CN101601122B - 涂有填充的、可旋涂的材料的半导体晶片 - Google Patents

涂有填充的、可旋涂的材料的半导体晶片 Download PDF

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Publication number
CN101601122B
CN101601122B CN2007800505767A CN200780050576A CN101601122B CN 101601122 B CN101601122 B CN 101601122B CN 2007800505767 A CN2007800505767 A CN 2007800505767A CN 200780050576 A CN200780050576 A CN 200780050576A CN 101601122 B CN101601122 B CN 101601122B
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coating
resin
semiconductor wafer
described semiconductor
ball
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CN101601122A (zh
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C·尤恩苏克
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Abstract

本发明是一种半导体晶片，其具有有源面和与有源面相反的背面，所述背面涂有填充的、可旋涂的涂料，其中涂料包含树脂和球形填料，所述球形填料的特征为平均粒径大于2μm和单峰粒度分布。在另一个实施方式中，本发明是生产可旋涂的、可B阶处理的具有1.2或更小的触变指数的涂料的方法。在第三个实施方式中，本发明是生产涂布半导体晶片的方法。

Description

涂有填充的、可旋涂的材料的半导体晶片
技术领域
本发明涉及在无源或背面的表面上涂有填充的、可旋涂的涂料的半导体晶片。
发明背景
半导体封装最近的进展已经引起“叠层”封装的发展，在“叠层”封装中两个或更多个半导体管芯在单个半导体封装中被安装在相互的顶部上。这种管芯的堆叠能够使小区域(footprint)的功能增加，使整个半导体封装的尺寸减小。通常，粘合膏或膜被用在两个半导体管芯之间，以确保在制造操作诸如引线键合、成型和回流焊接期间，以及最终使用期间封装的完整性。
存在多种以叠层构造组装封装的方法。每个管芯包含许多电端子(electrical terminals)，金属线——通常是金——从这些电端子延伸到衬底上的电端子。在叠层封装中，来自一个管芯的引线键合(wirebonds)必须避免与邻近的管芯接触和避免给邻近的管芯造成损害。另外，用于将管芯粘合到衬底和/或相互粘合的粘合剂一定不要侵占引线键合盘。因为，一般而言，封装移向更紧的公差(tighter tolerances)，特别是在叠层封装中，因此需要非常严密地控制粘合剂的圆角(fillet)，粘合剂圆角通常从被粘合管芯的边缘突出。
一种已被用于控制键合用粘合剂(bonding adhesive)流动的方法是利用胶带或薄膜而不是膏状粘合剂。在该方法中，胶带或薄膜粘合剂被施加至衬底或管芯中的一个上。当被施加至管芯时，粘合膜可以首先被粘附至晶片，然后再被单粒化成管芯，或可以直接将其施加至先前已单粒化的管芯。然后，通过使用热和压力，将该管芯粘附至其衬底并被粘合。这提供叠层封装所需的流动特征，其中圆角在管芯四周形成最小。然而，胶带和薄膜与传统的膏状管芯附着用粘合剂相比非常昂贵，会优选使用膏状或液体型粘合剂，该粘合剂可被施加到晶片，然后被部分固化或干燥(B-阶处理)，以能够进一步加工。
一种涂布晶片的已知方法是旋涂。这种方法具有快速的优点并且已被成功用于包含最少填料通常小于10wt％的粘合剂。然而，为了很多目的，包括降低应力；控制模量或热膨胀系数；减小吸湿性；通过提高粘结强度(cohesive strength)、电和/或热导率来强化材料；减小挥发性和流动控制，更高的填料荷载量是期望的。尽管可用于这些功能，但是更高的填料荷载量可能导致涂料厚度的均匀性丧失，并导致晶片中心的涂料比外缘的涂料厚。对于目前后续的加工步骤，包括切割和管芯附着，这种涂料厚度均匀性的缺乏是不期望的。
本发明通过提供涂有填充的(有填料的)、可旋涂的材料的半导体晶片——该材料具有良好的涂料厚度均匀性，提供上述问题的解决方案。
发明概述
本发明是半导体晶片，其包含具有有源面和与有源面相反的背面的半导体晶片，以及布置在晶片背面的涂料，所述涂料包含(a)树脂体系和(b)球形填料，所述球形填料具有大于2μm的平均粒径和单峰粒度分布。
在另一实施方式中，本发明是生产可旋涂的、可B阶处理的具有1.2或更小的触变指数的涂料的方法，其包含(a)提供树脂体系，该树脂体系包含(i)固体环氧树脂和(ii)选自以下的液体：单官能丙烯酸酯单体、有机溶剂或这些的组合，以及(b)添加到树脂中的10wt％至30wt％的球形填料，该填料具有大于2μm的平均粒径和单峰粒度分布。
在另一实施方式中，本发明是生产涂布半导体晶片的方法，其中半导体晶片具有有源面和与有源面相反的背面，其包含(a)提供涂料组合物，该涂料组合物包含(i)固体环氧树脂和(ii)选自以下的液体：单官能丙烯酸酯单体、有机溶剂或这些的组合，以及(iii)10wt％至30wt％的球形填料，该球形填料具有大于2μm的平均粒径和单峰粒度分布；(b)在晶片背面上旋涂该涂料组合物；以及(c)B阶处理该涂料。
定义
如本文所用，术语“烷基”是指有支链的或无支链的1至24个碳原子的饱和烃基团，例如甲基(“Me”)、乙基(“Et”)、正丙基、异丙基、正丁基、异丁基、叔丁基、辛基、癸基及类似基团。
如本文使用的术语化合物、产物或组合物的“有效量”意思是用以提供所期望结果的化合物、产物或组合物的足够量。如下文所指出，不同封装所需的精确量将有所变化，其取决于所使用的具体化合物、产物或组合物，它的施用方式等等。因此，不可能总能规定精确量；但是有效量可由本领域普通技术人员仅使用常规实验来确定。
如本文所用，术语“适合的”用于指与如本文提供用于所述目的的化合物、产物或组合物相容的部分。对所述目的的适合性可由本领域普通技术人员仅使用常规实验来确定。
如本文所用，“取代的”通常用于指碳或适合的杂原子被去除氢原子或其他原子并用其他部分代替。而且，“取代的”意图是指不改变本发明的下述化合物、产物或组合物的基本用途和新用途的取代。
如本文所用，“B阶处理(B-staging)”(及其变型)用于指用热或辐射对材料的处理，以使如果材料在溶剂中溶解或分散，则溶剂挥发而材料部分固化或不部分固化，或者如果材料是纯的、不含溶剂，则材料被部分固化至粘着或更硬化的状态。如果材料是易流动的粘合剂，B阶处理会提供极低的流动而不充分固化，以使粘合剂用于将一个物件连接至另一个物件后，可进行另外的固化。流动的降低可通过溶剂挥发、树脂或聚合物的部分提早处理或固化或二者兼有来实现。
如本文所用，术语“固化剂”用于指引发、传递或加速组合物固化的任何材料或材料的组合，并且包括，但不限于，促进剂、催化剂、引发剂和硬化剂。
如本文所用，术语“粒度”用于指颗粒的最大尺寸。例如，如果颗粒是球形的，则粒度等于颗粒的直径，以及如果颗粒是薄片，则粒度是薄片的长度。
如本文所用，术语“触变指数”用于指低剪切粘度(0.5rpm下测试)与高剪切粘度(为5.0rpm下测试)的比率。除非另有说明，所有测试都在锥-板型锭子粘度计上进行。
发明详述
半导体晶片可以是具体工业用途所需的任何类型、大小或厚度。
用于涂料的适合的树脂可以是热固性的或热塑性的，以及可以是任何单体、聚合物、低聚物或预聚物或溶于溶剂中的那些材料，其是可旋涂的，即具有1.2或更小的触变指数和在5.0rpm下3,000至10,000cP之间的粘度。示例性的树脂包括，但不限于，环氧树脂、丙烯酸酯树脂、乙烯醚树脂、甲基丙烯酸酯树脂、马来酰亚胺树脂、丁腈橡胶、聚酯树脂、聚(丁二烯)树脂、硅化烯烃树脂、有机硅树脂、苯乙烯树脂和氰酸酯树脂、聚烯烃树脂或两个或更多那些树脂的组合。触变指数被定义为低剪切粘度(0.5rpm下测试)与高剪切粘度(5.0rpm下测试)的比率。尽管对于大量生产优选的粘度为在5.0rpm下3,000至10,000cP之间，但是更高粘度的配制物可通过以更高的速度旋转晶片来提供。
尽管满足上述标准的任何树脂体系可用于可旋涂的涂料，但在优选的实施方式中，树脂体系包含(i)固体环氧树脂，(ii)固化剂，以及(iii)选自下述的液体：单官能丙烯酸酯单体和有机溶剂。这种组合物是特别期望的，因为它被涂布在晶片上之后，粘合剂可进行B阶处理。B阶处理包括将涂布晶片暴露于热(通常是90℃至125℃，15至30分钟)以在另外的加工步骤诸如储藏、切割、管芯拾取和管芯键合之前，蒸发溶剂和/或部分固化粘合剂。
适合的固体环氧树脂包括，但不限于，甲酚线性酚醛清漆环氧、苯酚线性酚醛清漆和双A型环氧。在该实施方式中，固体环氧树脂占涂料的15wt％至30wt％。
适合的马来酰亚胺树脂的实例包括，但不限于，从Dainippon Ink and Chemical，Inc购得的那些。其它适合的马来酰亚胺树脂选自如下：
Figure G2007800505767D00051
其中C36表示36个-CH2-部分的直链或支链(有或没有环部分)；
Figure G2007800505767D00052
Figure G2007800505767D00053
Figure G2007800505767D00054
Figure G2007800505767D00055
Figure G2007800505767D00056
Figure G2007800505767D00057
以及
Figure G2007800505767D00061
其中n是1至5。
适合的丙烯酸酯树脂的实例包括，但不限于，(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸烷基酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸正十八酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸异冰片酯、二(甲基)丙烯酸1，4-丁二醇酯、二(甲基)丙烯酸1，6-己二醇酯、二(甲基)丙烯酸1，9-壬二醇酯、(甲基)丙烯酸全氟辛基乙酯、二(甲基)丙烯酸1，10-癸二醇酯、壬基苯酚聚丙氧基化物(甲基)丙烯酸酯(nonylphenolpolypropoxylate(meth)acrylate)、以及聚戊氧基化物丙烯酸四氢糠酯，可从Kyoeisha Chemical Co.，LTD获得；聚丁二烯二甲基丙烯酸氨基甲酸乙酯(CN302、NTX6513)以及聚丁二烯二甲基丙烯酸酯(CN301、NTX6039、PRO6270)，可从Sartomer Company，Inc获得；聚碳酸酯二丙烯酸氨基甲酸乙酯(Art Resin UN9200A)，可从Negami ChemicalIndustries Co.，LTD获得；丙烯酸化脂族氨基甲酸乙酯低聚物(Ebecryl230、264、265、270、284、4830、4833、4834、4835、4866、4881、4883、8402、8800-20R、8803、8804)，可从Radcure Specialities，Inc获得；聚酯丙烯酸酯低聚物(Ebecryl 657、770、810、830、1657、1810、1830)，可从Radcure Specialities，Inc获得；以及环氧丙烯酸酯树脂(CN104、111、112、115、116、117、118、119、120、124、136)，可从Sartomer Company，Inc获得。
在一个实施方式中，丙烯酸酯树脂选自丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸十二酯、甲基丙烯酸十二酯、4-羟基丁基丙烯酸酯缩水甘油醚(4-hydroxybutyl glycidyl ether acrylate)、具有丙烯酸酯官能度的聚(丁二烯)以及具有甲基丙烯酸酯官能度的聚(丁二烯)。丙烯酸酯通常以15wt％至50wt％的量存在。
适合的乙烯醚树脂包括，但不限于，环己烷二甲醇二乙烯醚、十二烷基乙烯醚、环己基乙烯醚、2-乙基己基乙烯醚、双丙甘醇二乙烯醚、己二醇二乙烯醚、十八烷基乙烯醚和丁二醇二乙烯醚，可购自International Speciality Products(ISP)；Vectomer 4010、4020、4030、4040、4051、4210、4220、4230、4060、5015，可购自Sigma-Aldrich，Inc。乙烯醚通常以15wt％至50wt％的量存在。
适合的聚(丁二烯)树脂的实例包括聚(丁二烯)、环氧化的聚(丁二烯)、马来酸聚(丁二烯)、丙烯酸化的聚(丁二烯)、丁二烯-苯乙烯共聚物和丁二烯-丙烯腈共聚物。可购得的材料包括均聚物丁二烯(Ricon130、131、134、142、150、152、153、154、156、157、P30D，可购自Sartomer Company，Inc)；丁二烯和苯乙烯的无规共聚物(Ricon100、181、184，可购自Sartomer Company Inc.)；马来化的聚(丁二烯)(Ricon 130MA8、130MA13、130MA20、131MA5、131MA10、131MA17、131MA20、156MA17，可购自Sartomer Company，Inc.)；丙烯酸化的聚(丁二烯)(CN302、NTX6513、CN301、NTX6039、PRO6270、Ricacryl3100、Ricacryl 3500，可购自Sartomer Inc.)；环氧化的聚(丁二烯)(Polybd600、605，可购自Sartomer Company.Inc)、(Epolead PB3600，可购自Daicel Chemical Industries Ltd.)；以及丙烯腈和丁二烯共聚物(HycarCTBN系列、ATBN系列、VTBN系列和ETBN系列，可购自HanseChemical)。聚(丁二烯)通常以15wt％至50wt％的量存在。
固化剂的使用是任选的，其取决于所用的树脂体系是否能够自引发，以及取决于所期望的固化速度和温度。适用于涂料的固化剂以0至5wt％之间的量存在，包括但不限于酚醛塑料、芳香二胺、双氰胺、过氧化物、胺、咪唑(imidizole)、叔胺和聚酰胺。适合的酚醛塑料可从Schenectady International，Inc购得。适合的芳香二胺是伯二胺，包括二氨基二苯砜和二氨基二苯甲烷，可从Sigma-AIdrich Co购得。适合的双氰胺可从SKW Chemicals，Inc.购得。适合的聚酰胺可从Air Products and Chemicals，Inc.购得。适合的咪唑可从Air Products andChemicals，Inc.购得。适合的叔胺可从Sigma-AIdrich Co购得。适合的过氧化物包括过氧化苯甲酰、过氧化叔丁基、过氧化月桂酰、氢过氧化枯烯、过氧化环己酮、过辛酸丁酯和过氧化二枯基。另外适合的固化剂包括偶氮化合物，诸如2，2’-偶氮双(2-甲基-丙腈)、2，2’-偶氮双(2-甲基-丁腈)、4，4-偶氮双(4-氰戊酸)、1，1′-偶氮双(环己甲腈)和2，2′-偶氮二异丁腈。
适用于涂料的填料在外形上为球形，具有大于2μm的平均粒径和单峰粒度分布。更小的粒度和双峰分布导致无法接受的高触变指数，其又导致差的旋涂性能和不均匀的涂料厚度。
适合的绝缘填料的实例包括氧化铝、氢氧化铝、硅石、蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙子、玻璃、硫酸钡、锆、炭黑、有机填料，和有机聚合物——包括但不限于卤化的乙烯聚合物，诸如四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。适合的导电填料的实例包括炭黑、石墨、金、银、铜、铂、钯、镍、铝、金刚砂、一氮化硼、金刚石和氧化铝。填料的具体类型不是关键的，可由本领域的技术人员选择，以适于具体最终用途的需要，诸如减小应力和控制粘合层。垫片(spacers)也可以包括在配制物中，以控制粘合部分的粘合层厚度，由操作者选择其类型和量，以满足具体应用的需要。填料可以以操作者确定的任意量存在，以适于所选的树脂体系和最终用途，并且通常的范围在10wt％和30wt％之间。
其它的添加剂，包括但不限于助粘剂、消泡剂、防渗剂(antibleed agents)、流变调节剂和助熔剂(fluxing agents)——本领域的技术人员知晓其类型和量，也可包括在涂料配制物中。
涂料可以是用于具体制造用途的适当保护、粘合或加工性能所需的任意厚度，通常在12至60μm之间。
实施例
实施例1流变学对涂料性能的影响
制备具有各种高和低剪切粘度的涂料配制物，以说明粘度和触变指数对涂料性能的影响。对比配制物A被设计成具有高触变指数和高粘度。对比配制物B被设计成具有高触变指数和低粘度。本发明配制物C和D均具有低触变指数，分别具有高和低粘度。根据下面表1中列出的配方，使用标准粘合剂制造技术，制备涂料。这些配制物中的每一个所用的填料是球形的硅石，具有2.6μm的平均粒径和单峰粒度分布。
Figure G2007800505767D00091
在室温下测定涂料配制物的高和低剪切粘度并且计算每个的触变指数。然后，在室温下用60秒以1000rpm将涂料旋涂在20.3cm直径的晶片上，并且在110℃下将涂布晶片B阶处理30分钟。通过测量晶片中心的涂料高度和将该高度与离晶片外缘大约1英尺的涂料高度进行比较，评价每个配制物。如果外缘附近的高度与中间的高度之间的差值小于外缘附近高度的15％，则该配制物被称为是可旋涂的。即，该配制物给出跨过晶片表面的令人满意的厚度均匀性(在中心没有“***”)。粘度、触变指数和涂料厚度数据总结在下列表2中。
Figure G2007800505767D00101
具有高触变指数(大于1.2)的对比配制物是不可旋涂的，这是因为它们在中心“***”，中心厚度比晶片边缘附近的厚度高15％。如所预料的，粘度的确对涂料厚度有影响，这是因为所有样品都是在相同的速度下和用相同的时长涂布的，更高粘度的材料给出总体更厚的涂料。然而，粘度对可旋涂性(spin-coatability)没有影响，因为两种本发明的配制物(触变指数1.2或更小)都给出跨过晶片表面良好的厚度均匀性。
对于实施例2-5，使用标准粘合剂制造技术，用下述典型组成，配制涂料：单官能丙烯酸酯树脂(1)    12.1wt％单官能丙烯酸酯树脂(2)    18.2wt％过氧化物固化剂           0.5wt％固体环氧树脂             18.15wt％CTBN橡胶                 18.15wt％双氰胺固化剂             1.2wt％咪唑促进剂               0.3wt％环氧官能硅烷             0.7wt％消泡剂                   0.7wt％填料                     30wt％
改变填料类型，以显示填料尺寸、分布和形状对粘度、触变指数和可旋涂性的影响。高剪切粘度(5rpm下)报告为粘度以及低剪切粘度与高剪切粘度的比率(0.5rpm下/5rpm下)报告为触变指数。
将每个配制物在室温下用60秒以1000rpm涂布在20.3cm的晶片上，提供25μm或60μm的目标厚度并且将涂布晶片在110℃下B阶处理30分钟。通过测量晶片中心的涂料高度和将该高度与离晶片外缘大约1”的涂料高度进行比较，评价每个配制物。如果两个高度之间的差值小于边缘附近高度的15％，则该配制物被认为可旋涂。
实施例2填料类型的影响
Figure G2007800505767D00111
本发明配制物E(硅石填料)和F(聚合物填料)都是可旋涂的，表明填料类型不影响可旋涂性。
实施例3填料粒度分布的影响
Figure G2007800505767D00121
实施例3说明填料粒度分布的影响。对比配制物G——其填料具有类似于本发明配制物E使用的大小和形状，是不可旋涂的，这是因为其双峰分布导致触变指数高于1.2。
实施例4填料大小的影响
Figure G2007800505767D00122
实施例4说明填料大小的影响。对比配制物H——其具有平均粒径小于2μm的填料，是不可旋涂的，这是因为更小的颗粒大小导致触变指数高于1.2。
实施例5填料形状的影响
Figure G2007800505767D00123
实施例5说明填料形状的影响。对比配制物J和K使用的填料(分别为聚(***酮)和聚(四氟乙烯))具有非球形的形状。这些配制物是不可旋涂的，因为非球形的填料导致触变指数高于1.2。本发明的配制物I——其用球形的交联聚(甲基丙烯酸甲酯)，具有低于1.2的触变指数，因此是可旋涂的。
实施例6填料含量的影响用变化的填料含量制备实施例配制物，以说明填料荷载量对粘度、触变指数和所产生的可旋涂性的影响。实施例6的所有配制物均使用具有2.6μm的平均颗粒大小和单峰粒度分布的球形硅石填料进行制备。表7和8分别显示配制物和结果。
Figure G2007800505767D00131
在该树脂体系中和用该填料，配制物是可旋涂的，填料荷载量高达30wt％。应当注意的是，填料荷载量的有效限度(effectivelimit)将取决于所用的具体树脂体系和填料，可以更高或更低，这由具体工业用途的操作者确定。
可进行不偏离本发明精神和范围的许多修改和变化，这对本领域普通技术人员是明显的。本文所描述的具体实施方式仅以示例的方式提供，并且本发明仅通过所附权利要求以及与这些权利要求被赋予的权利等同的全部范围进行限制。

Claims (12)

1.半导体晶片，其具有有源面和与有源面相反的背面，其中所述背面涂有涂料，所述涂料包含(a)树脂和(b)球形填料，所述球形填料具有大于2μm的平均粒径和单峰粒度分布。
2.权利要求1所述的半导体晶片，其中所述涂料的厚度在12至60μm之间。
3.权利要求1所述的半导体晶片，其中所述球形填料以所述涂料的10wt％至30wt％之间的量存在。
4.权利要求1所述的半导体晶片，其中所述树脂选自：固体环氧树脂、液体环氧树脂、丙烯酸酯树脂、甲基丙烯酸酯树脂、马来酰亚胺树脂、乙烯醚树脂、聚酯树脂、聚(丁二烯)树脂、硅化烯烃树脂、有机硅树脂、苯乙烯树脂和氰酸酯树脂及那些中的两种或更多种的组合。
5.权利要求1所述的半导体晶片，其中所述树脂包含(i)固体环氧树脂和(ii)选自以下的液体：单官能丙烯酸酯单体、有机溶剂或这些的组合。
6.权利要求5所述的半导体晶片，其中所述液体以所述涂料的15wt％至50wt％之间的量存在。
7.权利要求5所述的半导体晶片，其中所述单官能丙烯酸酯单体是丙烯酸异冰片酯。
8.权利要求5所述的半导体晶片，其中所述有机溶剂选自4-羟基丁基丙烯酸酯缩水甘油醚、甲基·乙基酮和二甘醇一***乙酸酯。
9.权利要求5所述的半导体晶片，其中所述固体环氧树脂以所述涂料的15wt％至30wt％之间的量存在。
10.权利要求5所述的半导体晶片，其中所述固体环氧树脂是甲酚酚醛清漆环氧树脂。
11.生产可旋涂的、可B阶处理的具有1.2或更小的触变指数的涂料的方法，其包括：
a.提供固体环氧树脂，
b.将所述固体环氧树脂溶于液体中形成溶液，其中所述液体选自单官能丙烯酸酯单体、有机溶剂或两者的组合，以及
c.将10wt％至30wt％的球形填料混入所述液体溶液中，所述球形填料具有大于2μm的平均粒径和单峰粒度分布。
12.生产涂布半导体晶片的方法，其中所述半导体晶片具有有源面和与所述有源面相反的背面，所述方法包括：
a.提供涂料组合物，其包含(i)固体环氧树脂和(ii)选自以下的液体：单官能丙烯酸酯单体、有机溶剂或其组合，以及(iii)10wt％至30wt％的球形填料，所述球形填料具有大于2μm的平均粒径和单峰粒度分布；
b.将所述涂料组合物旋涂在所述晶片的所述背面上；以及
c.B阶处理所述涂料。
CN2007800505767A 2007-01-31 2007-01-31 涂有填充的、可旋涂的材料的半导体晶片 Expired - Fee Related CN101601122B (zh)

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JP2014511560A (ja) 2011-02-01 2014-05-15 ヘンケル コーポレイション プレカットされウェハに塗布されるダイシングテープ上のアンダーフィル膜
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CN101601122A (zh) 2009-12-09
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