CN112341985B - 暂时粘着组合物、暂时粘着膜、复合膜、及其使用方法 - Google Patents
暂时粘着组合物、暂时粘着膜、复合膜、及其使用方法 Download PDFInfo
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- CN112341985B CN112341985B CN201911028870.9A CN201911028870A CN112341985B CN 112341985 B CN112341985 B CN 112341985B CN 201911028870 A CN201911028870 A CN 201911028870A CN 112341985 B CN112341985 B CN 112341985B
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Abstract
本发明提供一种暂时粘着组合物,其包含多官能交联剂、聚合物以及溶剂。多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧亚甲基的官能基的化合物,且各封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基。聚合物具有能与多官能交联剂反应的官能基。藉此,本发明的暂时粘着组合物通过不同成分及配方,使其可同时具备优良的热压性以及耐溶剂性的功效,有利于暂时接着/剥离技术,并可应用于半导体晶圆封装上。
Description
【技术领域】
本发明涉及一种暂时粘着组合物、暂时粘着膜、复合膜、暂时粘着被加工物的方法以及半导体晶圆封装,特别是有关于一种具有良好热压性以及耐溶剂性的暂时粘着组合物、暂时粘着膜、复合膜及使用其的暂时粘着被加工物的方法与半导体晶圆封装。
【背景技术】
随着半导体装置的薄型化,暂时粘着/剥离技术成为近年来发展重要技术之一。一般而言,被加工物(例如晶圆)需利用暂时粘着剂将其与支撑基板接合,而得以对被加工物进行后续加工处理,待加工完毕后,再将暂时粘着剂移除而使被加工物与支撑基板分离。
然而,在现有的暂时粘着技术中,粘着层在压合过程中主要是以粘着特性为主,因此在涂布厚膜时,如旋转涂布、线棒涂布等,会造成厚边现象,进而无法在高变形量下达成无溢流,以及无法将30~40μm的厚边高低差做压平并同时兼顾耐化学性,另外在厚膜压合时会因压合载具的变形及弯曲性不足造成边缘会有未压合区。
藉此,如何改良暂时粘着组合物的配方以及搭配合适的剥离方法,使暂时粘着组合物可同时具备优良的热压性以及耐溶剂性的功效,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组合物、一种暂时粘着膜及使用其的复合膜,藉由不同成分及配方使其同时具有优良的热压性以及耐溶剂性的功效。
本发明的另一目的是提供一种暂时粘着被加工物的方法,藉由暂时粘着组合物,有利于应用在半导体晶圆封装制程。
本发明的一实施方式提供一种暂时粘着组合物,其包含多官能交联剂、聚合物以及溶剂。其中,前述多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧亚甲基的官能基的化合物,且各封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基。前述聚合物具有能与多官能交联剂反应的官能基。
依据前述实施方式的暂时粘着组合物,其中聚合物可为包含羟基、羧基或胺基中至少一种官能基的聚酰胺酸、聚酰亚胺、聚苯并噁唑、其共聚物或混合物。
依据前述实施方式的暂时粘着组合物,其中多官能交联剂可包含含有至少两个封端型异氰酸酯基的化合物、含有至少两个烯基醚基的化合物及含有至少两个烃氧亚甲基的化合物中的至少一种。
依据前述实施方式的暂时粘着组合物,其中各封端型异氰酸酯基可在90℃至200℃的温度范围下加热使封端剂解离。
依据前述实施方式的暂时粘着组合物,其中前述含有至少两个封端型异氰酸酯基的化合物可具有如式(I)所示的结构:
其中n1为2以上的整数,R1为含有经取代或未经取代的亚烷基、脂环基、芳香环基、异氰酸酯二聚体或异氰酸酯三聚体的有机基,R2各自独立为封端剂的残基。前述含有至少两个烯基醚基的化合物可具有式(II)所示的结构:
R4-(O-CH=CH2) 式(II),
其中R4为含有经取代或未经取代的亚烷基、脂环族或芳香环的有机基,n2为2以上的整数。前述含有至少两个烃氧亚甲基的化合物可具有如式(III)、式(IV)或式(V)所示的结构:
其中R5、R7、R8以及R10各自独立为含有烷基、脂环族或芳香环的有机基或氢,R6、R9以及R11为含有芳香环或杂环的有机基,n3、n4以及n5各自独立为2以上的整数。
依据前述实施方式的暂时粘着组合物,可还包含遮色材,其中遮色材可为有机颜料、无机颜料或染料。
依据前述实施方式的暂时粘着组合物,其中无机颜料可为碳黑、钛黑、氧化钛、氧化铁、钛氮化物或硅灰。
本发明的另一实施方式提供一种暂时粘着膜,其包含多官能交联剂、聚合物以及遮色材。其中,前述多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧亚甲基的官能基的化合物,且各封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基。前述聚合物具有能与多官能交联剂反应的官能基。
依据前述实施方式的暂时粘着膜,其中暂时粘着膜的玻璃化转换温度(Tg)可小于200℃。
本发明的又一实施方式提供一种复合膜,其包含可离型支撑膜以及前段所述的暂时粘着膜。其中暂时粘着膜设置于可离型支撑膜的表面。
本发明的再一实施方式提供一种暂时粘着被加工物的方法,其包含进行结合步骤、进行粘着步骤、进行第二加热步骤、进行加工步骤、进行剥离步骤。其中,前述结合步骤在至少一个基板及/或至少一个被加工物的表面形成粘着层。前述粘着步骤系使基板与被加工物藉由粘着层粘着接合。前述第二加热步骤系对基板与被加工物进行加热。前述加工步骤系对被加工物进行加工。前述剥离步骤系以激光照射粘着层,使被加工物与基板分离。其中粘着层系由前段所述的暂时粘着组合物所形成。
依据前述实施方式的暂时粘着被加工物的方法,其中第二加热步骤的温度范围可为90℃℃℃至200℃。
依据前述实施方式的暂时粘着被加工物的方法,其中结合步骤可包含进行涂布步骤以及第一加热步骤。前述涂布步骤系将暂时粘着组合物涂布于基板及/或被加工物的表面。前述第一加热步骤系加热暂时粘着组合物,使暂时粘着组合物转变为粘着层。
依据前述实施方式的暂时粘着被加工物的方法,其中结合步骤可包含提供前段所述的复合膜以及进行转印步骤。前述转印步骤系使基板及/或被加工物的表面与复合膜的暂时粘着膜接触并加热,以使暂时粘着膜转印至基板及/或被加工物的表面并转变为粘着层。
依据前述实施方式的暂时粘着被加工物的方法,可还包含进行溶解步骤,其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。
依据前述实施方式的暂时粘着被加工物的方法,其中被加工物可为芯片、晶圆或半导体制造的微装置。
本发明的另一实施方式提供一种半导体晶圆封装,其包含前段所述的暂时粘着组合物。
藉此,本发明的暂时粘着组合物通过不同成分及配方,使其可同时具备优良的热压性以及耐溶剂性的功效,有利于暂时接着/剥离技术,并可应用于半导体晶圆封装上。
【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为绘示依照本发明的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为绘示依照图1实施方式中步骤110的步骤流程图;
图3A为绘示依照图1实施方式中步骤110及步骤120的步骤示意图;
图3B为绘示依照图1实施方式中步骤110及步骤120的另一步骤示意图;
图3C为绘示依照图1实施方式中步骤110及步骤120的又一步骤示意图;
图4为绘示依照图1实施方式中步骤110的另一步骤流程图;
图5为绘示依照图4实施方式的步骤示意图;
图6A为绘示依照本发明的一实施方式的一种接合结构的侧视图;
图6B为绘示依照本发明的另一实施方式的一种接合结构的侧视图;以及
图7为绘示依照本发明的另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。
【附图标记说明】
100:暂时粘着被加工物的方法
110、120、130、140、150: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:暂时粘着组合物
340、540、640a、640b:粘着层
550a:可离型支撑膜
550b:暂时粘着膜
700:暂时粘着被加工物的方法
710、720、730、740、750、760:步骤
【具体实施方式】
下述将更详细讨论本发明各实施方式。然而,此实施方式可为各种发明概念的应用,可被具体实行在各种不同的特定范围内。特定的实施方式是仅以说明为目的,且不受限于公开的范围。
<暂时粘着组合物>
本发明的暂时粘着组合物包含多官能交联剂、聚合物以及溶剂,优选地,本发明的暂时粘着组合物可还包含遮色材。以下,将对上述各种组分进行详细说明。
<多官能交联剂>
在本实施方式中,多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧基亚甲基的官能基的化合物,优选地,本发明的多官能交联剂可包含含有至少两个封端型异氰酸酯基的化合物,含有至少两个烯基醚基的化合物及含有至少两个烃氧亚甲基的化合物中的至少一种,其中各封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基。以暂时粘着组合物的总重量计,多官能交联剂的添加量可为0.5重量百分比至20重量百分比,优选可为0.8重量百分比至15重量百分比,更优选可为2重量百分比至10重量百分比。
依据前述的含有至少两个封端型异氰酸酯基的化合物,其可具有如式(I)所示的结构:
其中n1为2以上的整数,R1为含有经取代或未经取代的亚烷基、脂环基、芳香环基、异氰酸酯二聚体或异氰酸酯三聚体的有机基,前述“经取代”意为有机基中的任意原子可被其他异种原子所取代;举例而言,前述经取代的烷基可为任意-CH2-被氧原子、-CH=CH-或-C≡C-取代,例如包含醚基的有机基;前述经取代的芳香环基中任意碳原子可为但不限于N原子取代,R2各自独立为封端剂的残基。
前述封端剂可为但不限于醇类、酚类、吡啶类、肟类、硫醇类、苯硫酚类、酰胺类、环酰胺类、酰亚胺类、咪唑啉类、咪唑类、三唑类、脒类、异羟肟酸酯类、吡唑类、胺类、甲酸盐类、活性亚甲基类、脲素类或二酮类。优选地,封端剂可为但不限于丁醇、乙醇、异丙醇、苯酚、甲基苯酚、乙基苯酚、环己醇、丁基溶纤剂、2-丁基苯酚、2-羟基吡啶、丁酮肟、环己酮肟、丙酮肟、乙醛肟、1-十二烷基硫醇、五氟苯硫酚、苯硫酚、乙酰苯胺、甲基乙酰苯胺、己内酰胺、丁内酰胺、戊内酰胺、马来酰亚胺、琥珀酰亚胺、2-苯基咪唑、咪唑、2-甲基咪唑、2-苯基咪唑、三氮唑、苯并三氮唑、3,5-二甲基吡唑、3-甲基吡唑、2-甲基-4-乙基-5-甲基吡唑、二异丙胺、苯胺、丙二酸乙酯、丙二酸二甲酯、乙酰乙酸乙酯、乙酰乙酸甲酯、丙二酸二乙酯、苯基脲或硫脲。另外,视半导体晶圆封装制程温度而定,其封端剂优选选择可在90℃℃℃至200℃℃的温度范围下加热使解离的结构,例如,己内酰胺类、丁酮肟类或丙二酸乙酯类等。
另外,前述式(I)的化合物经过加热后,会产生具有异氰酸酯基的可进行交联反应的结构,并与树脂反应,其可为但不限于结构如式(i-1)、式(i-2)、式(i-3)、式(i-4)、式(i-5)、式(i-6)、式(i-7)以及式(i-8)任一者所示的官能基,其中R3为含有经取代或未经取代的烷基、烯基、炔基、脂环族或芳香族的二价有机基:
依据前述的含有至少两个烯基醚基的化合物,其可具有如式(II)所示的结构:
其中R4为含有经取代或未经取代的亚烷基、脂环族或芳香环的有机基,前述“经取代”意为有机基中的任意原子可被其他异种原子所取代;举例而言,前述经取代的烷基可为任意-CH2-被氧原子、-CH=CH-或-C≡C-取代,例如包含醚基的有机基;前述经取代的芳香环基中任意碳原子可为但不限于N原子取代,n2为2以上的整数。式(II)的化合物具体可为但不限于结构如式(II-1)、式(II-2)、式(II-3)以及式(II-4)任一者所示的化合物,其中x为1以上的整数:
依据前述的含有至少两个烃氧亚甲基的化合物,其可具有如式(III)、式(IV)以及式(V)所示的结构:
其中R5、R7、R8以及R10各自独立为含有烷基、脂环族或芳香环的有机基或氢,优选为含烷基的有机基,R6、R9以及R11为含有芳香环或杂环的有机基,n3、n4以及n5各自独立为2以上的整数。式(III)的化合物具体可为但不限于结构如式(III-1)、式(III-2)、式(III-3)、式(III-4)以及式(III-5)任一者所示的化合物:
式(IV)的化合物具体可为但不限于结构如式(IV-1)、式(IV-2)以及式(IV-3)任一者所示的化合物:
式(V)的化合物具体可为但不限于结构如式(V-1)所示的化合物:
<聚合物>
在本实施方式中,聚合物具有能与多官能交联剂反应的官能基。详细的说,聚合物可为包含羟基、羧基或胺基中至少一种官能基的聚酰胺酸、聚酰亚胺、聚苯并噁唑(polybenzoxazole,PBO)、其共聚物或混合物。以暂时粘着组合物的总重量计,聚合物的添加量可为5重量百分比至60重量百分比,优选可为10重量百分比至55重量百分比,更优选可为10重量百分比至52重量百分比。
<溶剂>
在本实施方式中,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,N-二乙基甲酰胺、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。以暂时粘着组合物的总重量计,溶剂的添加量可为5重量百分比至95重量百分比,优选为20重量百分比至80重量百分比。
<遮色材>
在本实施方式中,视暂时接着材料离型时使用的光源波长范围,可视情况添加遮色材,在本发明材料中添加遮色材可扩大离型时可使用的光源的波长范围,前述的遮色材可为有机颜料、无机颜料或染料,而其中无机颜料优选地可为碳黑、钛黑、氧化钛、氧化铁、钛氮化物或硅灰。以暂时粘着组合物的总重量计,遮色材的添加量可为0重量百分比至30重量百分比,优选可为0.5重量百分比至25重量百分比。
<暂时粘着膜&复合膜>
本发明所公开的暂时粘着膜的一实施方式包含多官能交联剂、聚合物以及遮色材,其中关于多官能交联剂、聚合物以及遮色材可参照前文,在此不另赘述。另外,本发明的暂时粘着膜的玻璃化转换温度(Tg)可小于200℃。
本发明的复合膜包含可离型支撑膜以及暂时粘着膜,暂时粘着膜设置于可离型支撑膜的表面。详细来说,暂时粘着膜为多官能交联剂、聚合物、遮色材以及溶剂混合后涂布于可离型支撑膜的表面,并加热去除部分或全部溶剂后而得,且复合膜中的暂时粘着膜可被剥离。
前述可离型支撑膜可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。另外,前述涂布方式可包含但不限于旋转涂布、狭缝涂布、线棒涂布、网版印刷等。
<暂时粘着被加工物的方法>
请参照图1,其绘示依照本发明的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。暂时粘着被加工物的方法100包含步骤110、步骤120、步骤130、步骤140以及步骤150。
步骤110为进行结合步骤,系在至少一个基板及/或至少一个被加工物的表面形成粘着层,详细来说,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和被加工物的表面。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非方法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。
前述粘着层系由暂时粘着组合物所形成,关于暂时粘着组合物可参照前文,在此不另赘述。前述被加工物可为但不限于芯片、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晶体管、光学传感器、逻辑芯片、合格晶元(KnownGood Die,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。
步骤120为进行粘着步骤,系使基板与被加工物藉由粘着层粘着接合,为方便说明,以下将基板与被加工物藉由粘着层粘着接合所形成的结构称为接合结构。详细来说,步骤120可藉由热压实现,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为进行第二加热步骤,系对基板与被加工物进行加热,其中第二加热步骤的温度范围可为90℃至200℃,以进行交联固化反应,或可依据实际需求,如多官能交联剂的官能基的选择,适当调整第二加热步骤的温度与时间。
步骤140为进行加工步骤,系对被加工物进行加工,其中加工方式可包含但不限于镀铜、蚀刻、抛光、贴饰或印刷。
步骤150为进行剥离步骤,系以激光照射粘着层,使被加工物与基板分离。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(染料激光)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(二极管泵浦固体激光,Diode Pump Solid State Laser,DPSSL)、自由电子激光等。
藉此,通过本发明的暂时粘着组合物,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,并可轻易地将暂时粘着组合物从被加工物上移除干净。另外,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,藉由支撑基板提供晶圆于加工过程中所需支撑力,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。
请参照图2,其绘示依照图1实施方式中步骤110的步骤流程图。图2中,步骤110可包含步骤111以及步骤112。
步骤111为进行涂布步骤,系将暂时粘着组合物涂布于基板及/或被加工物的表面。涂布方式可包含但不限于旋转涂布、狭缝涂布、线棒涂布、网版印刷(丝网印刷)等。
步骤112为进行第一加热步骤,系加热暂时粘着组合物,使暂时粘着组合物转变为粘着层。步骤112可在50℃至200℃的温度下进行0.5小时至2小时,其主要目的为除去暂时粘着组合物中部分或全部溶剂,并可依据实际需求,如溶剂种类或溶剂含量,适当调整步骤112的温度与时间。
请参照图3A、图3B及图3C,其中图3A绘示依照图1实施方式中步骤110及步骤120的步骤示意图,图3B绘示依照图1实施方式中步骤110及步骤120的另一步骤示意图,图3C绘示依照图1实施方式中步骤110及步骤120的又一步骤示意图。如图3A所示,步骤110包含步骤111以及步骤112,进行步骤111时,可将暂时粘着组合物330涂布于基板310的表面(未另标号)。之后,进行步骤112,系加热暂时粘着组合物330,使暂时粘着组合物330转变为粘着层340,接着进行步骤120,使基板310与被加工物320藉由粘着层340粘着接合,以形成接合结构300。或者,如图3B所示,可将暂时粘着组合物330涂布于被加工物320的表面(未另标示),待要进行步骤120前再将被加工物320翻面,使暂时粘着组合物330面向基板310以便形成接合结构300。或者,如图3C所示,可将暂时粘着组合物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),待要进行步骤120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。
请参照图4,其绘示依照图1实施方式中步骤110另一步骤流程图。图4中,步骤110可包含步骤113以及步骤114。
步骤113为提供复合膜,关于复合膜可参照前文,在此不另赘述。
步骤114为进行转印步骤,系使基板及/或被加工物的表面与复合膜的暂时粘着膜接触并加热,以使暂时粘着膜转印至基板及/或被加工物的表面并转变为粘着层。详细来说,步骤114可以50℃至200℃的温度加热,并配合滚压或真空热压,使暂时粘着膜转印至基板及/或被加工物的表面,移除可离型支撑膜后,继续以50℃至200℃的温度加热约0.5小时至2小时,使暂时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暂时粘着膜软化,有利于进行转印,因此,藉由调整玻璃化转换温度可增加后续的转印效果。
请参照图5,其绘示依照图4实施方式的步骤示意图。如图5所示,步骤113是提供复合膜(未另标号),复合膜包含可离型支撑膜550a及暂时粘着膜550b,暂时粘着膜550b系将多官能交联剂、聚合物、遮色材以及溶剂混合后,涂布于可离型支撑膜550a的表面(未另标号),并加热去除部分或全部溶剂而得。之后,进行步骤114,系使基板510的表面(未另标号)与复合膜的暂时粘着膜550b接触并加热,以使暂时粘着膜550b转印至基板510的表面,移除可离型支撑膜550a后,继续加热使暂时粘着膜550b转变为粘着层540,并去除剩余溶剂,之后进行粘着步骤,使基板510与被加工物520藉由粘着层540粘着接合,以形成接合结构500。图5中,系将暂时粘着膜550b转印在基板510上,然而,本发明并不以此为限,实践中,可改成将暂时粘着膜550b转印在被加工物520上,或者,可改成将暂时粘着膜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。
请参照图6A以及图6B,其中图6A绘示依照本发明的一实施方式的一种接合结构600a的侧视图,图6B绘示依照本发明的另一实施方式的一种接合结构600b的侧视图。如图6A所示,接合结构600a包含一基板610a、二被加工物620a,且基板610a与被加工物620a藉由粘着层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。另外,如图6B所示,接合结构600b包含二基板610b、一被加工物620b,且基板610b与被加工物620b藉由粘着层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,在本发明中,基板与被加工物的数量关系可为一对一、一对多或多对一关系,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。
请参照图7,其绘示依照本发明的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。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、步骤750以及步骤760。
步骤710为进行结合步骤、步骤720为进行粘着步骤,步骤730为进行第二加热步骤,步骤740为进行加工步骤,步骤750为进行剥离步骤。关于步骤710至750可参照图1中步骤110至步骤150的相关说明,在此不另赘述。
步骤760为进行溶解步骤,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。前述清洗溶剂可为但不限于N,N-二乙基甲酰胺(N,N-diethylformamide,DEF)、环己酮(cyclohexanone)、N-甲基吡咯烷酮(N-methyl pyrrolidinone,NMP)或γ-丁内酯(gamma-butyl lactone,GBL)。然而,为了选择对环境或人体危害较小的溶剂,本发明的清洗溶剂优选地以N,N-二乙基甲酰胺为主溶剂。
<聚合物的制备方法>
本发明所公开的聚合物的一实施方式可以二胺与二酸酐作为反应物,在有机溶剂中进行聚缩合反应,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在120℃至150℃的温度持续3至6小时进行回流脱水死循环反应,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)共聚物为部分环化的聚酰胺酸,其中环化率可达70%以上,优选为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有机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。
前述有机溶剂用来溶解反应物及产物,包含溶解度较大的有机溶剂与溶解度较小的有机溶剂,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,亦可混合二种以上同时使用。由于有机溶剂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。
<半导体晶圆封装>
本发明的半导体晶圆封装包含前述的暂时粘着组合物。关于暂时粘着组合物请参照上文,在此不另赘述,关于半导体晶圆封装的结构与制造方法为常规方法,在此不另赘述。
<评估方法>
热压性:在2Kg/cm2下,将暂时粘着组合物与基板及/或被加工物的表面进行压合,并判断压合后的贴合面比例。贴合面大于95%表示优,贴合面在95%~75%之间表示佳,贴合面在75%~50%之间表示尚可,贴合面小于50%表示差。
固烤后耐溶剂性:将暂时粘着组合物经由加热固烤成膜后,浸泡于70℃溶剂中(AP7880T,购买于品化科技),并判断其膜损程度。膜损小于10%表示优,膜损于10%~20%之间表示佳,膜损于20%~40%之间表示尚可,膜损大于40%表示差。
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。
<合成例>
合成例中所使用的二胺如表一所示。表一中,二胺(A-1)的商品名称为BisAPAF,二胺(A-2)的商品名称为JEFFAMINE-D400,y依照商品规格。
合成例中所使用的二酸酐如表二所示。表二中,二酸酐(B-1)的商品名称为BPADA。
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,在有机溶剂中进行聚缩合反应,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℃的温度持续3至6小时进行回流脱水死循环反应,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有机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。
<实施例/比较例>
实施例/比较例中所使用的多官能交联剂如表四所示。表四中,多官能交联剂(a-1)、(a-2)以及(a-3)为异氰酸酯基搭配不同封端剂所形成的含有至少两个封端型异氰酸酯基的化合物,多官能交联剂(b-1)以及(b-2)为含有至少两个烯基醚基的化合物,多官能交联剂(c-1)以及(c-2)为含有至少两个烃氧亚甲基的化合物。另外,多官能交联剂(d-1)为环氧化合物的热交联剂,而多官能交联剂(d-2)则是非封端型异氰酸酯。
实施例/比较例中所使用的遮色材为碳黑,购买自达兴材料,商品名称为PK-127,平均粒径为120nm。
将聚合物、多官能交联剂、溶剂以及遮色材依照表五所示的种类与比例来制备实施例/比较例的暂时粘着组合物。
对实施例/比较例的接合结构进行热压性、固烤后耐溶剂性、激光剥离性等评估,各实施例/比较例所使用的激光波长以及评估结果如表六所示。
由表五及表六可知,比较例1的聚合物不含OH官能基,其导致比较例1的固烤后耐溶剂性差,另外,比较例2至比较例4的多官能交联剂与实施例1至实施例10不同,其中比较例2未添加本发明的多官能交联剂,比较例3的多官能交联剂具有环氧基结构,比较例4的多官能交联剂为非封端型异氰酸酯,可看出未添加本发明的多官能交联剂以及使用非本发明的多官能交联剂,皆无法同时具有优良的热压性及耐溶剂性。因此,依据本发明的实施例1至实施例10的暂时粘着组合物,热压性皆为优、佳或尚可,固烤后耐溶剂性皆为优或佳,激光剥离性皆为优或佳,显示本发明的暂时粘着组合物,其同时具有优良的热压性以及耐溶剂性,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公开如上,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 (12)
1.一种暂时粘着被加工物的方法,包含:
进行结合步骤,系在至少一个基板及/或至少一个被加工物的表面形成粘着层;
进行粘着步骤,系使该基板与该被加工物藉由该粘着层粘着接合;
进行第二加热步骤,系对该基板与该被加工物进行加热;
进行加工步骤,系对该被加工物进行加工;以及
进行剥离步骤,系以激光照射该粘着层,使该被加工物与该基板分离;
其中,该粘着层由暂时粘着组合物所形成,该暂时粘着组合物包含:
多官能交联剂,该多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧亚甲基的官能基的化合物,其中各该封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基;
聚合物,该聚合物具有能与该多官能交联剂反应的官能基,其中该聚合物为包含羟基、羧基或胺基中至少一种官能基的聚酰胺酸、聚酰亚胺、聚苯并噁唑、其共聚物或混合物;以及
溶剂。
2.如权利要求1所述的暂时粘着被加工物的方法,其中该第二加热步骤的温度范围为90℃至200℃。
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:
进行涂布步骤,系将该暂时粘着组合物涂布于该基板及/或该被加工物的该表面;以及
进行第一加热步骤,系加热该暂时粘着组合物,使该暂时粘着组合物转变为该粘着层。
4.如权利要求1所述的暂时粘着被加工物的方法,其中该结合步骤包含:
提供复合膜,该复合膜包含可离型支撑膜和暂时粘着膜,其中该暂时粘着膜设置于该可离型支撑膜的表面,其中该暂时粘着膜包含:
多官能交联剂,该多官能交联剂包含含有至少两个选自封端型异氰酸酯基、烯基醚基和烃氧亚甲基的官能基的化合物,其中各该封端型异氰酸酯基为具有被封端剂保护的异氰酸酯基;
聚合物,该聚合物具有能与该多官能交联剂反应的官能基;及
遮色材;以及
进行转印步骤,系使该基板及/或该被加工物的该表面与该复合膜的该暂时粘着膜接触并加热,以使该暂时粘着膜转印至该基板及/或该被加工物的该表面并转变为该粘着层。
5.如权利要求1所述的暂时粘着被加工物的方法,含包含进行溶解步骤,系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。
6.如权利要求1所述的暂时粘着被加工物的方法,其中该被加工物为芯片、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,其中该聚合物为包含羟基、羧基或胺基中至少一种官能基的聚酰胺酸、其共聚物或混合物。
8.如权利要求1所述的暂时粘着被加工物的方法,其中该多官能交联剂包含含有至少两个封端型异氰酸酯基的化合物、含有至少两个烯基醚基的化合物及含有至少两个烃氧亚甲基的化合物中的至少一种。
9.如权利要求1所述的暂时粘着被加工物的方法,其中各该封端型异氰酸酯基在90℃至200℃的温度范围下加热使该封端剂解离。
10.如权利要求8所述的暂时粘着被加工物的方法,其中该含有至少两个封端型异氰酸酯基的化合物具有如式(I)所示的结构:
其中n1为2以上的整数,R1为含有经取代或未经取代的亚烷基、脂环基、芳香环基、异氰酸酯二聚体或异氰酸酯三聚体的有机基,R2各自独立为该封端剂的残基;
其中该含有至少两个烯基醚基的化合物具有式(II)所示的结构:
其中R4为含有经取代或未经取代的亚烷基、脂环族或芳香环的有机基,n2为2以上的整数;
其中该含有至少两个烃氧亚甲基的化合物具有如式(III)、式(IV)或式(V)所示的结构:
其中R5、R7、R8以及R10各自独立为含有烷基、脂环族或芳香环的有机基或氢,R6、R9以及R11为含有芳香环或杂环的有机基,n3、n4以及n5各自独立为2以上的整数。
11.如权利要求1所述的暂时粘着被加工物的方法,还包含遮色材,其中该遮色材为有机颜料、无机颜料或染料。
12.如权利要求11所述的暂时粘着被加工物的方法,其中该无机颜料为碳黑、钛黑、氧化钛、氧化铁、钛氮化物或硅灰。
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