CN100421220C - 晶片加工用带 - Google Patents
晶片加工用带 Download PDFInfo
- Publication number
- CN100421220C CN100421220C CNB2005800015699A CN200580001569A CN100421220C CN 100421220 C CN100421220 C CN 100421220C CN B2005800015699 A CNB2005800015699 A CN B2005800015699A CN 200580001569 A CN200580001569 A CN 200580001569A CN 100421220 C CN100421220 C CN 100421220C
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- China
- Prior art keywords
- tape
- adhesive phase
- resin layer
- wafer
- middle resin
- Prior art date
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Abstract
一种晶片加工用带(10),其具有依次层压于基体膜(1)之上的中间树脂层(2)、可去除粘合剂层(3)、和如果必要时的粘合剂层(4),其中中间树脂层80℃时的储存弹性模量大于可去除粘合剂层80℃时的储存弹性模量。
Description
技术领域
本发明涉及一种晶片加工用带(wafer-processing tape),其可以用于在制备半导体器件如硅晶片中加工晶片。
背景技术
半导体器件如IC等的组装过程(assembly process)包括步骤:在形成图案之后,将半导体晶片等切分(切割)成单个芯片;将芯片装配在基体等之上;并以树脂等将它们密封。
在切割步骤(dicing step)中,预先将半导体晶片粘接和随后固定到切割管芯键合带(dicing die-bond tape)上,并随后将其切割成芯片形状。在随后的装配步骤中,由于粘合剂层和可去除的粘合剂层被设计成使得它们能够彼此相互剥离,因此可以从可去除的粘合剂层(removable adhesivelayer)上将粘结粘合剂的切割芯片剥离(拾取(pickup)),并随后例如通过用于粘结和固定的粘合剂,固定到基体上,所述粘合剂已粘结到芯片上。
用于上述目的的切割管芯键合带,包括通过将膜状粘合剂施加到切割带表面并将二者一体化而制备的带;和具有形成为一层的可去除粘合剂层与粘合剂层的带。这两种类型带需要具备足够的临时粘合强度,以使得晶片在切割时候不被从带上剥离,并且它们也需要具备在拾取时容易被剥离的剥离能力。
此外,在装配步骤中,在芯片之间或芯片与基体之间需要足够的粘合强度。已经提出了多种切割管芯键合带。
这些可去除的粘结带能够进行所谓的直接管芯键合(direct diebonding),用于在切割之后,拾取具有已粘结在芯片后侧的粘合剂层的芯片,在基体等上装配芯片,和通过加热等固化(硬化)并粘结芯片。通过这些可去除的粘结带,可以避免粘合剂的涂覆过程。
但是,用于这些切割管芯键合片材的膜状粘合剂含有大量的低分子量材料,例如环氧树脂,并且倾向于比通常切割带的可去除粘合剂层更软,且机械加工性(切割性能)差。因此带来的问题是:在切割时出现许多膜状粘合剂的须状碎片(屑(swarf))和毛刺(burr);在切割之后的拾取步骤中容易引起差的拾取;并且在半导体器件(如IC)装配过程中容易引起差的芯片粘结和例如IC的缺陷。
从以下的描述,以及结合附图,本发明的其它和进一步特征和优点将变得更充分。
附图说明
图1为显示其中半导体晶片和切割框被粘结于本发明的切割管芯键合带状态的示意性截面图。
图2为显示其中半导体晶片和切割框被粘结于本发明另一实施方式的切割管芯键合带状态的示意性截面图。
发明内容
本发明提供了以下方面:
(1)一种晶片加工用带,包括依次层压于基体膜之上的中间树脂层和可去除粘合剂层,其中中间树脂层80℃时的储存弹性模量大于可去除粘合剂层80℃时的储存弹性模量;
(2)一种晶片加工用带,包括依次层压于基体膜之上的中间树脂层、可去除粘合剂层和粘合剂层,其中中间树脂层80℃时的储存弹性模量大于可去除粘合剂层80℃时的储存弹性模量;
(3)根据上述项目(1)或(2)的晶片加工用带,其中中间树脂层80℃时的储存弹性模量范围为8×104~1×107Pa;
(4)根据上述项目(1)-(3)之一的晶片加工用带,其中中间树脂层25℃时的储存弹性模量范围为8×104~1×107Pa;
(5)根据上述项目(1)-(4)之一的晶片加工用带,其中中间树脂层由具有三维网络结构的丙烯酸树脂构成;
(6)根据上述项目(1)-(5)之一的晶片加工用带,其中中间树脂层由热固化树脂构成;
(7)根据上述项目(1)-(6)之一的晶片加工用带,其中中间树脂层是通过将至少包括丙烯酸树脂和硬化剂的混合物施加到基体膜,然后固化制备的;
(8)根据上述项目(1)-(7)之一的晶片加工用带,其中可去除粘合剂层含有:化合物(A),其分子中具有碘值为0.5~20的辐射可固化碳碳双键;和化合物(B),其为选自聚异氰酸酯、三聚氰胺甲醛树脂和环氧树脂中的至少一种;和
(9)根据上述项目(2)-(7)之一的晶片加工用带,所述晶片加工用带用于半导体器件制造中的键合过程(bonding process),所述键合过程包括:粘附晶片;将晶片粘附到切割框,同时切割晶片;和将切割的晶片装配到引线框或半导体芯片之上,
其中所述晶片加工用带包括依次层压于基体膜之上的中间树脂层和可去除粘合剂层,并且进一步包括粘合剂层,该粘合剂层至少层压于晶片待粘附的部分之上,并且切割框待粘附的部分不提供粘合剂层。
本文中,术语“可去除的粘合剂”表示为能够粘附并且在处理如固化之后可以被去除的试剂,并且术语“粘合剂”表示为只能够粘附的试剂。例如,术语“辐射固化可去除的粘合剂”表示为在将可去除的粘合剂施加到晶片等之后,能够通过辐射源如UV照射硬化而去除或剥离的粘合剂。
此外,术语“粘合剂层”表示为下述层,当装配半导体晶片等并切割,然后拾取芯片时,其可以从可去除粘合剂层上剥离并且保持粘附于芯片;并且当将芯片装备和固定到基体或引线框之上时,其可以用作粘合剂。
此外,术语“可去除的粘合剂层”表示为下述层,其对粘合剂层待粘结对象的剥离力低于对粘合剂层的剥离力,并且可以用于临时性粘结。
此外,术语“剥离力”表示将粘附表面剥离开所需的力,并且可以根据JIS Z0237中规定的方法来确定。
本发明的晶片加工用带可以应用于半导体晶片,例如硅晶片,当晶片被切割时候其被用作切割带,并且在晶片被切割时其在减少须状碎片等方面显示有益效果,且能获得良好切割性能。此外,作为切割管芯键合带,本发明确保了半导体元件和粘合剂层可以在拾取晶片芯片时容易地从可去除粘合剂层上剥离,从而提供了半导体元件的直接管芯键合。
发明实施方式
根据本发明,可以提供一种用于加工晶片的晶片加工用带,所述带为切割带,用于粘附和固定晶片等,以用于切割,并且所述带在切割时具有优良的切割性能。特别地,根据本发明,可以提供一种切割管芯键合带,其为半导体晶片切割管芯键合带,可以用于切割后将切割产品装配到引线框或半导体芯片上的粘结过程,并且其具有优良的切割性能。
以下将更详细地描述本发明。
本发明人进行了深入的研究,以解决常规技术中存在的上述问题。结果,我们发现,在基体膜(substrate film)与可去除粘合剂层之间提供中间树脂层。特别地,我们发现,通过使用在切割温度下具有比可去除粘合剂层更大的储存弹性模量的材料作为中间层,可以改进切割时的机械加工性。
在下文中将解释根据本发明的实施方式。
图1为显示其中半导体晶片11和切割环形框(dicing ring frame)12被粘结于本发明的切割管芯键合带10上的状态的示意性截面图。
本发明的切割管芯键合带(10)结构具有下述结构:中间树脂层2、可去除粘合剂层3和粘合剂层4形成在基体膜1之上。根据工作过程和装置,每层可以预先切割(预切割)成特定形状。切割管芯键合带或切割带可以在晶片等被粘附到其之上前,提供保护膜,以保护粘合剂层或可去除粘合剂层。
本发明的切割管芯键合带或切割带可以切割成单个晶片大小的块,或者可以是长筒状的(lengthy roll form)。
下面,将逐一地解释本发明的切割管芯键合带或切割带的每个结构。
(基体膜)
将解释构成本发明切割管芯键合带或切割带的基体膜。作为基体膜,可以使用任意的塑料或橡胶,并且无特别限定。通常使用热塑性塑料膜作为基体膜。基体膜材料优选具有透辐射性(radiation transmittance),并且特别是在可去除粘合剂层中使用辐射固化可去除粘合剂时,优选选择一种在可去除粘合剂被固化时的波长下具有高透辐射性的材料。
可以选择作为基体的聚合物实例包括α-烯烃的均聚物或共聚物,如聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚丁烯-1、聚4-甲基戊烯-1、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物,和这些化合物的离聚物或混合物;工程塑料,如聚对苯二甲酸乙二醇酯、聚碳酸酯、和聚(甲基丙烯酸甲酯);热塑性弹性体,如聚氨酯、苯乙烯-乙烯-丁烯或戊烯类共聚物、和聚酰胺-多元醇共聚物、和这些化合物的混合物。此外,可以使用由这些化合物制备多层而获得的材料。
同时,为了增加元件之间的间隙,优选颈缩(necking)(当基体膜放射状地伸展时,由于力的较差传播而产生的局部伸长)尽可能小的膜材料。所述材料的实例包括聚氨酯、和特定分子量与苯乙烯含量的苯乙烯-乙烯-丁烯或戊烯类共聚物。使用交联基体膜,有效地阻止了切割过程中的伸长或偏转(deflection)。
此外,可以任意处理其侧之上形成有中间树脂层的基体膜的表面,例如通过进行电晕放电处理、或通过形成底剂层(primer layer),以改进与中间树脂层的粘结性。
出于对强拉伸性能和透辐射性的考虑,基体膜厚度通常为30~300μm。可以对其表面之上未施加可去除粘合剂层的基体膜表面进行压花或表面涂覆润滑剂处理,由此防止当可去除粘结带放射状地伸展时被堵塞,并降低可去除粘结带与夹具之间的摩擦力,这有效地阻止了基体膜颈缩,因此是优选的。
(中间树脂层)
可以使用任意材料用于构成本发明切割带或切割管芯键合带的中间树脂层,对其无特别限定,只要其较可去除粘合剂膜更硬。中间树脂层的储存弹性模量优选范围为8×104~1×107Pa,更优选为1×105~5×106Pa,从而抑制切割过程中芯片的破裂和碎裂(chipping)。此外,中间树脂层25℃时的储存弹性模量优选范围为8×104~1×107Pa,更优选为1×105~1×106Pa。
可以通过将含可去除粘合剂组分和固化组分的混合物施加到基体膜表面,并随后进行固化,从而制备中间树脂层。对于中间树脂层,优选使用下述材料,当将该材料于室温下静置约1周时,其逐渐固化得到落在优选范围内的弹性模量。
制备较硬中间树脂层的方法的实例包括但是并不限于,增加用作主要组分(通常来说,其添加量为总量的60~98质量%)的可去除粘合剂组分的玻璃化转变温度(Tg)的方法;增加添加于中间树脂层的硬化剂的量的方法,添加无机化合物填料的方法。此外,可以使用通过辐射源照射固化的材料,并且通过辐射源照射来固化,以控制中间树脂层的硬度。本文中,术语“辐射源”表示光的总称,包括紫外线、激光、和电离辐射,如电子束(下文中被称作辐射源)。
作为可去除的粘合剂组分,可以使用各种常用的可去除粘合剂,如丙烯酸型、聚酯型、氨基甲酸酯型、硅树脂型或天然橡胶型。本发明中,特别优选力丙烯酸型可去除粘合剂。丙烯酸型可去除粘合剂的实例包括由(甲基)丙烯酸酯单体和由(甲基)丙烯酸衍生物衍生的结构单元所构成的(甲基)丙烯酸酯共聚物。本文中,作为(甲基)丙烯酸酯单体,可以使用(甲基)丙烯酸环烷酯、(甲基)丙烯酸苯甲酯、或(甲基)丙烯酸烷基酯(其中烷基具有1~18碳原子)。此外,(甲基)丙烯酸衍生物的实例可以包括具有缩水甘油基的(甲基)丙烯酸缩水甘油酯、和具有羟基的丙烯酸羟乙酯。
作为硬化剂,可以使用选自聚异氰酸酯、三聚氰胺甲醛树脂和环氧树脂的化合物,其可以单独使用,或者两种或更多组合使用。该硬化剂起到交联剂的作用;并且由硬化剂与可去除粘合剂组分(如丙烯酸树脂)的反应获得的交联结构,产生了中间树脂层的三维网络结构,这在由于切割等导致温度上升时能抗软化。
聚异氰酸酯的实例包括但是并不特别限于,芳族异氰酸酯,如4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、4,4’-二苯基醚二异氰酸酯和4,4’-[2,2-二(4-苯氧基苯基)丙烷]二异氰酸酯;六亚甲基二异氰酸酯,2,2,4-三甲基-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、2,4’-二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯、和赖氨酸三异氰酸酯。特别地,可以使用商业化的产品,如Coronate L(商标)等。
此外,作为三聚氰胺甲醛树脂,例如可以使用商业化的产品,如Nikarack MX-45(商标,由Sanwa Chemical Co.,Ltd.生产)、或Melan(商标,由Hitachi Chemical Co.,Ltd.生产)。
作为环氧树脂,例如可以使用TETRAD-X(商标,由MitsubishiChemical Co.,Ltd.生产)。
特别地,在本发明中优选使用聚异氰酸酯。
此外,可以使得中间树脂层具有辐射固化性,以在切割之后通过采用辐射固化来固化和收缩中间树脂层而改进芯片拾取特性。
使得中间树脂层具备辐射固化性的方法实例包括,添加具有可光聚合碳碳双键的丙烯酸酯型低聚物的方法。此外,作为上述低聚物,例如,可以广泛地使用分子中每个具有至少两个可光聚合碳碳双键的任意低分子量化合物,其可以通过光辐射显示三维网络。更特别地,例如,可以广泛地使用三羟甲基丙烷三丙烯酸酯、四羟甲基甲烷四丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇单羟基五丙烯酸酯、二季戊四醇六丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、和丙烯酸酯低聚物。
与上述丙烯酸酯类化合物一样,也可以使用聚氨酯丙烯酸酯类低聚物。聚氨酯丙烯酸酯类低聚物可以通过如下获得:将可以通过多元醇化合物(如聚酯型或聚醚型)和聚异氰酸酯化合物(例如2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二亚甲基二异氰酸酯、1,4-苯二亚甲基二异氰酸酯、二苯基甲烷-4,4-二异氰酸酯)反应获得的异氰酸酯封端的尿烷预聚物,与具有羟基的甲基丙烯酸酯或丙烯酸酯(例如丙烯酸2-羟乙酯、甲基丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、甲基丙烯酸2-羟丙酯、聚乙二醇丙烯酸酯、聚乙二醇甲基丙烯酸酯)反应。
当通过辐射聚合中间树脂层时,也可以一起使用光聚合引发剂,例如异丙基苯偶姻醚、异丁基苯偶姻醚、二苯甲酮、米蚩酮(Michler’sketone)、氯代噻吨酮、苯甲基甲基缩酮、α-羟基环己基苯基酮、或2-羟基甲基苯基丙烷。通过将这些化合物中的至少一种添加到中间树脂层中,可以有效地进行聚合反应。
可根据需要,向中间树脂层中,混入临时粘结赋予试剂(temporaryadhesion imparting agent)、临时粘结调节剂、表面活性剂、和其它改性剂。
中间树脂层厚度优选为至少5μm,更优选10μm或更大。中间树脂层可以具有其中层压多层的结构。
被施加到基体之上并随后进行固化的中间树脂层,可以由热固化树脂构成,以阻止所述层即使在接近切割温度的温度下突然被软化,由此带来良好的切割性能。
(可去除粘合剂层)
如上所述,在基体膜之上形成中间树脂层之后,进一步在中间树脂层之上形成可去除粘合剂层,以制备本发明的切割带。
对于形成可去除粘结带,采用通用切割带情形下的相同方式,将可去除粘合剂施加到形成于基体膜之上的中间树脂层表面,以制备可去除粘合剂层。可以在施加中间树脂层之后任意时刻施加可去除粘合剂。如果通过辐射源照射来控制中间树脂层的储存弹性模量,那么优选在辐射固化中间树脂层之后施加可去除粘合剂层。
可以使用任意材料作为构成本发明切割带或切割管芯键合带的可去除粘合剂层,对其无特别限定,只要其保持能力达到阻止切割过程中产生缺陷(例如,可去除粘合剂层与粘合剂层之间的芯片突变)的程度,并且只要其具有可去除粘合剂层在拾取时容易从粘合剂层剥离的特性。为了改进切割之后的拾取特性,可去除粘合剂层优选为辐射可固化类型,并且在切割管芯键合带情形下,特别优选为由容易从粘合剂层上剥离的材料构成。
例如,在本发明中,优选使用丙烯酸型可去除粘合剂,其包括:化合物(A),其分子中具有碘值为0.5~20的辐射可固化碳碳双键;和化合物(B),其为选自聚异氰酸酯、三聚氰胺甲醛树脂、和环氧树脂中的至少一种。
下面将解释化合物(A),其为可去除粘合剂层的主要组分之一。引入化合物(A)中的辐射可固化碳碳双键含量,以碘值表示,优选为0.5~20,更优选为0.8~10。当碘值为0.5或更大时,可以获得辐射源照射之后减小临时粘结强度的效果。当碘值为20或更小时,在通过辐射源照射之后可去除粘合剂的流动性是令人满意的,并且因此能在拉伸之后获得足够的元件间隙,使得能够抑制面对在拾取时每个元件图像识别变得困难的问题的情形。此外,化合物(A)自身具有稳定性,使得制备容易化。
前述化合物(A)的玻璃化转变温度优选为-70℃~0℃,更优选为-66℃~-28℃。当玻璃化转变温度(下文中称为Tg)为-70℃或更高时,能获得对于辐射源照射产生的热量具有足够的耐热性。当玻璃化转变温度为0℃或更低时,能够令人满意地获得在具有粗糙表面情形的晶片中切割之后阻止元件被分散的效果。
虽然对于如何制备上述化合物(A)并无特别限定,但是作为化合物(A),可以使用例如通过如下获得的化合物:将具有辐射可固化碳碳双键和官能团的化合物((1))(例如,丙烯酸型共聚物或甲基丙烯酸型共聚物)与化合物((2))反应,所述化合物((2))具有能与上述官能团反应的官能团。
在这些化合物之中,可以使用如下获得的具有辐射可固化碳碳双键和官能团的上述化合物((1)):将具有辐射可固化碳碳双键的单体((1)-1)(例如,丙烯酸烷基酯或甲基丙烯酸烷基酯),与具有官能团的单体((1)-2)共聚。
作为单体((1)-1),包括:例如丙烯酸己酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸2-乙基己酯、丙烯酸十二烷基酯、丙烯酸癸酯,每个具有6-12个碳原子;或具有5个或更少碳原子的单体,如丙烯酸戊酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸乙酯、和丙烯酸甲酯,或类似这些的甲基丙烯酸酯。
在单体((1)-1)情形下,随着单体碳原子数目增加,玻璃化转变温度变低,因此能够制备具有所期望玻璃化转变温度的化合物。此外,除了玻璃化转变温度之外,为了提高相容性和各种性能,可以混入具有碳碳双键的低分子量化合物,如乙酸乙烯酯、苯乙烯和丙烯腈,其范围占单体((1)-1)总质量的5质量%或更低。
单体((1)-2)所具有的官能团实例包括:羧基、羟基、氨基、环状酸酐基团、环氧基、和异氰酸基。单体((1)-2)的具体实例包括:丙烯酸、甲基丙烯酸、肉桂酸、衣康酸、富马酸、邻苯二甲酸、丙烯酸2-羟基烷基酯、甲基丙烯酸2-羟基烷基酯、乙二醇单丙烯酸酯、乙二醇单甲基丙烯酸酯、N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、烯丙醇、丙烯酸N-烷基氨基乙酯、甲基丙烯酸N-烷基氨基乙酯、丙烯酰胺、甲基丙烯酰胺、马来酸酐、富马酸酐、衣康酸酐、邻苯二甲酸酐、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、烯丙基缩水甘油醚、和聚异氰酸酯化合物,其中异氰酸基与具有羟基或羧基和辐射可固化碳碳双键的单体部分氨基甲酸酯化(urethanated)。
化合物(2)中,作为使用的官能团,在化合物(1)即单体((1)-2)中官能团为羧基或环状酸酐基团情形时,包括羟基、环氧基、异氰酸基等;或者在化合物(1)中官能团为羟基情形时,包括环状酸酐基团、异氰酸基等;在化合物(1)中官能团为氨基情形时,包括环氧基、异氰酸基等;在化合物(1)中官能团为环氧基情形时,包括羧基、环状酸酐基团、氨基等。化合物(2)中官能团的具体实例包括与在单体((1)-2)中作为具体实例所示相同的那些。
具有优选如本发明中所定义的特性例如酸值或羟基值的化合物,可以通过在化合物(1)和化合物(2)之间的反应中保留未反应的官能团来制备。
在上述化合物(A)的合成中,当通过溶液聚合来进行共聚反应时,可以使用酮类、酯类、醇类、或芳香类溶剂作为有机溶剂。其中,优选溶剂为丙烯酸类聚合物的常用良溶剂,其溶剂沸点为60~120℃。优选溶剂实例包括:甲苯、乙酸乙酯、异丙醇、苯甲基溶纤剂、乙基溶纤剂、丙酮、甲乙酮等。作为聚合引发剂,通常可以使用产生自由基的试剂:偶氮类,如α,α’-偶氮二异丁睛;和有机过氧化物类,如过氧化苯甲酰。此时,如果需要,可以任选地加入催化剂、阻聚剂等。这样,通过控制聚合温度和聚合时间,可以获得具有所期望分子量的化合物(A)。对于分子量的控制,优选使用硫醇类或四氯化碳类溶剂。此外,共聚并不限定于溶液聚合,但是其也可以以其它方式如本体聚合、悬浮聚合等来进行。
如上所述,可以获得化合物(A)。在本发明中,化合物(A)分子量优选为约300,000~约1,000,000。如果分子量太小,由辐射源照射产生的内聚力较少,这样在切割晶片时候,容易发生元件(芯片)的错位,并且图像识别可能困难。此外,为了尽可能阻止元件的错位(misalignment),优选分子量为400,000或更大。如果分子量过大,在合成和涂覆时可能存在凝胶化。
当化合物(A)具有羟基值为5~100的OH基团时,这可以降低辐射源照射之后的临时粘结强度,由此进一步降低拾取失败的风险,其为优选的。此外,化合物(A)优选具有酸值为0.5~30的COOH基团。
同时,如果化合物(A)羟基值过低,则辐射源照射之后的临时粘结强度不能足够地被降低;或者如果羟基值过高,辐射源照射之后可去除粘合剂的流动性倾向于被破坏。此外,如果酸值过低,不能足够地改进带恢复性能,或者如果过高,可去除粘合剂的流动性倾向于被破坏。
基于Das方法,在反应条件为40℃和24小时下,计算碘值。通过使用将试样溶解于四氢呋喃中获得的1%溶液,采用凝胶渗透色谱法(商标:150-C ALC/GPC,由Waters Company制造)测量的值,计算相对于苯乙烯的重均分子量。此外,根据FT-IR方法,计算羟基值;以及根据JISK 5407 11-1计算酸值。
其次,将解释化合物(B),其为可去除粘合剂层的另一主要组分。化合物(B)为选自聚异氰酸酯、三聚氰胺甲醛树脂、和环氧树脂的化合物,其可以单独使用,或两种或多种组合使用。化合物(B)起到交联剂的作用;并且由于化合物(B)与化合物(A)或基体膜反应而形成的交联结构,可以在施加可去除粘合剂之后,改进使用化合物(A)和(B)作为主要组分的可去除粘合剂的内聚力。
聚异氰酸酯实例包括,但是并不特别限于:芳族异氰酸酯,如4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、4,4’-二苯基醚二异氰酸酯和4,4’-[2,2-二(4-苯氧基苯基)丙烷]二异氰酸酯;六亚甲基二异氰酸酯,2,2,4-三甲基-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、2,4’-二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯、和赖氨酸三异氰酸酯。特别地,可以使用商业化的产品,如Coronate L等。
此外,作为三聚氰胺甲醛树脂,例如可以使用商业化的产品,如Nikarack MX-45(由Sanwa Chemical Co.,Ltd.生产)、或Melan(由HitachiChemical Co.,Ltd.生产)。
作为环氧树脂,例如可以使用TETRAD-X(由Mitsubishi ChemicalCo.,Ltd.生产)。
本发明中,特别地,优选使用聚异氰酸酯。
相对于100重量份化合物(A),化合物(B)的添加量优选为0.1~10重量份,更优选为0.4~3重量份。如果用量太少,改进内聚力的效果倾向于不充分;并且如果用量太大,操作性倾向于被损害,这是因为共混可去除粘合剂和涂覆操作时,固化反应进行迅速,导致形成交联结构。
此外,在本发明中,可去除粘合剂层优选含有光聚合引发剂(C)。对于可去除粘合剂层中所含有的光聚合引发剂(C)而言,并无特别限定,并且可以使用通常公知的那些。光聚合引发剂(C)实例包括:二苯甲酮类,如二苯甲酮、4,4’-二甲基氨基二苯甲酮、4,4’-二乙基氨基二苯甲酮、和4,4’-二氯二苯甲酮;苯乙酮类,如苯乙酮、和二乙氧基苯乙酮;蒽醌类,如2-乙基蒽醌、和叔丁基蒽醌;2-氯噻吨酮、苯偶姻乙基醚、苯偶姻异丁基醚、苄基、2,4,5-三芳基咪唑二聚物(洛粉碱二聚物)、和吖啶型化合物。这些化合物可以单独使用,或者两种或多种组合使用。
相对于100重量份化合物(A),化合物(C)的添加量优选为0.1~10重量份,更优选为0.5~5重量份。
根据需要,在本发明中可以使用的辐射固化可去除粘合剂,可以与临时粘结赋予试剂、临时粘结调节剂、表面活性剂、和其它改性剂混合。此外,可以任意添加无机化合物填料。
可去除粘合剂层厚度优选为至少5μm,更优选为10μm或更大。从阻止在芯片表面或基体上出现(大量)须状碎片来考虑,中间树脂层和可去除粘合剂层的总厚度优选为15μm或更大,且50μm或更小。可去除粘合剂层可以具有其中层压多层的结构。
可去除粘合剂80℃时的储存弹性模量优选范围为1×104~5×105Pa,更优选为2×104~5×104Pa。
(粘合剂层)
本发明的切割管芯键合带,具有以下结构:其中进一步将形成的粘合剂层层压在如上所述制备的切割带上。
此外,本文中,术语“粘合剂层”表示为下述层,当装配半导体晶片等并切割,然后拾取芯片时,其可以从可去除粘合剂层上剥离并且保持粘附于芯片;并且当将芯片装备和固定到基体或引线框之上时,其可以用作粘合剂。可以使用任意材料作为粘合剂层,并无特别限定,只要其为通常用于切割管芯键合带的膜状粘合剂。粘合剂优选为任意的丙烯酸类(可去除粘结或)粘合剂、和混合型(可去除粘结或)粘合剂,如环氧树脂/酚树脂/丙烯酸树脂。粘合剂层厚度优选为约5~100μm,但是其可以任意设定。
在本发明切割管芯键合带中,可以使用预先被制成薄膜形状的粘合剂层(下文中称为粘合剂膜)作为此粘合剂层;并且其可以通过层压在本发明切割带的可去除粘合剂层的表面上来形成,所述切割带在基体上提供有前述中间树脂层和可去除粘合剂层。层压优选在温度范围为10~100℃内,通过施加0.1~100kgf/cm的线压力来进行。在这种情形下,作为粘合剂膜,可以使用在隔离件(separator)上形成的膜,并且隔离件可以在层压之后被剥离,或者可供选择换地,其可以同作切割管芯键合带的覆盖膜(底膜(carrier film)),但是在装配晶片等时将其从带上剥离。此外,虽然可以在可去除粘合剂层整个表面上层压粘合剂膜,但是可以层压预先被切割(预切)成对应于待装配晶片的特定形状的粘合剂膜。当层压对应于晶片的粘合剂膜时,在使用本发明切割管芯键合带时,优选将粘合剂层施加到可去除粘合剂层上,使得粘合剂层存在于装配晶片的部分,而不存在于装配切割环框的部分。通常来说,粘合剂层避免从被装配的目标上剥离,并且容易在环框等上形成粘合剂残留物(即剥离之后残留和粘附的粘合剂)。使用预切的粘合剂膜,确保了环框可以粘附于可去除粘合剂层上,以显示当所使用的带被剥离时在环框(ring frame)上几乎不形成粘合剂残留物的效果。
根据下面给出的实施例,将更详细地描述本发明,但是本发明并不意味着限定于这些。“份数”含义为重量份。
实施例
实施例1~8,比较例1~4:
采用下列方式制备每个中间树脂层组合物、可去除粘合剂层组合物、和粘合剂膜。随后,在100μm厚的乙烯/乙酸乙烯酯共聚物膜(基体膜)上,施加中间树脂层组合物,使得随后在110℃下干燥3分钟之后,干燥膜厚度为如表1中所示值,并且然后在所获得的中间树脂层上,施加可去除粘合剂层组合物,使得随后在110℃下干燥3分钟之后,干燥膜厚度为如表1中所示值,由此分别制备可去除粘合带。分别将粘合剂膜施加到任何一个可去除粘合带上,使得粘结带层压于可去除粘合剂层之上,制得如表1中所示实施例1~8和比较例1~4的切割管芯键合带(晶片加工用带)。评价所获得带的下列特性。当使用该带时,从粘合剂膜上剥离底膜。
中间树脂层组合物制备
(中间树脂层组合物1A)
将100重量份丙烯酸树脂(重均分子量600,000,玻璃化转变温度-20℃)、和10重量份作为硬化剂的聚异氰酸酯化合物(商标:Coronate L,由Nippon Polyurethane Industry Co.,Ltd制造)混合,获得中间树脂层组合物1A。
(中间树脂层组合物1B)
将100重量份丙烯酸树脂(重均分子量600,000,玻璃化转变温度-20℃)、30重量份作为低聚物的丙烯酸酯型低聚物,其分子中具有碘值为0.5~20的可光聚合碳碳双键、1重量份作为光聚合引发剂的2,2-二甲氧基-2-苯基苯乙酮、和10重量份作为硬化剂的聚异氰酸酯化合物(商标:Coronate L,由Nippon Polyurethane Industry Co.,Ltd制造)混合,获得辐射可固化中间树脂层组合物1B。
(中间树脂层组合物1C)
将100重量份丙烯酸树脂(重均分子量800,000,玻璃化转变温度-7℃)、和10重量份作为硬化剂的聚异氰酸酯化合物(商标:Coronate L,由Nippon Polyurethane Industry Co.,Ltd制造)混合,获得辐射可固化中间树脂层组合物1C。
(中间树脂层组合物1D)
将100重量份丙烯酸树脂(重均分子量200,000,玻璃化转变温度-40℃)、100重量份作为低聚物的丙烯酸酯型低聚物,其分子中具有碘值为0.5~20的可光聚合碳碳双键、1重量份作为光聚合引发剂的2,2-二甲氧基-2-苯基苯乙酮、和1重量份作为硬化剂的聚异氰酸酯化合物(商标:Coronate L,由Nippon Polyurethane Industry Co.,Ltd制造)混合,获得辐射可固化中间树脂层组合物1D。
可去除粘合剂层组合物制备
(可去除粘合剂组合物2A)
往400g甲苯溶剂中,逐滴加入128g丙烯酸正丁酯、307g丙烯酸2-乙基己酯、67g甲基丙烯酸甲酯、1.5g甲基丙烯酸、和作为聚合引发剂的过氧化苯甲酰的混合物溶液,通过任意控制滴加量、控制反应温度和反应时间,反应该混合物,获得具有官能团的化合物(1)的溶液。
随后,往这样获得的聚合物溶液中,添加作为具有辐射可固化碳碳双键和官能团的化合物(2)的2.5g甲基丙烯酸2-羟乙酯(单独由甲基丙烯酸与乙二醇合成的),和作为阻聚剂的氢醌,适当控制滴加量;并且通过控制反应温度和反应时间来反应该混合物,获得具有可固化碳碳双键和具有如表1中所示碘值、分子量和玻璃化转变温度的化合物(A)的溶液。随后,往化合物(A)溶液中,相对于化合物(A)溶液中100重量份化合物(A),添加1重量份作为聚异氰酸酯(B)的Coronate L(商标,由NipponPolyurethane Industry Co.,Ltd制造)、0.5重量份作为聚合引发剂的Irgacure 184(商标,由Ciba-Geigy Corp.制造)、和150重量份作为溶剂的乙酸乙酯,将这些混合,由此制备辐射固化可去除粘合剂组合物2A。
(可去除粘合剂组合物2B)
将100重量份丙烯酸树脂(重均分子量600,000,玻璃化转变温度-20℃)、和10重量份作为硬化剂的聚异氰酸酯化合物(商标:Coronate L,由Nippon Polyurethane Industry Co.,Ltd制造)混合,获得可去除粘合剂组合物2B。
粘合剂膜制备
(粘合剂膜3A)
向作为环氧树脂的50重量份甲酚-线型酚醛环氧树脂(环氧当量197、分子量1,200、和软化点70℃)、作为硅烷偶联剂的1.5重量份γ-巯基丙基三甲氧基硅烷与3重量份γ-脲基丙基三乙氧基硅烷、和30重量份平均粒径16nm的硅石填料的组合物中,添加环己酮,随后搅拌混合,并且进一步使用球磨机捏合所获得的混合物90分钟。
向所获得的反应混合物中,添加100重量份丙烯酸树脂(重均分子量800,000,玻璃化转变温度-17℃)、5重量份作为六官能丙烯酸酯单体的二季戊四醇六丙烯酸酯、0.5重量份作为硬化剂的六亚甲基二异氰酸酯加合物、和2.5重量份Curesol 2PZ(商标,由Shikoku Kasei(K.K.)制造,2-苯基咪唑),并搅拌混合这些组分,随后在真空下脱气,获得粘合剂。
将所获得的粘合剂施加到25μm厚、已进行防粘处理(releasingtreatment)的聚对苯二甲酸乙二醇酯膜上,并随后在110℃下加热1分钟进行干燥,以形成膜厚度为40μm的涂覆膜,并置入B-阶状态(B-stagestate)下,由此制备提供有载体膜的粘合剂膜3A。
(粘合剂膜3B)
除了使用50重量份甲酚-线型酚醛环氧树脂(环氧当量197、分子量1,200、和软化点70℃)作为环氧树脂,和1重量份六亚甲基二异氰酸酯加合物作为硬化剂以外,采用在粘合剂膜3A制备中相同的方式来制备粘合剂膜3B。
(粘合剂膜3C)
除了使用0.5重量份六亚甲基二异氰酸酯加合物作为硬化剂、和使用2.5重量份Curesol 2PHZ(商标,由Shikoku Kasei(K.K.)制造,2-苯基-4,5-二羟基咪唑)代替Curesol 2PZ以外,采用在粘合剂膜3A制备中相同的方式来制备粘合剂膜3C。
性能评价
如表1中所示,制备实施例1~8和比较例1~4的切割管芯键合带,并且采用下列方式评价下列特性:中间树脂层在25℃和80℃时的弹性模量,可去除粘合剂层80℃时的弹性模量,芯片表面和基体上须状碎片数目,观察粘合剂是否有毛刺,侧面上碎裂(chipping)平均值(μm),和拾取成功率(%)。
(弹性模量)
采用下列方式测量中间树脂层和可去除粘合剂层在25℃或80℃时的弹性模量:利用粘弹性计(商标:ARES,由Reometric Science Company制造),从0℃开始测量,在5℃/分钟升温速率和1Hz频率的条件下,测量动态粘弹性,其中当温度到达25℃或80℃时的储存弹性模量G’被定义为每个弹性模量。
在这种情形下,对于将被测量的中间树脂层和可去除粘合剂层,使用制备之后静置14天而获得的那些。
(芯片表面须状碎片数目、和基体上须状碎片数目)
向实施例和比较例中所获得的任意切割管芯键合膜上,在70℃×10秒的加热条件下,粘结厚度为100μm和直径为200mm的硅晶片,随后使用切割机(商标:DAD340,由Disco Company制造),在旋转数为40,000rpm和切割速率为100mm/秒下,将其切割成尺寸为5mm×5mm的芯片。之后,对于在所获得硅晶片中心的100个芯片,通过显微镜观察来计算这些芯片表面上须状碎片数目,以确定芯片表面上须状碎片数目。此外,在晶片中心粘合剂已被转移到且粘结到其上的100个芯片被剥离之后,通过显微镜观察,计算对于在硅晶片中心部分上的100个芯片,所述带上须状碎片的数目,以确定基体上须状碎片数目。
(是否观察到粘合剂的毛刺)
向实施例和比较例中所获得的任意切割管芯键合膜上,在70℃×10秒的加热条件下,粘结厚度为100μm和直径为200mm的硅晶片,随后使用切割机(商标:DAD340,由Disco Company制造),在旋转数为40,000rpm和切割速率为100mm/秒下,将其切割成尺寸为5mm×5mm的芯片。随后,通过显微镜观察,对于在晶片中心管芯粘合剂已被转移到且粘结到其上的20个芯片侧面,考察是否观察到粘合剂的毛刺。
(侧面碎裂)
为了评价切割时的破裂和断裂(碎裂(chipping)),采用下列方式测量侧面上的碎裂。
向实施例和比较例中所获得的任意切割管芯键合膜上,在70℃×10秒的加热条件下,粘结厚度为100μm和直径为200mm的硅晶片,随后使用切割机(商标:DAD340,由Disco Company制造),在旋转数为40,000rpm和切割速率为100mm/秒下,将其切割成尺寸为5mm×5mm的芯片。在切割成尺寸为5mm×5mm的芯片之后,观察切割后硅晶片中心部分的50个芯片侧面上出现的碎裂尺寸,以确定平均值作为侧面碎裂值。此时,碎裂尺寸为从芯片边缘测量的尺寸。
(拾取成功率)
向实施例和比较例中所获得的任意切割管芯键合膜上,在70℃×10秒的加热条件下,粘结厚度为100μm的硅晶片,随后将其切割成尺寸为10mm×10mm的芯片。之后,使用来自空气冷却型高压汞灯(80W/cm,照明距离10cm)、强度为200mJ/cm2的紫外线,辐射可去除粘合剂层。随后,使用管芯键合测试仪(商标:CPS-100FM,由NEC Machinery制造),对50个晶片中心部分上的芯片进行拾取测试,以确定拾取成功率(%),基于每50个芯片中拾取的芯片的数目。此时,其中从可去除粘合剂层上剥离的粘合剂层由被拾取的元件支持的情形,被称作拾取成功,由此计算拾取成功率。
每个实施例和比较例中,中间树脂层在25℃和80℃时的弹性模量,可去除粘合剂层80℃时的弹性模量,芯片表面和基体上须状碎片数目,观察粘合剂是否有毛刺,侧面碎裂平均值(μm),和拾取成功率(%),全部描述于表1中。
在使用未提供中间树脂层的比较例1和2的带情形时,切割时出现粘合剂毛刺。在提供有薄的可去除粘合剂层的比较例1中,芯片表面和基体上须状碎片数目显著大于本发明的实施例中的数目。此外,在其中未形成中间树脂层且只有可去除粘合剂层厚度增加的比较例2中,侧面碎裂显著增加。此外,在对于中间树脂层使用比可去除粘合剂层更软材料的比较例3中,出现粘合剂毛刺,侧面碎裂显著增加,并且拾取成功率低。在对于可去除粘合剂层仅使用具有高弹性模量的硬质材料的比较例4中,虽然未观察到粘合剂毛刺,并且须状物或碎裂出现较少,但是不能拾取芯片。
不同于以上的是,在本发明的实施例1~8中,上述每个特性都优异。此外,使用实施例1~8中的任意切割管芯键合带切割晶片获得尺寸为5mm×5mm的IC芯片,使用管芯键合器将其直接装配到引线框上,随后在170℃下加热2小时,结果,证实引线框已经牢固地粘结于IC芯片。
(其它实施方式)
图2为显示其中半导体晶片(11)和切割环框(12)被粘结于本发明其它实施方式的切割管芯键合带状态的示意性截面图。与图1情形类似,管芯键合带具有下述结构:中间树脂层2、可去除粘合剂层3和粘合剂层4形成在基体膜1之上的结构。作为粘合剂层4,层压根据半导体晶片形状而预先预切成的层。将半导体晶片装配于其中存在粘合剂层的部分,而在其中粘附环框的部分上不存在粘合剂层,使得环框粘附于可去除粘合剂层。
在这种实施方式中,可将环框可以粘附于可去除粘合剂层,从而显示出的有益效果是,当所使用的带被剥离时,在环框上几乎不存在粘合剂残留物。
工业实用性
本发明晶片加工用带可以用作切割带,其在切割半导体晶片时确保了良好的切割性能。此外,本发明的晶片加工用带为切割管芯键合带时,其可以用作切割之后将芯片与粘合剂一起拾取的切割管芯键合带,并且可以直接装配于引线框或基体之上。
虽然已经通过这些实施方式对本发明进行了描述,但是除非特别说明,本发明不限定于该描述的任意细节,而应在如附属权利要求中陈述的精神和范围内更宽泛地解释。
Claims (15)
1. 一种晶片加工用带,其包括中间树脂层和可去除粘合剂层,所述中间树脂层和可去除粘合剂层层压于基体膜上,使得从上面开始依次为可去除粘合剂层、中间树脂层、基体膜,其中中间树脂层80℃时的储存弹性模量大于可去除粘合剂层80℃时的储存弹性模量。
2. 权利要求1的晶片加工用带,其中中间树脂层80℃时的储存弹性模量范围为8×104~1×107Pa。
3. 权利要求1的晶片加工用带,其中中间树脂层25℃时的储存弹性模量范围为8×104~1×107Pa。
4. 权利要求1的晶片加工用带,其中中间树脂层具有三维网络结构,并且由丙烯酸树脂和硬化剂构成。
5. 权利要求1的晶片加工用带,其中中间树脂层由热固化树脂构成。
6. 权利要求1的晶片加工用带,其中中间树脂层是通过将至少包括丙烯酸树脂和硬化剂的混合物施加到基体膜,然后固化而制备的。
7. 权利要求1的晶片加工用带,其中可去除粘合剂层含有:化合物(A),其分子中具有碘值为0.5~20的辐射可固化碳碳双键;和化合物(B),其选自聚异氰酸酯、三聚氰胺甲醛树脂和环氧树脂中的至少一种。
8. 一种晶片加工用带,其包括中间树脂层、可去除粘合剂层和粘合剂层,所述中间树脂层、可去除粘合剂层和粘合剂层层压于基体膜之上,使得从上面开始依次为粘合剂层、可去除粘合剂层、中间树脂层、基体膜,其中中间树脂层80℃时的储存弹性模量大于可去除粘合剂层80℃时的储存弹性模量。
9. 权利要求8的晶片加工用带,其中中间树脂层80℃时的储存弹性模量范围为8×104~1×107Pa。
10. 权利要求8的晶片加工用带,其中中间树脂层25℃时的储存弹性模量范围为8×104~1×107Pa.
11. 权利要求8的晶片加工用带,其中中间树脂层具有三维网络结构,并且由丙烯酸树脂和硬化剂构成。
12. 权利要求8的晶片加工用带,其中中间树脂层由热固化树脂构成。
13. 权利要求8的晶片加工用带,其中中间树脂层是通过将至少包括丙烯酸树脂和硬化剂的混合物施加到基体膜,然后固化而制备的。
14. 权利要求8的晶片加工用带,其中可去除粘合剂层含有:化合物(A),其分子中具有碘值为0.5~20的辐射可固化碳碳双键;和化合物(B),其选自聚异氰酸酯、三聚氰胺甲醛树脂和环氧树脂中的至少一种。
15. 权利要求8的晶片加工用带,所述晶片加工用带用于半导体器件制造中的键合过程,所述键合过程包括:粘附晶片;将晶片粘附到切割框,同时切割晶片;和将切割的晶片装配到引线框或半导体芯片之上,
其中所述晶片加工用带包括依次层压于基体膜之上的中间树脂层和可去除粘合剂层,并且进一步包括粘合剂层,该粘合剂层至少层压于晶片待粘附的部分之上,并且切割框待粘附的部分不提供粘合剂层。
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Also Published As
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KR20060090302A (ko) | 2006-08-10 |
EP1775760A1 (en) | 2007-04-18 |
CN1906737A (zh) | 2007-01-31 |
MY147687A (en) | 2012-12-31 |
EP1775760A4 (en) | 2011-07-27 |
TW200613508A (en) | 2006-05-01 |
WO2006014000A1 (ja) | 2006-02-09 |
US20060204749A1 (en) | 2006-09-14 |
TWI334435B (en) | 2010-12-11 |
KR100743772B1 (ko) | 2007-07-30 |
EP1775760B1 (en) | 2021-01-20 |
JP2006049509A (ja) | 2006-02-16 |
JP4776189B2 (ja) | 2011-09-21 |
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