TWI721364B - 背面研磨膠帶 - Google Patents

背面研磨膠帶 Download PDF

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TWI721364B
TWI721364B TW108101993A TW108101993A TWI721364B TW I721364 B TWI721364 B TW I721364B TW 108101993 A TW108101993 A TW 108101993A TW 108101993 A TW108101993 A TW 108101993A TW I721364 B TWI721364 B TW I721364B
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meth
acrylate
group
adhesive layer
resin
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TW108101993A
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TW201932560A (zh
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尹美善
金世羅
李光珠
延寶拉
朴成燦
金殷英
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南韓商Ｌｇ化學股份有限公司
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Abstract

本發明係關於背面研磨膠帶，其包括聚合物基底和黏著層，其中該黏著層包括(甲基)丙烯酸酯樹脂，其含有30至60重量%自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元，且其中該黏著層具有-20℃至10℃的玻璃轉變溫度，及一種使用該背面研磨膠帶研磨晶圓之方法。

Description

背面研磨膠帶
本發明係關於背面研磨膠帶。
近來，電子設備的小型化、高功能化和容量加大的趨勢已經擴大，並且對半導體封裝的密集化和高整合性的需求迅速提高。
反映此情況，半導體晶片的尺寸變大且同時晶片的厚度變薄，且電路的整合度提高。但是，晶片本身的模數降低，因此引發製程中或最終產物之可靠性的問題。
為符合關於半導體的放大和薄化的要求，基本上藉由以由細鑽石粒所構成的拋光輪研磨晶圓的背面以降低晶片的厚度而進行有助於組裝品的研磨(背面研磨)程序。但是，研磨程序的期間內，常會因為大量的矽殘留物(塵)和粒子導致晶圓受損(如，污染或破裂)。
據此，進一步強調黏著膜或背面研磨膠帶用於保護半導體晶圓表面的角色。
隨著半導體裝置的進一步小型化和薄化，須要一種將晶圓研磨成比傳統晶圓更薄的厚度的程序。據此，當在將晶圓研磨至約100μm的厚度的步驟中使用的黏著膜應用於將晶圓研磨至約50μm的厚度的程序時，黏著膠帶的潛變變形高，這可能導致研磨之後模具未對準等問題。
技術問題
本發明的目的是提供一種背面研磨膠帶，其能夠容易地應用於研磨具有薄的厚度的晶圓的程序，並且藉由使得黏著膠帶的潛變變形維持於低度來防止諸如研磨後的模具未對準之類的問題。
本發明的另一目的是試圖提供使用背面研磨膠帶研磨晶圓之方法。 技術手段
為了要達到上述目的，本發明提供一種背面研磨膠帶，其包括聚合物基底；和黏著層，其中該黏著層包括(甲基)丙烯酸酯樹脂，其含有30至60重量%自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元，且其中該黏著層具有-20℃至10℃的玻璃轉變溫度。
本發明亦提供使用該背面研磨膠帶研磨晶圓之方法。
下文中，將更詳細地描述根據本發明之特定具體實施例之背面研磨膠帶和研磨晶圓之方法。
此中使用的術語“(甲基)丙烯酸酯”意欲涵蓋丙烯酸酯和甲基丙烯酸酯二者。
如上述者，根據本發明的一個具體實施例，提供一種背面研磨膠帶，其包括聚合物基底和黏著層，其中該黏著層包括(甲基)丙烯酸酯樹脂，其含有30至60重量%自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元，且其中該黏著層具有-20℃至10℃的玻璃轉變溫度。
本發明者執行包括聚合物基底和黏著層的背面研磨膠帶之研究，並經由實驗發現當黏著層包括含有30至60重量%自有0℃或更高的玻璃轉變溫度之單體或具寡聚物衍生的重複單元之(甲基)丙烯酸酯樹脂時，其具有-20℃至10℃的玻璃轉變溫度，其容易應用至研磨具有約50μm之薄的厚度之晶圓的程序，且可經由使得黏著膠帶的潛變變形維持於低程度而防止研磨之後模具未對準之類的問題，藉此完成本發明。
更明確言之，具有-20℃至10℃的玻璃轉變溫度的黏著層，於90℃施以20,000Pa的力時，潛變應變為10至30%。於90℃施以20,000Pa的力的條件可對應於在背面研磨程序中在背面研磨期間內自研磨輪接收到的水平力。隨著黏著層在以上條件下具有10至30%的潛變變形，能夠防止模具在背面研磨程序之後未對準。
如果當將20,000Pa的力於90℃施於黏著層時的潛變變形低於10%，則黏著層的模數高並因此降低黏著安定性，使其會在程序中脫離。如果當將20,000Pa的力於90℃施於黏著層時的潛變變形高於30%，則黏著層的模數低，因此模具會未對準或者會在半導體電路表面上形成黏著劑殘留物。
潛變變形是指當某些力長時間施於預定材料時，材料隨著時間變形，且隨著時間的流逝，變形程度也會提高。
藉由包括上述黏著層，具體實施例之背面研磨膠帶會展現低度的潛變變形率。因此，即使當力施用至背面研磨膠帶已經在背面研磨程序中接合至彼的半導體晶圓時，黏著層的變形不大，且能夠抑制因為在背面研磨程序中施用至晶圓的力而發生的模具偏移事件。
隨著黏著層包括含有30至60重量%自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元之(甲基)丙烯酸酯樹脂，該黏著層具有-20℃至10℃的玻璃轉變溫度。
更具體言之，該具有0℃或更高的玻璃轉變溫度之單體或寡聚物可具有0℃至100℃的玻璃轉變溫度。
該具有0℃或更高的玻璃轉變溫度之單體或寡聚物的具體例子包括至少一種選自由丙烯酸甲酯、(甲基)丙烯酸異莰酯、和(甲基)丙烯酸羥基環己酯所組成群組之化合物。
此外，該(甲基)丙烯酸酯樹脂可以另包括具有具2至12個碳原子的烷基之(甲基)丙烯酸酯系重複單元或含有可交聯官能基的(甲基)丙烯酸酯系重複單元及自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元。
具體言之，該(甲基)丙烯酸酯樹脂可包括30至60重量%自具有0℃或更高的玻璃轉變溫度之單體或寡聚物衍生的重複單元，和40至70重量%具有具2至12個碳原子的烷基之(甲基)丙烯酸酯系重複單元或含有可交聯官能基的(甲基)丙烯酸酯系重複單元。
該具有具2至12個碳原子的烷基之(甲基)丙烯酸酯系重複單元可為自至少一種選自由(甲基)丙烯酸戊酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸癸酯等所組成群組之單體或寡聚物衍生的重複單元。
該含有可交聯官能基的(甲基)丙烯酸酯系重複單元的具體例子包括含有羥基、羧基、含氮官能基之(甲基)丙烯酸酯系重複單元等，而該含有可交聯官能基的(甲基)丙烯酸酯系重複單元可以衍生自含有可交聯官能基的(甲基)丙烯酸酯系單體。
此情況中，含有羥基的(甲基)丙烯酸酯系單體的例子可包括(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等。含有羧基的(甲基)丙烯酸酯系單體的例子可包括(甲基)丙烯酸等。含有含氮官能基的(甲基)丙烯酸酯單體的例子包括(甲基)丙烯腈、N-乙烯基吡咯烷酮、N-乙烯基己內醯胺等，但不在此限。
該(甲基)丙烯酸酯樹脂可具有100,000至1,500,000、較佳200,000至1,000,000的重量平均分子量。
當該(甲基)丙烯酸酯樹脂的重量平均分子量低於100,000時，塗覆性質或黏著力降低，且在剝離期間內，殘留物會留在黏著物上，或者會發生黏著劑的毀壞現象。
此外，當該(甲基)丙烯酸酯樹脂的重量平均分子量超過1,500,000時，則因為高黏度而須添加額外的稀釋溶劑，且塗覆性質會受損。
同時，該黏著層可包括紫外光可固化的黏著劑或熱可固化的黏著劑。
使用紫外光可固化的黏著劑時，照射紫外光以提高黏著劑的附著力和玻璃轉變溫度，藉此降低黏著強度。在熱可固化黏著劑的情況中，提高溫度以降低黏著強度。
該(甲基)丙烯酸酯系樹脂可以另外包括含有乙酸乙烯酯、苯乙烯、或丙烯腈的碳-碳雙鍵的低分子量化合物。
該黏著層可以另外包括多官能性(甲基)丙烯酸酯化合物。
該多官能性(甲基)丙烯酸酯化合物具有100至100,000的重量平均分子量，且其可包括選自由多官能性胺甲酸酯(甲基)丙烯酸酯和多官能性(甲基)丙烯酸酯單體或寡聚物所組成群組中之至少一者。
該重量平均分子量是藉GPC方法測定之相關於聚苯乙烯的重量平均分子量。
基於100重量份的該(甲基)丙烯酸酯樹脂，該多官能性(甲基)丙烯酸酯化合物的含量可為5重量份至400重量份，較佳為10重量份至200重量份。
當該多官能性(甲基)丙烯酸酯化合物的含量低於5重量份時，固化之後的黏著強度的降低程度不足。當該多官能性(甲基)丙烯酸酯化合物的含量超過400重量份時，在紫外光照射之前，該黏著劑的附著力可能不足。
該黏著層可以另外包括光引發劑。
未特別限定該光引發劑的類型，且可使用此技術中已知的一般引發劑。基於100重量份的該多官能性(甲基)丙烯酸酯化合物，其含量可為0.05重量份至20重量份。該光引發劑的含量低於0.05重量份時，藉紫外光照射之固化反應的效果可能會不足。
當該光引發劑的含量超過20重量份時，在固化程序中，交聯反應發生於短單元或者產生未反應的紫外光可固化化合物，此會引發在黏著物表面上的殘留物，或者固化之後的剝離力可能過低。
該黏著層可以包括至少一種交聯劑，其選自由異氰酸酯系化合物、吖啶系化合物、環氧系化合物、和金屬螯合物系化合物所組成群組。
基於100重量份的該多官能性(甲基)丙烯酸酯化合物，該交聯劑的含量可為2至40重量份，較佳為2至20重量份。
當該交聯劑的含量低於2重量份時，該黏著劑的附著力可能會不足，而當其含量超過20重量份時，紫外光照射之前的黏著性可能會不足。
該黏著層可以另外包括至少一種賦黏劑，其選自由松香樹脂、萜烯樹脂、酚樹脂、苯乙烯樹脂、脂族石油樹脂、芳族石油樹脂、及脂族和芳族共聚的石油樹脂所組成群組。
對於塗覆和乾燥用於形成黏著層之黏著劑組成物之方法沒有特別的限制，且例如，可以是含有以上組份各者之組成物以原狀態使用或經適當有機溶劑稀釋的狀態使用，並藉已知設備(如，間隔塗佈機、凹版塗佈機、模具塗佈機、或往復塗佈機)塗覆及之後溶劑於60℃至200℃乾燥10秒鐘至30分鐘之方法。
此外，以上程序中，可以另外進行用於執行黏著劑之足夠的交聯反應之老化步驟。
未特別限制該黏著層的厚度，但是可以在例如，5μm至300μm、或10μm至100μm的範圍內。
另一方面，未特別限制該聚合物基底，且該聚合物基底的例子包括聚胺甲酸酯、聚對酞酸乙二酯、低密度聚乙烯、線形聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯的隨機共聚物、聚丙烯的嵌段共聚物、均聚丙烯、聚甲基戊烯、乙烯–乙酸乙烯酯共聚物、乙烯–甲基丙烯酸共聚物、乙烯–甲基丙烯酸甲酯共聚物、乙烯–離子聚合物共聚物、乙烯–乙烯醇共聚物、聚丁烯、和苯乙烯共聚物。
未特別限制該聚合物基底的厚度，且例如，其可以在10μm至500μm的範圍內。
另一方面，根據本發明的另一具體實施例，可提出一種使用上述背面研磨膠帶之研磨晶圓之方法。
研磨半導體晶圓的步驟可以在該背面研磨膠帶黏著至該半導體晶圓的一表面的狀態下進行。研磨步驟之後，該背面研磨膠帶可以紫外光照射或進行熱處理等以剝離該膠帶。
在研磨半導體晶圓的步驟中，未特別限制使用該背面研磨膠帶之方法，且例如，在該背面研磨膠帶於室溫以50μm的厚度接合至半切穿電路表面之後，研磨膠帶接合的表面可固定至真空桌，並藉此能夠研磨電路表面的背面。
之後，可經由以500 mJ/cm2 或更高的 UV A 照射在經研磨的晶圓上的背面研磨膠帶之方法移除該背面研磨膠帶。 有利功效
根據本發明，可提出一種背面研磨膠帶，其能夠容易地應用於研磨具有薄的厚度之晶圓的程序，並且藉由使得黏著膠帶的潛變變形維持於低度來防止諸如研磨後的模具未對準之類的問題，及一種使用該背面研磨膠帶研磨晶圓之方法。
將藉以下所示實例更詳細地描述本發明。
但是，提出這些實例僅用於說明之目的且本發明之範圍不欲限於這些實例或由這些實例限制。
[製備例：(甲基)丙烯酸酯樹脂之製備]
製備例1
將由27g的丙烯酸2-乙基己酯(2-EHA)、48g的丙烯酸甲酯(MA，玻璃轉變溫度為 86℃)、和 25g的丙烯酸羥基乙酯(HEA)所組成之單體混合物加至配備冷卻系統的反應器以達到氮氣回流和易於溫度控制。
之後，基於100重量份的該單體混合物，將400 ppm的n-DDM作為鏈轉移劑(CTA)和100重量份的乙酸乙酯(EAc)作為溶劑加至其中，各者於30℃充分混合30分鐘或更長時間，同時注射氮以自反應器移除氧。
之後，溫度提高至並維持於50℃，且將V-70 [2,2'-偶氮基雙(4-甲氧基-2,4-二甲基戊腈)]以300ppm作為反應引發劑加至其中以藉此引發反應，之後進行聚合反應達24小時，以製備主要反應材料。
將24.6重量份的2-甲基丙烯醯氧乙基異氰酸酯(MOI)(70mol%，基於主要反應材料中的HEA)和基於MOI為1重量%的觸媒(二丁基二月桂酸錫：DBTDL)在主要反應材料中混合，之後使其於40℃反應24小時，藉此，將紫外光固化基團引至主要反應材料中之聚合物的支鏈中。藉此，製備(甲基)丙烯酸酯系聚合物樹脂(重量平均分子量：約900,000g/mol)。
製備例2
以與製備例1中相同的方式製得(甲基)丙烯酸酯系聚合物樹脂(重量平均分子量：約900,000 g/mol)，但添加由27g的丙烯酸2-乙基己酯(2-EHA)和25g的丙烯酸羥基乙酯(HEA)所組成的單體混合物。
[實例和比較例：背面研磨膠帶之製備]
實例1
將7g的TDI系異氰酸酯固化劑和3g的光引發劑(Irgacure 184)與100g製備例1的(甲基)丙烯酸酯系聚合物樹脂混合以製備黏著劑組成物。
將該黏著劑組成物塗覆於經脫模處理之具有38um的厚度的PET上，並於110℃乾燥3分鐘以形成具有20 um的厚度之黏著層(玻璃轉變溫度Tg-17℃)。
比較例1
將7g的TDI系異氰酸酯固化劑和3g的光引發劑(Irgacure 184)與100g製備例2的(甲基)丙烯酸酯系聚合物樹脂混合以製備黏著劑組成物。
將該黏著劑組成物塗覆於經脫模處理之具有38um的厚度的PET上，並於110℃乾燥3分鐘以形成具有20 um的厚度之黏著層(玻璃轉變溫度Tg-55℃)。
[實驗例]
實驗例1：潛變變形之測定
將20,000Pa的力於90℃施於實例和比較例的黏著層以測定潛變變形。
更具體言之，在實例和比較例的黏著層製成1mm或更高的厚度之後，將它們使用ARES-G2設備(TA Instruments)測定。
使用8mm不銹鋼板，於90℃施加20,000Pa的力達100秒鐘以測定該黏著層的潛變變形。
實驗例2：晶圓的研磨測試
使用以實例和比較例之黏著劑製得的各種背面研磨膠帶，背面研磨膠帶以50μm的厚度接合至已進行半切穿的半導體電路表面，且將780μm晶圓進行背面表面研磨至50μm的厚度。
將該背面研磨膠帶藉UV A以500mJ/cm2 照射而移除，並比較研磨之前和之後的模具對準情況。 [表1]
Figure 108101993-A0304-0001
如以上表1中可見者，證實將20,000Pa的力於90℃施於實例1的背面研磨膠帶的黏著層時，潛變變形是20%且研磨之前和之後的模具對準未改變。
另一方面，證實將20,000Pa的力於90℃施於比較例1的背面研磨膠帶的黏著層時，潛變變形是100%且發生研磨之前和之後的模具未對準的情況。

Claims (6)

  1. 一種背面研磨膠帶，其包括聚合物基底和黏著層，其中該黏著層包括(甲基)丙烯酸酯樹脂，其含有30至60重量%自具有0℃至100℃的玻璃轉變溫度之單體或寡聚物衍生的重複單元，40至70重量%具有具2至12個碳原子的烷基之(甲基)丙烯酸酯系重複單元及含有可交聯官能基的(甲基)丙烯酸酯系重複單元，和形成自2-甲基丙烯醯氧乙基異氰酸酯且引至(甲基)丙烯酸酯樹脂的支鏈中之紫外光固化基團；且其中該具有0℃至100℃的玻璃轉變溫度之單體或寡聚物係丙烯酸甲酯，其中該黏著層具有-20℃至10℃的玻璃轉變溫度，其中當將20,000Pa的力於90℃施於黏著層時，潛變變形是10至30%。
  2. 如請求項1之背面研磨膠帶，其中該黏著層另包括多官能性(甲基)丙烯酸酯化合物。
  3. 如請求項2之背面研磨膠帶，其中該多官能性(甲基)丙烯酸酯化合物具有100至100,000的重量平均分子量，並包括選自由多官能性胺甲酸酯(甲基)丙烯酸酯所組成群組中之至少一者。
  4. 如請求項1之背面研磨膠帶，其中該黏著層包括光引發劑，至少一種交聯劑，其選自由異氰酸酯系化合物、吖啶系化合物、環氧系化合物、和金屬螯合物系化合物所組成群組，或至少一種賦黏劑，其選自由松香樹脂、萜烯樹脂、酚樹脂、苯乙烯樹脂、脂族石油樹脂、芳族石油樹脂、及脂族和芳族共聚的石油樹脂所組成群組。
  5. 如請求項1之背面研磨膠帶，其中該聚合物基底包括至少一種聚合物樹脂，其選自由聚胺甲酸酯、聚對酞酸乙二酯、低密度聚乙烯、線形聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯的隨機共聚物、聚丙烯的嵌段共聚物、均聚丙烯、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-離子聚合物共聚物、乙烯-乙烯醇共聚物、聚丁烯、和苯乙烯共聚物所組成群組。
  6. 一種研磨晶圓之方法，其使用如請求項1之背面研磨膠帶。
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