CN101341212B - 可用作欠填充部分的密封剂并具有再操作性的低放热的热固性树脂组合物 - Google Patents

可用作欠填充部分的密封剂并具有再操作性的低放热的热固性树脂组合物 Download PDF

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CN101341212B
CN101341212B CN2006800478197A CN200680047819A CN101341212B CN 101341212 B CN101341212 B CN 101341212B CN 2006800478197 A CN2006800478197 A CN 2006800478197A CN 200680047819 A CN200680047819 A CN 200680047819A CN 101341212 B CN101341212 B CN 101341212B
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circuit card
semi
semiconducter device
compositions
conductor chip
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CN101341212A (zh
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Q·吉
C·B·陈
H·K·尹
R·赵
W·史
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Henkel American Intellectual Property LLC
Dial Corp
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Henkel Corp
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer

Abstract

本发明涉及可用于在电路板上安装半导体器件，例如芯片大小或芯片规模的封装件(“CSP”)、焊球阵列(“BGA”)、焊盘格栅阵列(“LGA”)、和类似物的热固性树脂组合物，所述半导体器件各自在承载基板上具有半导体芯片，例如大规模集成电路(“LSI”)。类似地，该组合物可用于在电路板上安装半导体芯片本身。当置于合适的条件下时，本发明组合物的反应产物可受控地再操作。和重要的是，与许多商业快速固化的欠填充部分密封剂(“快速固化的欠填充部分”)不同，本发明的组合物拥有在300焦耳/克以下的放热或者在55℃下显示出封装稳定性7天，和因此不要求特殊的封装通过航空快递运输或者得到国际运输当局，例如美国运输局的特殊批准以允许这种空运。本发明的组合物用于300焦耳/克以下的放热和/或在55℃下证明显示出封装稳定性7天，因此不要求特殊的封装通过航空快递运输或者得到国际运输当局，例如美国运输局的特殊批准以允许这种空运。

Description

可用作欠填充部分的密封剂并具有再操作性的低放热的热固性树脂组合物
技术领域
本发明涉及适用于安装到电路板上的半导体器件，例如芯片大小或芯片规模的封装(“CSP”)、焊球阵列(“BGA”)、焊盘格栅阵列(landgrid array)(“LGA”)和类似物上的热固性树脂组合物，所述半导体器件各自在承载基板上具有半导体芯片，例如大规模集成电路(“LSI”)。类似地，该组合物可用于在电路板上安装半导体芯片本身。当置于合适的条件下时，本发明的组合物的反应产物是可控地可再操作的。重要的是，与许多商业快速固化的欠填充部分(underfill)密封剂(“快速(snap)固化的欠填充部分”)不同，本发明的组合物放热在300焦耳/克以下，或者证明在55℃下包装稳定7天，因此不需要通过航空快递(air courier)输送特殊的包装，或者国际运输当局，例如美国运输局的特殊批准以允许这种空运。
背景技术
小型数码记录器、蜂窝(或移动)电话装置、便携式数码音乐记录器/播放器(例如iPod)和兼有这些特征的器件的大众化具有使LSI器件尺寸下降的期望。结果，使用CSP、BGA和LGA降低封装件的尺寸基本上为裸芯片的尺寸。CSP、BGA和LGA改进电子器件的特征同时保留许多它们的操作特征，因此起到保护裸露的半导体芯片，例如LSI的作用且有助于其测试。
通常通过使用焊接连接，将CSP/BGA/LGA组件与电路板上的导电体相连。然而，当所得CSP/BGA/LGA/电路板结构暴露于热循环、振动、扭曲下或下落时，在电路板与CSP/BGA/LGA之间的焊接连接的可靠度常常遭到怀疑。在CSP/BGA/LGA组件安装到电路板上之后，在CSP/BGA/LGA组件和电路板之间的空间常常用密封树脂(常常称为欠填充部分密封)填充，以便减少因热循环引起的应力，从而改进热冲击性能并提高组装结构的可靠度。
然而，由于形成交联网络的热固性树脂组合物固化时典型地用作欠填充部分密封材料，因此在CSP/BGA/LGA组件安装在电路板上之后最终出现的故障中，在没有破坏或刮伤CSP/BGA/LGA组件-电路板结构的情况下，难以完整地更换CSP/BGA/LGA组件。
美国专利No.6316528(Iida)提到能密封在半导体器件(它包括在承载基板上安装的半导体芯片)和所述半导体器件电连接到其上的电路板之间欠填充部分(underfill)的热固性树脂组合物，该组合物包括约100重量份环氧树脂，约3-约60重量份固化剂，和约1-约90重量份增塑剂。其中在约190-约260℃的温度下加热在固化的热固性体周围的区域范围约10秒-约1分钟的时间段，以便实现软化和其粘合性的很大损失。
另外，设计一些欠填充部分密封剂在低温下快速固化。设计这种产品的技术挑战之一是平衡所需的低温和快速固化与寿命稳定性和低放热。通过冷储存和运输来改进寿命稳定性；然而，产品的放热性质是产品配方所固有的。
国际运输管理当局要求反应性配方具有或者低于一定值(300焦耳/克)的放热，以证明在稍微升高的温度下在设定的时间段内具有稳定性，或者在通过航空运输的专门设计的包装内包装，和在一些管辖区域内要求二者。作为专门设计的包装的实例，参见美国专利No.6070427。
显然，希望提供反应性配方，其放热在设定值以下和结果不要求专门设计的包装，同时提供最终使用者所需的物理性能曲线。
汉高公司(Henkel Corporation)将产品No.3593引入快速固化的欠填充部分，这是一种尤其针对CSP，设计用作毛细流动的底部填充胶的快速固化、快速流动的液体。产品No.3593在商业上被很好地接受。然而，产品No.3593的一些物理性能，例如抗致裂性和湿气吸收可能仍需要改进。
因此希望提供一种可用作欠填充部分密封剂的热固性树脂组合物，它拥有在300J/g以下的放热或者证明在55℃下7天包装稳定性。
尽管现有技术的状况如此，但希望欠填充部分密封材料能被运输且不要求专门设计的包装，以便符合国际运输当局的要求，在例如CSP、BGA或LGA和电路板之间的填充不足的空间内通过毛细作用快速流动，在低温条件下快速固化，提供良好的产率和抗热冲击，同时允许使用它的基板容易加工，和在没有可能牺牲半导体器件保留在基板上或者基板本身完整性的太极端的条件下容易从半导体器件中分离，和在CSP、BGA或LGA中的半导体一旦安装到电路板上最终出现故障的情况下可再操作。
发明内容
本发明提供一种可用作欠填充部分密封剂树脂的热固性树脂组合物。该组合物能通过短暂地热固化使半导体器件，例如CSP/BGA/LGA组件(它包括在承载基板上安装的半导体芯片)牢固地与电路板相连且产率良好，这证明了优良的抗热冲击性能(或热循环性能)，并且在半导体器件或连接故障的情况下，允许CSP/BGA/LGA组件容易地从电路板中除去。类似地，使用本发明的组合物，半导体芯片可牢固地安装到电路板上和视需要从电路板中除去。
本发明的组合物也可在不要求专门设计的包装情况下运输，以便符合国际运输当局的要求；在例如CSP、BGA或LGA和电路板之间的填充不足的空间内通过毛细作用快速流动，和在低温条件下快速固化。
该组合物包括环氧树脂组分、其平均粒度分布是在纳米级(即在约1纳米-约1000纳米范围内)的无机填料组分和释放阳离子催化剂的热引发剂。
这些组合物的反应产物能例如通过暴露于超过固化该组合物所使用的那些温度条件下和/或酸性条件下，通过软化和损失其粘合性可控地再操作。
尽管本发明的热固性树脂组合物在相对低温下在短时间段内可固化，但其固化反应产物具有优良的热冲击性能，而且可通过在加热条件下施加力容易劈开。也就是说，可通过加热本发明的热固性树脂组合物的固化反应产物，容易地除去通过该反应产物固定到电路板上的半导体器件或半导体芯片，从而允许它用溶剂溶胀，或者在加热条件下允许它用溶剂溶胀。
通过使用本发明的热固性树脂组合物，半导体器件，例如CSP、BGA或LGA组件，或者半导体芯片可通过短时间的加热固化牢固地连接到电路板上且具有良好的产率，和所得安装结构显示出优良的热冲击性能(或热循环性能)。而且，在故障的情况下，可容易地除去半导体器件或半导体芯片。这使得可再利用电路板，从而实现生产工艺产率的改进并降低生产成本。
在阅读了本发明“具体实施方式”部分之后，参考附图，本发明的优势和优点将更加容易变得显而易见。
附图说明
图1描述了显示本发明的热固性树脂组合物在其内使用的半导体器件的实例的截面视图。
图2描述了为了修理目的从电路板中除去的半导体器件的截面视图。
图3描述了本发明的热固性树脂组合物在其内使用的半导体倒装片组件的实例的截面视图。
图4描述了再操作本发明的热固性树脂组合物可用的工序流程图，以便从它固定到其上的电路板中除去半导体器件。
图5描述了NANOPOX E的粒度分布。
具体实施方式
热固性树脂组合物广义地包括环氧树脂组分。平均粒度分布范围为约1纳米-约1000纳米的无机填料，和释放阳离子催化剂的热引发剂。
另外，该组合物可包括一种或更多种橡胶增韧剂，粘合促进剂，润湿剂，着色剂，消泡剂，和流动剂。
与本发明的再操作性有关的是，进行在本发明范围内的组合物的这种软化和粘合损失所使用的温度可以大至50℃，这低于这一目的所使用的常规环氧基组合物，例如仅仅基于双酚A型环氧树脂或双酚F型环氧树脂作为环氧树脂的那些组合物降解所要求的温度，通常在约300℃附近或更大。
例如，环氧树脂组分包括两种或更多种不同双酚基环氧树脂的结合物。这些双酚基环氧树脂可选自双酚A、双酚F或双酚S环氧树脂，或其结合物。另外，可使用相同类型树脂内的两种或更多种不同的双酚环氧树脂(例如A、F或S)。
此处使用所期望的双酚环氧树脂的可商购的实例包括双酚F型环氧树脂(例如获自日本Nippon Kayaku公司的RE-404-S和获自Dai NipponInk & Chemicals，Inc.，的EPICLON 830(RE1801)、830S(RE1815)、830A(RE1826)和830W，以及获自Resolution公司的YL-983U)和双酚A型环氧树脂(例如获自Resolution公司的YL-979和980)。
可商购于Dai Nippon公司且如上所述的双酚环氧树脂被提倡作为液体未稀释的表氯醇-双酚F环氧树脂，其粘度比基于双酚A环氧树脂的常规环氧树脂低得多，且具有类似于液体双酚A环氧树脂的物理性能。双酚F环氧树脂的粘度低于双酚A环氧树脂，在这两类环氧树脂的所有其他方面相同的情况下，这提供了较低的粘度和因此快速流动的欠填充部分密封剂材料。这四种双酚F环氧树脂的EEW(环氧当量)为165至180。在25℃下的粘度为3000至4500厘泊(除了其粘度上限为4000厘泊的RE1801以外)。据报道，可水解的氯化物含量对于RE1815和830W来说为200ppm，和对于RE1826来说为100ppm。
商购于Resolution公司且如上所述的双酚环氧树脂被提倡作为含氯化物低的液体环氧树脂。双酚A环氧树脂的EEW(克/当量)为180至195，和在25℃下的粘度为100至250厘泊。YL-979的总氯化物含量据报道为500至700ppm，和YL-980为100至300ppm。双酚F环氧树脂的EEW(克/当量)为165至180和在25℃下的粘度为30至60。RSL-1738的总氯化物含量据报道为500至700ppm，和YL-983U为150至350ppm。
除了双酚环氧树脂以外，其他环氧化合物也包括在本发明的环氧组分内。例如，使用脂环族环氧树脂，例如3，4-环氧基环己基甲基-3，4-环氧基环己基碳酸酯。还使用单官能、双官能或多官能的反应性稀释剂调节粘度和/或降低Tg，例如丁基缩水甘油基醚、邻甲苯基(cresyl)缩水甘油基醚、聚乙二醇缩水甘油基醚或聚丙二醇缩水甘油基醚。
适合于此处使用的环氧树脂当中，还包括酚类化合物的聚缩水甘油基衍生物，例如以商品名EPON商购的那些，例如获自Resolution公司的EPON 828、EPON 1001、EPON 1009和EPON 1031；获自DowChemical Co.，的DER 331、DER 332、DER 334和DER 542；和获自Nippon Kayaku公司的BREN-S。其他合适的环氧树脂包括由多羟基化合物和类似物制备的聚环氧化物，以及可溶可熔酚醛树脂的聚缩水甘油基衍生物，其中后者例如是获自Dow Chemical公司的DEN 431、DEN438和DEN 439。甲酚类似物也以商品名ARALDITE商购，例如获自CibaSpecialty Chemicals Corporation的ARALDITE ECN 1235、ARALDITEECN 1273和ARALDITE ECN 1299。SU-8是获自Resolution公司的双酚A型环氧基可溶可熔酚醛树脂。胺、氨基醇和多聚羧酸的聚缩水甘油基加合物也可用于本发明，其商购树脂包括获自F.I.C.Corporation的GLYAMINE 135、GLYAMINE 125和GLYAMINE 115；获自Ciba Specialty Chemicals公司的ARALDITE MY-720、ARALDITE 0500和ARALDITE 0510以及获自Sherwin-Williams Co.的PGA-X和PGA-C。
此处所使用的合适的单官能的环氧共反应物稀释剂包括粘度低于环氧树脂组分的那些，通常小于约250厘泊。
单官能的环氧共反应物稀释剂应当具有带约6-约28个碳原子的烷基的环氧基，其实例包括C6-28烷基缩水甘油基醚、C6-28脂肪酸缩水甘油基酯和C6-28烷基苯酚缩水甘油基醚。
在包括这种单官能的环氧共反应物稀释剂的情况下，应当基于组合物的总重量，使用用量为最多约5重量％-约15重量％，例如约8重量％-约12重量％的这种共反应物稀释剂。
环氧树脂组分应当以范围为约10重量％-约95重量％，理想地约20重量％-约80重量％，例如约60重量％的用量存在于组合物内。
作为无机填料组分，许多物质潜在地是有用的。例如，无机填料组分可常常包括增强二氧化硅，例如熔凝硅石，且可以未处理或者被处理，以便改变其表面的化学性质。然而，无机填料组分包括平均粒度分布范围为1-1000纳米(“nm”)的颗粒。这种填料颗粒的可商购实例以商品名NANOPOX，例如NANOPOX XP 22由德国Hans Chemie公司销售。NANOPOX填料是在环氧树脂内的单分散的二氧化硅填料分散体，其含量最多约50重量％。通常认为NANOPOX填料的粒度为约5纳米-约80纳米。据报道NANOPOX XP 22在双酚F环氧树脂的二缩水甘油基醚内含有40重量％的粒度为约15纳米的二氧化硅颗粒。
Hans Chemie公司还以NANOPOX E牌号生产材料。例如，HansChemie公司报道的NANOPOX E牌号的产品能完全浸渍在其他情况下难以密封的电子组件并提供大范围的机械和热性能，例如降低的收缩率和热膨胀，断裂韧度和模量。在下表1中，Hahs Chemie公司提供关于四种所述NANOPOX E产品的信息：
表1
  类型   SiO2含量[重量％]   基础树脂   EEW[克/当量]   动态粘度，25℃[毫帕·秒]   特征
  NANOPOX E430   40   DGEBA/DGEBF   290   45,000   没有结晶
  NANOPOX E470   40   DGEBA   295   60,000   基础类型
  NANOPOX E500   40   DGEBF   275   20,000   低粘度
  NANOPOX E600   40   EEC1   220   4,000   脂环族配方
13，4-环氧基环己基甲基-3，4-环氧基环己基碳酸酯
Hans Chemie公司报道了可通过使用NANOPOX E牌号的产品，在环氧配方内显著改进重要的性能。例如：
·与常规的增强填料相比，该配方的粘度较低
·没有沉降
·断裂韧度、抗冲击性和模量增加
·改进的抗划伤性和耐磨性
·降低的收缩率和热膨胀
·改进或至少没有负面影响许多所需的性能，例如热稳定性、耐化学性、玻璃化转变温度、耐候性、介电性能。
NANOPOX E与常规填料，例如石英的结合物使得能降低配方中的树脂含量，这意味着可增加总的填料含量到以前达不到的水平。
与各基础树脂相比，加工性基本上保持不变。
在其中期望或需要上述性能改进且没有因过量增加粘度(已知其来自于热解法二氧化硅)导致牺牲加工性的应用中使用NANOPOX E。应用实例是封装材料和涂层。重要的是强调NANOPOX E的优良浸渍性能，这归因于小的粒度和不存在聚集体。这还使得能完全浸渍在其他情况下难以密封的电子组件。
取决于制造者，NANOPOX E牌号的产品是在环氧树脂基体内的胶态硅溶胶。分散相由直径低于50纳米和基于极窄粒度分布的表面改性的球形SiO2纳米颗粒组成(参见图5)。这些尺寸仅仅数纳米的球以不具有聚集体的形式分配在树脂基体内。这产生SiO2含量最多40重量％的非常低粘度的分散体。由硅酸钠水溶液化学合成纳米颗粒。在这一独特的方法中，粘合剂没有受损，这与其中粉化的填料用溶解器或者使用高剪切能量的其他设备分散的工艺不同。
用作无机填料组分的其他所需的材料包括由氧化铝、氮化硅、氮化铝、二氧化硅涂布的氮化铝、氮化硼及其结合物组成或者包含它们的那些物质，当然条件是该颗粒的平均粒度分布范围为1-1000纳米。
无机填料组分的使用量应当为组合物的约10-约80重量％，例如约12-约60重量％，理想地在约15-约35重量％范围内。
作为释放阳离子催化剂的热引发剂，可根据期望发生固化时的温度来使用许多不同的物质。例如为了实现在约120℃的温度下固化，合适的热引发剂是锑酸铵。对于约150℃-约180℃的温度来说，可使用各种其他物质。
阳离子催化剂的使用量范围应当是全部组合物的约0.05重量％-约10重量％，理想地约0.1重量％-约5重量％，例如约1重量％。
另外，可使用粘合促进剂，例如硅烷、缩水甘油基三甲氧基硅烷(以牌号A-187商购于OSI公司)或γ-氨基丙基三乙氧基硅烷(以牌号A-1100商购于OSI)。
也可在本发明的组合物中使用常规的添加剂实现组合物、固化反应产物或二者的一些所需的物理性能。
本发明的热固性树脂组合物能渗透到电路板和半导体器件之间的空间内。这些本发明的组合物还显示出降低的粘度，至少在升高的温度条件下降低的粘度，和因此能渗透到该空间内。期望通过选择各种成分的类型和比例，实现在25℃下小于或等于5000毫帕·秒的粘度，例如300-2000毫帕·秒，以便改进其渗透到电路板和半导体器件之间的空间(例如10-500微米)内的能力，以制备该热固性树脂组合物。
参考图1，示出了半导体器件安装结构，例如CSP的实例，其中使用本发明的热固性树脂组合物。
半导体器件4是通过连接半导体芯片(所谓的裸芯片)2，例如LSI到承载基板1上并用树脂3合适地密封在其间的空间而形成的半导体器件。该半导体器件安装在电路板5的预定位置上，和通过合适的连接机构，例如焊料6电连接电极8和9。为了改进可靠度，用热固性树脂组合物的固化产物10密封在承载基板1和电路板5之间的空间。热固性树脂组合物的固化产物10不需要完全填充承载基板1和电路板5之间的空间，但可填充到减轻热循环引起的应力的这一程度。
可由下述基板构造承载基板：由Al2O3、SiN3和富铝红柱石(Al2O3-SiO2)制成的所述陶瓷基板；由耐热树脂，例如聚酰亚胺制成的基板或带状物(tape)；由通常还可用作电路板的玻璃增强的环氧树脂、ABS和酚醛基板；和类似物。
关于倒装片组件，参考图3，示出了其中半导体芯片安装在电路板上的倒装片组件，和用本发明的热固性树脂组合物密封的欠填充部分。
通过连接半导体芯片(裸芯片)32到电路板31上并用热固性树脂组合物33合适地密封在其间的空间，形成倒装片组件34。这一半导体器件安装在电路板31的预定位置处，且通过合适的电连接机构37和38，例如焊料电连接电极35和36。为了改进可靠度，用热固性树脂组合物33密封半导体芯片32和电路板31之间的空间，然后固化。热固性树脂组合物的固化产物完全填充该空间。
对电连接半导体芯片到承载基板上的机构没有特别限制，和可使用通过高熔融焊料，或者导电(或各向异性传导)粘合剂、引线接合等连接。为了有助于连接，可以以隆起物形式形成电极。而且，为了改进连接的可靠度和耐久性，可用合适的树脂密封在半导体芯片和承载基板之间的空间。可在本发明中使用的半导体器件包括CSP、BGA和LGA。
对在本发明中所使用的电路板的类型没有特别限制，和可使用任何各种常见的电路板，例如玻璃增强的环氧、ABS和酚醛板。
接下来，以下将描述安装工艺。最初，在电路板的所需位置处印刷焊糊，并合适地干燥，以驱除溶剂。然后，在电路板上与图案保形地安装半导体器件。这一电路板穿过软熔炉，使焊料软熔，从而焊接半导体器件。在半导体器件和电路板之间的电连接不限于使用焊糊，可使用焊球。或者，也可通过导电粘合剂或各向异性传导粘合剂进行这一连接。而且，焊糊或类似物可施加在或者电路板或者半导体器件上或者在其上形成。为了有助于随后的修理，应当牢记其熔点、粘结强度和类似性能来选择所使用的焊料、导电粘合剂或各向异性传导粘合剂。
在半导体器件按照这一方式电连接到电路板上之后，通常应当对所得结构进行继续试验或类似试验。在这一试验合格之后，可用树脂组合物将半导体器件固定到其上。按照这一方式，在最终出现故障的情况下，比较容易除去半导体器件，之后用树脂组合物固定它。
然后，使用合适的施加设备，例如分配器，将热固性树脂组合物施加到半导体器件的周边。当将这一组合物施加到半导体器件上时，它通过毛细作用渗透到电路板与半导体器件的承载基板之间的空间内。
接下来，通过施加热量固化热固性树脂组合物。在这一加热的早期阶段，热固性树脂组合物显示出粘度的显著下降和因此流度的增加，结果它更加容易渗透到电路板与半导体器件之间的空间内。而且，通过提供具有合适通气孔的电路板，允许热固性树脂组合物充分地渗透到电路板和半导体器件之间的全部空间内。
应当合适地调节所施加的热固性树脂组合物的用量，以便几乎完全填充电路板与半导体器件之间的空间。
当使用以上所述的热固性树脂组合物时，通常通过在约80℃-约150℃的温度下加热约5-约60分钟的时间段，例如约120℃下约30分钟的时间段来固化它。因此，本发明可使用相对低温和短时间的固化条件，和因此实现非常良好的产率。按照这一方式完成了图1所示的半导体器件安装结构。
在使用本发明的热固性树脂组合物的安装工艺中，在半导体器件如上所述安装在电路板上之后，测试所得结构的半导体器件特征、半导体器件与电路板之间的连接、其他电特征和密封状态。在最终发现故障的情况下，可按照下述方式进行修理。
在约190℃-约290℃的温度下加热出现故障的半导体器件周围的区域，其时间段范围为约10秒-约60秒，例如在约285℃下30秒。尽管对加热设备没有特别限制，但优选局部加热。可使用相对简单的设备，例如施加热空气到故障位置上。
一旦焊料熔融，和树脂软化，引起粘结强度下降，则牵引开该半导体器件。
在如图2所示除去半导体器件4之后，在电路板5上残留热固性树脂组合物的固化反应产物的残渣12和焊料的残渣14。可例如在加热残渣到预定温度软化残渣之后，擦掉它，允许用溶剂溶胀它，或者允许用溶剂溶胀它同时加热它到预定温度，从而除去热固性树脂组合物的固化产物的残渣。
可通过使用加热和溶剂二者最容易地除去残渣。例如，可在允许残留的树脂用溶剂溶胀同时保持整个电路板在约100℃的温度下(通常范围为约80℃-约120℃)使之软化之后，擦掉残渣(参见图4)。
这一目的所使用的溶剂是引起热固性树脂组合物的固化反应产物溶胀，从而降低粘结强度到固化物质可从电路板上擦掉这一程度的溶剂。有用的溶剂包括有机溶剂，例如烷基氯，例如二氯甲烷；二元醇醚，例如乙基纤维素和丁基纤维素；二元酸的二酯，例如琥珀酸二乙酯；和N-甲基吡咯烷酮。当然也可使用合适的结合物。
在保护电路的抗蚀剂已经与电路板相连的情况下，所选溶剂应当不引起对抗蚀剂损坏。牢记理想的溶剂包括二元醇醚和N-甲基吡咯烷酮。
可例如通过使用吸收焊料的编织线除去焊料残渣。
最后，在根据以上所述的工序清洁电路板时，可再次以与前面所述相同的方式安装新的半导体器件。因此，完成故障位置的修理。
在电路板内发现故障的情况下，可通过以与以上所述相同的方式除去在半导体器件底部上保留的热固性树脂组合物的固化反应产物的残渣12和焊料的残渣14，从而再利用该半导体器件。
通过下述非限定性实施例进一步阐述本发明。
实施例
实施例1
热固性树脂组合物
可由如下表1所示的组分制备本发明的热固性树脂组合物。
表1
Figure S2006800478197D00121
  橡胶增韧剂   ABS5  5
  润湿剂   丙烯酸乙酯-丙烯酸-2-乙基己酯共聚物  ＜1
  粘合促进剂   γ-环氧丙氧丙基三甲氧基硅烷  ＜1
1RE1801获自Dai Nippon Ink & Chemicals公司
2RSL 1738获自Resolution公司
3聚丙二醇缩水甘油基醚
43，4-环氧基环己基甲基-3，4-环氧基环己基碳酸酯
5丙烯腈-丁二烯-苯乙烯共聚物
物理性能
在8×8毫米CSP上在约75℃的分配温度下，由注射器分配未固化状态下的组合物。组合物通过毛细作用在小于30秒内流动到封装件与封装件固定到其上的电路板之间的填充不足的空间内。
尽管在成形时使用该组合物，但预期该组合物可在约5℃的温度下储存最多约3-约6个月的时间段且没有经历任何显著的粘度增加。这是重要的，因为常规的可商购快速固化的欠填充部分密封剂材料通常要求在约-40℃的温度下储存以实现该储存稳定性水平。
可通过将一部分组合物置于铝盘内，和通过差示扫描量热法(“DSC”)分析反应热量(或焓)，从而测定这一组合物的放热。测定焓为约290焦耳/克。
在120℃的温度下约5分钟之后组合物开始固化。
与目前可商购但不具有300焦耳/克以上放热的欠填充部分密封剂材料相比，在低温下快速固化和突出的操作温度稳定性，在室温下的储存期大于1周的结合是相当有利的。
跌落(Dropping)和热循环试验
将组合物暴露于热冲击试验下，同时反复维持在约-55℃的温度下约10分钟的时间段和之后经约10分钟的时间段升高温度到约+125℃。在达到预定次数的热循环之后，进行反复继续试验，以证实在CSP和电路板之间的电连接。当证实继续到至少1000个循环之后，重复测定被视为可接受。
修理
使用热空气发生器，通过施加285℃下的热空气30秒，加热如上所述用热固性树脂组合物固定到电路板上的CSP周围的区域。然后，可通过在CSP和玻璃增强的环氧板之间插入金属片，并抬升CSP，容易地除去CSP。
通过权利要求确定本发明的全部范围。

Claims (3)

1.一种热固性树脂组合物，它能分别密封在半导体芯片和所述半导体芯片电连接到其上的电路板之间，或者在包括安装在承载基板上的半导体芯片的半导体器件和所述半导体器件电连接到其上的电路板之间的填充不足的空间，所述组合物的反应产物可受控降解，所述组合物包括：
(a)含第一双酚环氧树脂、第二双酚环氧树脂和脂环族环氧树脂的环氧树脂组分；
(b)平均粒度分布为1-1000纳米且被处理以便改变其表面化学性质的增强二氧化硅；和
(c)锑酸铵；
其中所述组合物显示出小于300焦耳/克的放热。
2.一种电子器件，它包括使用权利要求1的热固性树脂组合物分别作为半导体器件和电路板之间或者半导体芯片和电路板之间的欠填充部分的密封剂，组装半导体器件和所述半导体器件电连接到其上的电路板，或者组装半导体芯片和所述半导体芯片电连接到其上的电路板，其中该组合物的反应产物在暴露于超过固化该组合物所使用的那些的温度条件下能软化并丧失其粘合性。
3.密封在包括半导体芯片安装在承载基板上的半导体器件和所述半导体器件电连接到其上的电路板之间，或者在半导体芯片和所述半导体芯片电连接到其上的电路板之间的填充不足的空间的方法，其步骤包括：
(a)在半导体器件和电路板或者半导体芯片和电路板之间的填充不足的空间内分配权利要求1的组合物；和
(b)将如此分配的组合物暴露于范围为60-150℃的温度下5分钟的时间段，引起组合物形成反应产物。
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WO2007050611A1 (en) 2007-05-03
CN101341212A (zh) 2009-01-07
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