CN101016445A - 用于晶片封装的底部填充包封剂及其应用方法 - Google Patents

用于晶片封装的底部填充包封剂及其应用方法 Download PDF

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Publication number
CN101016445A
CN101016445A CNA2007100070381A CN200710007038A CN101016445A CN 101016445 A CN101016445 A CN 101016445A CN A2007100070381 A CNA2007100070381 A CN A2007100070381A CN 200710007038 A CN200710007038 A CN 200710007038A CN 101016445 A CN101016445 A CN 101016445A
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Prior art keywords
encapsulation agent
agent
described encapsulation
epoxy
composition
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A·Y·肖
G·杜特
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National Starch and Chemical Investment Holding Corp
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National Starch and Chemical Investment Holding Corp
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)
  • Wire Bonding (AREA)
  • Tires In General (AREA)
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  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

可固化底部填充包封剂组合物，其在半导体晶片被切割为单个芯片之前被直接应用到该晶片上。该组合物包括可热固化环氧树脂、溶剂、咪唑磷酸盐催化剂、助熔剂和任选的湿润剂。根据需要，也可以加入各种其它添加剂，如消泡剂、助粘剂、流动添加剂和流变改性剂。该底部填充包封剂是可B阶段的，以便在晶片上提供平滑且非粘性的涂层，并使晶片能够被干净利落地切割为单个芯片。生产含有可B阶段材料的电子封装件的方法也可以在芯片将要被附着的基板上使用未填充的液体可固化助熔材料。

Description

用于晶片封装的底部填充包封剂及其应用方法
相关申请
[0001]本申请是2002年3月1日提交的正在审查的美国专利申请系列号10/084,869的部分继续申请。
技术领域
[0002]本发明涉及底部填充包封剂及其应用于半导体晶片的方法。
背景技术
[0003]本发明涉及由环氧树脂制备的底部填充包封剂化合物，用于保护和加固微电子器件中电子元件和基板之间的互连。微电子器件包含多种类型的电路元件，主要是在集成电路(IC)芯片中组装在一起的晶体管，但是也有电阻器、电容器和其它元件。这些电子元件相互连接，形成电路，并且最终连接到并承载于载体或基板诸如印刷线路板上。所述集成电路元件可以包括单个裸芯片、单个包封芯片或包封的多芯片封装件。所述单个裸芯片可以被连接于引线框架，引线框架又被封装并连接于印刷线路板上，或者所述单个裸芯片可以被直接连接于印刷线路板。这些芯片最初是作为包含多个芯片的半导体晶片而被制成的。所述半导体晶片按所需被切割为单个芯片或芯片封装件。
[0004]不管所述元件是连接于引线框架的裸芯片还是连接于印刷线路板或其它基板的封装件，该连接都在电子元件上的电端子(electrical termination)和基板上相应的电端子之间形成。一种制作这些连接的方法使用了聚合物材料或金属材料，这些材料以焊凸(bump)的形式被应用于所述元件端子或基板端子上。将所述端子对准并接触在一起，并且加热所形成的组装件，以回流该金属材料或聚合物材料并固化该连接。
[0005]在所述电子组装件正常使用寿命期间，其经历了多次宽泛改变温度范围的循环。由于所述电子元件、互连材料和基板的热膨胀系数的差异，此热循环可能对所述组装件的各部件施加应力并使其失效。为防止这种失效，所述元件和基板间的缝隙被用聚合物包封剂——此后称为底部填充剂(underfill)或底部填充包封剂填充，以加固互连材料并吸收热循环所产生的一些应力。
[0006]底部填充技术的两个突出用途是用于加固封装，它们在本行业中被称为芯片尺寸封装(chip scale package(CSP))——其中芯片封装件被连接于基板，和倒装片封装(flip-chip package)——其中芯片通过互连阵列被连接于基板。
[0007]在常规的毛细流动底部填充应用中，底部填充剂的分配和固化发生在回流金属互连或聚合物互连之后。在此方法中，首先是将焊剂应用于基板上的金属垫上。其次，将芯片放置在所述基板的焊剂处理区域，置于焊接点顶部。然后加热所述组装件，以使该焊接接头回流。此时，测定量的底部填充包封剂材料沿着所述电子组装件的一条或多条周边进行分配，并且元件-基板间缝隙内的毛细作用将此材料吸向其中。在该缝隙被填充后，可以沿整个组装件的周边分配额外的底部填充包封剂，以帮助减轻压力的集中并延长该组装结构的疲劳寿命。接着将所述底部填充包封剂固化，以达到其优化的最终特性。
[0008]最近，已有人尝试将此过程流水线化，并通过在将半导体晶片切割为单个芯片之前，将底部填充包封剂直接涂在所述半导体晶片上来提高效率。涂布过程——其可以通过各种方法进行，包括丝网印刷、模版印刷和旋转涂布——允许底部填充剂单独应用于单个半导体晶片，所述单个半导体晶片随后被切割为很多单个芯片。
[0009]为了用作晶片级底部填充包封剂，所述底部填充剂必须具有若干重要特性。首先，该材料必须容易均匀地应用在晶片上，以使整个晶片具有一致的涂层。应用于晶片的底部填充包封剂必须不干扰晶片干净利落地切割为单个芯片。所述底部填充包封剂必须是可B阶段的——意味着所述底部填充剂必须在被放置于晶片上以后被固化，以提供具有最少量残留溶剂的平滑非粘性涂层。
[0010]如果起始底部填充材料是固体，则固体被分散或溶解在溶剂中，形成膏，并将膏应用于晶片。然后将底部填充胶加热至蒸发溶剂，在晶片上留下固态而未固化的底部填充胶。如果起始底部填充材料是液体或膏，则将该底部填充胶分配到晶片上并加热，以使其部分固化为固体状态。
[0011]所述B阶段过程通常是在大约150℃以下的温度下发生，而没有过早地固化底部填充包封剂。所述底部填充包封剂的最终固化必须延迟到焊料熔融(在焊料是互连材料的情况下)和互连以后，在锡/铅低共熔焊料的情况下，此过程在183℃的温度下发生，而在无铅焊料的情况下，此过程在200℃以上的温度下发生。所述底部填充剂的最终固化应当在焊凸(solder bump)流动并互连后迅速发生。在此将各个芯片最终连接于基板的过程中，底部填充包封剂必须流动，以能够形成圆角，熔化焊凸，并在芯片或芯片钝化层、基板或阻焊剂(soldermask)以及焊接接头之间提供良好的粘附。在特别的情况下，直接在基板上提供底部填充的液体可固化助熔材料可能是有帮助的，以便促进互连。
附图说明
[0012]图1是DSC固化差示热分析图。
发明内容
[0013]本发明涉及可固化底部填充包封剂组合物，其在晶片被切割为单个芯片之前被直接应用到半导体晶片上。所述组合物包括可热固化的树脂体系，其包含环氧树脂、溶剂、咪唑-酸酐催化剂(imidazole-anhydride catalyst)和任选的助熔剂。根据需要，也可以加入各种其它添加剂，如消泡剂、湿润剂、助粘剂、流动添加剂(flowadditive)和流变改性剂。在一个可选实施方式中，用咪唑磷酸盐代替咪唑-酸酐催化剂。所述底部填充包封剂是可B阶段的，以便在晶片上提供平滑且非粘性的涂层，并使晶片能够被干净利落地切割为单个芯片。然后，单个芯片被直接附着至基板。
具体实施方式
[0014]本发明的底部填充包封剂组合物中所用的树脂是可固化的化合物，这意味着它们能够聚合。如本说明书中所用，固化意味着伴随交联的聚合。交联，如本领域所理解，是两聚合物链通过元素桥、分子基团桥或者化合物桥而形成的连接，并且一般在加热后发生。
[0015]本发明的可B阶段底部填充包封剂组合物的成分包括一种或多种环氧树脂、充当催化剂的咪唑-酸酐加合物和一种或多种溶剂的掺合物。在可选的实施方式中，用作为催化剂的咪唑磷酸盐代替咪唑-酸酐加合物。任选地，可以包括助熔剂、脱气剂、流动添加剂、助粘剂、流变改性剂、表面活性剂和其它成分。这些成分经过特别挑选，以获得针对具体树脂用途所期望的特性平衡。挑选溶剂，以溶解所述树脂(一种或多种)，并因此将所述组合物制成具有合适粘性的膏状，其通过旋转涂布(spin coating)、丝网印刷(screen printing)、模版印刷(stencilprinting)应用到晶片上。在优选的实施方式中，所述组合物是可B阶段的，即所述组合物能够初步固化，在半导体晶片上形成平滑、非粘性的涂层。所述B阶段固化优选地在范围为大约80℃至大约160℃的温度下发生。在B阶段过程以后，在晶片上得到平滑、非粘性的固体涂层，以确保将所述晶片干净利落地切割为单个芯片。最终完全固化在大约180℃或以上的第二温度下发生，该温度高于B阶段固化温度。一般而言，所述组合物的最终固化发生于互连形成之后。在Pb/Sn低共熔焊料的情况下，互连的形成发生在焊料熔点以上的温度下，该熔点为183℃。在无铅焊料的情况下，对于AgSnCu而言，互连的形成发生在大约217℃的温度下，而对于AgCu焊料合金，互连的形成发生在大约225℃的温度下。潜催化剂——酸酐与咪唑的加合物或咪唑磷酸盐用于组合物中，以确保组合物的适当固化，而不干扰互连的形成。在B阶段期间所选择的催化剂必须防止除少许最小预固化之外的任何固化，并且必须确保在B阶段之后无胶凝出现在所形成的非粘性表面上。优选地，B阶段固化发生在比最终固化温度低至少30℃的温度下。催化剂也必须允许在一步回流步骤中进行熔化和固化。底部填充胶必须首先熔化，然后固化，以确保适当的焊接互连形成。
[0016]适合用在本发明晶片级底部填充组合物中的环氧树脂的例子包括双酚-A和双酚-F的单官能和多功能缩水甘油醚、脂族和芳族环氧树脂、饱和和不饱和环氧树脂或脂环系环氧树脂或它们的组合。脂族环氧树脂的例子包括Flex Epoxy1。
Figure A20071000703800111
[0017]芳族环氧树脂的例子包括RAS-1、RAS-5和Flex Epoxy3。
Figure A20071000703800112
不饱和环氧树脂的例子包括Cardolite NC513。
Cardolite NC513
[0018]非缩水甘油醚环氧衍生物的例子包括3，4-环氧环己基甲基-3，4-环氧环己烷羧酸酯，其含有为环状结构部分的两个环氧基和酯键；乙烯基环己烯二酮，其含有两个环氧基，其中的一个为环状结构的部分；3，4-环氧-6-甲基环己基甲基-3，4-环氧环己烷羧酸酯；和二氧化双环戊二烯。
[0019]在本发明中，缩水甘油醚环氧衍生物是优选的，或者单独使用，或者结合非缩水甘油醚环氧衍生物。优选的此种类型的环氧树脂是双酚A树脂。另一种优选的环氧树脂是双酚F型树脂。优选的环氧酚醛清漆树脂是苯基缩水甘油醚/甲醛共聚物。联苯型环氧树脂也可以被用在本发明中。此种类型的树脂通常通过联苯树脂与表氯醇反应而制备。双环戊二烯-苯酚环氧树脂、萘醛树脂、环氧官能丁二烯丙烯腈共聚物、环氧官能聚二甲基硅氧烷和它们的混合物是可以使用的另外类型的环氧树脂。商业可得的双酚-F型树脂可来自新泽西MapleShade的CVC Specialty Chemicals，其名称为8230E，以及来自Resolution Performance Products LLC，名称为RSL1739。双酚-A型树脂以EPON828、EPON1001、EPON1002商业供应自ResolutionTechnology，以及双酚-A和双酚-F的掺合物以名称ZX-1059供应自Nippon Chemical Company。可以使用的另外的环氧树脂为XP71756.00，其商业得自Vantico。
[0020]除树脂之外，咪唑-酸酐加合物或咪唑磷酸盐作为催化剂被包括在底部填充组合物中。所述加合物为底部填充剂提供了与通过将咪唑和酸酐作为单独组分加入而提供的性质所不同的性质。所述盐为底部填充剂提供了与通过将咪唑和磷酸作为单独组分加入而提供的性质所不同的性质。可以被包括在加合物或盐中的优选的咪唑包括非-N-取代的咪唑，如2-苯基-4-甲基咪唑、2-乙基-4-甲基-咪唑、2-苯基咪唑、2-甲基咪唑和咪唑。其它有用的咪唑组分包括烷基-取代的咪唑、N-取代的咪唑、N-甲基咪唑及它们的混合物。所述盐也包括磷酸组分。优选的催化剂包括2-苯基-咪唑磷酸二氢盐，其以AMICURE 2PIP商业供应自Air Products，和2-十七基咪唑，其商业供应自Curezol，以及CUREZOL 17A。所述加合物也包含酸酐组分。优选的酸酐优选为脂环族酸酐，最优选苯均四酸二酐，其以PMDA商业供应自Aldrich。另外的优选酸酐包括甲基六氢化邻苯二甲酸酐，以MHHPA商业供应自Lonza Inc.Intermediates and Actives。可以使用的其它酸酐包括甲基四氢化邻苯二甲酸酐、甲基桥亚甲基四氢化邻苯二甲酸酐(nadic methylanhydride)、六氢化邻苯二甲酸酐、四氢化邻苯二甲酸酐、邻苯二甲酸酐、十二烷基琥珀酸酐、联苯二酐(bisphenyl dianhydride)、二苯甲酮四酸二酐及它们的混合物。优选的催化剂是通过结合1摩尔份的1，2，4，5-苯四酸二酐(1，2，4，5-benzenetetracarboxylic dianhydride)和2摩尔份的2-苯基-4-甲基咪唑合成的。将两种组分首先在加热下溶解在丙酮中，而当该两种组分结合时，咪唑-二酐盐作为沉淀物而形成。该优选的催化剂结合环氧和溶剂产生底部填充剂，其具有远高于160℃的起始固化温度和183℃以上的固化峰温度。此外，与仅使用咪唑相比，所述优选的催化剂提供了改进的潜伏状态(latency)。
[0021]也可以将助熔剂掺入底部填充组合物中。助熔剂主要去除金属氧化物以及防止再氧化。尽管可以使用很多不同的助熔材料，但优选从羧酸中选择助熔剂。这些羧酸包括松香胶、十二烷二酸(以Corfree M2商业供应自Aldrich)、己二酸、癸二酸(sebasic acid)、聚癸二酸酐(polysebasic polyanhydride)、顺丁烯二酸、酒石酸和柠檬酸。也可以从醇、羟基酸(hydroxyl acid)和羟基碱(hydroxyl base)中选择助熔剂。优选的助熔材料包括多元醇，如乙二醇、甘油、3-[双(缩水甘油氧甲基)甲氧基]-1，2-丙二醇、D-核糖、D-纤维素二糖、纤维素、3-环己烯-1，1-二甲醇及类似物质。酸的强度是一个重要的因素，因为酸应当足够强，以便将氧化物从焊料和基板中洗掉。优选地，pKa应当为5以上。酸在大约183℃温度下的稳定性是重要的，并且酸在183℃以下的温度下不应当分解。当焊料在183℃下回流时，不能忍耐该温度的助熔剂材料对于合适的配方是不适合的。
[0022]溶剂被用于改变组合物的粘度。优选地，溶剂将在于大约150℃以下的温度下发生的B阶段期间蒸发。容易溶解环氧树脂、非活性的且具有范围在100℃至200℃的合适沸点的普通溶剂优选用于本应用。可以使用的溶剂的例子包括酮、酯、醇、醚以及其它稳定且溶解组合物中的环氧和酚醛树脂的普通溶剂。优选的溶剂包括γ-丁内酯和丙二醇甲醚乙酸酯(PGMEA)。
[0023]可以将另外的成分加入底部填充包封剂中，以生产具有期望性质的组合物。例如，单官能活性稀释剂可以逐增地延迟粘度的增加，而不会不利地影响固化的底部填充剂的物理性质。优选的稀释剂包括对-叔丁基-苯基缩水甘油醚、烯丙基缩水甘油醚、甘油二环氧甘油醚(glycerol diblycidyl ether)、烷基酚的缩水甘油醚(以Cardolite NC513商业供应自Cardolite Corporation)和丁二醇二环氧甘油醚(butanediodiglycidylether)(以BDGE商业供应自Aldrich)，但也可以使用其它稀释剂。可以使用表面活性剂，以便有助于防止在倒装片粘接工艺以及随后的焊接接头回流和材料固化期间的工艺空隙(processvoiding)。可以使用的各种表面活性剂包括有机丙烯酸类聚合物、硅氧烷、聚氧乙烯/聚氧丙烯嵌段共聚物、乙二胺基聚氧乙烯/聚氧丙烯嵌段共聚物、多元醇基聚氧化烯、脂肪醇基聚氧化烯、脂肪醇聚氧化烯烷基醚及它们的混合物。另外，也可以根据需要加入偶联剂、脱气剂、流动添加剂、助粘剂、无机填料和其它成分。
[0024]本发明的底部填充包封剂的优选实施方式包括至少一种环氧树脂、作为催化剂的咪唑-酸酐加合物、助熔剂、溶剂以及需要的其它成分。树脂将占所述底部填充组合物的20wt％至大约90wt％。咪唑-酸酐加合物作为催化剂也被加入。所述加合物占所述底部填充组合物的大约0.01wt％至大约10wt％，优选占所述组合物的大约0.1wt％至大约5wt％。任选地，加入助熔剂，其占所述组合物的大约0.5wt％至大约20wt％，优选占所述组合物的大约1wt％至大约10wt％。另外，可加入可达80wt％的溶剂(一种或多种)。最后，可以将任选的成分如表面活性剂、脱气剂、流动添加剂、流变改性剂、无机填料和助粘剂加入组合物中，其范围为所述组合物的大约0.01wt％至大约5wt％。
[0025]本发明的底部填充包封剂的进一步优选的实施方式包括至少一种环氧树脂、作为催化剂的咪唑磷酸盐、助熔剂、溶剂、无机填料以及如需要的其它成分。所述环氧树脂将占所述底部填充组合物的大约20wt％至大约80wt％。咪唑磷酸盐被加入作为催化剂。咪唑磷酸盐占所述底部填充组合物的大约0.01wt％至大约10wt％，优选占所述组合物的大约0.1wt％至大约5wt％。任选地，加入助熔剂，其占所述组合物的大约0.5wt％至大约20wt％，优选占所述组合物的大约1wt％至大约10wt％。另外，所述组合物含有可达约70wt％的填料物和可达约60wt％的溶剂(一种或多种)。最后，可以将任选的成分如表面活性剂、脱气剂、流动添加剂、流变改性剂和助粘剂加入组合物中，其范围为所述组合物的大约0.01wt％至大约5wt％。
[0026]为利用可B阶段的底部填充组合物，首先通过丝网印刷、旋转涂布或模版印刷将它直接应用到半导体晶片或单独芯片上。在大约10分钟至1小时内将具有该涂层的晶片或芯片加热至范围为大约100℃至大约140℃的初始B阶段温度，以使所述组合物以光滑、非粘性且无空隙膜的形式进行B阶段固化。在晶片的情况下，晶片被切割为单个芯片。具有已B阶段的组合物的芯片被放置在基板上，其中该已B阶段的组合物邻近该基板，并将整个组装件加热至约183℃的温度(在使用铅/锡焊料的情况下)。该第二次加热使基板与芯片之间的互连形成，并引起焊料球在芯片上熔化。
[0027]在一个可选的实施方式中，在放置芯片之前将包含未填充的液体可固化助熔材料的组合物直接应用于基板，所述助熔材料包括环氧树脂、含酚化合物和咪唑/酸酐加合物或咪唑磷酸盐。在底部填充剂被B阶段固化在晶片上并且晶片被切割为单个芯片之后，将芯片放置在基板上，其中已B阶段的材料邻近并与未填充的液体可固化材料接触。所述未填充的液体可固化材料促进改进的焊料熔化以及基板与单个芯片之间的互连。当可选实施方式的组合物被放置在基板上及具有可B阶段组合物的芯片被放置在该基板上时，在回流工艺之后优异的互连得以形成。
[0028]通过参考下面的实施例，可以更好地理解本发明：
[0029]实施例1：如表1所列，配制五个底部填充包封剂组合物。为制作每一个配方，首先将环氧树脂在加热下溶解在溶剂中。当纯松香被用作助熔剂时，如组合物1中，在该第一步骤中将其加入并加热，直到均匀的环氧树脂-溶剂-松香混合物得以形成。首先必须对要加入的松香进行处理以形成纯松香胶。所述处理包括在真空炉中加热商业松香，以去除任何杂质而形成“纯”助熔剂。另一方面，如果Corfree M2被用作助熔剂，如在组合物2-5，则仅在环氧树脂-溶剂混合物已经冷却至室温之后将其加入。在环氧树脂-溶剂或环氧树脂-溶剂-松香材料已经冷却至室温之后，也将其余组分(催化剂、湿润剂和消泡剂)加入。
然后完全混合该材料，并在室温下抽真空，以使底部填充剂脱气。
表1：底部填充剂组合物
编号 环氧树脂1 溶剂2 助熔剂3 催化剂4 湿润剂5 消泡剂6
1 57.00 40.00 2.85 0.29 0.29 0.29
2 55.04 38.63 5.50 0.28 0.27 0.28
3 57.00 40.00 5.7 0.29 0.29 0.29
4 70.70 29.60 7.07 0.35 0.71 0.71
5 70.70 29.60 7.07 0.35 0.71 0.71
1对于样品1-3为EPON1001，来自Resolution Products，对于样品4-5为XP71756，也称为Tactix556，来自Vantico
2对于样品1-4为溶剂BLO(γ-丁内酯)，对于样品5为PGMEA(乙二醇甲醚乙酸酯)，二者均来自Aldrich Chemical
3对于样品1为助熔剂纯松香(在加热下抽真空以去除杂质)；对于样品2-5为Corfree M2
4催化剂为咪唑-酸酐加合物
5湿润剂为G6715，3-环氧丙氧丙基五甲基二硅氧烷，来自United Technologies
6对于样品1为消泡剂BYKA500(Chemie)，对于样品2为酞菁蓝(phthalo blue)(Plasticolors)，对于样品3-5为Agitan731(Ultra Additives)。
[0030]五个组合物的粘度列在表2中。使用由Rheometric Scientific制造的Advanced Rheology Expansion System(先进流变膨胀系统)测量粘度，采用25mm平行板，在1％应变、1s-1的稳定预剪切速率以及室温下1-100拉德/秒的范围内进行。
表2底部填充剂组合物的粘度
组合物 粘度(cP)
1 5,550
2 3,350
3 4,600
4 4,360
5 12,070
样品的粘度全部在丝网印刷和模版印刷所必需的范围内。
[0031]实施例2：为了发现合适的B阶段条件，需要两个标准。这些标准是：在B阶段之后，材料必须是非粘性的且不固化。为测试是否满足这些标准，将八个玻璃片用20密耳的焊料球形成凸起。然后将列在表1中的大约20密耳的组合物1模版印制到玻璃片上。然后将每个玻璃片放置到130℃烤箱中。然后，在烤箱中对每一个片进行不同时间的B阶段(30、40、50、60、70、80、90或100分钟)。在每一个片已经冷却之后，将木棍放在膜的上面，以评价粘性。如果木棍在膜上留下痕迹，则认为该膜是粘性的。如果木棍没有留下痕迹，则认为该膜是非粘性的。为进行固化试验，将每一个片放置经过低共熔焊料回流炉。在所述片经历回流过程之后，检查每个片，以确定焊料是否已经熔化。当焊料熔化时，固化时间被认为是非固化B阶段时间：留在炉中的时间没有开始总固化过程。然而，当焊料没有熔化时，B阶段时间被认为太长，并且已经固化了底部填充剂。结果示于表3中。
表3底部填充剂的B阶段性质
时间(在130℃的分钟数) 粘性 固化
30 Y N
40 Y N
50 N N
60 N N
70 N Y
80 N Y
90 N Y
100 N Y
[0032]如在表3中所示，当所述底部填充剂被进行B阶段最佳时间以下时，所得的膜对于触摸保持粘性。当所述底部填充剂被进行B阶段最佳时间以上时，膜的固化开始，这对附着工艺具有不利影响。在130℃时，最佳固化时间是大约50-60分钟。因为所述底部填充剂的固化起始温度是约150℃，所以进行B阶段很少采用130℃以上的温度。可以使用130℃以下的温度，但是温度越低，达到合适B阶段状态所需的时间越长。
[0033]实施例3：已经进行B阶段的底部填充剂的合适Tg是关键的。如用于切割晶片的金刚石锯可以干净利落地切穿具有Tg范围在约50℃至95℃的材料。如果所述Tg远高于目标范围，则断裂可能发生并将所述已进行B阶段的底部填充剂从晶片中断裂出去。如果Tg为50℃以下，则膜在切割的过程中可能变为粘性并粘住金刚石锯。制备了几种具有低Tg的组合物，观察结果示于表4中。以5℃/分钟的速率使温度渐升，并通过TA Instruments热机械分析仪，使用TA分析程序，测量每一个样品的Tg。类似于表1中的组合物，制备组合物A和B。在这些组合物中使用低Tg树脂(组合物A由EPON1001和马来酰亚胺的混合物组成。组合物B由EPON1001和甲基丙烯酸缩水甘油酯(glycidal methacrylate)组成)。表4也阐明了表1的五个样品的Tg。这五个样品的Tg落在可切割范围内(50℃-90℃)，并且显示是可切割的。
表4底部填充剂的切割性质
组合物 Tg(℃) 切割观察
A 21 与锯粘连
B 48 与锯粘连
1 62-64 干净利落地切割
2 79-84 干净利落地切割
3 58-60 干净利落地切割
4 87-94 干净利落地切割
5 74-80 干净利落地切割
[0034]实施例4：测量几种不同的环氧树脂/助熔剂混合物的粘度。通过将90 wt％环氧树脂(Z＝EPON1001、Y＝EPON1002、X＝EPON1004、W＝EPON1007和V＝EPON1009)和10％助熔剂PSPA(聚癸二酸酐(polysebaeic polyanhydride))混合在一起，制备每一个混合物Z、Y、X、W和V。将每一个都具有20密耳直径的三个焊料球放置在五个独立的铜基板上。将混合物之一印刷在每一个基板上的焊料球顶部。然后将每一个印刷的基板加热至150℃2分钟，之后即刻加热至190℃ 1分钟。对所述焊料的观察结果示于表5。同样在表5中，报告每一种混合物的粘度。在100拉德/秒的频率下，采用Rheometric ScientificInstrument的单点分析，使用5％应变、190℃温度以及50mm平行板来测定每一个粘度。
表5：焊料熔化观察结果
样品 在190℃的粘度(cP) 焊料熔化观察结果
Z 874 完全熔化
Y 2,905 完全熔化
X 5,951 部分熔化
W 16,615 没有熔化
V 351,141 没有熔化
[0035]如在表5中所示，优选粘度为约5,900cP或更低的树脂，以提供助熔性能。
[0036]通过焊料球半径的变化可以测量发生助熔的程度。测量含有各种助熔剂的焊料球的半径，结果示于表6中。
表6助熔剂
酸 PKa 焊料半径(密耳)
柠檬酸 3.14 35.68
Corfree M2 4.59 31.67
L-半胱氨酸 7.85 10.00
间苯二酚 9.87 10.00
氢醌 10.35 10.00
[0037]如在表6中所示，在被测试的助熔剂中，柠檬酸和CorfreeM2是优选的。使用如上所述的方法，测试表1中所列组合物的助焊性能。表1中的所有组合物都显示焊料球半径的增大。
[0038]实施例5：下面的实施例显示催化剂类型对已进行B阶段的环氧-低聚物基底部填充剂涂层的固化行为的影响。在DSC法中，已进行B阶段的涂层的热固化曲线被用于证明和底部填充剂组合物在一起的催化剂的潜在固化能力。
[0039]为制备组合物，在140℃，将100份Epon 1001F(双酚-A缩水甘油醚低聚物，来自Resolution Performance Products)溶解在67份γ-丁内酯(Aldrich Chemical)中1小时。在将该均匀混合物冷却至室温之后，加入10份Corefree M2(来自DuPont的十二烷二酸作为助熔剂)、0.25份消泡剂Agitan731(Dee Foo Products)、0.5份A-187(Silquest)和0.25份催化剂(如表7中所列)。
[0040]在所有组分已经被手动混合在一起之后，在室温下使它们通过3-辊研磨机，并在真空炉中脱气。所有组合物是均匀的且无气泡，并且具有接近3500cP的粘度(5rpm下的Brookfield粘度计)。
[0041]为评价固化，通过模版印制方法(stenciling process)，将底部填充材料分配在盖玻片(glass cover-slips)(25×25mm)上，得到175微米厚的涂层。B阶段在预热至140℃的对流炉中进行，持续30分钟。在B阶段之后，所有涂层是光滑的、非粘性且无空隙的。然后，将这些经B阶段的涂层用于固化研究。
[0042]根据DSC固化曲线(以20℃/min缓升)，记录经B阶段的环氧-低聚物基底部填充剂体系(在0.25wt％环氧基础上具有不同催化剂)的峰固化温度和固化焓，并示于表7中。在DSC样品已经冷却至室温之后，将它们再次缓慢升温(此次为10℃/分钟)，记录固化Tg。DSC固化差示热分析图示于图1中。
表7具体不同催化剂的环氧-低聚物基底部填充剂
组合物 2P4MZ 2P4MZ-PMDA加合物 AMICURE2PIP Curezol17Z B阶段Tg(℃) 固化峰温(℃) 固化焓(J/g) 固化Tg(℃)
A 0.25 ----- ----- ----- 83.9 无 无 84.0
B ----- 0.25 ------ ------ 39.5 219.4 22.4 63.1
C ----- ------ 0.25 ------ 41.0 218.4 33.4 68.3
D ----- ------ ------ 0.25 39.4 213.2 18.4 52.1
[0043]如在表7和图1中所示，在B阶段步骤期间，2P4MZ(在组合物A中)完全固化涂层，并且在DSC升温中未观察到固化放热。在B阶段和DSC固化之后相同的Tg(固化Tg)也显示在B阶段期间的显著增加。在B阶段期间的该早期固化导致流动差，并且干扰回流期间的焊料互连。
[0044]对于体系B-D，固化放热被延迟超过200℃(超过在183℃下的锡/铅液相线并接近典型的无铅焊料熔融温度)。固化的延迟(与传统2P4MZ型咪唑固化剂相比)为焊料在底部填充树脂固化之前熔化并形成互连提供了较大的时间期间(time window)。当通过经历标准回流焊接工艺而装配用组合物(B-D)涂布的、焊料凸起的芯片时，良好熔化、回流以及焊凸与基板的互连得以形成。在用组合物A涂布形成凸起的芯片的情况下，固化的底部填充材料在回流期间不流动，不能实现焊料互连。
[0045]在三种组合物(B-D)中，组合物C提供了最高B阶段Tg和固化焓。较高的B阶段Tg是期望的，以确保晶片的干净利落切割。较高的固化焓表明更宽的B阶段期间(B-stage window)，其中在回流期间(而不是B阶段步骤)发生更多的反应。
[0046]在不违背本发明的精神和范围的条件下，可以对本发明做出许多修改和变化，这对于本领域的技术人员而言将是显而易见的。本文所述的具体实施方案仅以实施例的方式提供，并且本发明仅通过所附权利要求以及这样的权利要求所授权的等效物的全部范围来加以限定。

Claims (25)

1.可B阶段的底部填充包封剂，其中所述包封剂在所述B阶段过程中在第一温度下固化，以在半导体晶片或硅芯片上产生光滑、非粘性表面，以及其中基本上全部的所述包封剂在第二温度下固化，所述第二温度高于所述第一温度，其中所述包封剂包括：
a)可热固化树脂：
b)咪唑磷酸盐催化剂；
c)至少一种溶剂；
d)一种或多种助熔剂；和
e)任选地，表面活性剂、湿润剂、消泡剂、偶联剂、无机填料、助粘剂、流动添加剂、脱气剂及其混合物中一种或多种。
2.权利要求1所述的包封剂，其中所述可热固化树脂选自双酚A的单官能和多功能缩水甘油醚、双酚F的单官能和多功能缩水甘油醚、脂族环氧树脂、芳族环氧树脂、饱和环氧树脂、不饱和环氧树脂、脂环系环氧树脂，所述环氧树脂具有如下结构：
Figure A2007100070380002C1
Figure A2007100070380003C1
以及它们的混合物。
3.权利要求2所述的包封剂，其中所述可热固化树脂选自3，4-环氧环己基甲基-3，4-环氧环己烷羧酸酯、乙烯基环己烯二酮、3，4-环氧-6-甲基环己基甲基-3，4-环氧环己烷羧酸酯、二氧化双环戊二烯、双酚A环氧树脂、双酚F环氧树脂、环氧酚醛清漆树脂、苯基缩水甘油醚/甲醛共聚物、联苯型环氧树脂、双环戊二烯-苯酚环氧树脂、萘醛环氧树脂、环氧官能丁二烯丙烯腈共聚物、环氧官能聚二甲基硅氧烷和它们的混合物。
4.权利要求3所述的包封剂，其中所述可热固化树脂占所述包封剂的约20wt％至约90wt％。
5.权利要求5所述的包封剂，其中所述可热固化树脂占所述包封剂的约20wt％至约80wt％。
6.权利要求1所述的包封剂，其中所述咪唑磷酸盐包括2-苯基咪唑磷酸二氢盐。
7.权利要求6所述的包封剂，其中所述咪唑磷酸盐包含磷酸含量。
8.权利要求1所述的包封剂，其中所述咪唑磷酸盐占所述包封剂的约0.01wt％至约10wt％。
9.权利要求8所述的包封剂，其中所述咪唑磷酸盐占所述包封剂的约0.1wt％至约5wt％的范围。
10.权利要求1所述的包封剂，其中所述至少一种溶剂选自稳定且溶解所述组合物中的环氧树脂的溶剂。
11.权利要求9所述的包封剂，其中所述至少一种溶剂选自酮、酯、醇、醚、γ-丁内酯和丙二醇甲醚乙酸酯(PGMEA)及它们的混合物。
12.权利要求11所述的包封剂，其中所述至少一种溶剂选自γ-丁内酯、丙二醇甲醚乙酸酯(PGMEA)及它们的混合物。
13.权利要求9所述的包封剂，其中所述溶剂占所述包封剂的可达大约80wt％。
14.权利要求1所述的包封剂，其中所述至少一种助熔剂选自羧酸、松香胶、十二烷二酸、己二酸、癸二酸、聚癸二酸酐、顺丁烯二酸、酒石酸、柠檬酸、醇、羟基酸和羟基碱、多元醇、乙二醇、甘油、3-[双(缩水甘油氧甲基)甲氧基]-1，2-丙二醇、D-核糖、D-纤维素二糖、纤维素、3-环己烯-1，1-二甲醇以及它们的混合物。
15.权利要求14所述的包封剂，其中所述至少一种助熔剂包括松香胶、十二烷二酸、己二酸或它们的混合物。
16.权利要求15所述的包封剂，其中所述至少一种助熔剂占所述包封剂的约0.5wt％至约20wt％。
17.权利要求16所述的包封剂，其中所述至少一种助熔剂占所述包封剂的约1wt％至约10wt％。
18.权利要求1所述的包封剂，其中所述包封剂还包括表面活性剂、湿润剂、消泡剂、偶联剂、无机填料、助粘剂、流动添加剂、脱气剂及其混合物中一种或多种。
19.权利要求18所述的包封剂，其中所述表面活性剂选自有机丙烯酸类聚合物、硅氧烷、环氧-硅氧烷、聚氧乙烯/聚氧丙烯嵌段共聚物、乙二胺基聚氧乙烯/聚氧丙烯嵌段共聚物、多元醇基聚氧化烯、脂肪醇基聚氧化烯、脂肪醇聚氧化烯烷基醚以及它们的混合物。
20.具有可B阶段底部填充组合物的硅晶片，所述可B阶段底部填充组合物沉积在所述晶片的一面上，在单一温度下可固化，所述可B阶段组合物包括：
a)可热固化树脂；
b)咪唑磷酸盐催化剂；
c)至少一种溶剂；
d)一种或多种助熔剂；和
e)任选地，选自表面活性剂、湿润剂、消泡剂、偶联剂、无机填料、助粘剂、流动添加剂、脱气剂及其混合物中的一种或多种添加剂。
21.一种制备一个或多个硅芯片的方法，包括步骤：
a)将权利要求1所述的包封剂应用于半导体晶片；
b)在所述半导体晶片上对所述包封剂进行B阶段加工，以使所述包封剂固化为光滑、非粘性涂层；和
c)将所述半导体晶片切割为单个硅芯片。
22.权利要求21所述的方法，其中所述包封剂通过旋转涂布、丝网印刷或模版印刷被应用于所述半导体晶片。
23.一种制备电子封装件的方法，包括步骤：
a)将权利要求1所述的包封剂应用于半导体晶片；
b)在所述半导体晶片上对所述包封剂进行B阶段加工，以使所述包封剂固化为光滑、非粘性涂层；
c)将所述半导体晶片切割为多个硅芯片，每一个芯片具有用所述包封剂涂敷的第一面；
d)将一个或多个所述硅芯片放置在基板上，以使所述硅芯片的所述第一面紧邻所述基板；和
e)将所述一个或多个硅芯片和所述基板加热至足以在所述一个或多个硅芯片与所述基板之间形成互连的温度。
24.权利要求23所述的方法，包括以下另外步骤：在将所述硅芯片放置在所述基板上之前，将未填充的液体固化助熔材料放置在所述基板上。
25.权利要求24所述的方法，其中所述未填充的液体固化助熔材料包括：
a)可热固化环氧树脂；
b)咪唑-酸酐加合物；和
c)至少一种助熔剂，
其中所述咪唑-酸酐加合物包括2-苯基-4-甲基咪唑和苯均四酸二酐的加合物。
CNA2007100070381A 2006-02-10 2007-02-07 用于晶片封装的底部填充包封剂及其应用方法 Pending CN101016445A (zh)

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