CN1639852A - B-阶底填密封剂及其应用方法 - Google Patents
B-阶底填密封剂及其应用方法 Download PDFInfo
- Publication number
- CN1639852A CN1639852A CNA038049341A CN03804934A CN1639852A CN 1639852 A CN1639852 A CN 1639852A CN A038049341 A CNA038049341 A CN A038049341A CN 03804934 A CN03804934 A CN 03804934A CN 1639852 A CN1639852 A CN 1639852A
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- Prior art keywords
- sealant
- acid
- anhydride
- epoxy resin
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 and optionally Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
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- 150000001875 compounds Chemical class 0.000 claims abstract description 22
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- 239000004065 semiconductor Substances 0.000 claims abstract description 19
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- 239000007788 liquid Substances 0.000 claims abstract description 16
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- 230000004927 fusion Effects 0.000 claims description 21
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
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- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
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- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
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- GVXVZOSSRRPQRZ-UHFFFAOYSA-N propane-1,2-diol;propan-2-yl acetate Chemical compound CC(O)CO.CC(C)OC(C)=O GVXVZOSSRRPQRZ-UHFFFAOYSA-N 0.000 claims description 3
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 2
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
一种在将晶片分割成单芯片之前直接应用在半导体晶片上的可固化底填密封剂组合物。该组合物包括由环氧树脂、含有苯酚的化合物例如苯酚和酚醛树脂组成的热固化树脂体系、溶剂、咪唑-酸酐固化剂、无机填充物、融合剂、和可选择的润湿剂。根据需要也可加入各种其它辅助物例如消泡剂、附着力促进剂、流动添加剂和流变调节剂。底填密封剂可经B-阶处理以在晶片上提供光滑、不粘的涂层并允许晶片被清洁地切割成单芯片。一种生产包含B-阶材料的电子封装件的方法,该方法也可以在与芯片连接的基板上利用未填充液态可固化融合材料。
Description
发明领域
本发明涉及一种底填(underfill)密封剂及其应用到半导体晶片的方法。
发明背景
本发明涉及由环氧树脂和酚醛树脂制备的以保护并增强微电子器件中电子元件与基板之间互连的底填密封剂化合物。微电子器件包括多种类型的电子电路元件,大体上有一同装配在集成电路(IC)芯片中的晶体管,也有电阻、电容、和其它元件。将这些电子元件互连以形成电路,并最终连接到并被支撑在支座或基板上,例如印刷线路板。集成电路元件包括单一裸芯片、单一密封芯片或多芯片的密封组合件。单一裸晶片连接到引线架上,依次密封并连接到印刷线路板,或将其直接连接到印刷线路板。最初,这些芯片由作为包含多芯片的半导体晶片而形成。将半导体晶片切割成所希望的单芯片或芯片封装件。
不管元件是连接到引线架的裸芯片,还是连接到印刷线路板或其它基板的封装件,都在电子元件上的电气终端和基板上对应的电气终端之间进行连接。完成这些连接的一种方法是使用以凸点的形式应用到元件或基板端子的聚合或金属材料。将端子对准并接触在一起,加热最终的组合体以反流金属或聚合材料并固化该连接。
在其正常的有效寿命期间,电子组合体经受升温和降温的周期。由于电子元件、互连材料和基板的热膨胀系数的差异,热循环压迫组合体的元件并引起组合件损坏。为了防止损坏,在元件与基板之间的间隙充满在下文中称为底填或底填密封剂的聚合密封剂,以增强互连材料并吸收一些热循环应力。
底填技术的两个突出的用途是增强工业中已知的封装例如芯片尺寸封装(CSP),其中芯片封装件连接到基板,在弹抛片封装中芯片通过互连阵列连接到基板。
在常规的毛细流动底填应用中,底填的分配和固化发生在金属或聚合物互连的反流之后。在该工序中,熔剂最初应用在基板上的金属衬垫上。其次,将芯片放在基板的熔剂区上,在焊接点的顶部。然后,加热组合件以允许焊点的反流。在这一点上,底填密封剂材料的精确数量沿电子组合件的一个或多个外围侧分配,元件-基板内的间隙毛细管作用向内拉动材料。在充满间隙之后,辅助的底填密封剂沿整个组合件周围分配,以促进减少应力集中并延长组合结构的疲劳寿命。其后固化底填密封剂以达到最佳的最终特性。
最近,提出了将工序制成流水线的设想,并在将晶片切割成单芯片之前通过在半导体晶片上涂敷底填密封剂来提高效率。考虑底填单一应用到以后被切割成大量单芯片的单一半导体晶片的情况,能够通过各种方法包括丝网印刷、镂花印刷术和旋涂执行涂敷工序。
为了用作晶片量级底填密封剂,底填材料必须具有几个重要的特性。首先,必须容易地将材料均一地应用在晶片上,由此整个晶片有一致的涂层。应用到晶片的底填密封剂一定不干扰将晶片分成单芯片的规则地分割。底填密封剂必须是B-阶的,其意味着在密封剂设置在晶片上之后底填材料必须固化以提供具有最小的残留溶剂的光滑、非粘性涂层。
如果起始的底填材料是固体,在溶剂中分散或溶解该固体,以形成浆料和应用到晶片。然后加热底填材料以蒸发溶剂,在晶片上剩下固体但未凝固的底填材料。如果起始的底填材料是液态或浆料,将底填材料分散到晶片上并加热底填材料以部分地将其固化为固态。
B-阶工序通常发生在低于大约150℃的温度下,而不会过早地固化底填密封剂。底填密封剂的最终固化必须延迟到焊料熔化(在焊料是互连材料的情况下)并互连之后,在锡/铅低熔点焊料的情况下B-阶工艺发生在183℃的温度下。在焊料凸点流动并互连之后,底填剂的最终固化应当快速地发生。在单芯片最终连接到基板期间,为了能够有凸起形式,熔化焊料凸点,并在芯片、或芯片钝化层、基板、或焊接掩膜与焊点之间提供优良的粘附力,底填密封剂必须流动。在具体的例子中,直接在基板上提供未填液态可固化融合材料以促进互连是有效的。
发明内容
本发明涉及一种在将晶片切割成单芯片之前直接应用到半导体晶片上的可固化B-阶底填密封剂组合物。该组合物包括由环氧树脂、含有苯酚的化合物例如苯酚或酚醛树脂组成的热可固化树脂体系、溶剂、咪唑-酸酐催化剂、无机填充物、和任意地,融合剂和/或润湿剂。也可以根据要求加入各种其它辅助物,例如去沫剂、附着力促进剂、流动添加剂和流变改良剂。底填密封剂经B-阶处理以在晶片上设置光滑、不粘的涂层并允许晶片被清洁地切割成单芯片。然后将单芯片直接连接到基板。在可选择的实施例中,将未填液态可固化融合材料直接应用到基板以促进与芯片的互连。
本发明的详细描述
在本发明的底填密封剂组合物中使用的树脂是可固化化合物,其意味着它们能够聚合。当在说明书中使用时,固化意味随着交联而聚合。如在现有技术中所理解,交联是通过元素、分子团、或化合物的桥实现两个聚合物链的连接,并主要依靠加热实现。
本发明的B-阶底填密封剂组合物的成分包括一种或多种环氧树脂与含有苯酚的化合物的混合物、充当催化剂的咪唑-酸酐的加合物、一种或多种溶剂、和无机填充物。可选择地,可以包括融合剂、除气剂、流量添加剂、附着力促进剂、流变改进剂、表面活性剂和其它成分。特别地选择这些成分以获得希望的特殊树脂的使用的特性平衡。选择溶剂以溶解树脂并因此在晶片上通过旋涂、丝网印刷或镂花印刷术使组合物成为所应用的具有适当粘性的浆料。在优选实施例中,组合物包括无机填充物、溶剂,并且可经B阶处理,即组合物能最初固化在半导体晶片上产生光滑、非粘性涂层。B阶凝固优选发生在大约100℃至大约150℃的温度范围内。在B阶处理之后,在晶片上获得光滑、非粘性固体涂层以确保将晶片清洁地分割成单晶片。最终完全的固化发生在比B-阶固化温度高的第二温度。通常,组合物的最终固化发生在互连形成之后。在Pb/Sn低熔点焊料的情况下,互连的形成发生在高于焊料熔点的183℃温度下。在组合物中使用潜在催化剂、酸酐与咪唑的加合物以确保组合物适当的固化,而不干扰互连的形成。在B-阶期间,选择的催化剂必须阻止除了最小的预固化之外的任何固化,并必须确保胶凝不发生在B-阶之后形成的非粘性表面上。优选地,B-阶固化发生在至少小于最终固化温度30℃的温度下。
适合用在本晶片量级底填组合物的环氧树脂的实例包括双酚A和双酚F的单官能和多官能缩水甘油醚、脂肪族和芳香环氧树脂、饱和和不饱和环氧树脂、或脂环族环氧树脂或其组合。脂肪族环氧树脂的实例包括挠性环氧树脂1。芳香环氧树脂的实例包括RAS-1、RAS-5和挠性环氧树脂3。
挠性环氧树脂1
挠性环氧树脂-3
不饱和环氧树脂的实例包括Cardolite NC513。
非缩水甘油醚环氧化物的实例包括含有为环状结构的部分的两个环氧化物基团和酯键的3,4-环氧环己基甲基-3,4-环氧环己烷羧化物、含有两个环氧化物基团和其中之一是环状结构的部分的乙烯基环己烯二氧化物、3,4-环氧-6-甲基环己基甲基-3,4-环氧环己烷羧化物和双环戊二烯二氧化物。
在本发明中,优选的是缩水甘油醚环氧化物,可以是单独的或者结合非缩水甘油醚环氧化物的缩水甘油醚环氧化物。该类型较佳的环氧树脂是双酚A树脂。另一个较佳的环氧树脂是双酚F型树脂。这些树脂一般通过一摩尔的双酚F环氧树脂与两摩尔的环氧氯丙烷反应来制备。进一步优选型的环氧树脂是线型酚醛环氧树脂。线型酚醛环氧树脂一般通过酚醛树脂和环氧氯丙烷反应来制备。优选的环氧酚醛清漆树脂是聚(苯基缩水甘油醚)-共聚-甲醛。也可以在本发明中使用联苯型环氧树脂。一般通过联苯树脂与环氧氯丙烷反应制备这种类型的树脂。双环戊二烯-苯酚环氧树脂、萘树脂、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其混合物是可以使用的其他类型的环氧树脂。商用的双酚F型树脂是从CVC Specialty Chemicals,Maple Shade,New Jersey得到,其名称为8230E,并可以从Resolution Performance Products LLC获得,其名称为RSL1739。商用双酚A型树脂可以从Resolution Technology买到,像EPON828,EPON1001,EPON 1002,并且混合的双酚A和双酚F可以从Nippon ChemicalCompany得到,其名称为ZX-1059。也可以使用从Vantico买到的名称为XP71756.00的树脂。
希望的含有苯酚的化合物与非苯酚树脂结合以生产混合物。含有苯酚的化合物优选是苯酚或酚醛树脂,并选择含有苯酚的化合物以为最终的组合物提供高玻璃转化温度。特别优选的酚醛树脂是线型酚醛树脂特别优选的酚是双酚A和二烯丙基双酚A酚醛树脂。线型酚醛树脂的商用的实例是Durez12686(Oxychem),HRJ-2190(Schenectady),SP-560(Schenectady),HRJ-2606(Schenectady),HRJ-1166(Schenectady),HRJ-11040(Schenectady),HRJ-2210(Schenectady),CRJ-406(Schenectady),HRJ-2163(Schenectady),HRJ-10739(Schenectady),HRJ-13172(Schenectady),HRJ-11937(Schenectady),HRJ-2355(Schenectady),SP-25(Schenectady),SP-1068(Schenectady),CRJ-418(Schenectady),SP-1090(Schenectady),SP-1077(Schenectady),SP-6701(Schenectady),HRJ-11945(Schenectady),SP-6700(Schenectady),HRJ-11995(Schenectady),SP-553(Schenectady),HRJ-2053(Schenectady),SP-560(Schenectady),BRWE5300(Georgia-PacificResins),BRWE5555(Georgia-Pacific Resins),和GP2074(Georgia-Pacific Resins)。
除了树脂之外,咪唑-酸酐加合物作为催化剂包含在底填组合物中。加合物为底填提供的特性与由作为独立成分的咪唑和酸酐提供的特性不同。包含在加合物中的优选的咪唑包括非N-取代咪唑例如2-苯基-4-甲基咪唑、2-乙基-4-甲基-咪唑、2-苯基咪唑和咪唑。其它有用的咪唑成分包括烷基-取代咪唑、N-取代咪唑和其混合物。加合物也包括酸酐组分。较佳的酸酐优选是脂环族酸酐,最优选均苯四酸双酸酐,其可以从Aldrich买到,名称为PMDA。其他的优选酸酐包括甲基六-氢邻苯二甲酸酐,其可以从Lonza Inc.Intermediates and Actives买到,名称为MHHPA。其它可以使用的酸酐包括甲基四-氢化邻苯二甲酸酐、nadic甲基酸酐、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、邻苯二甲酸酐、十二烷基琥珀酸酐、二苯基双酸酐、二苯甲酮四羧酸双酸酐、和其混合物。优选的催化剂是通过合并1摩尔份1,2,4,5-苯四羧酸双酸酐和2摩尔份2-苯基-4-甲基咪唑来合成的。两种组分首先在加热的条件下溶解在丙酮中,并且当二者结合时,咪唑-双酸酐盐作为沉淀物形成。结合环氧树脂和溶剂的优选催化剂生产具有大大高于150℃初始固化温度和高于183℃固化峰值温度的未填材料。而且,优选的催化剂提供与仅仅使用咪唑不同的改良的等待时间。
融合剂也掺合到底填组合物中。融合剂主要除去金属氧化物并阻止再氧化。虽然可以使用许多不同的融合材料,最好优先从羧酸组中选择融合剂。这些羧酸包括松香树胶、十二烷二酸(从Aldrich买到的Corfree M2)、己二酸、癸二酸、多癸二酸多酐、马来酸、酒石酸、和柠檬酸。融合剂也可以从包括醇、羟酸和羟碱的组中选择。优选的融合材料包括多元醇例如乙二醇、丙三醇、3-[双(缩水甘油基氧甲基)甲氧基]-1,2-丙烷二醇、D-核糖、D-纤维素二糖、纤维素、3-环己烯-1,1-二甲醇和类似材料。因为酸应当足够强以清洗焊料和基板中的氧化物,所以酸的强度是重要的因素。优选地,酸的pKa应当大于5。温度为大约183℃时的酸的稳定性是重要的,并且酸不应当在低于183℃的温度下分解。由于焊料在183℃时反流,经不起该温度的融合材料不适合用于适合的配方。
利用溶剂改变组合物的粘性。优选地,溶剂将在发生在低于大约150℃的温度时的B-阶处理期间蒸发。容易溶解环氧树脂和酚醛树脂、非活性的和具有从100℃至200℃范围的适当沸点的普通溶剂可以用于本申请。可以使用的溶剂的实例包括酮、酯、醇、醚、和稳定并溶解组合物中环氧树脂和酚醛树脂的其它普通溶剂。优选的溶剂包括γ-丁内酯和丙二醇甲基乙基醋酸酯(PGMEA)。
利用无机填充物以控制组合物的热膨胀系数(CTE)。优选,在由芯片与基板之间的CTE差异产生的在热循环期间,无机填充物将CTE降到帮助减少焊料凸点上的应力的大约30ppm的范围。可以使用的无机填充物的实例包括蛭石颗粒、云母、硅灰石、碳酸钙、二氧化钛、沙、玻璃、熔凝二氧化硅、煅制二氧化硅、氧化铝、硫酸钡、和卤代乙烯高聚物例如四氟乙烯、三氟-乙烯、偏二氟乙烯、氟化乙烯、偏二氯乙烯、和氯乙烯。优选的无机填充物是二氧化硅,从Admatechs买到,商标为FUSOFE。
可以将附加成分加到底填密封剂中以生产具有希望特性的组合物。例如,单官能活性稀释剂能够增量地延迟粘性的增加,而对固化底填材料的物理特性没有不利地影响。尽管可以使用其它的稀释剂,但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、甘油二缩水甘油醚、烷基酚的缩水甘油醚(从Cardolite公司买到,名称为Cardolite NC513)、和丁二醇二缩水甘油醚(从Aldrich买到,名称为BDGE)。可以利用表面活性剂帮助阻止在弹抛芯片焊接工艺和随后的焊点反流及材料固化期间的成孔过程。可以利用的各种表面活性剂包括有机丙烯酸系聚合物、硅酮、聚氧乙烯/聚氧丙烯嵌段共聚物、基于乙二胺的聚氧乙烯/聚氧丙烯嵌段共聚物、基于多元醇的聚氧化烯、基于脂肪醇的聚氧化烯、脂肪醇聚氧化烯烷基醚和其混合物。另外,也可以根据需要加入偶合剂、除气剂、流动添加剂、附着力促进剂和其它成分。
本发明的底填密封剂的优选实施例包括至少一种环氧树脂和至少一种苯酚/酚醛树脂的混合物、作为催化剂的咪唑-酸酐加合物、融合剂、溶剂、无机填充物和根据要求的其它组分。树脂混合物包括大约0.1wt%至大约99.9wt%的环氧树脂和大约0.1%至大约99.9wt%的酚醛树脂。优选地,树脂混合物包括大约40wt%至大约95wt%的环氧树脂和大约5%至大约60wt%的苯酚/酚醛树脂。该混合物将占底填组合物的大约20wt%至大约80wt%。咪唑-酸酐加合物也作为催化剂加入。加合物占底填组合物的大约0.01wt%至大约10wt%,并优选占组合物的大约0.1wt%至大约5wt%。可选地,加入占组合物的大约0.5wt%至大约20wt%并优选在组合物的大约1wt%至大约10wt%的融合剂。此外,组合物包含直至大约70wt%的填充物含量和直至60wt%的溶剂。最终,可以将占组合物的大约0.01wt%至大约5wt%的可选的组分例如表面活性剂、除气剂、流动添加剂、流变调节剂、和附着力促进剂加入组合物。
对于使用B-阶底填组合物,首先通过丝网印刷、旋涂或镂花印刷术将其直接加在半导体晶片或单芯片上。将具有涂层的晶片或芯片加热到初始B-阶温度并B-阶固化组合物。优选地,这产生了光滑并非粘性的涂层。就晶片来说,将晶片分割成单芯片。将具有B-阶组合物的芯片放置在基板上,使基板邻近B-阶组合物,并将整个组合件加热到近似183℃的温度(在使用铅/锡焊料的情况下)。该第二次加热促成了基板与芯片之间互连的形成。
在可选择的实施例中,在放置芯片之前,将包括由环氧树脂、含有酚醛的化合物组成的未填液态可固化融合材料与咪唑/酸酐加合物的组合物直接加到基板。在底填密封剂在晶片上被B-阶固化并将晶片分割成单芯片之后,将芯片放置在基板上,使未填液态可固化材料邻近并接触B-阶材料。未填液态可固化材料易于改善焊料融合并在基板与单芯片之间实现互连。如实例7-9中所示,当将替换实施例的组合物放在基板上并将具有B-阶组合物的芯片放置在基板上时,在反流工艺完成之后,形成优良互连。
参照下面实例可以更好地理解本发明:
实例1:制造包括与53份丙二醇乙基甲基醋酸酯(PGMEA-AldrichChemical)一起混合的各50份的EPON826(Shell Epoxy Resins)和HRJ2190(Schenectady International)的底填密封剂材料。将该混合物加热到143℃并保持5小时30分钟。将最终均匀的混合物冷却到25℃。冷却后,加入108份FUSOFE(Admatechs)、0.5份BYK-W9010(BYK-Chemie)、0.5份A-187(Silquest)、1.8份乙烯基甲基硅氧烷-二甲基硅氧烷共聚物(VDT-131,从Gelest有限公司买到)、和0.4份2-苯基4-甲基咪唑(2P4MZ)/均苯四酸二酸酐(PMDA)加合物。然后,将配方在Double Planetary Ross混合器中分散六小时。混合的底填材料不含气泡,在缓慢剪切时没有夹带空气,并在1s-1的剪切速率时具有30,000cP(30Pa’s)的粘度。然后,通过镂花工艺将底填材料分配在玻璃覆盖片(25mm×25mm)上,以生成110微米厚的涂层。然后,将涂层片放置在预热到135℃的加热板上并B-阶处理15分钟。在B-阶处理之后,发现涂层光滑、不粘并且无空隙。通过DSC发现涂层的玻璃转化温度为大约46℃。玻璃转化温度在用于提供规则切割由B-阶底填组合物涂覆的晶片的希望的范围内。
实例2:根据实施例1中陈述的方法配制底填组合物。材料分配在一片OSP Cu终加工的FR4板上。20毫英寸直径的低熔点焊球放置在材料中。通过在材料的顶部上放置25mm×25mm玻璃盖片并将玻璃片推进与焊球接触而将过量的材料切断。以这种方法,将材料的厚度控制在20毫英寸之内。在除去片之后,将该组合件放置在120℃的真空烘炉上并B-阶处理30分钟。在B-阶处理之后,获得光滑、无空隙、并且不粘的涂层。由于在B-阶处理期间蒸发了溶剂并且涂层薄了大约20%,所以涂层中的焊球从涂层突出。在样品被面向下地放置在1’×3’玻璃片上后,将整个组合件放在被预热到160℃的加热板上。两分钟后,该组合件被转移到另一个被预热到240℃的加热板上加热1分钟。检查玻璃片,观察到焊球润湿了玻璃片并扩大了面积。焊球的增大暗示着密封材料没有过早地固化并没有干扰焊球的扩展和互连的形成。
实例3:为了在也涉及未填环氧树脂/酚醛材料的连接方法中测试底填材料的工作性能,根据实施例1的工艺配制底填组合物。然后,将材料放置在25mm×25mm玻璃盖片上并将低熔点焊球放在接着进行B-阶处理的涂层上。也制备未填组合物。用70份的RSL1739、10份的Flex-1及10份酚醛HRJ1166配制未填环氧树脂/酚醛组合物。这三种树脂混合在一起,而没有加入溶剂,然后加入0.5份的2P4MZ/PMDA咪唑/酸酐加合物及10份的Corfree M2。最终的材料在室温下是液态并在1S -1时具有大约6,500cP(6.5Pa·s)的粘度。将一滴未填组合物放置在用Cu终加工的FR-4板上。用填充的环氧树脂/酚醛材料涂覆25mm×25mm盖片,将低熔点焊球放置在涂层中并对组合件进行B-阶处理。将含有B-阶环氧树脂/酚醛涂层的盖片面向下地放置在基板上,其上有一滴未填组合物。然后,将上述组合件放在已被预热到240℃的加热板上。观察到焊球的融合和与基板的互连。也通过由2P4MZ/PMDA加合物提供的潜在固化,确保未填组合物的固化之前的焊球流向。未填组合物也流动并在固化之前形成围绕盖片的完整的焊脚。在该实例中使用的方法与现行的表面安装技术兼容。在反流工艺中未填组合物的表面张力有助于保持并自动对准该盖片。同时,未填组合物的液态形式在盖片与基板之间提供了更好的焊脚形成、润湿和附着力。这种对芯片和基板使用不同材料的方法也预防了在焊料凸点和晶片上夹带空气和填充物的潜在的问题。
实例4:如表1中所示根据实例1的方法制备底填密封组合物的五种配方。为了确定催化剂的比例和存在的影响,改变2P4MZ/PMDA加合物的装入量并且在一种配方中催化剂是2P4MZ而不是加合物。
表1使用不同的催化剂的环氧树脂/酚醛配方
EPON826 | HRJ2190 | 2P4MZ/PMDA | 2P4MZ | 峰值固化温度(℃) | 固化热函(J/g) | |
A1 | 50 | 50 | 0.5 | 172.9 | 33.2 | |
A2 | 50 | 50 | 0.5 | 157.8 | 31.1 | |
B1 | 50 | 50 | 0.4 | 181.0 | 53.6 | |
B2 | 50 | 50 | 0.25 | 190.3 | 70.5 | |
B3 | 50 | 50 | 0.1 | 203.4 | 90.4 |
如表1中所示,2P4MZ/PMDA加合物的使用将环氧树脂-酚醛体系的固化改变为比那些使用2P4MZ的配方至少高15℃的温度。该温度变换提供了用于融合并在底填材料固化之前形成互连的低熔点焊料的更长时间的窗口。当用配方A1涂覆的焊料凸点芯片通过反流工艺时,确定了焊料凸点到基板的融合、反流和互连。在用配方A2涂覆的凸起芯片情况下,涂层在焊料反流之前固化。而且,表1说明了当减少2P4MZ/PMDA的加入量时,固化被延迟到更高的温度并且固化的热函也更高。这暗示能够最小化在B-阶期间的任何预固化并且在加入较低的催化剂时能够更高效地利用催化剂的潜在固化。可以根据不同的焊料类型调整并选择希望的组合物催化剂加入量,因而得到不同的固化形式。
实例5:如表2中所示配制底两种填密封剂。改变环氧树脂-酚醛树脂的比例以确定比例对于系统固化的影响。
表2树脂/加合物的DSC固化结果
EPON826 | HRJ2190 | 2P4MZ/PMDA | 峰值固化温度(℃) | 固化热函(J/g) | |
C1 | 90 | 10 | 0.5 | 167.2 | 107.7 |
C2 | 80 | 20 | 0.5 | 166.7 | 219.9 |
表2说明了环氧树脂/酚醛的混合比率对固化的热函的影响。当将环氧树脂/酚醛的比例从9∶1降到4∶1时,固化的热函增加一倍以上。加倍归因于每单位酚醛树脂重量的更多的官能团。根据实例1中所述的方法配制三种补充的底填密封剂。如表3所示,改变树脂和加合物的比例。这些配方的涂层经B-阶处理并在DSC中研究它们的固化形式。
表3.B-阶涂层的DSC固化结果
EPON826 | HRJ2190 | 2P4MZ/PMDA | 峰值固化温度(℃) | 固化热函(J/g) | |
D1 | 60 | 40 | 0.5 | 176.6 | 55.3 |
D2 | 57 | 43 | 0.5 | 175.5 | 50.6 |
D3 | 50 | 50 | 0.5 | 172.9 | 33.2 |
如表3中所示,随着酚醛树脂从40份增加到50份,固化峰值改变为稍微低的温度。更重要地,较大地降低了固化的热函。结果与记录的非B-阶配方的结果相反并且暗示着较高的酚醛含量加速了固化并导致了在B-阶期间实质的预固化。因而,能够调整环氧树脂/酚醛的比率和催化剂的含量以在B-阶期间达到希望的固化量。由于在连接工艺期间过早固化大大地影响了流动特性,所以应当最小化在B-阶期间的过早固化。例如,在连接工艺期间由配方D3形成的涂层具有不良的基板可湿性和流动。因而,结果是在芯片和基板之间有不良的连接以及在封装件周围几乎没有焊脚形成。当通过加热及加压连接基板时,配方D1有极少的B-阶固化并具有良好的流动特性。该配方完全地湿润了基板并形成了完整的焊脚。
实例6:根据实例1提出的过程形成两种底填密封剂配方。为了确定融合剂对组合物的影响,将松香树胶加入一种配方中,如表4中提出的。
表4具有/没有融合剂的DSC固化结果
EPON826 | HRJ2190 | 2P4MZ/PMDA | 松香树胶 | 峰值固化温度(℃) | 固化热函(J/g) | |
E1 | 50 | 50 | 0.5 | 172.9 | 33.2 | |
E2 | 50 | 50 | 0.5 | 5 | 174.3 | 68.4 |
如表4中所示,作为助融合的松香树胶的加入将固化峰值提高到稍高的温度。同时,也提高了固化的热函。在B-阶期间,酸基融合剂对延迟涂层的固化有作用。
实例7:通过实例1的方法形成底填密封剂组合物。在25mm×25mm玻璃盖片上涂覆密封剂并在涂层上放置低熔点焊球。在135℃下对涂层B-阶固化15分钟。在B-阶固化后,涂层变得光滑、不粘并无空隙。通过DSC发现涂层的玻璃转化温度为大约46℃。对于该实例的目的,这第一组合物被称为材料A。
用90份的环氧树脂RSL1739和10份的酚醛HRJ1166分别地配制未填液态可固化融合材料。两种树脂混合在一起,而没有加入溶剂,然后加入0.5份的2P4MZ和PMDA加合物及10份的融合剂Corfree M2。最终的材料在室温下是液态并具有大约10,000cP的粘度。对于该实例的目的,这第二组合物被称为材料B。
在充当基板的一片FR4板上放置一滴材料B。将用B-阶固化材料A涂覆的玻璃盖片面向下地放置在基板上,所以材料A和B彼此接触。然后,将整个组合件放置在已预热到240℃的加热板上。在加热之后,观察到焊球面积增大,表明焊料融合并形成互连。并且,在反流工艺之后,观察到围绕盖片的整个焊脚。
实例8:实施这个实例以确定使用实例7的方法组合的封装件相对于不用底填液态可固化材料组合的封装件的附着力。起初,用实例1中描述的含有环氧树脂/酚醛的底填组合物涂敷2mm×2mm硅管芯。在125℃真空条件下对管芯进行B-阶处理30分钟以在管芯的表面上获得光滑、不粘涂层。切割1/2英寸×1/2英寸多片FR-4基板并在150℃下对其预烘烤40分钟以消除任何湿气。在第一测试方法(方法I)中,将一滴未填液态可固化材料放置在预烘烤的FR-4基板片并将管芯面向下地放置在基板上。在第二测试方法(方法II)中,将硅管芯直接放置在裸FR-4基板片上,而在基板上没有未填可固化材料。然后,根据两种方法准备的组合件通过反流炉以形成封装件。在根据方法II形成的封装件中观察到填充的底填材料沿管芯的边缘散开,但没有沿管芯的边缘攀移以形成完整的焊脚。根据方法I准备的薄片围绕管芯的边界形成完整的焊脚。低粘度未填液态可固化材料精确地流动并沿芯片的边缘攀移以形成焊脚。然后,通过记录从FR-4基板剪切管芯的最高力的管芯剪切测试来测试所有芯片。通过Royce仪器管芯-剪切测试器来记录峰值切断力。剪切由各种方法形成的二十个封装件并记录平均剪切力。发现所有的封装件在芯片/材料A界面处都损坏。根据方法II形成的封装件的平均峰值力是13.5±3.5kgf。根据方法I形成的封装件的平均峰值力是19.9±2.6kgf。由于由未填材料B的帮助形成更大焊脚,所以发现在根据方法A形成的封装件的损坏之前的峰值力更高。因而,通过在连接之前使用两种不同但兼容的材料涂敷芯片和基板使附着力提高了大约25%。如现有技术中所理解,优良的润湿和那些材料之间的附着力、以及形成良好的焊脚是获得封装件的可靠性的根本。表5中显示了管芯剪切结果。
表5管芯剪切测试结果
应力(千克/峰值剪切) | |
一层封装 | 10-17 |
两层封装(填充B-阶) | 17-22.5 |
两层封装(填充层固化) | 2.5-7.5 |
Claims (39)
1、一种B-阶底填密封剂,其中密封剂在B-阶处理期间固化以在半导体晶片或硅芯片上产生光滑、不粘表面。
2、根据权利要求1的B-阶密封剂,包括:
a)包括至少一种环氧树脂和至少一种含有苯酚的化合物的混合物的热可固化树脂体系;
b)咪唑-酸酐加合物;
c)至少一种溶剂;以及
d)至少一种无机填充物。
3、根据权利要求2的密封剂,其中至少一种环氧树脂选自包括双酚A的单官能和多官能缩水甘油醚、双酚F的单官能和多官能缩水甘油醚、脂肪族环氧树脂、芳香环氧树脂、饱和环氧树脂、不饱和环氧树脂、脂环族环氧树脂、具有以下结构的环氧树脂或其混合物的组
4、根据权利要求3的密封剂,其中至少一种环氧树脂选自由3,4-环氧环己基甲基-3,4-环氧环己烷羧化物、乙烯基环己烯二氧化物、3,4-环氧-6-甲基环己基甲基-3,4-环氧环己烷羧化物、双环戊二烯二氧化物、双酚A树脂、双酚F型树脂、环氧酚醛清漆树脂、聚(苯基缩水甘油醚)-共聚-甲醛、联二苯型环氧树脂、二环戊二烯-苯酚环氧树脂、萘环氧树脂、环氧官能丁二烯丙烯腈共聚物、环氧官能聚二甲基硅氧烷、和其混合物组成的组。
5、根据权利要求2的密封剂,其中含有苯酚的化合物选自包括酚醛树脂、苯酚或其混合物的组。
6、根据权利要求5的密封剂,其中含有苯酚的化合物包括酚醛清漆树脂、二烯丙基双酚A、双酚A或其混合物。
7、根据权利要求4的密封剂,其中至少一种环氧树脂占环氧树脂/含有苯酚的化合物的混合物的大约0.1wt%至大约99.9wt%。
8、根据权利要求5的密封剂,其中环氧树脂占密封剂的大约40wt%至大约95wt%。
9、根据权利要求8的密封剂,其中至少一种含有苯酚的化合物占环氧树脂/含有苯酚的化合物的混合物的大约0.1wt%至大约99.9wt%。
10、根据权利要求9的密封剂,其中至少一种含有苯酚的化合物占环氧树脂/含有苯酚的化合物的混合物的大约5wt%至大约60wt%。
11、根据权利要求9的密封剂,其中至少一种环氧树脂/含有苯酚混合物占密封剂的大约20wt%至大约80wt%。
12、根据权利要求2的密封剂,其中咪唑-酸酐加合物包括选自包括苯均四酸二酐、甲基六-氢邻苯二甲酸酐、甲基四-氢化邻苯二甲酸酐、nadic甲基酸酐、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、十二烷基丁二酸酐、邻苯二甲酸酐、二苯基双酸酐、二苯甲酮四羧酸双酸酐、1-氰乙基-2-乙基-4-甲基-咪唑、烷基-取代咪唑、三苯膦、鎓硼酸盐、非N-取代咪唑、2-苯基-4-甲基咪唑、2-乙基-4-甲基-咪唑、2-苯基咪唑、咪唑、N-取代咪唑及其混合物的组的咪唑和酸酐的加合物。
13、根据权利要求12的密封剂,其中咪唑-酸酐加合物包括2-苯基-4-甲基咪唑和均苯四酸二酐的加合物。
14、根据权利要求13的密封剂,其中咪唑-酸酐加合物占密封剂的大约0.01wt%至大约10wt%。
15、根据权利要求13的密封剂,其中咪唑-酸酐加合物占密封剂的大约0.1wt%至大约5wt%。
16、根据权利要求2的密封剂,其中至少一种溶剂选自包括在组合物中稳定并溶解环氧树脂和酚醛树脂的溶剂的组。
17、根据权利要求16的密封剂,其中至少一种溶剂选自包括酮、酯、醇、醚、γ-丁内酯和丙二醇甲基乙基醋酸酯(PGMEA)和其混合物的组。
18、根据权利要求17的密封剂,其中至少一种溶剂包括γ-丁内酯和丙二醇甲基乙基醋酸酯(PGMEA)和其混合物。
19、根据权利要求17的密封剂,其中溶剂占密封剂的最高大约60wt%。
20、根据权利要求2的密封剂,其中至少一种无机填充物选自包括蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙、玻璃、熔凝二氧化硅、煅制二氧化硅、氧化铝、硫酸钡、和卤代乙烯高聚物例如四氟乙烯、三氟-乙烯、偏二氟乙烯、氟化乙烯、偏二氯乙烯、氯乙烯和其混合物的组。
21、根据权利要求20的密封剂,其中至少一种无机填充物是二氧化硅。
22、根据权利要求20的密封剂,其中至少一种无机填充物占密封剂的最高大约70wt%。
23、根据权利要求2的密封剂,还包括至少一种融合剂。
24、根据权利要求23的密封剂,其中至少一种融合剂选自包括羧酸、松香树胶、十二烷二酸、己二酸、癸二酸、多癸二酸多酐、马来酸、酒石酸、柠檬酸、醇、羟酸和羟碱、多元醇例如乙二醇、丙三醇、3-[双(缩水甘油基氧甲基)甲氧基]-1,2-丙烷二醇、D-核糖、D-纤维素二糖、纤维素、3-环己烯-1,1-二甲醇和其混合物的组。
25、根据权利要求24的密封剂,其中至少一种融合剂包括松香树胶、十二烷二酸、己二酸、或其混合物。
26、根据权利要求25的密封剂,其中至少一种融合剂占密封剂的大约0.5wt%至大约20wt%。
27、根据权利要求26的密封剂,其中至少一种融合剂占密封剂的大约1wt%至大约10wt%。
28、根据权利要求2的密封剂,其中密封剂还包括一个或多个由表面活性剂、偶合剂、活性稀释剂、除气剂、流动添加剂、粘合促进剂和其混合物组成的组。
29、根据权利要求28的密封剂,其中表面活性剂选自由有机丙烯酸系聚合物、硅酮、环氧硅酮、聚氧乙烯/聚氧丙烯嵌段共聚物、基于乙二胺的聚氧乙烯/聚氧丙烯嵌段共聚物、基于多元醇的聚氧化烯、基于脂肪醇的聚氧化烯、脂肪醇聚氧化烯烷基醚和其混合物组成的组。
30、根据权利要求28的密封剂,其中活性稀释剂选自包括对叔丁基-苯基缩水甘油醚、烯丙基缩水甘油醚、甘油二缩水甘油基醚、烷基的缩水甘油醚、丁二醇二缩水甘油基醚和其混合物的组。
31、根据权利要求2的密封剂,其中将底填密封剂应用到半导体晶片并在将半导体晶片切割成单芯片之前进行B-阶处理。
32、一种具有沉积在晶片的一个表面上的B-阶底填组合物的硅晶片,B-阶组合物包括
a)包括至少一种环氧树脂和至少一种含有苯酚的化合物的混合物的热可固化树脂体系;
b)咪唑-酸酐加合物;
c)至少一种溶剂;以及
d)至少一种无机填充物。
33、一种制备一个或多个硅芯片的方法,包括如下步骤:
a)将权利要求2的密封剂应用于半导体晶片;
b)B-阶处理半导体晶片上的密封剂由此密封剂固化成光滑、不粘涂层;以及
c)将半导体晶片分割成单硅芯片。
34、根据权利要求33的方法,其中通过旋涂、丝网印刷或镂花印刷术将密封剂应用于半导体晶片。
35、一种制备电子封装件的方法,包括:
a)将权利要求2的密封剂应用于半导体晶片;
b)B-阶处理半导体晶片上的密封剂由此密封剂固化成光滑、不粘涂层;
c)将半导体晶片分割成多于一片硅芯片,每一个芯片都有用密封剂涂敷的第一面;
d)将一个或多个硅芯片放置在基板上由此硅芯片的第一面邻接到基板;以及
e)将基板和至少一个硅芯片加热到足以在至少一个硅芯片与基板之间形成互连的温度并固化密封剂。
36、根据权利要求35的方法,包括在将硅芯片放置在基板上之前将未填液态可固化融合材料放置在基板上的辅助步骤。
37、根据权利要求36的方法,其中未填液态可固化融合材料包括:
a)包括至少一种环氧树脂和至少一种含有苯酚的化合物的混合物的热可固化树脂体系;
b)咪唑-酸酐加合物;以及
c)至少一种融合剂。
38、根据权利要求37的方法,其中咪唑-酸酐加合物包括选自包括苯均四酸二酐、甲基六-氢邻苯二甲酸酐、甲基四-氢化邻苯二甲酸酐、nadic甲基酸酐、六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、十二烷基丁二酸酐、邻苯二甲酸酐、二苯基双酸酐、二苯甲酮四羧酸双酸酐、1-氰乙基-2-乙基-4-甲基-咪唑、烷基-取代咪唑、三苯膦、鎓硼酸盐、非N-取代咪唑、2-苯基-4-甲基咪唑、2-乙基-4-甲基-咪唑、2-苯基咪唑、咪唑、N-取代咪唑及其混合物的组的咪唑和酸酐的加合物。
39、根据权利要求38的方法,其中咪唑-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。
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US10/084,873 US20030164555A1 (en) | 2002-03-01 | 2002-03-01 | B-stageable underfill encapsulant and method for its application |
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EP (1) | EP1481420A1 (zh) |
JP (1) | JP4352126B2 (zh) |
KR (1) | KR20040088569A (zh) |
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US20030164555A1 (en) | 2003-09-04 |
KR20040088569A (ko) | 2004-10-16 |
AU2003210985A1 (en) | 2003-09-16 |
US20060125119A1 (en) | 2006-06-15 |
JP4352126B2 (ja) | 2009-10-28 |
US7608487B2 (en) | 2009-10-27 |
WO2003075339A1 (en) | 2003-09-12 |
EP1481420A1 (en) | 2004-12-01 |
CN100350579C (zh) | 2007-11-21 |
JP2005519169A (ja) | 2005-06-30 |
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