CN110396371A - 暂时粘着被加工物的方法及粘着剂 - Google Patents
暂时粘着被加工物的方法及粘着剂 Download PDFInfo
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- CN110396371A CN110396371A CN201910332739.5A CN201910332739A CN110396371A CN 110396371 A CN110396371 A CN 110396371A CN 201910332739 A CN201910332739 A CN 201910332739A CN 110396371 A CN110396371 A CN 110396371A
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Classifications
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- 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
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- 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
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- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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
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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
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- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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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
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- 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
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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
- 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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- 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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- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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Abstract
一种暂时粘着被加工物的方法,包含以下步骤。进行结合步骤,在至少一个基板和/或至少一个被加工物的表面形成粘着层。进行粘着步骤,使基板与被加工物通过粘着层粘着接合。进行加工步骤,对被加工物进行加工。进行剥离步骤,以激光照射粘着层,使被加工物与基板分离。粘着层由粘着剂所形成,粘着剂包含聚合物以及遮色材,粘着剂的固成分中包含50重量百分比至98重量百分比的聚合物,粘着剂的固成分中包含2重量百分比至50重量百分比的遮色材。藉此,有利于提升粘着剂的粘着性、耐热性及可移除性。
Description
【技术领域】
本发明是有关于一种暂时粘着被加工物的方法及粘着剂,且特别是有关于一种可以激光离型的粘着剂及使用其的暂时粘着被加工物的方法。
【背景技术】
随着半导体装置的薄型化,暂时接着/剥离技术成为近年来发展的重要技术之一,其因为薄型化元件易脆、无支撑性,需利用暂时粘着剂将被加工物(例如晶圆)与支撑基板接合,而得以对被加工物进行布线、连结冶金等后续加工处理,待加工完毕,再将暂时粘着剂移除而使被加工物与支撑基板分离。由于半导体制程常需高温操作条件,例如焊锡或回焊等制程通常需在大于250℃的高温下进行,因此,暂时粘着剂除了需具备优良粘着性,尚需具备耐热性以及可移除性,藉此,在加工过程中,暂时粘着剂可将被加工物稳定地固定于支撑基板上并可承受半导体制程的高温操作条件,而在加工处理结束后,可容易剥离及洗净。
因此,如何改良暂时粘着剂的配方以及搭配合适的剥离方法,使暂时粘着剂具备优良的粘着性、耐热性,且有利于由被加工物上清洗干净,遂成为相关业者努力的目标。
【发明内容】
本发明的一目的是提供一种暂时粘着被加工物的方法,通过改良粘着剂的成分,有利于应用在薄型化元件的加工制程,且有利于应用在半导体制程。
本发明的另一目的是提供一种粘着剂,其具有优良的粘着性、耐热性及可移除性。
依据本发明的一实施方式是在提供一种暂时粘着被加工物的方法,包含以下步骤。进行结合步骤,在至少一个基板和/或至少一个被加工物的表面形成粘着层。进行粘着步骤,使基板与被加工物通过粘着层粘着接合。进行加工步骤,对被加工物进行加工。进行剥离步骤,以激光照射粘着层,使被加工物与基板分离。粘着层由粘着剂所形成,粘着剂包含聚合物以及遮色材(光吸收材料,light absorbing material),粘着剂的固成分中包含50重量百分比至98重量百分比的聚合物,粘着剂的固成分中包含2重量百分比至50重量百分比的遮色材,聚合物为聚酰亚胺或(酰胺酸/酰亚胺)共聚物,聚合物的骨架包含5重量百分比至45重量百分比的含羟基单元,聚合物的骨架还包含5重量百分比至40重量百分比的含脂肪醚单元或含硅氧烷单元,且聚合物的环化率为90百分比以上。
依据本发明的另一实施方式是在提供一种粘着剂,粘着剂如上段所述,在此不另赘述。
【附图说明】
为让本发明的上述和其他目的、特征、优点与实施例能更明显易懂,所附图式的说明如下:
图1为依照本发明一实施方式的一种暂时粘着被加工物的方法的步骤流程图;
图2为图1中步骤110依照本发明一实施方式的步骤流程图;
图3A为图2的步骤示意图;
图3B为图2的另一步骤示意图;
图3C为图2的又一步骤示意图;
图4为图1中步骤110依照本发明另一实施方式的步骤流程图;
图5为图4的步骤示意图;
图6A为依照本发明一实施方式的一种接合结构的侧视图;
图6B为依照本发明另一实施方式的一种接合结构的侧视图;以及
图7为依照本发明另一实施方式的一种暂时粘着被加工物的方法700的步骤流程图。
【附图标记说明】
100:暂时粘着被加工物的方法
110、120、130、140:步骤
111、112、113、114:步骤
300、500、600a、600b:接合结构
310、510、610a、610b:基板
320、520、620a、620b:被加工物
330:粘着剂
340、540、640a、640b:粘着层
550a:可离型基材
550b:粘着膜
700:暂时粘着被加工物的方法
710、720、730、740、750:步骤
【具体实施方式】
本发明中,如果没有特别指明某一基团是否经过取代,则该基团可表示经取代或未经取代的基团。例如,“烷基”可表示经取代或未经取代的烷基。另外,对某一基团冠以“CX”来描述时,表示该基团的主链具有X个碳原子。
本发明中,有时以键线式(skeleton formula)表示化合物结构,此种表示法可以省略碳原子、氢原子以及碳氢键。倘若,结构式中有明确绘出官能基的,则以绘示者为准。
本发明中,由“一数值至另一数值”表示的范围,是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此,某一特定数值范围的记载,涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围,如同在说明书中明文写出该任意数值和该较小数值范围一样。例如,“0.1重量%~1重量%”的范围,无论说明书中是否列举其他数值,均涵盖“0.5重量%~0.8重量%”的范围。
本发明中,描述数值范围时,“以上”是指大于或等于该数值,例如,聚合物的环化率为90百分比以上,其包含以下两种情形:聚合物的环化率等于90百分比,以及聚合物的环化率大于90百分比。
<粘着剂>
本发明提供一种粘着剂,包含聚合物、遮色材及溶剂,且可选择性地包含添加剂。
粘着剂的固成分中包含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,聚合物为聚酰亚胺或(酰胺酸/酰亚胺)共聚物,聚合物的骨架包含5重量百分比至45重量百分比的含羟基单元,聚合物的骨架还包含5重量百分比至40重量百分比的含脂肪醚单元或含硅氧烷单元,且聚合物的环化率为90百分比以上。藉此,粘着剂具有优良的粘着性、耐热性及可移除性。通过优良的粘着性,在加工过程中,粘着剂可将被加工物稳定地固定于基板上。通过优良的耐热性,有利于高温制程,而具有应用于半导体制程的潜力。通过优良的可移除性,在加工处理结束后,有利于将粘着剂从被加工物上移除干净,前述优良的移除性包含使用激光离型(下文中亦称为激光剥离)以及激光离型后的可清洗性。此外,依据本发明的粘着剂可在低于250℃的温度烘烤成膜,可避免过高的烘烤成膜温度伤害被加工物中对温度较敏感的元件。
优选地,粘着剂的固成分中聚合物的含量可为50重量百分比至95重量百分比。藉此,有利于提升粘着剂的粘着性、耐热性及可移除性。更优选地,粘着剂的固成分中聚合物的含量可为55重量百分比至90重量百分比。
优选地,聚合物的骨架可包含7重量百分比至40重量百分比的含羟基单元。藉此,可进一步提升聚合物的溶解性,有利于提升激光离型后的清洗性。更优选地,聚合物的骨架可包含9重量百分比至35重量百分比的含羟基单元。
前述含羟基单元可具有但不限于式(I-1)、式(I-2)、式(I-3)、式(I-4)或是(I-5)所示的结构:
在式(I-1)及式(I-5)中,X各自独立为单键或二价有机基,例如,X可各自独立为但不限于单键、C1~C4亚烷基、-CO-、-COO-、-O-、-SO2-或C(CF3)2。
前述含羟基单元的结构式中包含的代表该单元与聚合物其他部分的连接键(连接位置)。
前述含羟基单元可由聚合物的反应物,如二胺和/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的定义如上段所述,在此不另赘述。
优选地,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单元或含硅氧烷单元。藉此,可进一步提升热压接着性。更优选地,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单元或含硅氧烷单元。
前述含脂肪醚单元可为聚脂肪醚单元,藉此,可进一步提升热压接着性。聚脂肪醚单元可包含但不限于式(II-1)或式(II-2)所示的片段:
式(II-1)中,m1可为1至22的整数。式(II-2)中,m2可为1至22的整数。
前述含脂肪醚单元可由聚合物的反应物,如二胺和/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可为1至22的整数。式(II-2-2)中,x2+y2+z2可为1至22的整数,R可为一价烷基,n3可为1至3的整数。更具体举例来说,式(II-2-2)可由商品名称为JEFFAMINE T-403所提供,此时,R为乙基,x2+y2+z2可为5至6的整数,n3为1,且其重均分子量(MW)约为440。
前述含硅氧烷单元可为聚硅氧烷单元,藉此,可提升热压接着性。聚硅氧烷单元可但不限于包含式(III-1)所示的片段:
(III-1)中,R1各自独立为甲基或苯基,n1为0至5的整数。
前述含硅氧烷单元可由聚合物的反应物,如二胺和/或二酸酐提供。
优选地,粘着剂的固成分中可包含5重量百分比至47重量百分比的遮色材。藉此,可进一步提升激光离型性。更优选地,粘着剂的固成分中可包含7重量百分比至47重量百分比的遮色材。
前述遮色材可为碳黑、钛黑、氧化铁、钛氮化物、有机颜料或染料。
<暂时粘着被加工物的方法>
配合参照图1,其系依照本发明一实施方式的一种暂时粘着被加工物的方法100的步骤流程图。在图1中,暂时粘着被加工物的方法100包含步骤110、步骤120、步骤130及步骤140。
步骤110是进行结合步骤,系在至少一个基板和/或至少一个被加工物的表面形成粘着层,粘着层由粘着剂所形成,关于粘着剂可参照前文,在此不另赘述。
步骤120是进行粘着步骤,系使基板与被加工物通过粘着层粘着接合,为方便说明,以下将基板与被加工物通过粘着层粘着接合所形成的结构称为接合结构。步骤120可通过热压实现,即对被加工物、粘着层、基板施加温度及压力进行粘合,温度可为室温至250℃,压力可为0.5kgf/cm2~5kgf/cm2。
步骤130是进行加工步骤,系对被加工物进行加工。
步骤140是进行剥离步骤,系以激光照射粘着层,使被加工物与基板分离。
藉由粘着剂具有优良的粘着性、耐热性及可移除性,依据本发明的暂时粘着被加工物的方法100有利于将被加工物暂时固定在基板上,即在加工过程中,可将被加工物稳定地固定在基板上,待加工结束后,可轻易地将被加工物与基板分离,并可轻易地将粘着剂从被加工物上移除干净。另外,依据本发明的暂时粘着被加工物的方法100有利于高温制程,因此,依据本发明的暂时粘着被加工物的方法100可作为半导体制程中的暂时接着/剥离技术,例如,被加工物可为晶圆,基板可为支撑基板,通过支撑基板提供晶圆在加工过程中所需的支撑力,可避免晶圆在加工过程中破裂,待加工完毕,再将晶圆与支撑基板分离。再者,依据本发明的暂时粘着被加工物的方法100,由于粘着剂可在低于250℃的温度烘烤成膜,可避免过高的烘烤成膜温度伤害被加工物中对温度较敏感的元件。前述优良的移除性包含使用激光离型以及激光离型后的可清洗性。
前述“在至少一个基板和/或至少一个被加工物的表面形成粘着层”是指粘着层可仅设置于基板的表面,或者,粘着层可仅设置于被加工物的表面,或者,粘着层可同时设置于基板的表面与加工物的表面。此外,基板的数量与被加工物的数量可为一对一的关系、多对一的关系或一对多的关系。换句话说,依照本发明的一种暂时粘着被加工物的方法100,可使用一个基板承载一个被加工物,或者,可使用多个基板共同承载一个被加工物,或者,可使用一个基板同时承载多个被加工物。
前述被加工物可为晶片、晶圆或半导体制造的微装置,其中半导体制造的微装置可为但不限于在晶圆上沉积多层结构、布线等冶金处理后再进行切割所得的微装置,微装置的具体实例包含但不限于场效电晶体、光学感测器、逻辑晶片、合格晶元(Known GoodDie,KGD),且前述微装置中的尺寸为1微米至数毫米。
前述基板可为玻璃、硅晶圆或其他可被激光穿透的材料所制成。
前述激光可为YAG激光、、红宝石激光、YVO4激光、光纤激光等的固体激光、色素激光等的液体激光、CO2激光、准分子激光、Ar激光、He-Ne激光等气体激光、半导体激光、半导体激发固体激光(Diode Pump Solid State Laser,DPSSL)、自由电子激光等。
配合参照图2,其为图1中步骤110依照本发明一实施方式的步骤流程图。图2中,步骤110包含步骤111以及步骤112。
步骤111是进行涂布步骤,系将粘着剂涂布于基板和/或被加工物的表面。涂布方式包含但不限于旋转涂布、狭缝涂布、线棒涂布、丝网印刷等。
步骤112是进行加热步骤,系加热粘着剂,使粘着剂转变为粘着层。步骤112可于50℃至200℃温度进行0.5小时至2小时,步骤112主要目的是除去粘着剂中的部分或全部溶剂,当粘着剂中包含(酰胺酸/酰亚胺)共聚物,还可促进其中的酰胺酸片段环化,当粘着剂中包含可固化成分如交联剂时,还可进一步促进固化,因此,只要可达上述目的,可依据实际需求,如溶剂种类、溶剂含量以及环化程度,适当调整步骤112的温度与时间。另外,当粘着剂中包含可固化成分如交联剂时,可在进行步骤120后及进行步骤130前,另外进行一次加热步骤(其温度高于步骤112的温度)以进行交联固化反应,关于产生交联固化反应的具体温度及时间可依据交联剂的种类、用量相应调整。
同时配合参照图3A、图3B及图3C,图3A为图2的步骤示意图,图3B为图2的另一步骤示意图,图3C为图2的又一步骤示意图。如图3A所示,进行步骤111时,可将粘着剂330涂布于基板310的表面(未另标号)。之后,进行步骤112,加热粘着剂330,使粘着剂330转变为粘着层340,接着,进行粘着步骤,使基板310与被加工物320通过粘着层340粘着接合,以形成接合结构300。图3B中,系将粘着剂330涂布于被加工物320的表面(未另标号),待要进行粘着步骤前再将被加工物320翻转,使粘着层340面向基板310以便形成接合结构300。图3C中,系将粘着剂330同时涂布于被加工物320的表面(未另标号)以及基板310的表面(未另标号),待要进行粘着步骤前再将被加工物320翻转,使被加工物320的粘着层340面向基板310的粘着层340以便形成接合结构300。关于图3B及图3C的其余细节可与图3A相同,在此不另赘述。
配合参照图4,其为图1中步骤110依照本发明另一实施方式的步骤流程图。图4中,步骤110包含步骤113以及步骤114。
步骤113是提供复合膜,所述复合膜包含可离型基材及粘着膜,粘着膜设置于可离型基材的表面,且粘着膜系将粘着剂涂布于可离型基材的所述表面并干燥后而得,复合膜中的粘着膜可被剥离。可离型基材包含但不限于聚对苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等的膜厚15~200μm的合成树脂薄膜。涂布方式包含但不限于旋转涂布、狭缝涂布、线棒涂布、丝网印刷等,前述干燥可以50℃至200℃进行1~60分钟,干燥主要目的是除去粘着剂中的部分或全部溶剂,因此,只要可达上述目的,可依据实际需求,如溶剂种类以及溶剂含量,适当调整干燥的温度与时间。
步骤114是进行转印步骤,使基板和/或被加工物的表面与复合膜的粘着膜接触并加热,以使粘着膜转印至基板和/或被加工物的表面并转变为粘着层。步骤114可以50℃至200℃的温度加热,并配合滚压或真空热压,使粘着膜转印至基板和/或被加工物的表面,移除可离型基材后,继续以50℃至200℃的温度加热约0.5小时至2小时以去除残存溶剂,并使粘着膜转变成粘着层,再进行粘着接合。步骤114中加热主要目的是使粘着膜软化,有利于进行转印。因此,只要可达上述目的,可依据实际需求,如溶剂种类、溶剂含量以及环化程度,适当调整加热的温度与时间。
同时配合参照图5,其为图4的步骤示意图。如图5所示,步骤113是提供一复合膜(未另标号),复合膜包含可离型基材550a及粘着膜550b,粘着膜550b系将粘着剂(图未绘示)涂布于可离型基材550a的表面(未另标号)并干燥后而得。之后,进行步骤114,使基板510的表面(未另标号)与复合膜的粘着膜550b接触并加热,以使粘着膜550b转印至基板510的表面,移除可离型基材550a后,继续加热以去除残存溶剂,并使粘着膜550b转变为粘着层540,之后进行粘着步骤,使基板510与被加工物520通过粘着层540粘着接合,以形成接合结构500。图5中,系将粘着膜550b转印在基板510上,然而,本发明并不以此为限,实务中,可改成将粘着膜550b转印在被加工物520上,或者,可改成将粘着膜550b同时转印在基板510上与被加工物520上,再进行粘着步骤。另外,图5中,基板510与被加工物520的数量、形状及尺寸皆仅为例示,本发明并不以此为限。
配合参照图6A及图6B,图6A是依照本发明一实施方式的一种接合结构600a的侧视图,图6B是依照本发明另一实施方式的一种接合结构600b的侧视图。图6A中,接合结构600a包含一个基板610a、二个被加工物620a,且基板610a与被加工物620a通过粘着层640a粘着接合,在本实施方式中,基板610a与被加工物620a的数量为一对多的关系。图6B中,接合结构600b包含二个基板610b、一个被加工物620b,且基板610b与被加工物620b通过粘着层640b粘着接合,在本实施方式中,基板610b与被加工物620b的数量为多对一的关系。
由图3A至图3C中、图5、图6A及图6B可知,本发明中,基板与被加工物的数量关系可为一对一、一对多或多对一,另外,图3A至图3C中、图5、图6A及图6B中,基板与被加工物的数量、形状及尺寸皆仅为例示,本发明并不以此为限。
配合参照图7,其是依照本发明另一实施方式的一种暂时粘着被加工物的方法700的步骤流程图。在图7中,暂时粘着被加工物的方法700包含步骤710、步骤720、步骤730、步骤740及步骤750。
步骤710是进行结合步骤,步骤720是进行粘着步骤,步骤730是进行加工步骤,步骤740是进行剥离步骤。关于步骤710至740可参照图1中步骤110至步骤140的相关说明,在此不另赘述。
步骤750进行溶解步骤,系在进行剥离步骤后,以清洗溶剂将残留在被加工物上的粘着层溶解移除。清洗溶剂的溶解度参数(Solubility Parameter,简称SP)可为9.6至12.8。藉此,有利于将经激光照射后的粘着剂溶解移除。可使用的溶剂可为但不限于二乙基甲酰胺(N,N-diethyl formamide,DEF;SP值9.6)、环己酮(cyclohexanone;SP值9.6)、N-甲基吡咯烷酮(N-methyl pyrrolidinone,NMP;SP值11.2)或γ-丁内酯(gamma-butyllactone,GBL;SP值12.8)。
<聚合物的制备方法>
依据本发明的粘着剂中的聚合物为(酰胺酸/酰亚胺)共聚物或聚酰亚胺,聚合物可以二胺与二酸酐作为反应物,在有机溶剂中进行聚缩反应,根据反应量多寡而调整,于25℃至50℃的温度进行8至12小时搅拌,以得到包含聚酰胺酸的反应溶液。上述包含聚酰胺酸的反应溶液可利用热环化或化学环化(添加吡啶、醋酸酐等方式)进行脱水闭环反应。举例来说,可通过添加甲苯利用共沸除水进行热环化反应,依据本发明一实施例,添加甲苯并于120℃至150℃的温度进行3至6小时进行回流脱水闭环反应,以得到包含酰胺酸/酰亚胺共聚物或聚酰亚胺的反应溶液,其中(酰胺酸/酰亚胺)共聚物的环化率为90%以上。最后,将上述(酰胺酸/酰亚胺)共聚物或聚酰亚胺反应溶液蒸馏出甲苯、并以减压蒸馏或添加溶剂方式调整固含量,即可得到(酰胺酸/酰亚胺)共聚物溶液或聚酰亚胺溶液。
前述二胺与二酸酐的比例关系,以二酸酐的酸酐基含量为1当量,二胺的胺基为0.5~2当量为佳,0.7~1.5当量为更佳。前述二胺和/或二酸酐可包含羟基单元,且可包含含脂肪醚单元和/或含硅氧烷单元,藉此,使所生成的聚合物的骨架包含5wt%至45wt%的含羟基单元,并包含5wt%至40wt%的含脂肪醚单元和/或含硅氧烷单元。另外,前述脱水闭环反应为本领域技术人员的熟知技术,在此不赘述。
前述有机溶剂系用来溶解反应物及产物,包含溶解度较佳的有机溶剂与溶解度较差的有机溶剂,溶解度较佳的有机溶剂包含但不限于:N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基己内酰胺、二甲基亚砜、四甲基尿素、六甲基磷酰胺、γ-丁内酯、吡啶。溶解度较差的有机溶剂包含但不限于:甲醇、乙醇、异丙醇、正丁醇、环己醇、乙二醇、乙二醇甲基醚、乙二醇单乙基醚、乙二醇单丁基醚、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、环己酮、乙酸甲酯、乙酸乙酯、四氢呋喃、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。以上有机溶剂可单独使用,亦可混合两种以上同时使用。由于有机溶剂系用来溶解反应物及产物,因此,举凡可溶解反应物及产物的有机溶剂皆可使用,并不以上述为限。
<粘着剂的制备方法>
依据本发明的粘着剂包含聚合物、遮色材及溶剂,且可选择性地包含添加剂。
将聚合物溶液、遮色材与溶剂混合,并选择性地加入添加剂混合均匀,即可形成粘着剂。制备粘着剂的温度可为室温至200℃。粘着剂可根据粘度与挥发性调整其所包含的固成分的含量(以下亦可简称为固含量),粘着剂可包含10wt%至60wt%的固含量。此外,以固成分为100wt%,前述聚合物于固成分中的含量为50wt%至98wt%,遮色材在固成分中的含量为2wt%至50wt%。
可用于粘着剂的溶剂可为有机溶剂,所述有机溶剂可包含但不限于N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基己内酰胺、二甲基亚砜、γ-丁内酯、γ-丁内酰胺、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单正丙基醚、乙二醇单丁基醚等,前述溶剂可二种以上混合使用,此外,举凡可溶解聚合物的溶剂或二种以上混合的溶剂皆可作为此处的溶剂。
可用于粘着剂的添加剂包含但不限于交联剂、有机硅(氧)烷化合物或环氧化合物。
<评估方法>
转印性:在温度120℃及压力1kgf/cm2贴合后,表面平整无缺陷表示好,表面大于或等于90%贴合表示尚可,表面小于90%贴合表示差。
固含量30wt%的溶解度:粘着剂外观澄清透明表示好,外观略雾表示尚可,外观明显析出表示差。
200℃的热压接着性:室温粘着力大于、等于10N/cm2表示好,室温粘着力小于10N/cm2表示差。
260℃的溢胶情形:观察接合结构的溢胶情形,有溢胶情形纪录为有,无溢胶情形纪录为无。
激光剥离性:以激光照射粘着层,直到发生剥离,以累积激光功率为大于、等于2W及小于5W表示好,以累积激光功率大于、等于5W及小于8W表示尚可,以累积激光功率大于8W表示差。
可清洗性:进行激光离型后,以清洗溶剂清洗被加工元件,若清洗时间小于或等于10分钟表示好,若清洗时间大于10分钟且小于或等于30分钟表示尚可,若清洗时间大于30分钟表示差。
<实施例/比较例>
实施例/比较例中所使用的二胺如表一所示。表一中,二胺(a-3)的商品名称为PAM-E,购买自信越化学股份有限公司(Shin-Etsu Chemical Co.,Ltd.),其粘度(25℃)为4mm2/s,比重(25℃)为0.9,官能基当量(functional group equivalent weight,FGEW)为130g/mol,R2与n2依照商品规格。二胺(a-4)的商品名称为JEFFAMINE-D400,购买自亨斯迈公司(Huntsman Corporation),其平均分子重约为430,m3依照商品规格。
实施例/比较例中所使用的二酸酐如表二所示。表二中,二酸酐(b-3)的商品名称为X22-168AS,购买自信越化学股份有限公司,其粘度(25℃)为160mm2/s,比重(25℃)为1.03,FGEW为500g/mol,R3与n3依照商品规格。
实施例/比较例中所使用的遮色材为碳黑,系购买自达兴材料,商品名称为PK-127,平均粒径为120nm。
将二胺及二酸酐依照表三所示的比例,依序添加于溶剂中,制备固含量为20wt%的(酰胺酸/酰亚胺)共聚物溶液或聚酰亚胺溶液。具体来说,将二胺及二酸酐依照表三所示的比例,于有机溶剂中进行聚缩反应,根据反应量多寡而调整,在25℃至50℃的温度进行8至12小时搅拌,以得到包含聚酰胺酸的反应溶液。将上述包含聚酰胺酸的反应溶液添加甲苯并于120℃至150℃的温度进行3至6小时进行回流脱水闭环反应,以得到包含酰胺酸/酰亚胺共聚物或聚酰亚胺的反应溶液,其中(酰胺酸/酰亚胺)共聚物的环化率为90%以上。最后,将上述(酰胺酸/酰亚胺)共聚物或聚酰亚胺反应溶液蒸馏出甲苯、并以减压蒸馏或添加溶剂方式调整固含量,即可得到固含量为20wt%的(酰胺酸/酰亚胺)共聚物溶液或聚酰亚胺溶液。
再依据表三所示的有机溶剂种类及遮色材含量(表三中遮色材含量为遮色材占粘着剂的固成分的重量百分比),制备粘着剂,粘着剂的固含量为30wt%。将粘着剂涂布于基板的表面以形成粘着层,再将被加工物放置在设置有粘着层的基板上进行粘着得到实施例/比较例的接合结构,或将本发明的粘着剂涂布于可离基材形成包含粘着膜的复合膜后,进行转印步骤,即以50℃至200℃温度加热粘着膜使其转印至基板,待除去可离型基材后继续以50℃至200℃温度加热0.5至2小时去除残存溶剂以得到设置有粘着层的基板,再将被加工物放置在设置有粘着层的基板上进行粘着,得到实施例/比较例的接合结构。
对实施例/比较例进行转印性、固含量30wt%的溶解度、200℃的热压接着性、260℃的溢胶情形、激光剥离性、可清洗性等评估,各实施例/比较例所使用的激光波长以及评估结果如表四所示。
由表四可知,依据本发明的暂时粘着被加工物的方法,转印性皆为好或尚可,固含量30wt%的溶解度皆为好,200℃的热压接着性皆为好或尚可,260℃的溢胶情形皆为无,激光剥离性皆为好或尚可,可清洗性皆为好,显示依据本发明的粘着剂,其具有优良的粘着性、耐热性及可移除性,有利于暂时接着/剥离技术的应用。
虽然本发明已以实施方式揭露如上,然其并非用以限定本发明,任何本领域技术人员在不脱离本发明的精神和范围内,应可作各种更动与润饰,因此本发明的保护范围应视所附权利要求书所界定的范围为准。
Claims (17)
1.一种暂时粘着被加工物的方法,包含:
进行结合步骤,在至少一个基板和/或至少一个被加工物的表面形成粘着层;
进行粘着步骤,使该基板与该被加工物通过该粘着层粘着接合;
进行加工步骤,对该被加工物进行加工;以及
进行剥离步骤,以激光照射该粘着层,使该被加工物与该基板分离;
其中,该粘着层由粘着剂所形成,该粘着剂包含聚合物以及遮色材,该粘着剂的固成分中包含50重量百分比至98重量百分比的该聚合物,该粘着剂的固成分中包含2重量百分比至50重量百分比的该遮色材,该聚合物为聚酰亚胺或(酰胺酸/酰亚胺)共聚物,该聚合物的骨架包含5重量百分比至45重量百分比的含羟基单元,该聚合物的骨架还包含5重量百分比至40重量百分比的含脂肪醚单元或含硅氧烷单元,且该聚合物的环化率为90百分比以上。
2.如权利要求1所述的暂时粘着被加工物的方法,其中该结合步骤包含:
进行涂布步骤,将该粘着剂涂布于该基板和/或该被加工物的该表面;以及
进行加热步骤,加热该粘着剂,使该粘着剂转变为该粘着层。
3.如权利要求1所述的暂时粘着被加工物的方法,其中该结合步骤包含:
提供复合膜,该复合膜包含可离型基材及粘着膜,该粘着膜设置于该可离型基材的一表面,且该粘着膜是将该粘着剂涂布于该可离型基材的该表面并干燥后而得;以及
进行转印步骤,使该基板和/或该被加工物的该表面与该复合膜的该粘着膜接触并加热,以使该粘着膜转印至该基板和/或该被加工物的该表面并转变为该粘着层。
4.如权利要求1所述的暂时粘着被加工物的方法,还包含进行溶解步骤,在进行该剥离步骤后,以清洗溶剂将残留在该被加工物上的该粘着层溶解移除。
5.如权利要求4所述的暂时粘着被加工物的方法,其中该清洗溶剂的溶解度参数为9.6至12.8。
6.如权利要求1所述的暂时粘着被加工物的方法,其中该被加工物为晶片、晶圆或半导体制造的微装置。
7.如权利要求1所述的暂时粘着被加工物的方法,其中该含脂肪醚单元为聚脂肪醚单元。
8.如权利要求1所述的暂时粘着被加工物的方法,其中该含硅氧烷单元为聚硅氧烷单元。
9.如权利要求1所述的暂时粘着被加工物的方法,其中该遮色材为碳黑、钛黑、氧化铁、钛氮化物、有机颜料或染料。
10.一种粘着剂,包含:
聚合物,该粘着剂的固成分中包含50重量百分比至98重量百分比的该聚合物,该聚合物为聚酰亚胺或(酰胺酸/酰亚胺)共聚物,该聚合物的骨架包含5重量百分比至45重量百分比的含羟基单元,该聚合物的骨架还包含5重量百分比至40重量百分比的含脂肪醚单元或含硅氧烷单元,且该聚合物的环化率为90百分比以上;以及
遮色材,该粘着剂的固成分中包含2重量百分比至50重量百分比的该遮色材。
11.如权利要求10所述的粘着剂,其中该含羟基单元具有式(I-1)、式(I-2)、式(I-3)、式(I-4)或是(I-5)所示的结构:
式(I-1)及式(I-5)中,X各自独立为单键或二价有机基。
12.如权利要求11所述的粘着剂,其中该X各自独立为单键、C1~C4亚烷基、-CO-、-COO-、-O-、-SO2-或C(CF3)2。
13.如权利要求10所述的粘着剂,其中该含脂肪醚单元为聚脂肪醚单元。
14.如权利要求13所述的粘着剂,其中该聚脂肪醚单元包含式(II-1)或式(II-2)所示的片段:
其中,m1为1至22的整数,m2为1至22的整数。
15.如权利要求10所述的粘着剂,其中该含硅氧烷单元为聚硅氧烷单元。
16.如权利要求15所述的粘着剂,其中该聚硅氧烷单元包含式(III-1)所示的片段:
其中R1各自独立为甲基或苯基,n1为0至5的整数。
17.如权利要求10所述的粘着剂,其中该遮色材为碳黑、钛黑、氧化铁、钛氮化物、有机颜料、或染料。
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