TW201945485A - 暫時黏著被加工物之方法及黏著劑 - Google Patents
暫時黏著被加工物之方法及黏著劑 Download PDFInfo
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- TW201945485A TW201945485A TW107114075A TW107114075A TW201945485A TW 201945485 A TW201945485 A TW 201945485A TW 107114075 A TW107114075 A TW 107114075A TW 107114075 A TW107114075 A TW 107114075A TW 201945485 A TW201945485 A TW 201945485A
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—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
- H01L21/683—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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/27—Manufacturing methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
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Abstract
一種暫時黏著被加工物之方法,包含以下步驟。進行一結合步驟,係於至少一基板及/或至少一被加工物之一表面形成黏著層。進行一黏著步驟,係使基板與被加工物藉由黏著層黏著接合。進行一加工步驟,係對被加工物進行加工。進行一剝離步驟,係以雷射照射黏著層,使被加工物與基板分離。黏著層係由黏著劑所形成,黏著劑包含聚合物以及遮色材,黏著劑之固成分中包含50重量百分比至98重量百分比的聚合物,黏著劑之固成分中包含2重量百分比至50重量百分比的遮色材。藉此,有利於提升黏著劑的黏著性、耐熱性及可移除性。
Description
本發明是有關於一種暫時黏著被加工物之方法及黏著劑,且特別是有關於一種可以雷射離型之黏著劑及使用其之暫時黏著被加工物之方法。
隨著半導體裝置的薄型化,暫時接著/剝離技術成為近年來發展重要技術之一,其係因為薄型化元件易脆、無支撐性,需利用暫時黏著劑將被加工物(例如晶圓)與支撐基板接合,而得以對被加工物進行佈線、連結冶金等後續加工處理,待加工完畢,再將暫時黏著劑移除而使被加工物與支撐基板分離。由於半導體製程常需高溫操作條件,例如焊錫或迴焊等製程通常需在大於250℃的高溫下進行,因此,暫時黏著劑除了需具備優良黏著性,尚需具備耐熱性以及可移除性,藉此,在加工過程中,暫時黏著劑可將被加工物穩定地固定於支撐基板上並可承受半導體製程的高溫操作條件,而於加工處理結束後,可容易剝離及洗淨。
因此,如何改良暫時黏著劑的配方以及搭配合適的剝離方法,使暫時黏著劑具備優良的黏著性、耐熱性, 且有利於由被加工物上清洗乾淨,遂成為相關業者努力的目標。
本發明之一目的是提供一種暫時黏著被加工物之方法,藉由改良黏著劑的成分,有利於應用在薄型化元件的加工製程,且有利於應用在半導體製程。
本發明之另一目的是提供一種黏著劑,其具有優良的黏著性、耐熱性及可移除性。
依據本發明之一實施方式是在提供一種暫時黏著被加工物之方法,包含以下步驟。進行一結合步驟,係於至少一基板及/或至少一被加工物之一表面形成黏著層。進行一黏著步驟,係使基板與被加工物藉由黏著層黏著接合。進行一加工步驟,係對被加工物進行加工。進行一剝離步驟,係以雷射照射黏著層,使被加工物與基板分離。黏著層係由黏著劑所形成,黏著劑包含聚合物以及遮色材,黏著劑之固成分中包含50重量百分比至98重量百分比的聚合物,黏著劑之固成分中包含2重量百分比至50重量百分比的遮色材,聚合物為聚醯亞胺或(醯胺酸/醯亞胺)共聚物,聚合物的骨架包含5重量百分比至45重量百分比的含羥基單元,聚合物的骨架更包含5重量百分比至40重量百分比的含脂肪醚單元或含矽氧烷單元,且聚合物的環化率為90百分比以上。
依據本發明之另一實施方式是在提供一種黏著劑,黏著劑如上段所述,在此不另贅述。
100‧‧‧暫時黏著被加工物之方法
110、120、130、140‧‧‧步驟
111、112、113、114‧‧‧步驟
300、500、600a、600b‧‧‧接合結構
310、510、610a、610b‧‧‧基板
320、520、620a、620b‧‧‧被加工物
330‧‧‧黏著劑
340、540、640a、640b‧‧‧黏著層
550a‧‧‧可離型基材
550b‧‧‧黏著膜
700‧‧‧暫時黏著被加工物之方法
710、720、730、740、750‧‧‧步驟
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:第1圖係依照本發明一實施方式的一種暫時黏著被加工物之方法的步驟流程圖;第2圖係第1圖中步驟110依照本發明一實施方式的步驟流程圖;第3A圖係第2圖的步驟示意圖;第3B圖係第2圖的另一步驟示意圖;第3C圖係第2圖的又一步驟示意圖;第4圖係第1圖中步驟110依照本發明另一實施方式的步驟流程圖;第5圖係第4圖的步驟示意圖;第6A圖係依照本發明一實施方式的一種接合結構的側視圖;第6B圖係依照本發明另一實施方式的一種接合結構的側視圖;以及第7圖係依照本發明另一實施方式的一種暫時黏著被加工物之方法的步驟流程圖。
本發明中,如果沒有特別指明某一基團是否經過取代,則該基團可表示經取代或未經取代的基團。例如,「烷基」可表示經取代或未經取代的烷基。另外,對某一基團冠以「Cx」來描述時,表示該基團的主鏈具有X個碳原子。
本發明中,有時以鍵線式(skeleton formula)表示化合物結構,此種表示法可以省略碳原子、氫原子以及碳氫鍵。倘若,結構式中有明確繪出官能基的,則以繪示者為準。
本發明中,由「一數值至另一數值」表示的範圍,是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此,某一特定數值範圍的記載,涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍,如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。例如,「0.1重量%~1重量%」的範圍,無論說明書中是否列舉其他數值,均涵蓋「0.5重量%~0.8重量%」的範圍。
本發明中,描述數值範圍時,「以上」係指大於或等於該數值,例如,聚合物的環化率為90百分比以上,其包含以下兩種情形:聚合物的環化率等於90百分比,以及聚合物的環化率大於90百分比。
本發明提供一種黏著劑,包含聚合物、遮色材及溶劑,且可選擇性地包含一添加劑。
黏著劑之固成分中包含50重量百分比至98重量百分比的聚合物以及2重量百分比至50重量百分比的遮色材,其中,聚合物為聚醯亞胺或(醯胺酸/醯亞胺)共聚物,聚合物的骨架包含5重量百分比至45重量百分比的含羥基單元,聚合物的骨架更包含5重量百分比至40重量百分比的含脂肪醚單元或含矽氧烷單元,且聚合物的環化率為90百分比以上。藉此,黏著劑具有優良的黏著性、耐熱性及可移除性。藉由優良的黏著性,在加工過程中,黏著劑可將被加工物穩定地固定於基板上。藉由優良的耐熱性,有利於高溫製程,而具有應用於半導體製程的潛力。藉由優良的可移除性,於加工處理結束後,有利於將黏著劑從被加工物上移除乾淨,前述優良的移除性包含使用雷射離型(下文中亦稱為雷射剝離)以及雷射離型後的可清洗性。此外,依據本發明的黏著劑可於低於250℃的溫度烘烤成膜,可避免過高的烘烤成膜溫度傷害被加工物中對溫度較敏感的元件。
較佳地,黏著劑之固成分中聚合物的含量可為50重量百分比至95重量百分比。藉此,有利於提升黏著劑的黏著性、耐熱性及可移除性。更佳地,黏著劑之固成分中聚合物的含量可為55重量百分比至90重量百分比。
較佳地,聚合物的骨架可包含7重量百分比至40重量百分比的含羥基單元。藉此,可進一步提升聚合物的溶解性,有利於提升雷射離型後的清洗性。更佳地,聚合物的骨架可包含9重量百分比至35重量百分比的含羥基單元。
前述含羥基單元可具有但不限於式(I-1)、式(I-2)、式(I-3)、式(I-4)或是(I-5)所示之一結構:
式(I-1)及式(I-5)中,X係各自獨立為單鍵或二價有機基,例如,X可各自獨立為但不限於單鍵、C1~C4之伸烷基、-CO-、-COO-、-O-、-SO2-或C(CF3)2。
前述含羥基單元可由聚合物的反應物,如二胺及/或二酸酐提供。例如,式(I-1)可由式(I-1-1)的二胺提供,式(I-2)可由式(I-2-1)的二胺提供,式(I-4)可由式(I-4-1)的二胺提供,式(I-5)可由式(I-5-1)的二胺提供:
其中,X的定義如上段所述,在此不另贅述。
較佳地,聚合物的骨架可包含5重量百分比至35重量百分比的含脂肪醚單元或含矽氧烷單元。藉此,可進一步提升熱壓接著性。更佳地,聚合物的骨架可包含10重量百分比至35重量百分比的含脂肪醚單元或含矽氧烷單元。
前述含脂肪醚單元可為聚脂肪醚單元,藉此,可進一步提升熱壓接著性。聚脂肪醚單元可包含但不限於式(II-1)或式(II-2)所示之一片段:
式(II-1)中,m1可為1至22的整數。式(II-2)中,m2可為1至22的整數。
前述含脂肪醚單元可由聚合物的反應物,如二胺及/或二酸酐提供。例如,式(II-1)可由式(II-2-1)的二胺 提供,式(II-2)可由式(II-2-1)的二胺或式(II-2-2)的三胺提供:
式(II-2-1)中,x1+y1+z1可為1至22的整數。式(II-2-2)中,x2+y2+z2可為1至22的整數,R可為一價烷基,n3可為1至3整數。更具體舉例來說,式(II-2-2)可由商品名稱為JEFFAMINE T-403所提供,此時,R為乙基,x2+y2+z2可為5至6的整數,n3為1,且其平均重量分子量(MW)約為440。
前述含矽氧烷單元可為聚矽氧烷單元,藉此,可提升熱壓接著性。聚矽氧烷單元可但不限於包含式(III-1)所示之一片段:
(III-1)中,R1各自獨立為甲基或苯基,n1為0至5的整數。
前述含矽氧烷單元可由聚合物的反應物,如二胺及/或二酸酐提供。
較佳地,黏著劑之固成分中可包含5重量百分比至47重量百分比的遮色材。藉此,可進一步提升雷射離型性。更佳地,黏著劑之固成分中可包含7重量百分比至47重量百分比的遮色材。
前述遮色材可為碳黑、鈦黑、氧化鈦、氧化鐵、鈦氮化物、矽灰、有機顏料或染料。
配合參照第1圖,其係依照本發明一實施方式的一種暫時黏著被加工物之方法100的步驟流程圖。在第1圖中,暫時黏著被加工物之方法100包含步驟110、步驟120、步驟130及步驟140。
步驟110是進行一結合步驟,係於至少一基板及/或至少一被加工物之一表面形成一黏著層,黏著層係由一黏著劑所形成,關於黏著劑可參照前文,在此不另贅述。
步驟120是進行一黏著步驟,係使基板與被加工物藉由黏著層黏著接合,為方便說明,以下將基板與被加工物藉由黏著層黏著接合所形成之結構稱為接合結構。步驟120可藉由熱壓實現,即對被加工物、黏著層、基板施加溫度及壓力進行黏合,溫度可為室溫至250℃,壓力可為0.5kgf/cm2~5kgf/cm2。
步驟130是進行一加工步驟,係對被加工物進行加工。
步驟140是進行一剝離步驟,係以一雷射照射黏著層,使被加工物與基板分離。
藉由黏著劑具有優良的黏著性、耐熱性及可移除性,依據本發明之暫時黏著被加工物之方法100有利於將被加工物暫時固定在基板上,即在加工過程中,可將被加工物穩定地固定在基板上,待加工結束後,可輕易地將被加工物與基板分離,並可輕易地將黏著劑從被加工物上移除乾淨。另外,依據本發明之暫時黏著被加工物之方法100有利於高溫製程,因此,依據本發明之暫時黏著被加工物之方法100可作為半導體製程中的暫時接著/剝離技術,例如,被加工物可為晶圓,基板可為支撐基板,藉由支撐基板提供晶圓於加工過程中所需支撐力,可避免晶圓於加工過程中破裂,待加工完畢,再將晶圓與支撐基板分離。再者,依據本發明之暫時黏著被加工物之方法100,由於黏著劑可於低於250℃的溫度烘烤成膜,可避免過高的烘烤成膜溫度傷害被加工物中對溫度較敏感的元件。前述優良的移除性包含使用雷射離型以及雷射離型後的可清洗性。
前述「於至少一基板及/或至少一被加工物之一表面形成一黏著層」是指黏著層可僅設置於基板的一表面,或者,黏著層可僅設置於被加工物的一表面,或者,黏著層可同時設置於基板的一表面與加工物的一表面。此外,基板的數量與被加工物的數量可為一對一的關係、多對一的關係或一對多的關係。換句話說,依照本發明的一種暫時黏著被加工物之方法100,可使用一個基板承載一個被加工物,或 者,可使用多個基板共同承載一個被加工物,或者,可使用一個基板同時承載多個被加工物。
前述被加工物可為晶片、晶圓或半導體製造之微裝置,其中半導體製造之微裝置可為但不限於在晶圓上沉積多層結構、佈線等冶金處理後再進行切割所得的微裝置,微裝置的具體實例包含但不限於場效電晶體、光學感測器、邏輯晶片、合格晶元(Known Good Die,KGD),且前述微裝置中的尺寸為1微米至數毫米。
前述基板可為玻璃、矽晶圓或其他可被雷射穿透的材料所製成。
前述雷射可為YAG雷射、紅寶石雷射、YVO4雷射、光纖雷射等之固體雷射、色素雷射等之液體雷射、CO2雷射、準分子雷射、Ar雷射、He-Ne雷射等氣體雷射、半導體雷射、半導體激發固體雷射(Diode Pump Solid State Laser,DPSSL)、自由電子雷射等。
配合參照第2圖,其係第1圖中步驟110依照本發明一實施方式的步驟流程圖。第2圖中,步驟110包含步驟111以及步驟112。
步驟111是進行一塗布步驟,係將黏著劑塗布於基板及/或被加工物之表面。塗布方式包含但不限於旋轉塗布、狹縫塗布、線棒塗布、網版印刷等。
步驟112是進行一加熱步驟,係加熱黏著劑,使黏著劑轉變為黏著層。步驟112可於50℃至200℃溫度進行0.5小時至2小時,步驟112主要目的是除去黏著劑中的部 分或全部溶劑,當黏著劑中包含(醯胺酸/醯亞胺)共聚物,還可促進其中的醯胺酸片段環化,當黏著劑中包含可固化成分如交聯劑時,還可進一步促進固化,因此,只要可達上述目的,可依據實際需求,如溶劑種類、溶劑含量以及環化程度,適當調整步驟112的溫度與時間。另外,當黏著劑中包含可固化成分如交聯劑時,可在進行步驟120後及進行步驟130前,另外進行一次加熱步驟(其溫度高於步驟112的溫度)以進行交聯固化反應,關於產生交聯固化反應的具體溫度及時間可依據交聯劑的種類、用量相應調整。
同時配合參照第3A圖、第3B圖及第3C圖,第3A圖係第2圖的步驟示意圖,第3B圖係第2圖的另一步驟示意圖,第3C圖係第2圖的又一步驟示意圖。如第3A圖所示,進行步驟111時,可將黏著劑330塗布於基板310的表面(未另標號)。之後,進行步驟112,係加熱黏著劑330,使黏著劑330轉變為黏著層340,接著,進行黏著步驟,使基板310與被加工物320藉由黏著層340黏著接合,以形成接合結構300。第3B圖中,係將黏著劑330塗布於被加工物320的表面(未另標號),待要進行黏著步驟前再將被加工物320翻轉,使黏著層340面向基板310以便形成接合結構300。第3C圖中,係將黏著劑330同時塗布於被加工物320的表面(未另標號)以及基板310的表面(未另標號),待要進行黏著步驟前再將被加工物320翻轉,使被加工物320的黏著層340面向基板310的黏著層340以便形成接合結構300。關於 第3B圖及第3C圖的其餘細節可與第3A圖相同,在此不另贅述。
配合參照第4圖,其係第1圖中步驟110依照本發明另一實施方式的步驟流程圖。第4圖中,步驟110包含步驟113以及步驟114。
步驟113是提供一複合膜,所述複合膜包含一可離型基材及黏著膜,黏著膜設置於可離型基材之表面,且黏著膜係將黏著劑塗布於可離型基材之所述表面並乾燥後而得,複合膜中的黏著膜可被剝離。可離型基材包含但不限於聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等之膜厚15~200μm的合成樹脂薄膜。塗布方式包含但不限於旋轉塗布、狹縫塗布、線棒塗布、網版印刷等,前述乾燥可以50℃至200℃進行1~60分鐘,乾燥主要目的是除去黏著劑中的部分或全部溶劑,因此,只要可達上述目的,可依據實際需求,如溶劑種類以及溶劑含量,適當調整乾燥的溫度與時間。
步驟114是進行一轉印步驟,係使基板及/或被加工物之表面與複合膜之黏著膜接觸並加熱,以使黏著膜轉印至基板及/或被加工物之表面並轉變為黏著層。步驟114可以50℃至200℃的溫度加熱,並配合滾壓或真空熱壓,使黏著膜轉印至基板及/或被加工物之表面,移除可離型基材後,繼續以50℃至200℃的溫度加熱約0.5小時至2小時以去除殘存溶劑,並使黏著膜轉變成黏著層,再進行黏著接合。步驟114中加熱主要目的是使黏著膜軟化,有利於進行 轉印。因此,只要可達上述目的,可依據實際需求,如溶劑種類、溶劑含量以及環化程度,適當調整加熱的溫度與時間。
同時配合參照第5圖,其係第4圖的步驟示意圖。如第5圖所示,步驟113是提供一複合膜(未另標號),複合膜包含可離型基材550a及黏著膜550b,黏著膜550b係將黏著劑(圖未繪示)塗布於可離型基材550a之表面(未另標號)並乾燥後而得。之後,進行步驟114,係使基板510之表面(未另標號)與複合膜之黏著膜550b接觸並加熱,以使黏著膜550b轉印至基板510之表面,移除可離型基材550a後,繼續加熱以去除殘存溶劑,並使黏著膜550b轉變為黏著層540,之後並進行黏著步驟,使基板510與被加工物520藉由黏著層540黏著接合,以形成接合結構500。第5圖中,係將黏著膜550b轉印在基板510上,然而,本發明並不以此為限,實務中,可改成將黏著膜550b轉印在被加工物520上,或者,可改成將黏著膜550b同時轉印在基板510上與被加工物520上,再進行黏著步驟。另外,第5圖中,基板510與被加工物520的數量、形狀及尺寸皆僅為例示,本發明並不以此為限。
配合參照第6A圖及第6B圖,第6A圖係依照本發明一實施方式的一種接合結構600a的側視圖,第6B圖係依照本發明另一實施方式的一種接合結構600b的側視圖。第6A圖中,接合結構600a包含一基板610a、二被加工物620a,且基板610a與被加工物620a藉由黏著層640a黏著接合,在本實施方式中,基板610a與被加工物620a的數量為 一對多的關係。第6B圖中,接合結構600b包含二基板610b、一被加工物620b,且基板610b與被加工物620b藉由黏著層640b黏著接合,在本實施方式中,基板610b與被加工物620b的數量為多對一的關係。
由第3A圖至第3C圖中、第5圖、第6A及第6B圖可知,本發明中,基板與被加工物的數量關係可為一對一、一對多或多對一,另外,第3A圖至第3C圖中、第5圖、第6A及第6B圖中,基板與被加工物的數量、形狀及尺寸皆僅為例示,本發明並不以此為限。
配合參照第7圖,其係依照本發明另一實施方式的一種暫時黏著被加工物之方法700的步驟流程圖。在第7圖中,暫時黏著被加工物之方法700包含步驟710、步驟720、步驟730及、步驟740及步驟750。
步驟710是進行一結合步驟,步驟720是進行一黏著步驟,步驟730是進行一加工步驟,步驟740是進行一剝離步驟。關於步驟710至740可參照第1圖中步驟110至步驟140的相關說明,在此不另贅述。
步驟750進行一溶解步驟,係於進行剝離步驟後,以清洗溶劑將殘留在被加工物上的黏著層溶解移除。清洗溶劑的溶解度參數(Solubility Parameter,簡稱SP)可為9.6至12.8。藉此,有利於將經雷射照射後的黏著劑溶解移除。可使用的溶劑可為但不限於二乙基甲醯胺(N,N-diethyl formamide,DEF;SP值9.6)、環己酮(cyclohexanone;SP值9.6)、N-甲基吡咯烷酮(N-methyl pyrrolidinone,NMP;SP值11.2)或γ-丁內酯(gamma-butyl lactone,GBL;SP值12.8)。
依據本發明之黏著劑中的聚合物為(醯胺酸/醯亞胺)共聚物或聚醯亞胺,聚合物可以二胺與二酸酐作為反應物,於有機溶劑中進行聚縮合反應,根據反應量多寡而調整,於25℃至50℃的溫度進行8至12小時攪拌,以得到一包含聚醯胺酸之反應溶液。上述包含聚醯胺酸之反應溶液可利用熱環化或化學環化(添加吡啶、醋酸酐等方式)進行脫水閉環反應。舉例來說,可藉由添加甲苯利用共沸除水進行熱環化反應,依據本發明一實施例,係添加甲苯並於120℃至150℃的溫度進行3至6小時進行回流脫水閉環反應,以得到一包含醯胺酸/醯亞胺共聚物或聚醯亞胺之反應溶液,其中(醯胺酸/醯亞胺)共聚物的環化率為90%以上。最後,將上述(醯胺酸/醯亞胺)共聚物或聚醯亞胺反應溶液蒸餾出甲苯、並以減壓蒸餾或添加有機溶劑方式調整固含量,即可得到(醯胺酸/醯亞胺)共聚物溶液或聚醯亞胺溶液。
前述二胺與二酸酐之比例關係,以二酸酐之酸酐基含量為1當量,二胺之胺基為0.5~2當量為佳,0.7~1.5當量為更佳。前述二胺及/或二酸酐可包含羥基單元,且可包含含脂肪醚單元及/或含矽氧烷單元,藉此,使所生成的聚合物的骨架包含5wt%至45wt%的含羥基單元,並包含5wt%至40wt%的含脂肪醚單元及/或含矽氧烷單元。另 外,前述脫水閉環反應為本領域通常知識者的熟知技術,在此不贅述。
前述有機溶劑係用來溶解反應物及產物,包含溶解度較佳的有機溶劑與溶解度較差的有機溶劑,溶解度較佳的有機溶劑包含但不限於:N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、六甲基磷醯胺、γ-丁內酯、吡啶。溶解度較差的有機溶劑包含但不限於:甲醇、乙醇、異丙醇、正丁醇、環己醇、乙二醇、乙二醇甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、二乙基醚、丙酮、甲基乙基酮、環己酮、乙酸甲酯、乙酸乙酯、四氫呋喃、二氯甲烷、三氯甲烷、1,2-二氯乙烷、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷。以上有機溶劑可單獨使用,亦可混合二種以上同時使用。由於有機溶劑係用來溶解反應物及產物,因此,舉凡可溶解反應物及產物的有機溶劑皆可使用,並不以上述為限。
依據本發明之黏著劑包含聚合物、遮色材及溶劑,且可選擇性地包含一添加劑。
將聚合物溶液、遮色材與溶劑混合,並選擇性地加入添加劑混合均勻,即可形成黏著劑。製備黏著劑之溫度可為室溫至200℃。黏著劑可根據黏度與揮發性調整其所包含之固成分的含量(以下亦可簡稱為固含量),黏著劑可包含10wt%至60wt%之固含量。此外,以固成分為100wt%, 前述聚合物於固成分中的含量為50wt%至98wt%,遮色材於固成分中的含量為2wt%至50wt%。
可用於黏著劑的溶劑可為有機溶劑,所述有機溶劑可包含但不限於N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基己內醯胺、二甲基亞碸、γ-丁內酯、γ-丁內醯胺、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單丁基醚等,前述溶劑可二種以上混合使用,此外,舉凡可溶解聚合物的溶劑或二種以上混合之溶劑皆可作為此處的溶劑。
可用於黏著劑的添加劑包含但不限於交聯劑、有機矽(氧)烷化合物或環氧化合物。
離型層轉印性:於溫度120℃及壓力1kgf/cm2貼合後表面平整無缺陷表示好,表面大於或等於90%貼合表示尚可,表面小於90%貼合表示差。
固含量30wt%的溶解度:黏著劑外觀澄清透明表示好,外觀略霧表示尚可,外觀明顯析出表示差。
200℃的熱壓接著性:室溫黏著力大於、等於10N/cm2表示好,室溫黏著力小於10N/cm2表示差。
260℃的溢膠情形:觀察接合結構的溢膠情形,有溢膠情形紀錄為有,無溢膠情形紀錄為無。
雷射剝離性:以雷射照射黏著層,直到發生剝離,以累積雷射功率為大於、等於2W及小於5W表示好,以 累積雷射功率大於、等於5W及小於8W表示尚可,以累積雷射功率大於8W表示差。
可清洗性:進行雷射離型後,以清洗溶劑清洗被加工元件,若清洗時間小於或等於10分鐘表示好,若清洗時間大於10分鐘且小於或等於30分鐘表示尚可,若清洗時間大於30分鐘表示差。
實施例/比較例中所使用的二胺如表一所示。表一中,二胺(a-3)的商品名稱為PAM-E,購買自信越化學股份有限公司(Shin-Etsu Chemical Co.,Ltd.),其黏度(25℃)為4mm2/s,比重(25℃)為0.9,官能基當量(functional group equivalent weight,FGEW)為130g/mole,R2與n2依照商品規格。二胺(a-4)的商品名稱為JEFFAMINE-D400,購買自亨斯邁公司(Huntsman Corporation),其平均分子重約為430,m3依照商品規格。
實施例/比較例中所使用的二酸酐如表二所示。表二中,二酸酐(b-3)的商品名稱為X22-168AS,購買自信越化學股份有限公司,其黏度(25℃)為160mm2/s,比重(25℃)為1.03,FGEW為500g/mole,R3與n3依照商品規格。
實施例/比較例中所使用的遮色材為碳黑,係購買自達興材料,商品名稱為PK-127,平均粒徑為120nm。
將二胺及二酸酐依照表三所示之比例,依序添加於溶劑中,製備固含量為20wt%之(醯胺酸/醯亞胺)共聚物溶液或聚醯亞胺溶液。具體來說,將二胺及二酸酐依照表三所示之比例,於有機溶劑中進行聚縮合反應,根據反應量多寡而調整,於25℃至50℃的溫度進行8至12小時攪拌,以得到一包含聚醯胺酸之反應溶液。將上述包含聚醯胺酸之反應溶液添加甲苯並於120℃至150℃的溫度進行3至6小時進行回流脫水閉環反應,以得到一包含醯胺酸/醯亞胺共 聚物或聚醯亞胺之反應溶液,其中(醯胺酸/醯亞胺)共聚物的環化率為90%以上。最後,將上述(醯胺酸/醯亞胺)共聚物或聚醯亞胺反應溶液蒸餾出甲苯、並以減壓蒸餾或添加有機溶劑方式調整固含量,即可得到固含量為20wt%之(醯胺酸/醯亞胺)共聚物溶液或聚醯亞胺溶液。
再依據表三所示之有機溶劑種類及遮色材含量(表三中遮色材含量為遮色材佔黏著劑之固成分的重量百分比),製備黏著劑,黏著劑的固含量為30wt%。將黏著劑塗布於基板之表面以形成黏著層,再將被加工物放置在設置有黏著層的基板上進行黏著得到實施例/比較例的接合結構,或將本發明液的黏著劑塗布於可離基材形成包含黏著膜的複合膜後,進行轉印步驟,即以50℃至200℃溫度加熱黏著膜使其轉印至基板,待除去可離型基材後繼續以50℃至200℃溫度加熱0.5至2小時去除殘存溶劑以得到設置有黏著層的基板,再將被加工物放置在設置有黏著層的基板上進行黏著得到實施例/比較例的接合結構。
對實施例/比較例的接合結構進行離型層轉印性、固含量30wt%的溶解度、200℃的熱壓接著性、260℃的溢膠情形、雷射剝離性、可清洗性等評估,各實施例/比較例所使用之雷射波長以及評估結果如表四所示。
由表四可知,依據本發明的暫時黏著被加工物之方法,接合結構的離型層轉印性皆為好或尚可,固含量30wt%的溶解度皆為好,200℃的熱壓接著性皆為好或尚可,260℃的溢膠情形皆為無,雷射剝離性皆為好或尚可,可清洗性皆為好,顯示依據本發明的黏著劑,其具有優良的黏著性、耐熱性及可移除性,有利於暫時接著/剝離技術的應用。
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (17)
- 一種暫時黏著被加工物之方法,包含:進行一結合步驟,係於至少一基板及/或至少一被加工物之一表面形成一黏著層;進行一黏著步驟,係使該基板與該被加工物藉由該黏著層黏著接合;進行一加工步驟,係對該被加工物進行加工;以及進行一剝離步驟,係以一雷射照射該黏著層,使該被加工物與該基板分離;其中,該黏著層係由一黏著劑所形成,該黏著劑包含一聚合物以及一遮色材,該黏著劑之固成分中包含50重量百分比至98重量百分比的該聚合物,該黏著劑之固成分中包含2重量百分比至50重量百分比的該遮色材,該聚合物為聚醯亞胺或(醯胺酸/醯亞胺)共聚物,該聚合物的骨架包含5重量百分比至45重量百分比的含羥基單元,該聚合物的骨架更包含5重量百分比至40重量百分比的含脂肪醚單元或含矽氧烷單元,且該聚合物的環化率為90百分比以上。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該結合步驟包含:進行一塗布步驟,係將該黏著劑塗布於該基板及/或該被加工物之該表面;以及 進行一加熱步驟,係加熱該黏著劑,使該黏著劑轉變為該黏著層。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該結合步驟包含:提供一複合膜,該複合膜包含一可離型基材及一黏著膜,該黏著膜設置於該可離型基材之一表面,且該黏著膜係將該黏著劑塗布於該可離型基材之該表面並乾燥後而得;以及進行一轉印步驟,係使該基板及/或該被加工物之該表面與該複合膜之該黏著膜接觸並加熱,以使該黏著膜轉印至該基板及/或該被加工物之該表面並轉變為該黏著層。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,更包含進行一溶解步驟,係於進行該剝離步驟後,以一清洗溶劑將殘留在該被加工物上的該黏著層溶解移除。
- 如申請專利範圍第4項所述的暫時黏著被加工物之方法,其中該清洗溶劑的溶解度參數為9.6至12.8。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該被加工物為一晶片、一晶圓或一半導體製造之微裝置。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該含脂肪醚單元為一聚脂肪醚單元。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該含矽氧烷單元為一聚矽氧烷單元。
- 如申請專利範圍第1項所述的暫時黏著被加工物之方法,其中該遮色材為碳黑、鈦黑、氧化鈦、氧化鐵、鈦氮化物、矽灰、有機顏料或染料。
- 一種黏著劑,包含:一聚合物,該黏著劑之固成分中包含50重量百分比至98重量百分比的該聚合物,該聚合物為聚醯亞胺或(醯胺酸/醯亞胺)共聚物,該聚合物的骨架包含5重量百分比至45重量百分比的含羥基單元,該聚合物的骨架更包含5重量百分比至40重量百分比的含脂肪醚單元或含矽氧烷單元,且該聚合物的環化率為90百分比以上;以及一遮色材,該黏著劑之固成分中包含2重量百分比至50重量百分比的該遮色材。
- 如申請專利範圍第10項所述的黏著劑,其中該含羥基單元具有式(I-1)、式(I-2)、式(I-3)、式(I-4)或是(I-5)所示之一結構:
- 如申請專利範圍第11項所述的黏著劑,其中該X係各自獨立為單鍵、C 1~C 4之伸烷基、-CO-、-COO-、-O-、-SO 2-或C(CF 3) 2。
- 如申請專利範圍第10項所述的黏著劑,其中該含脂肪醚單元為一聚脂肪醚單元。
- 如申請專利範圍第13項所述的黏著劑,其中該聚脂肪醚單元包含式(II-1)或式(II-2)所示之一片段:
- 如申請專利範圍第10項所述的黏著劑,其中該含矽氧烷單元為一聚矽氧烷單元。
- 如申請專利範圍第15項所述的黏著劑,其中該聚矽氧烷單元包含式(III-1)所示之一片段:
- 如申請專利範圍第10項所述的黏著劑,其中該遮色材為碳黑、鈦黑、氧化鈦、氧化鐵、鈦氮化物、矽灰、有機顏料或染料。
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2018
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JP2019189868A (ja) | 2019-10-31 |
EP3561862A1 (en) | 2019-10-30 |
US20190330504A1 (en) | 2019-10-31 |
EP3561862B1 (en) | 2021-05-26 |
JP6810188B2 (ja) | 2021-01-06 |
KR20190124163A (ko) | 2019-11-04 |
SG10201903680SA (en) | 2019-11-28 |
CN110396371A (zh) | 2019-11-01 |
TWI675899B (zh) | 2019-11-01 |
KR102256577B1 (ko) | 2021-05-27 |
US10703945B2 (en) | 2020-07-07 |
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