膜。更具體地，本發明涉及一種用於半導體裝置的黏合劑膜，所述黏合劑膜在低溫下儲存較長時間後穩定地保持捲繞形狀。
 發明背景
一般而言，銀漿被用於使半導體裝置黏結在一起，或者被用以將半導體裝置黏結到支撐元件上。為了跟上半導體裝置向更小且更高容量的趨勢，用於半導體裝置的支撐元件也正在變得更小且更精密。
被廣泛應用的銀漿會洩漏或導致半導體裝置傾斜。因此，在引線焊接過程中Ag漿會導致故障、氣泡產生和厚度控制困難。近來，黏結膜已廣泛用作這種銀漿的替代品。
用於半導體組裝的黏合劑膜通常與切片膜組合使用。切片膜在半導體晶片製造的切片工藝中用於固定半導體晶圓。切片工藝是將半導體晶圓切成單個晶片的工藝，且緊隨有後續工藝如延展、拾取和貼裝。
切片膜通過將UV固化黏合劑或可固化的黏合劑塗布至具有聚烯烴結構的下層膜，並對其貼附PET覆蓋膜形成。
用於半導體組裝的常用黏合劑膜依據下述方式使用。將黏結膜貼附至半導體晶圓上，然後在其上沉積具有以上構造的切片膜，略去覆蓋膜，隨後將晶圓切成單個晶片。近來，作為用於切片晶片焊接的半導體組裝黏合劑，略去PET覆蓋膜的切片膜和將黏結膜堆疊成單個膜，且半導體晶圓沉積於其上，隨後將晶圓切成單個晶片。
第1圖是表示基膜因熱收縮產生的傾斜的透視圖。
參照第1圖，用於半導體組裝的基膜14或黏結帶(膜)通常在5℃或更低的溫度下圍繞捲軸12捲繞，並在使用前於低溫下長期儲存。然而，基膜由於在低溫下因熱損壞而熱收縮，從而當基膜在低溫下儲存較長時間時，在基膜中產生空隙。
因此，用於半導體組裝的黏結帶趨向於在其移動和運行期間按一個方向傾斜。也就是說，如第1圖所示，繞捲軸12捲繞的用於半導體組裝的基膜或黏結帶14可能從一側移動至另一側(按箭頭方向)，使得圓形的晶圓在預切割型貼裝過程中不能貼附到適當位置。
 發明概要
本發明的一個態樣提供了一種用於半導體裝置的黏合劑膜，所述黏合劑膜在低溫下長時間儲存期間保持捲繞形式的穩定性。
所述用於半導體裝置的黏合劑膜包括在0℃至5℃下具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數的基膜。
所述基膜在5℃放置120小時後可具有大於0且小於等於0.1%的熱收縮率。
所述基膜可包括以下至少一種：聚烯烴膜，如聚乙烯(PE)、聚丙烯(PP)、乙烯/丙烯共聚物、聚1-丁烯、乙烯/乙酸乙烯酯共聚物、聚乙烯/苯乙烯丁二烯橡膠混合物；聚氯乙烯；聚對苯二甲酸乙二醇酯(PET)、聚碳酸酯(PC)、聚(甲基丙烯酸甲酯)、聚醯亞胺(PI)、聚萘二酸乙二醇酯(PEN)、聚酯碸、聚苯乙烯(PS)、聚丙烯酸酯(PAR)；和熱塑性彈性體，如聚氨酯、聚醯胺-多元醇共聚物等。
所述用於半導體裝置的黏合劑膜可進一步包括在所述基膜一面上的壓敏黏合劑層。
所述壓敏黏合劑層可包括壓敏黏合黏結劑、熱固化劑和光引發劑。
具體地，所述壓敏黏合黏結劑可具有100,000至1,000,000的重均分子量。
所述用於半導體裝置的黏合劑膜可進一步包括依次堆疊在所述壓敏黏合劑層一面上的黏結層和保護膜。
所述黏合劑膜在5℃放置120小時後可具有大於0且小於等於0.2%的熱收縮率。
所述黏結層可包括丙烯酸樹脂和環氧樹脂。
具體地，所述丙烯酸樹脂可具有-30℃至10℃的玻璃化轉變溫度，且所述環氧樹脂可為雙酚-A環氧樹脂、酚醛環氧樹脂或甲酚醛環氧樹脂。
圖式簡單說明
由以下結合附圖的詳細說明，本發明的以上和其它態樣、特徵和優點將變得明顯，其中：第1圖是表示基膜因熱收縮產生的傾斜的透視圖；第2圖是表示熱收縮率的概念的截面圖；第3圖是表示根據一個示例性實施方式的用於半導體裝置的黏合劑膜的截面圖；第4圖是黏合劑膜的區域圖，表示捲繞形狀穩定性的評價方法；第5圖是從第4圖的箭頭A方向的黏合劑膜的側視圖；且第6圖是從第4圖的箭頭B方向看到的黏合劑膜的側視圖。
 具體實施方式
現將參照附圖詳細說明本發明的實施方式。
本發明的各個態樣提供用於半導體生產工藝的基膜和包括該基膜的用於半導體裝置的黏合劑膜，上述基膜在低溫儲存方面優異。該基膜在約0℃至5℃可具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數，較佳為50μm/m‧℃至120μm/m‧℃，且更佳為60μm/m‧℃至100μm/m‧℃。此外，上述基膜在5℃放置120小時後可具有大於0且小於等於0.1%的熱收縮率，較佳為大於0且小於等於0.06%。
熱收縮率和線性膨脹係數在以上範圍內時，即使基膜以低張力捲繞，基膜也可具有優異的低溫儲存和用於半導體封裝工藝如擴展工藝的適宜性能。
基膜可具有單層結構或至少兩層的多層結構。此外，基膜可由對可見光或UV光等透明的材料形成。或者，基膜可由不透明的材料形成。
上述基膜可根據其應用和條件選擇。例如，基膜可包括以下至少一種：聚烯烴膜，如聚乙烯(PE)、聚丙烯(PP)、乙烯/丙烯共聚物、聚1-丁烯、乙烯/乙酸乙烯酯共聚物、聚乙烯/苯乙烯丁二烯橡膠混合物、聚氯乙烯膜等、聚對苯二甲酸乙二醇酯(PET)、聚碳酸酯、聚(甲基丙烯酸甲酯)、聚醯亞胺(PI)、聚萘二酸乙二醇酯(PEN)、聚酯碸、聚苯乙烯(PS)、聚丙烯酸酯(PAR)；和熱塑性彈性體，如聚氨酯、聚醯胺-多元醇共聚物等，但不限於此。
第2圖是表示熱收縮率的概念的截面圖。
參照第2圖，基膜的熱收縮率可定義為基膜捲繞成捲的軸的垂直方向上的收縮率。也就是說，將沿捲軸102捲繞的基膜104在低溫下放置較長時間後，測定與軸垂直的方向上長度(d)的變化，從而定義熱收縮率。此外，基膜的線性膨脹係數可定義為將溫度以5℃/分鐘從-20℃升至300℃時測定的熱膨脹係數。
第3圖是根據一個示例性實施方式的用於半導體裝置的黏合劑膜的截面圖。在此，“黏合劑膜”是指具有壓敏黏合功能或黏結功能中至少一種功能的膠帶或膜。
參照第3圖，根據該實施方式的用於半導體裝置的黏合劑膜110包括基膜112、壓敏黏合劑層114、黏結層116和保護膜118。儘管第3圖中黏合劑膜110表示為包括黏結層116和保護膜118，需要時黏合劑膜110可略去黏結層116和保護膜118或者只略去黏結層116。例如，當用作切片膠帶時，黏合劑膜可包括基膜112和壓敏黏合劑層114。
具有包括基膜112、壓敏黏合劑層114、黏結層116和保護層118的四層結構的用於半導體裝置的黏合劑膜在5℃放置120小時後可具有0至0.2%之間的熱收縮率，較佳為0和0.1%之間，且更佳為0和0.08%之間。在此範圍內，即使黏合劑膜以低張力捲繞，黏合劑膜可呈現出優異的低溫儲存和膨脹性能，且不會存在因低溫儲存而產生傾斜現象的缺陷。
現將更詳細地說明根據本實施方式的黏合劑膜的組分和性能。
(1)基膜
構成用於半導體裝置的黏合劑膜110的基膜112在約0℃至5℃可具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數，較佳為50μm/m‧℃至120μm/m‧℃，且更佳為60μm/m‧℃至100μm/m‧℃。此外，該基膜在5℃放置120小時後可具有大於0且小於等於0.1%的熱收縮率，較佳為大於0且小於等於0.06%。具體地，該基膜適用於背面打磨工藝和切片工藝。
可將多種塑膠膜用作背面打磨工藝的基膜。具體地，可延展的熱塑性塑膠膜可用作上述基膜。具有電路圖案的晶圓由於在背面打磨期間受到物理衝擊所產生的裂紋而易受損或破裂。因此，將可延展的熱塑性塑膠膜用作基膜，以通過吸收和釋放衝擊來保護晶圓在背面打磨工藝中不受衝擊。
基膜112不僅是可延展的，而且對UV光還是透明的。具體地，當壓敏黏合劑層114包含UV固化黏合劑組合物時，希望基膜對黏合劑組合物固化所處頻率的UV光呈現出優異的透明性。因此，在此情況下，基膜112不含UV光吸收劑。
希望基膜112是化學穩定的。儘管係因考慮在背面打磨工藝期間的重衝擊而製備基膜112，基膜112需要具有化學穩定性，因為最終打磨階段使用化學機械打磨(CMP)漿料進行。通常，聚合物化合物如聚烯烴是化學穩定的，並可適用於基膜112。然而，也可使用其他材料。
基膜112的實例可包括以下至少一種聚烯烴膜：如聚乙烯(PE)、聚丙烯(PP)、乙烯/丙烯共聚物、聚1-丁烯、乙烯/乙酸乙烯酯共聚物、聚乙烯/苯乙烯丁二烯橡膠混合物；聚氯乙烯膜等；聚對苯二甲酸乙二醇酯(PET)、聚碳酸酯、聚(甲基丙烯酸甲酯)、聚醯亞胺(PI)、聚萘二酸乙二醇酯(PEN)、聚酯碸、聚苯乙烯(PS)、聚丙烯酸酯(PAR)；和熱塑性彈性體，如聚氨酯、聚醯胺-多元醇共聚物等，但不限於此。
基膜可通過共混並熔融這些材料的片之後的擠出工藝形成。或者，基膜可通過吹塑形成。由共混的片的種類決定基膜的耐熱性和機械性能。
可對基膜進行表面改性以改善對壓敏黏合劑層114的附著力。可通過物理或化學方法實現該表面改性。物理方法可包括電暈或等離子體處理，且化學方法可包括線上塗布或底漆處理(primer treatment)。
考慮到可加工性、UV透過性等，基膜112可具有30μm至300μm的厚度。在此範圍內，基膜能在背面打磨工藝中充分釋放物理衝擊。此外，單捲最終膜產品具有適宜的長度厚度比，以防止頻繁更換捲，從而耗費較少的時間並提供成本方面的優勢。為了確保基膜與上面形成有凸起的晶圓不規則表面充分接觸，基膜112可具有50μm至200μm的厚度。
(2)壓敏黏合劑層
用於半導體裝置的黏合劑膜110可包括基膜112一面上的壓敏黏合劑層114。壓敏黏合劑層114可為UV固化壓敏黏合劑層，但不限於此。
UV輻射前，壓敏黏合劑層通過強黏性堅固地支撐其上的絕緣黏結層116和晶圓，從而防止背面打磨工藝期間的偏移或移動產生晶圓損壞，並防止CMP期間化學材料滲入各個層之間的介面。
UV輻射後，壓敏黏合劑層由於交聯反應而具有增大的黏附性和收縮，從而在與絕緣黏結層116的介面處附著力顯著降低，由此容易使壓敏黏合劑層114和基膜112與貼裝到黏結層116上的晶圓分離。
壓敏黏合劑層114可包括UV固化或非UV固化組合物。在普通的背面打磨膠帶中，非UV固化組合物在UV輻射前具有較低的黏合強度，使得非UV固化組合物的壓敏黏合劑層即使未經UV輻射，也能容易用捲型黏合劑膜從壓敏黏合劑層和晶圓之間的介面處剝離。
然而，對於晶圓級堆疊組裝(wafer-level stack package，WSP)膜，在光固化壓敏黏合劑層114和黏結層116之間的有機介面處必須實現剝離。在此情況下，用捲型黏合劑膜基本不能使非UV固化組合物的壓敏黏合劑層剝離。因此，希望壓敏黏合劑層可由UV固化組合物形成。
因此，為了用於WSP膜，光固化壓敏黏合劑層114可由黏結劑的側鏈上導入UV可固化的碳-碳雙鍵的組合物代替混合組合物形成。這種通過向黏合劑樹脂側鏈導入碳-碳雙鍵的低分子量材料表現為單分子的組合物被稱作包覆型黏合劑組合物。
包覆型黏合黏結劑可具有100,000至1,000,000的分子量，並可通過聚氨酯反應向共聚的黏結劑側鏈添加具有C-C雙鍵的低分子量化合物製備，其中具有異氰酸酯端基的低分子量化合物用作該具有C-C雙鍵的低分子量化合物。
UV固化黏合劑組合物可通過將黏合黏結劑與熱固化劑、光引發劑等混合來製備。對於該黏合劑組合物，可使用任何熱固化劑，只要它能通過導入黏合黏結劑側鏈的官能團反應而固化。
如果提供至側鏈的官能團為羧基，可使用環氧固化劑。如果提供至側鏈的官能團為羥基，可使用異氰酸酯固化劑。此外，可使用三聚氰胺固化劑，或可使用環氧固化劑、異氰酸酯固化劑和三聚氰胺固化劑中至少兩種的混合物。
對於上述黏合劑組合物，可使用任何光引發劑，如酮和苯乙酮光引發劑，只要它在UV輻射下能在分子鍵斷裂時產生自由基。當對黏合劑組合物加入光引發劑時，黏合黏結劑的側鏈C-C雙鍵與自由基進行交聯反應，且壓敏黏合劑層的玻璃化轉變溫度升高，從而降低壓敏黏合劑層的黏性。當壓敏黏合劑層失去黏性時，壓敏黏合劑層可用較低力與絕緣黏結層116分離。
壓敏黏合劑層114可通過直接塗覆或轉移塗覆形成在基膜112上。在轉移塗覆中，將壓敏黏合劑層114在剝離膜上沉積並乾燥，然後轉移至基膜112。壓敏黏合劑層114可通過形成層的任何塗覆方法形成，如棒塗、凹版印刷、逗號印刷、反向-輥塗、塗料器塗覆、噴塗等。
(3)黏結層
用於半導體裝置的黏合劑膜110可進一步包括黏結層116。也就是說，黏結層116可省去，或堆疊在沉積於基膜112上的壓敏黏合劑層114上。
黏結層116是與晶圓表面直接接觸的層。在WSP膜中，晶圓表面因上面形成有凸起等非常不規則，但希望黏結層堆疊在晶圓表面上而沒有空隙，然後通過晶片貼裝使晶片的上下兩面緊密黏結。
也就是說，因為黏結層116用作最終黏結晶片上下兩面的黏合劑，希望黏結層具有滿足半導體封裝級別的可靠性和用於封裝的可加工性。即，理想的是晶圓的不規則表面被黏結層填充，而不會在貼裝工藝期間出現空隙，從而防止切片工藝期間碎片或破裂出現以及因晶片貼裝工藝後膨脹而產生可靠性變差。在60℃下將黏結層116貼附至上面具有凸起的晶圓表面，在該表面上形成了電路圖案。
對黏結層116組成沒有特別限制，但可由例如具有成膜性的高分子量丙烯酸樹脂和作為固化劑的環氧樹脂的混合物形成。由於黏結層116為膜型黏合劑，可將具有優異成膜性的丙烯酸樹脂用作除呈現出黏附性的固化部分以外的熱塑性樹脂。
此外，環氧樹脂沒有特別限制，只要它在固化時呈現出黏附性，但為了進行固化反應可具有至少兩個官能團。因此，可使用雙酚-A環氧樹脂、酚醛環氧樹脂和甲酚醛環氧樹脂中的至少一種。
可將固化促進劑用作固化環氧樹脂的固化劑，其實例可包括咪唑、胺或酚類固化促進劑，但不限於此。
如上所述，黏結層116可由作為黏結劑的丙烯酸樹脂、作為固化部分的環氧樹脂和能與它們反應的固化促進劑形成，其中基於100重量份的除該丙烯酸黏結劑以外的黏結層116的剩餘組分，該丙烯酸樹脂含量可為60至150重量份，並具有-30℃至10℃的玻璃化轉變溫度。
當丙烯酸樹脂的玻璃化轉變溫度為-30℃至10℃時，丙烯酸樹脂可具有足以在60℃的貼裝溫度下用該丙烯酸樹脂填充具有凸起的不規則表面的流動性。此外，當該黏結劑不僅具有-30℃至10℃的玻璃化轉變溫度，而且基於100重量份的除該丙烯酸黏結劑以外的黏結層116的剩餘組分，該黏結劑含量為60重量份或更高時，由於黏結劑的絕對量充足，因而能得到優異的成膜性，並能有利於捲繞成捲狀。此外，當丙烯酸黏結劑含量少於150重量份時，在100℃或更高溫度下可獲得充足的流動性，從而能實現晶片黏結而不產生氣泡。
此外，可添加無機顆粒，如二氧化矽來改善黏結層116的尺寸穩定性和耐熱性。具體地，與晶圓表面接觸的黏結層116可包括各種矽烷偶聯劑中的至少一種以增強對晶圓的附著力。
可使用任何塗覆方法形成黏結層116，只要它能形成均勻的黏結層。黏結層116可具有2μm至30μm的塗層厚度。當其厚度為2μm或更大時，黏結層在晶片上下面之間提供適宜的附著力。當其厚度為30μm或更小時，黏結層在趨光、薄而小的半導體組裝方面有優勢。
(4)保護膜
用於半導體裝置的黏合劑膜110可包括基膜112、壓敏黏合劑層114、黏結層116和貼附到黏結層116上的保護膜118。
任何膜均可用作保護膜118，只要它能保護絕緣黏結層116不受外來材料或外部衝擊的影響。例如，用作塗覆絕緣黏結層116的運行膜(running film)的膜可用作保護膜。因為半導體封裝工藝在去除最外部的保護膜後進行，因此可使用可剝離的膜。
保護膜118可為例如聚對苯二甲酸乙二醇酯膜。為了提供脫模性能，保護膜118可用聚二甲基矽氧烷脫模劑、含氟脫模劑等進行表面改性。
以下，將說明製備壓敏黏合劑層和黏結層的組合物的方法。
壓敏黏合劑層的組合物的製備
向一側裝有回流冷凝器、另一側裝有溫度計且第三側裝有滴液漏斗的20L四口燒瓶加入作為有機溶劑的2.4kg乙酸乙酯和1.2kg甲苯。
將該溶液加熱至60℃，用510g甲基丙烯酸甲酯、540g丙烯酸丁酯單體、2.85kg丙烯酸-2-乙基己酯、1.8kg甲基丙烯酸-2-羥乙酯、300g丙烯酸和39g過氧化苯甲醯製備混合溶液，在60至70℃下3小時內用滴液漏斗滴加至該燒瓶中。此時，在以250rpm攪拌的同時，滴加該溶液。
完成滴加後，在相同溫度下使反應物老化3小時，然後向該反應物加入600g乙酸甲氧基丙酯和2g偶氮二異丁腈，並放置4小時，隨後測定黏度和固含量並終止反應。聚合後的產物具有10,000至15,000cps的黏度和40%的固含量。
然後，向製得的丙烯酸黏合黏結劑加入450g甲基丙烯酸縮水甘油醚酯，並在50℃下反應1小時以製得包覆型黏合黏結劑。將100g製得的黏合黏結劑與2g芳族聚異氰酸酯熱固化劑(AK-75,Aekyung Chemical有限公司)和1g 1-羥基環己基-苯基酮光引發劑IC-184(Ciba-Geigy有限公司)，從而製備固化黏合劑組合。
黏結層組合物的製備
混合30g具有350,000的重均分子量和12℃的玻璃化轉變溫度的丙烯酸樹脂(SG-80H,Nagase ChemTech Co.,Ltd.)、4.5g具有10,000或更小分子量的甲酚醛環氧樹脂(YDCN-500-90P,Kukdo Chemical Co.,Ltd.)、4.5kg二甲酚固化劑(MEH7800C,Meiwa Plastic Industries Co.,Ltd.)、10g咪唑固化促進劑(2P4MZ,Sikoku Chemical Co.,Ltd.)、100g氨基矽烷偶聯劑(KBM-573,Shin Estu Chemical Co.,Ltd.)和1.5g圓形二氧化矽填料(PLV-6XS,Tatsumori)，並以700rpm進行初次分散2小時，隨後碾磨，從而製備黏結組合物。
實施例和對比例 實施例1
用試驗塗覆系統(pilot coating system)將製備例的光固化黏合劑組合物沉積在38μm PET剝離膜(SRD-T38,Saehan Media Co.,Ltd.)的一面上。然後，在80℃下將產物堆疊在100μm聚烯烴膜上，該聚烯烴膜在5℃下具有0.06%熱收縮率且在0℃至5℃下具有101μm/m‧℃的線性膨脹係數(C.T.E),並在40℃的乾燥室內老化3天，從而製備光固化壓敏黏合劑層。
同樣地，用試驗塗覆系統將製備例的黏結組合物沉積在38μm PET剝離膜(SRD-T38,Saehan Media Co.,Ltd.)的一面上至20μm的厚度，然後在80℃下乾燥2分鐘。然後，在80℃下將產物堆疊在38μm PET(SRD-T38,Saehan Media Co.,Ltd.)上，並在25℃的室溫下老化3天，從而製備絕緣黏結層。從黏合劑膜的一面上去除剝離膜後，通過預切割將黏合劑膜以晶圓形狀堆疊在具有光固化壓敏黏合劑層的黏合劑膜上。
實施例2
以與實施例1相同的方式製備黏合劑膜，不同之處在於使用在5℃下具有0.02%熱收縮率且在0℃至5℃下具有60μm/m‧℃的線性膨脹係數(C.T.E)的100μm聚烯烴膜作為基膜。
對比例1
以與實施例1相同的方式製備黏合劑膜，不同之處在於使用在5℃下具有0.3%熱收縮率且在0℃至5℃下具有168μm/m‧℃的線性膨脹係數(C.T.E)的100μm聚烯烴膜作為基膜。
對比例2
以與實施例1相同的方式製備黏合劑膜，不同之處在於使用在5℃下具有0.15%熱收縮率且在0至5℃下具有98μm/m‧℃的線性膨脹係數(C.T.E)的100μm聚烯烴膜作為基膜。
表1示出了實施例和對比例中製備的用於半導體裝置的黏合劑膜的捲繞形狀穩定性。如表1所示，使用了在5℃下放置120小時後具有大於0且小於等於0.1%熱收縮率，且在0至5℃下具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數的基膜的黏合劑膜，具有優異的捲繞形狀穩定性。詳言之，當使用在5℃下放置120小時後具有大於0且小於等於0.06%熱收縮率且在0至5℃下具有60至100μm/m‧℃的線性膨脹係數的基膜時，黏合劑膜具有優異的捲繞形狀穩定性。
具有優異的捲繞穩定性時，黏合劑膜在移動和運行期間不會朝一個方向傾斜，從而當固定預切型時，晶圓以合適的位置貼附，並且可以降低半導體組裝工藝中的缺陷率。
此外，在具有四層結構的基膜的用於半導體裝置的黏合劑膜中，實施例1和2中的在5℃下放置120小時後具有大於0且小於等於0.2%熱收縮率的黏合劑膜具有優異的捲繞形狀穩定性。
[線性(熱)膨脹係數(C.T.E)]
將具有100μm厚度的各個基膜切成7 mm x 14 mm(寬度×長度)樣品，隨後在將溫度以5℃/分鐘從-20升至300℃，同時用TMA Q7200(TA Instrument)測定線性膨脹係數。
[基膜的熱收縮率]
將各基膜分成300mm寬的樣品，並用捲繞器R/M#002(Master Co.,Ltd)以5N的捲繞器張力捲繞各樣品，在5℃的低溫儲存室中儲存120小時，隨後測定收縮程度。對第2圖中四個部分的各個長度(d)測定三次，得到低溫儲存前/後的平均值之差，從而計算熱收縮率。
[捲繞形狀穩定性]
在5℃下將實施例1和2以及對比例1和2的各個黏合劑膜貼附到夾具上，並以20N推動中心部分(核部分)20秒，隨後測定向外側傾斜的長度。
O：傾斜20mm或更少
X：傾斜大於20mm
第4圖是黏合劑膜的側面截面圖，表示捲繞形狀穩定性的評價；第5圖是第4圖中按箭頭A方向的黏合劑膜的側視圖，且第6圖是第4圖中箭頭B方向的黏合劑膜的側視圖。
如第4至6圖所示，用固定夾具210固定沿軸230捲繞的黏合劑膜200厚度方向的相對末端，並將中間夾具220以長度方向安裝在黏合劑膜200的一端。然後，在推動中間夾具220(以第4圖中的X方向)後，測定傾斜長度。
[四層晶片貼裝膜(DAF)輥的熱收縮率]
將實施例1中製備的用於半導體裝置的黏合劑膜分成300mm寬的樣品，並用捲繞器R/M #002(Master Co.,Ltd)以5N的捲繞器張力捲繞200m的膜，在5℃的低溫儲存室中儲存120小時，隨後測定收縮程度。對第2圖中四個部分的各個長度(d)測定三次，得到低溫儲存前/後的平均值之差，從而計算熱收縮率。
如上所述，根據本發明的基膜和使用該基膜的用於半導體裝置的黏合劑膜在低溫儲存較長時間後具有優異的捲繞形狀穩定性，從而不出現傾斜現象，因此有利於處理並基本降低在以後的半導體封裝工藝中出現的缺陷。
儘管文中已公開了一些實施方式，應理解的是僅以說明的方式提供這些實施方式，並能進行各種修改、變更和置換而不背離本發明的精神和範圍。因此，本發明的範圍應僅由所附權利要求及其等效物限定。
12．．．繞捲軸
14．．．黏結帶
102．．．捲軸
104．．．基膜
110．．．黏合劑膜
112．．．基膜
114．．．壓敏黏合劑層
116．．．黏結層
118．．．保護膜
200．．．黏合劑膜
210．．．固定夾具
220．．．中間夾具
230．．．軸
第1圖是表示基膜因熱收縮產生的傾斜的透視圖；
第2圖是表示熱收縮率的概念的截面圖；
第3圖是表示根據一個示例性實施方式的用於半導體裝置的黏合劑膜的截面圖；
第4圖是黏合劑膜的區域圖，表示捲繞形狀穩定性的評價方法；
第5圖是從第4圖的箭頭A方向的黏合劑膜的側視圖；且
第6圖是從第4圖的箭頭B方向看到的黏合劑膜的側視圖。
110．．．黏合劑膜
112．．．基膜
114．．．壓敏黏合劑層
116．．．黏結層
118．．．保護膜

Claims (10)

  1. 一種用於半導體裝置的黏合劑膜，包括在0℃至5℃下具有50μm/m‧℃至150μm/m‧℃的線性膨脹係數的基膜。
  2. 根據申請專利範圍第1項所述的黏合劑膜，其中所述基膜在5℃下放置120小時後具有大於0且小於等於0.1%的熱收縮率。
  3. 根據申請專利範圍第1項所述的黏合劑膜，其中所述基膜包括以下至少一種：聚烯烴膜，包括聚乙烯、聚丙烯、乙烯/丙烯共聚物、聚1-丁烯、乙烯/乙酸乙烯酯共聚物、聚乙烯/苯乙烯丁二烯橡膠混合物；聚氯乙烯；聚對苯二甲酸乙二醇酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚醯亞胺、聚萘二酸乙二醇酯、聚酯碸、聚苯乙烯、聚丙烯酸酯；和熱塑性彈性體，包括聚氨酯和聚醯胺-多元醇共聚物。
  4. 根據申請專利範圍第1項所述的黏合劑膜，進一步包括：在所述基膜一面上的壓敏黏合劑層。
  5. 根據申請專利範圍第4項所述的黏合劑膜，其中所述壓敏黏合劑層包括壓敏黏合黏結劑、熱固化劑和光引發劑。
  6. 根據申請專利範圍第5項所述的黏合劑膜，其中所述壓敏黏合黏結劑具有100,000至1,000,000的重均分子量。
  7. 根據申請專利範圍第4項所述的黏合劑膜，進一步包括：依次堆疊在所述壓敏黏合劑層一面上的黏結層和保護膜。
  8. 根據申請專利範圍第7項所述的黏合劑膜，其中所述黏合劑膜在5℃下放置120小時後具有大於0且小於等於0.2%的熱收縮率。
  9. 根據申請專利範圍第7項所述的黏合劑膜，其中所述黏結層包括丙烯酸樹脂和環氧樹脂。
  10. 根據申請專利範圍第9項所述的黏合劑膜，其中所述丙烯酸樹脂具有-30℃至10℃的玻璃化轉變溫度，且所述環氧樹脂為雙酚-A環氧樹脂、酚醛環氧樹脂或甲酚醛環氧樹脂。
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