CN108137903B - 配制物及其用于3d tsv封装的用途 - Google Patents
配制物及其用于3d tsv封装的用途 Download PDFInfo
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- CN108137903B CN108137903B CN201680055617.0A CN201680055617A CN108137903B CN 108137903 B CN108137903 B CN 108137903B CN 201680055617 A CN201680055617 A CN 201680055617A CN 108137903 B CN108137903 B CN 108137903B
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- Wire Bonding (AREA)
Abstract
本发明提供混合的树脂体系以及其用于三维TSV封装的晶片级底部填充(WAUF)的用途。在一方面,提供包含至少下述组分的组合物:(1)环氧树脂、(2)马来酰亚胺、纳特酰亚胺或衣康酰亚胺、(3)丙烯酸酯和(4)填料。在某些方面,所述环氧树脂为硅氧烷改性的树脂。在某些方面,本发明涉及由本发明组合物制得的底部填充膜。在某些方面,本发明涉及包含本文描述的底部填充膜的制品。
Description
发明领域
本发明涉及混合树脂体系及其用于制备用于三维硅通孔(TSV)封装的晶片级底部填充(WAUF)的方法。在一方面,本发明涉及包含至少下述组分的组合的组合物:(1)环氧树脂、(2)马来酰亚胺、纳特酰亚胺(nadimide)或衣康酰亚胺、(3)丙烯酸酯和(4)填料。在某些方面,所述环氧树脂为硅氧烷改性的树脂。在某些方面,本发明涉及由本发明组合物制得的底部填充膜。在某些方面,本发明涉及包含本文描述的底部填充膜的制品。在某些实施方式中,本发明涉及包含第一制品的组装件,所述第一制品通过本文描述的配制物的固化试样永久粘附至第二制品。
发明内容
根据本发明,提供混合树脂体系及其用于制备用于三维硅通孔(TSV)封装的晶片级底部填充(WAUF)的方法。
在一方面,提供包含至少下述组分的组合的组合物:(1)环氧树脂、(2) 马来酰亚胺、纳特酰亚胺或衣康酰亚胺、(3)丙烯酸酯和(4)填料。在某些方面,所述环氧树脂为硅氧烷改性的树脂。
在某些方面,提供由本发明组合物制得的底部填充膜。
在某些方面,提供包含本文描述的底部填充膜的制品。
在某些方面,提供包含第一制品的组装件,所述第一制品通过本文描述的配制物的固化试样永久粘附至第二制品。
附图简介
图1示出使用根据本发明的配制物施加晶片级底部填充(WAUF)的示例性步骤的流程图。
图2示出各种配制物的熔融粘度数据。一旦扫描温度达到主体材料的起始凝胶温度,其熔融粘度在5℃温度范围内显著增大,并且所述材料变成凝胶。
图3示出一些配制物的差示扫描量热仪(DCS)数据。所有配制物均显示尖锐的DSC起始,并且"DSC起始"温度与"DSC峰"温度之间的ΔT小于15℃。
图4示出使用根据本发明的配制物制备的膜的组装和可靠性测试的示例性工艺流程。
图5示出根据本发明的配制物的施加测试结果。底部填充膜材料显示良好的裸片(die)角覆盖、间隙填充和电互连接头形成。
发明详述
根据本发明,提供包含下述组分的组合物:
环氧树脂;
马来酰亚胺、纳特酰亚胺或衣康酰亚胺;
丙烯酸酯;和
填料;
其中:
所述环氧树脂为可固化成三维聚合物网络的热固性树脂;
所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺为单体的或低聚的,并且可经历自由基固化以形成聚合物网络;
所述丙烯酸酯为单体的或低聚的,并且可经历自由基固化以形成聚合物网络;和
所述填料调节所得到的组合物的热膨胀系数(CTE);
其中:
所述组合物固化后具有:
100℃-205℃的DSC起始温度;
200泊-40,000泊范围内的熔融粘度,和
130℃-180℃的凝胶温度,通过Ares流变仪在10Rad频率下以10℃/ 分钟的变温速率使用直径为1英寸和1mm厚的样品测定。
在一些实施方式中,DSC起始温度落在120℃-205℃的范围内;在一些实施方式中,DSC起始温度落在140℃-205℃的范围内;在一些实施方式中, DSC起始温度落在160℃-205℃的范围内;在一些实施方式中,DSC起始温度落在180℃-205℃的范围内。
在一些实施方式中,熔融粘度落在200泊-20,000泊的范围内;在一些实施方式中,熔融粘度落在200泊-10,000泊的范围内;在一些实施方式中,熔融粘度落在200泊-5,000泊的范围内;在一些实施方式中,熔融粘度落在 200泊-1,000泊的范围内。
在一些实施方式中,所述凝胶温度落在140℃-180℃的范围内,通过 Ares流变仪在10Rad频率下以10℃/分钟的变温速率使用直径为1英寸和1 mm厚的样品测定。在一些实施方式中,所述凝胶温度落在140℃-170℃的范围内,在一些实施方式中,所述凝胶温度落在150℃-180℃的范围内,在一些实施方式中,所述凝胶温度落在150℃-170℃的范围内。
如上所述,本发明的热固性树脂组合物除其他成分之外,还包括环氧树脂组分。各种环氧官能化的树脂可预期用于本文中,例如,基于双酚A 的液体型环氧树脂、基于双酚A的固体型环氧树脂、基于双酚F的液体型环氧树脂(例如,Epiclon EXA-835LV)、基于苯酚-酚醛清漆树脂的多官能环氧树脂、二环戊二烯型环氧树脂(例如,Epiclon HP-7200L)、萘型环氧树脂等,以及它们任意两种或更多种的混合物。
预期用于本文的示例性的环氧官能化的树脂包括脂环族醇的双环氧化物、氢化双酚A(可作为Epalloy 5000商购获得)、六氢领苯二甲酸酐的双官能脂环族缩水甘油酯(可作为Epalloy 5200商购获得)、Epiclon EXA-835LV、Epiclon HP-7200L等,以及它们的任意两种或更多种的混合物。
在某些实施方式中,所述环氧树脂组分可包括两种或更多种不同的基于双酚的环氧树脂的组合。这些基于双酚的环氧树脂可选自双酚A、双酚F 或双酚S环氧树脂,或它们的组合。另外,可使用相同类型的树脂(如A、 F或S)中的两种或更多种不同双酚环氧树脂。
预期用于本文的双酚环氧树脂的可商购获得的实例包括双酚-F-型环氧树脂(如来自Nippon Kayaku,Japan的RE-404-S,和来自Dai Nippon Ink& Chemicals,Inc.的EPICLON 830(RE1801)、830S(RE1815)、830A(RE1826) 和830W,和来自Resolution的RSL1738和YL-983U)和双酚-A-型环氧树脂(如来自Resolution的YL-979和980)。
可从Dai Nippon商购获得和以上指出的双酚环氧树脂以液体未稀释的表氯醇-双酚F环氧树脂推广,其具有比基于双酚A环氧树脂的常规环氧树脂低得多的粘度,并且具有与液体双酚A环氧树脂类似的物理性质。双酚 F环氧树脂具有比双酚A环氧树脂更低的粘度,两种类型的环氧树脂之间所有其他性质相同,双酚F环氧树脂提供更低的粘度,由此提供快速流动的底部填充密封材料。这四种双酚F环氧树脂的EEW为165至180。25℃下的粘度在3,000-4,500cps之间(除RE1801以外,其粘度上限为4,000cps)。据报道,可水解的氯化物含量:RE1815和830W为200ppm,RE1826为 100ppm。
可从Resolution商购获得且以上指出的双酚环氧树脂以含有低氯化物的液体环氧树脂推广。双酚A环氧树脂具有180至195的EEW(g/eq)和 100-250cps的25℃下的粘度。据报道,YL-979的总氯化物含量为500-700 ppm,YL-980的总氯化物含量为100-300ppm。双酚F环氧树脂具有165-180 的EEW(g/eq)和30至60的25℃下的粘度。据报道,RSL-1738的总氯化物含量为500-700ppm,YL-983U的总氯化物含量为150-350ppm。
除双酚环氧树脂之外,其它环氧化合物也预期用作本发明配制物的环氧树脂组分。例如,可使用脂环族环氧树脂,如3,4-环氧基环己基甲基-3,4- 环氧环己基碳酸酯。此外,单官能的、双官能的或多官能的活性稀释剂可用于调节所得到的树脂材料的粘度和/或降低其Tg。示例性的活性稀释剂包括丁基缩水甘油醚、甲苯基缩水甘油醚、聚乙二醇缩水甘油醚、聚丙二醇缩水甘油醚等。
适合用于本文的环氧树脂包括酚类化合物的聚缩水甘油衍生物,如可根据商品名EPON如EPON 828、EPON 1001、EPON 1009和EPON 1031 从Resolution商购获得的那些;可根据商品名DER 331、DER 332、DER 334 和DER 542从Dow Chemical Co.商购获得的那些;和可根据商品名BREN-S 从Nippon Kayaku商购获得的那些。其他适合的环氧树脂包括由多元醇等制得的聚环氧化合物和苯酚-甲醛酚醛清漆的聚缩水甘油衍生物,后者例如是来自DowChemical的DEN 431、DEN 438和DEN 439。甲酚类似物也可根据商品名ARALDITE如ARALDITEECN 1235、ARALDITE ECN 1273和 ARALDITE ECN 1299从Ciba Specialty ChemicalsCorporation商购获得。 SU-8为可从Resolution获得的双酚-A-型环氧酚醛清漆树脂。胺的聚缩水甘油加合物、氨基醇的聚缩水甘油加合物和多羧酸的聚缩水甘油加合物也可用于本发明中,其可商购获得的树脂包括来自F.I.C.Corporation的 GLYAMINE 135、GLYAMINE125和GLYAMINE 115;来自Ciba Specialty Chemicals的ARALDITE MY-720、ARALDITE 0500和ARALDITE 0510;和来自Sherwin-Williams Co的PGA-X和PGA-C。
任选用于本文的适合的单官能环氧共反应物稀释剂包括其粘度低于环氧树脂组分的粘度的那些,通常小于约250cps。
单官能环氧共反应物稀释剂应具有含有约6至约28个碳原子的烷基的环氧基,其实例包括C6-28烷基缩水甘油醚、C6-28脂肪酸缩水甘油酯、C6-28烷基酚缩水甘油醚等。
在包括此类单官能环氧共反应物稀释剂的情况下,此类共反应物稀释剂应以约0.5重量%至约10重量%的量使用,基于所述组合物的总重量;在一些实施方式中,此类共反应物稀释剂应以约0.25重量%至约5重量%的量使用,基于所述组合物的总重量。
所述环氧树脂组分应以约1重量%至约20重量%的量存在于所述组合物中;在一些实施方式中,本发明的配制物包含约2重量%至约18重量%的环氧树脂;在一些实施方式中,本发明的配制物包含约5重量%至约15 重量%的环氧树脂。
在一些实施方式中,本文使用的环氧树脂组分为硅烷改性的环氧树脂,例如,包括下述组分的物质的组合物:
(A)由下述结构包含的环氧树脂组分:
其中:
Y可存在或不存在,当Y存在时,其为直接的键、CH2、CH(CH3)2、 C=O或S,
在此R1为烷基、烯基、羟基、羧基和卤素,和
在此x为1-4;
(B)由下述结构包含的环氧官能化的烷氧基硅烷:
R1-Si(OR2)3
其中
R1为含有环氧乙烷的基团,和
R2为烷基或烷氧基取代的烷基、芳基或芳烷基,具有1至10个碳原子;和
(C)组分(A)和(B)的反应产物。
一种此类硅烷改性的环氧树脂的实例作为芳族环氧树脂如双酚A、E、 F或S环氧树脂或联苯环氧树脂与环氧树脂硅烷的反应产物来形成,其中所述环氧树脂硅烷由下述结构所包含:
R1—Si(OR2)3
其中
R1为含有环氧乙烷的基团,其实例包括2-(乙氧基甲基)环氧乙烷、2-(丙氧基甲基)环氧乙烷、2-(甲氧基甲基)环氧乙烷和2-(3-甲氧基丙基)环氧乙烷,和
R2为烷基或烷氧基取代的烷基、芳基或芳烷基,具有1至10个碳原子。
在一个实施方式中,R1为2-(乙氧基甲基)环氧乙烷和R2为甲基。
用于制备所述硅烷改性的环氧树脂的芳族环氧树脂的理想化结构包括
其中
Y可存在或不存在,当Y存在时,其为直接的键、CH2、CH(CH3)2、 C=O或S,
R1为烷基、烯基、羟基、羧基或卤素,或
x为1-4。
当然,当x为2-4时,所述芳族环氧树脂的链扩展变型也预期被包含在该结构中。
例如,芳族环氧树脂的链扩展变型可被以下结构包含:
在一些实施方式中,所述硅氧烷改性的环氧树脂具有下述结构:
-(O-Si(Me)2-O-Si(Me)(Z)-O-Si(Me)2-O-Si(Me)2)n-
其中:
Z为-O-(CH2)3-O-Ph-CH2-Ph-O-(CH2-CH(OH)-CH2-O-Ph-CH2-Ph-O-)n- CH2-环氧乙烷,和
n落在约1-4的范围内。
在一些实施方式中,所述硅氧烷改性的环氧树脂通过使下述组分的组合在适合于促进它们反应的条件下接触来制备:
其中"n"落在约1-4的范围内。
所述硅烷改性的环氧树脂也可以是芳族环氧树脂、环氧树脂硅烷、芳族环氧树脂与环氧树脂硅烷的反应产物的组合。所述反应产物可由重量比为1:100至100:1如1:10至10:1的重量比的芳族环氧树脂与环氧树脂硅烷来制备。
预期用于本发明的组合物的环氧树脂单体的量为足以使得所得到的配制物包含约1-20wt%范围内的所述环氧树脂。在某些实施方式中,所得到的配制物包含约2-18wt%范围内的所述环氧树脂。在某些实施方式中,所得到的配制物包含约5-15wt%范围内的所述环氧树脂。
环氧树脂固化剂任选地与环氧树脂单体组合使用。示例性的环氧树脂固化剂包括脲、脂族和芳族胺、胺硬化剂、聚酰胺、咪唑、双氰胺、酰肼、脲-胺混合的固化体系、自由基引发剂(例如,过氧化酯、过氧碳酸酯、氢过氧化物、烷基过氧化物、芳基过氧化物、偶氮化合物等)、有机碱、过渡金属催化剂、苯酚、酸酐、路易斯酸、路易斯碱等。
当存在环氧树脂固化剂时,本发明的组合物包含约0.1-2wt%范围内的环氧树脂固化剂。在某些实施方式中,本发明的组合物包含约0.5-5wt%范围内的环氧树脂固化剂。
预期用于本文中的马来酰亚胺、纳特酰亚胺或衣康酰亚胺分别为具有下述结构的化合物:
其中:
m为1-15,
p为0-15,
R2各自独立地选自氢或低级烷基(如C1-5),和
J为包含有机基团或有机硅氧烷基团和它们的两种或更多种的组合的单价或多价基团。
在本发明的一些实施方式中,J为选自下述的单价或多价基团:
-通常在约6个-约500个碳原子范围内的烃基或取代的烃基种类,其中所述烃基种类选自烷基、烯基、炔基、环烷基、环烯基、芳基、烷基芳基、芳基烷基、芳基烯基、烯基芳基、芳基炔基或炔基芳基,然而,条件是只有当J包含两种或更多种不同种类的组合时,J可以是芳基;
-通常在约6个-约500个碳原子范围内的亚烃基或取代的亚烃基种类,其中所述亚烃基种类选自亚烷基、亚烯基、亚炔基、亚环烷基、亚环烯基、亚芳基、烷基亚芳基、芳基亚烷基、芳基亚烯基、烯基亚芳基、芳基亚炔基或炔基亚芳基,
-通常在约6个约500个碳原子范围内的杂环或取代的杂环种类,
-聚硅氧烷,或
-聚硅氧烷-聚氨酯嵌段共聚物,以及
一个或多个上述基团与选自下述的连接基团的组合:共价键、-O-,-S-, -NR-,-NR-C(O)-,-NR-C(O)-O-,-NR-C(O)-NR-,-S-C(O)-,-S-C(O)-O-, -S-C(O)-NR-,-O-S(O)2-,-O-S(O)2-O-,-O-S(O)2-NR-,-O-S(O)-,-O-S(O)-O-, -O-S(O)-NR-,-O-NR-C(O)-,-O-NR-C(O)-O-,-O-NR-C(O)-NR-,-NR-O-C(O)-, -NR-O-C(O)-O-,-NR-O-C(O)-NR-,-O-NR-C(S)-,-O-NR-C(S)-O-, -O-NR-C(S)-NR-,-NR-O-C(S)-,-NR-O-C(S)-O-,-NR-O-C(S)-NR-,-O-C(S)-, -O-C(S)-O-,-O-C(S)-NR-,-NR-C(S)-,-NR-C(S)-O-,-NR-C(S)-NR-,-S-S(O)2-,-S-S(O)2-O-,-S-S(O)2-NR-,-NR-O-S(O)-,-NR-O-S(O)-O-,-NR-O-S(O)-NR-, -NR-O-S(O)2-,-NR-O-S(O)2-O-,-NR-O-S(O)2-NR-,-O-NR-S(O)-, -O-NR-S(O)-O-,-O-NR-S(O)-NR-,-O-NR-S(O)2-O-,-O-NR-S(O)2-NR-, -O-NR-S(O)2-,-O-P(O)R2-,-S-P(O)R2-,或-NR-P(O)R2-;其中R各自独立地为氢、烷基或取代的烷基。
示例性的组合物包括其中J为下述基团的那些:氧烷基、硫烷基、氨基烷基、羧基烷基、氧烯基、硫烯基、氨基烯基、羧基烯基、氧炔基、硫炔基、氨基炔基、羧基炔基、氧环烷基、硫环烷基、氨基环烷基、羧基环烷基、氧环烯基、硫环烯基、氨基环烯基、羧基环烯基、杂环、氧杂环、硫杂环、氨基杂环、羧基杂环、氧芳基、硫芳基、氨基芳基、羧基芳基、杂芳基、氧杂芳基、硫杂芳基、氨基杂芳基、羧基杂芳基、氧烷基芳基、硫烷基芳基、氨基烷基芳基、羧基烷基芳基、氧芳基烷基、硫芳基烷基、氨基芳基烷基、羧基芳基烷基、氧芳基烯基、硫芳基烯基、氨基芳基烯基、羧基芳基烯基、氧烯基芳基、硫烯基芳基、氨基烯基芳基、羧基烯基芳基、氧芳基炔基、硫芳基炔基、氨基芳基炔基、羧基芳基炔基、氧炔基芳基、硫炔基芳基、氨基炔基芳基或羧基炔基芳基、氧亚烷基、硫亚烷基、氨基亚烷基、羧基亚烷基、氧亚烯基、硫亚烯基、氨基亚烯基、羧基亚烯基、氧亚炔基、硫亚炔基、氨基亚炔基、羧基亚炔基、氧亚环烷基、硫亚环烷基、氨基亚环烷基、羧基亚环烷基、氧亚环烯基、硫亚环烯基、氨基亚环烯基、羧基亚环烯基、氧亚芳基、硫亚芳基、氨基亚芳基、羧基亚芳基、氧烷基亚芳基、硫烷基亚芳基、氨基烷基亚芳基、羧基烷基亚芳基、氧芳基亚烷基、硫芳基亚烷基、氨基芳基亚烷基、羧基芳基亚烷基、氧芳基亚烯基、硫芳基亚烯基、氨基芳基亚烯基、羧基芳基亚烯基、氧烯基亚芳基、硫烯基亚芳基、氨基烯基亚芳基、羧基烯基亚芳基、氧芳基亚炔基、硫芳基亚炔基、氨基芳基亚炔基、羧基芳基亚炔基、氧炔基亚芳基、硫炔基亚芳基、氨基炔基亚芳基、羧基炔基亚芳基、杂亚芳基、氧杂亚芳基、硫杂亚芳基、氨基杂亚芳基、羧基杂亚芳基、含有杂原子的二或多价环状基团、含有氧杂原子的二或多价环状基团、含有硫杂原子的二或多价环状基团、含有氨基杂原子的二或多价环状基团、或含有羧基杂原子的二或多价环状基团。
预期用于本发明实践的丙烯酸酯是本领域中熟知的。例如,参见US专利号5,717,034,其整体内容在此通过引用方式并入本文中。
预期用于本文的示例性的丙烯酸酯包括单官能的(甲基)丙烯酸酯、双官能的(甲基)丙烯酸酯、三官能的(甲基)丙烯酸酯、多官能的(甲基)丙烯酸酯等。
示例性的单官能的(甲基)丙烯酸酯包括丙烯酸苯基苯酚酯、丙烯酸甲氧基聚乙烯酯(methoxypolyethylene acrylate)、琥珀酸丙烯酰氧基乙酯、脂肪酸丙烯酸酯、甲基丙烯酰氧基乙基邻苯二甲酸、苯氧基乙二醇甲基丙烯酸酯、脂肪酸甲基丙烯酸酯、丙烯酸β-羧乙酯、丙烯酸异冰片酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸二氢环戊二乙酯、甲基丙烯酸环己酯、甲基丙烯酸叔丁酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙基氨基乙酯、甲基丙烯酸叔丁基氨基乙酯、丙烯酸4-羟基丁酯、丙烯酸四氢糠基酯、丙烯酸苄酯、丙烯酸乙基卡必醇酯、丙烯酸苯氧基乙酯、丙烯酸甲氧基三乙二醇酯、丙烯酸单季戊四醇酯、丙烯酸二季戊四醇酯、丙烯酸三季戊四醇酯、丙烯酸聚季戊四醇酯等。
示例性的双官能的(甲基)丙烯酸酯包括二甲基丙烯酸己二醇酯、甲基丙烯酸羟基丙烯酰氧基丙酯、二丙烯酸己二醇酯、氨基甲酸酯丙烯酸酯、环氧丙烯酸酯、双酚A型环氧丙烯酸酯、改性的环氧丙烯酸酯、脂肪酸改性的环氧丙烯酸酯、胺改性的双酚A型环氧丙烯酸酯、甲基丙烯酸烯丙酯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸二乙二醇酯、乙氧基化的双酚A二甲基丙烯酸酯、二甲基丙烯酸三环癸烷二甲醇酯、二甲基丙烯酸甘油酯、聚丙二醇二丙烯酸酯、丙氧基化乙氧基化双酚A二丙烯酸酯、9,9-双(4-(2- 丙烯酰氧基乙氧基)苯基)芴、三环癸烷二丙烯酸酯、二丙烯酸二丙二醇酯、聚丙二醇二丙烯酸酯、PO改性的二丙烯酸新戊二醇酯、三环癸烷二甲醇二丙烯酸酯、1,12-十二烷二醇二甲基丙烯酸酯等。
示例性的三官能的(甲基)丙烯酸酯包括三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷乙氧基三丙烯酸酯、聚醚三丙烯酸酯、甘油丙氧基三丙烯酸酯等。
示例性的多官能的(甲基)丙烯酸酯包括二季戊四醇聚丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇乙氧基四丙烯酸酯、二- 三羟甲基丙烷四丙烯酸酯等。
预期用于本发明实践的其他示例性的丙烯酸酯包括US专利号 5,717,034中描述的那些,其整体内容在此通过引用方式并入本文中。
任选地,一种或多种其他单体或由其衍生的树脂可存在于本发明的配制物中,例如氰酸酯、聚硅氧烷、氧杂环丁烷、聚酯、聚氨酯、聚酰亚胺、三聚氰胺、脲醛树脂、酚醛树脂等。当存在时,此类材料可以约0.1-约60wt%的范围存在,基于最终配制物的总重量。
当存在时,预期用于本发明实践的氰酸酯单体含有两个或更多个形成氰酸酯(-O-C≡N)基团的环,其在加热时环三聚化以形成取代的三嗪环。因为在氰酸酯单体固化期间没有离去基团或挥发性副产物形成,因而所述固化反应称为加成聚合。可用于本发明实践的适合的聚氰酸酯单体包括,例如,1,1-双(4-氰酰苯基)甲烷、1,1-双(4-氰酰苯基)乙烷、2,2-双(4-氰酰苯基) 丙烷、双(4-氰酰苯基)-2,2-丁烷、1,3-双[2-(4-氰酰苯基)丙基]苯、双(4-氰酰苯基)醚、4,4'-二氰酰二苯基、双(4-氰酰-3,5-二甲基苯基)甲烷、三(4-氰酰苯基)乙烷、氰酸化的酚醛清漆树脂、1,3-双[4-氰酰苯基-1-(1-甲基亚乙基)]苯、氰酸化的苯酚二环戊二烯加合物等。根据本发明使用的聚氰酸酯单体可容易通过使适合的二元或多元酚与卤化氰在酸受体存在下反应来制备。
可任选与根据本发明的聚氰酸酯单体组合的单体选自经历加成聚合的那些单体。此类单体包括乙烯基醚、二乙烯基醚、二烯丙基醚、二甲基丙烯酸酯、二炔丙基醚、混合的炔丙基烯丙基醚、单马来酰亚胺、双马来酰亚胺等。此类单体的实例包括环己烷二甲醇单乙烯基醚、三烯丙基氰尿酸酯、1,1-双(4-烯丙氧基苯基)乙烷、1,1-双(4-炔丙氧基苯基)乙烷、1,1-双(4- 烯丙氧基苯基-4'-炔丙氧基苯基)乙烷、3-(2,2-二甲基三亚甲基缩醛)-1-马来酰亚胺苯、2,2,4-三甲基六亚甲基-1,6-双马来酰亚胺、2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷等。
预期用于本发明实践的其他氰酸酯是本领域中熟知的。例如,参见US 专利号5,718,941,其整体内容在此通过引用方式并入本文中。
当存在时,预期用于本发明实践的聚硅氧烷是本领域中熟知的。例如,参见US专利号5,717,034,其整体内容在此通过引用方式并入本文中。
当存在时,氧杂环丁烷(即,1,3-环氧丙烷)为具有分子式C3H6O的杂环有机化合物,其具有含有3个碳原子和1个氧原子的四元环。所述术语氧杂环丁烷通常也指含有氧杂环丁烷环的任何有机化合物。例如,参见Burkhard等人,Angew.Chem.Int.Ed.2010,49,9052-9067,其整体内容在此通过引用方式并入本文中。
当存在时,预期用于本发明实践的聚酯是指通过多元醇(亦称多羟基醇) 与饱和或不饱和的二元酸的反应形成的缩合聚合物。使用的典型多元醇为二醇如乙二醇;通常使用的酸为邻苯二甲酸和马来酸。连续除去酯化反应的副产物水,驱动反应至完成。使用不饱和聚酯和添加剂如苯乙烯降低树脂的粘度。通过交联链,将初始液体树脂转变成固体。这通过在不饱和键处产生自由基,自由基在链反应中传播至相邻分子中的其它不饱和键,从而在过程中将邻接链连接来完成。
当存在时,预期用于本发明实践的聚氨酯是指由通过氨基甲酸酯(尿烷) 连接的有机单元链组成的聚合物。聚氨酯聚合物通过使异氰酸酯与多元醇反应来形成。用于制备聚氨酯的异氰酸酯和多元醇二者平均每分子均含有两个或更多个官能团。
当存在时,预期用于本发明实践的聚酰亚胺是指由通过酰亚胺键(即,-C(O)-N(R)-C(O)-)连接的有机单元链组成的聚合物。聚酰亚胺聚合物可通过各种反应来形成,即通过二酸酐与二胺的反应,通过二酸酐与二异氰酸酯之间的反应等。
当存在时,预期用于本发明实践的三聚氰胺是指由三聚氰胺(即,1,3,5- 三嗪-2,4,6-三胺)和甲醛通过聚合制得的硬质热固性塑料材料。在其丁基化的形式中,其可溶于正丁醇和/或二甲苯。其可用于与其它树脂如醇酸树脂、环氧树脂、丙烯酸类树脂和聚酯树脂交联。
当存在时,预期用于本发明实践的脲醛树脂是指由脲和甲醛在弱碱如氨水或吡啶存在下加热制得的不透明热固性树脂或塑料。
当存在时,预期用于本发明实践的酚醛树脂是指通过苯酚或取代酚与甲醛反应得到的合成聚合物。
预期用于本发明实践的粒状填料包括二氧化硅、硅酸钙、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、氧化铝(Al2O3)、氧化锌(ZnO)、氧化镁(MgO)、氮化铝(AIN)、氮化硼(BN)、碳纳米管、金刚石、粘土、铝硅酸盐等以及它们的任何两种或更多种的混合物。在一些实施方式中,所述粒状填料为二氧化硅。
通常,用于本发明的配制物的填料具有在约0.005μm(即,5nm)-约20μm 范围内的粒径。在某些实施方式中,本文使用的填料具有在约0.1μm-约5μm 范围内的粒径。
根据本发明的组合物包含在约30-75wt%范围内的所述粒状填料。在一些实施方式中,根据本发明的组合物包含在约40-60wt%范围内的所述粒状填料。
本发明的组合物通常包含:
至少1wt%的所述环氧树脂,
至少6wt%的所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺,
至少4wt%的所述丙烯酸酯,和
至少30wt%的所述填料。
在一些实施方式中,本发明的组合物可进一步包含一种或多种下述组分:
至少1wt%的助熔剂,
至少0.1wt%的粘合促进剂;和/或
至少4wt%的增韧剂。
在一些实施方式中,本发明的组合物可进一步包含一种或多种下述组分:
至多约10wt%的助熔剂,
至多约2wt%的粘合促进剂;和/或
至多约16wt%的增韧剂。
在一些实施方式中,本发明的组合物包含:
在约1-20wt%范围内的所述环氧树脂,
在约6-16wt%范围内的所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺,
在约4-12wt%范围内的所述丙烯酸酯,和
在约30-75wt%范围内的所述填料。
此类组合物可进一步包含一种或多种下述组分:
至少1,至多约10wt%的助熔剂,
至少0.1,至多约2wt%的粘合促进剂;和/或
至少4,至多约16wt%的增韧剂。
本发明的组合物可任选进一步包含在约0.2-2wt%范围内的自由基聚合引发剂。在某些实施方式中,本发明的组合物可进一步包含在约0.2-1wt%范围内的自由基聚合引发剂。
示例性的自由基引发剂包括过氧化酯、过氧碳酸酯、氢过氧化物、烷基过氧化物、芳基过氧化物、偶氮化合物等。
本发明的组合物任选进一步包含一种或多种流动添加剂、粘合促进剂、流变改性剂、增韧剂、助熔剂、膜柔韧剂、环氧固化催化剂(例如,咪唑)、固化剂(例如,自由基引发剂如过氧化二异丙苯)、自由基聚合调节剂(例如, 8-羟基喹啉)、和/或自由基稳定剂,以及它们的任意两种或更多种的混合物。
在此使用的术语"流动添加剂"是指改变其所引入的配制物的粘度的化合物。赋予此类性质的示例性化合物包括硅聚合物、丙烯酸乙酯/丙烯酸2- 乙基己酯共聚物、酮肟的磷酸酯的烷醇铵盐等,以及它们的任何两种或更多种的组合。
在此使用的术语"粘合促进剂"是指提高其所引入的配制物的粘合性质的化合物。
在此使用的术语"流变改性剂"是指改变其所引入的配制物的一种或多种物理性质的添加剂。
在此使用的术语"增韧剂"是指提高其所引入的配制物的耐冲击性的添加剂。
在此使用的术语"助熔剂"是指防止在熔融金属的表面上形成氧化物的还原剂。权利要求1所述的组合物,其中所述助熔剂为羧酸,包括松香胶、十二烷二酸(可从Aldrich作为Corfree M2商购获得)、己二酸、癸二酸、聚癸二酸聚酐、马来酸、酒石酸、柠檬酸等。助熔剂还可包括醇、羟基酸和羟基碱。示例性的助熔材料包括多元醇(例如,乙二醇、甘油、3-[双(缩水甘油基氧基甲基)甲氧基]-1,2-丙烷二醇、D-核糖、D-纤维二糖、纤维素、3-环己烯-1,1-二甲醇等。
在此使用的术语"自由基稳定剂"是指化合物如氢醌、苯醌、受阻酚、受阻胺(例如,硫代羰基硫系化合物)、苯并三唑系紫外线吸收剂、三嗪系紫外线吸收剂、二苯甲酮系紫外线吸收剂、苯甲酸酯系紫外线吸收剂、受阻胺系紫外线吸收剂、硝基氧自由基系化合物等,以及它们的任何两种或更多种的组合。
当存在时,本发明的组合物包含在约0.1-1wt%范围内的所述自由基稳定剂。在一些实施方式中,本发明的组合物包含在约0.1-0.6wt%范围内的所述自由基稳定剂。
本发明的组合物还可任选含有一种或多种稀释剂。当存在稀释剂时,本发明的组合物包含在约10-50wt%范围内的稀释剂,相对于整个组合物。在某些实施方式中,本发明的组合物包含在约20-40wt%范围内的稀释剂。
当存在时,预期用于本文的示例性稀释剂包括芳族烃(例如,苯、甲苯、二甲苯等)、饱和烃(例如,己烷、环己烷、庚烷、十四烷)、氯代烃(例如,二氯甲烷、氯仿、四氯化碳、二氯乙烷、三氯乙烯等)、醚(例如,二乙醚、四氢呋喃、二噁烷、乙二醇醚、乙二醇的单烷基或二烷基醚等)、多元醇(例如,聚乙二醇、丙二醇、聚丙二醇等)、酯(例如,醋酸乙酯、醋酸丁酯、甲氧基醋酸丙酯等);二元酯、α-萜品醇、β-萜品醇、煤油、邻苯二甲酸二丁酯、丁基卡必醇、丁基卡必醇醋酸酯、卡必醇醋酸酯、乙基卡必醇醋酸酯、己二醇、高沸点的醇及其酯、乙二醇醚、酮(例如,丙酮、甲基乙基酮等)、酰胺(例如,二甲基甲酰胺、二甲基乙酰胺等)、杂芳族化合物(例如,N-甲基吡咯烷酮等)等,以及它们的任何两种或更多种的混合物。
预期用于本文的含羟基的稀释剂包括水和具有C1-约C10主链的含羟基化合物。示例性的含羟基稀释剂包括水、甲醇、乙醇、丙醇、乙二醇、丙二醇、甘油、萜品醇等,以及它们的任何两种或更多种的混合物。
根据本发明预期使用的含羟基稀释剂的量可宽范围地变化,通常落在所述组合物的约5-约80重量%的范围内。在某些实施方式中,含羟基稀释剂的量落在整个组合物的约10-60重量%的范围内。在一些实施方式中,含羟基稀释剂的量落在整个组合物的约20-约50重量%的范围内。
任选地,本文描述的组合物可包括流动添加剂等。预期任选地用于本文的流动添加剂包括硅聚合物、丙烯酸乙酯/丙烯酸2-乙基己酯共聚物、酮肟的磷酸酯的烷醇铵盐等,以及它们的任何两种或更多种的组合。
根据本发明的另一实施方式,提供包含将根据本发明的组合物固化的反应产物的底部填充膜。
当暴露于85%相对湿度和85℃下约2天时,根据本发明的底部填充膜通常吸收小于2重量%的水分;在一些实施方式中,当暴露于85%相对湿度和85℃下约2天时,根据本发明的底部填充膜通常吸收小于1.5重量%的水分;在一些实施方式中,当暴露于85%相对湿度和85℃下约2天时,根据本发明的底部填充膜通常吸收小于1.2重量%的水分;在一些实施方式中,当暴露于85%相对湿度和85℃下约2天时,根据本发明的底部填充膜通常吸收小于1.0重量%的水分。
当固化后处于B-阶段时,根据本发明的底部填充膜具有大于约80℃的Tg,Tg通过热力学分析(TMA)测定。
根据本发明的底部填充膜可进一步表征为具有至少5kg/cm2的260℃下的裸片剪切(die shear)(用SiN裸片/PI裸片/SiO2(尺寸:3.81×3.81×700mm3) 所测试,其中所述裸片是在120℃/1kg力/5秒下附着在BT基板上,然后通过在30分钟内将温度从室温升温至175℃来固化,然后在175℃下保持5 小时)。
根据本发明的另一实施方式,提供底部填充膜的制备方法,所述方法包括在将本文描述的组合物施加至适合的基板后将其固化。
根据本发明的另一实施方式,提供包含粘附至其适合的基板的本文描述的底部填充膜的制品。
预期用于本文的适合的基板包括聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚碳酸酯、环氧树脂、聚酰亚胺、聚酰胺、聚酯、玻璃、具有氮化硅钝化层的Si裸片、具有聚酰亚胺钝化层的Si裸片、 BT基板、裸Si、SR4基板、SR5基板等。
本发明的制品中的所述底部填充膜对所述基板的粘合性通常为至少5 kg/cm2,用SiN裸片/PI裸片/SiO2(尺寸:3.81×3.81×700mm3)所测试,其中所述裸片是在120℃/1kg力/5秒下附着在BT基板上,然后通过在30分钟内将温度从室温升温至175℃来固化,然后在175℃下保持5小时。
可使用本发明的材料制备各种制品,例如,包括覆晶封装、堆叠裸片、混合存储立方、TSV装置等。
本发明的各种方面通过下述非限制性实施例来说明。所述实施例用于说明性目的,不是对本发明任何实践的限制。将理解在不背离本发明的精神和范围的情况下可作出变型和修改。本领域普通技术人员容易知晓如何合成或商购获得本文描述的试剂和组分。
实施例
根据本发明的一个方面,提供根据本发明的组合物的制备方法。在本发明的一个实施方式中,所述方法包括使用诸如3辊研磨、球磨等方法将填料分散到液体中的第一步。其目的是将所有的颗粒团聚体分解成单独的亚微米颗粒。随后步骤是添加预期使用的所有其它原料,并对所得到的组合物进行足以制备用于膜涂层的清漆的剪切混合。属于本发明权利要求范围内的示例性配制物呈现在表1中。
表1
1示例性的组合包括Epiclon 850CRP和硅氧烷改性的环氧树脂
2示例性的树脂包括SEA-187环氧丙烯酸酯
3示例性的树脂包括BMI-1700无定形树脂
4示例性的引发剂包括Perkadox 14S、Luperox 101、过氧化二异丙苯和Trigonox145-E85
将以上描述的各配制物进行性能测试(其结果示出在下表2中)。
表2
配制物1 | 配制物2 | 配制物3 | |
DSC起始温度(℃) | 163 | 161 | 173 |
DSC峰值温度(℃) | 168 | 169 | 189 |
起始温度与峰值温度之间的ΔT(℃) | 5 | 8 | 16 |
表2中的差示扫描量热仪(DCS)数据表明,所有配制物具有快速固化性质,"DSC起始"温度与"DSC峰"温度之间的ΔT小于20℃;在一些实施方式中,ΔT小于15℃;和在一些实施方式中,ΔT小于10℃。
以上显示的结果表明,使用独特的混合树脂体系如本文描述的树脂体系,能够获得快速固化型底部填充膜材料。
除本文示出和描述的那些之外,本发明的各种修改对于以上描述的领域的技术人员来说将是显然的。此类修改也意图落在所附的权利要求的范围内。
说明书中提及的专利和出版物指示了本发明所属领域的技术人员的水平。这些专利和出版物通过引用方式并入本文,如同每个单独的出版物或专利申请具体地和单独地通过引用的方式并入本文。
以上描述是对本发明的特定实施方式的说明,但并不意味着对其实践的限制。所附权利要求,包括其所有等同物,用来限定本发明的范围。
Claims (33)
1.一种组合物,其包含:
环氧树脂;
马来酰亚胺、纳特酰亚胺或衣康酰亚胺;
丙烯酸酯;和
填料;
其中:
所述环氧树脂为能够固化成三维聚合物网络的热固性树脂;
所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺为单体的或低聚的,并且能够经历自由基固化以形成聚合物网络;
所述丙烯酸酯为单体的或低聚的,并且能够经历自由基固化以形成聚合物网络;和
所述填料调节所得到的组合物的热膨胀系数(CTE);
其中:
所述组合物固化后具有:
100℃-205℃的DSC起始温度;
200泊-40,000泊范围内的熔融粘度,和
130℃-180℃的凝胶温度,通过Ares流变仪在10Rad频率下以10℃/分钟的变温速率使用直径为1英寸和1mm厚的样品测定。
2.权利要求1所述的组合物,其中所述环氧树脂包含其上具有一个或多个环氧基团的聚合物主链。
3.权利要求2所述的组合物,其中所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、萘环氧树脂、酚醛清漆环氧树脂、硅氧烷改性的环氧树脂、脂环族环氧树脂、联苯环氧树脂、DCPD环氧树脂,以及它们的任何两种或更多种的组合。
4.权利要求1所述的组合物,其进一步包含一种或多种流动添加剂、粘合促进剂、流变改性剂、增韧剂、助熔剂、膜柔韧剂、环氧固化催化剂、固化剂、和/或自由基聚合调节剂,以及它们的任何两种或更多种的混合物;其中,当将组合物用于金属表面时,所述助熔剂与金属表面上的氧化物反应,促进熔融金属的润湿,以及通过充当氧气阻隔层,防止熔融金属表面的氧化。
5.权利要求4所述的组合物,其中所述助熔剂为羧酸、醇或羟基碱。
6.权利要求4所述的组合物,其中所述助熔剂为羟基酸或松香胶。
7.权利要求5所述的组合物,其中所述羧酸为十二烷二酸、己二酸、癸二酸、聚癸二酸聚酐、马来酸、酒石酸或柠檬酸。
8.权利要求5所述的组合物,其中所述助熔剂为多元醇。
9.权利要求4所述的组合物,其中所述粘合促进剂提高所述组合物对基板表面的粘合性。
10.权利要求4所述的组合物,其中所述增韧剂降低所述组合物的材料脆性,并提高其耐冲击性。
11.权利要求3所述的组合物,其中所述硅氧烷改性的环氧树脂具有下述结构:
-(O-Si(Me)2-O-Si(Me)(Z)-O-Si(Me)2-O-Si(Me)2)n-
其中:
Z为-O-(CH2)3-O-Ph-CH2-Ph-O-(CH2-CH(OH)-CH2-O-Ph-CH2-Ph-O-)n-CH2-环氧乙烷,和
n落在1-4的范围内。
14.权利要求13所述的组合物,其中所述低级烷基为C1-5烷基。
15.权利要求13所述的组合物,其中,J为包含有机硅氧烷基团的单价或多价基团。
16.权利要求13所述的组合物,其中J为选自下述的单价或多价基团:
-在6个-500个碳原子范围内的烃基或取代的烃基种类,其中所述烃基种类选自烷基、烯基、炔基、环烷基、环烯基、芳基、烷基芳基、芳基烷基、芳基烯基、烯基芳基、芳基炔基或炔基芳基,然而,条件是只有当J包含两种或更多种不同种类的组合时,J能够是芳基;
-在6-500个碳原子范围内的亚烃基或取代的亚烃基种类,其中所述亚烃基种类选自亚烷基、亚烯基、亚炔基、亚环烷基、亚环烯基、亚芳基、烷基亚芳基、芳基亚烷基、芳基亚烯基、烯基亚芳基、芳基亚炔基或炔基亚芳基,
-在6个-500个碳原子范围内的杂环或取代的杂环种类,
-聚硅氧烷,或
-聚硅氧烷-聚氨酯嵌段共聚物,以及
一个或多个上述基团与选自下述的连接基团的组合:共价键,-O-,-S-,-NR-,-NR-C(O)-,-NR-C(O)-O-,-NR-C(O)-NR-,-S-C(O)-,-S-C(O)-O-,-S-C(O)-NR-,-O-S(O)2-,-O-S(O)2-O-,-O-S(O)2-NR-,-O-S(O)-,-O-S(O)-O-,-O-S(O)-NR-,-O-NR-C(O)-,-O-NR-C(O)-O-,-O-NR-C(O)-NR-,-NR-O-C(O)-,-NR-O-C(O)-O-,-NR-O-C(O)-NR-,-O-NR-C(S)-,-O-NR-C(S)-O-,-O-NR-C(S)-NR-,-NR-O-C(S)-,-NR-O-C(S)-O-,-NR-O-C(S)-NR-,-O-C(S)-,-O-C(S)-O-,-O-C(S)-NR-,-NR-C(S)-,-NR-C(S)-O-,-NR-C(S)-NR-,-S-S(O)2-,-S-S(O)2-O-,-S-S(O)2-NR-,-NR-O-S(O)-,-NR-O-S(O)-O-,-NR-O-S(O)-NR-,-NR-O-S(O)2-,-NR-O-S(O)2-O-,-NR-O-S(O)2-NR-,-O-NR-S(O)-,-O-NR-S(O)-O-,-O-NR-S(O)-NR-,-O-NR-S(O)2-O-,-O-NR-S(O)2-NR-,-O-NR-S(O)2-,-O-P(O)(R)2-,-S-P(O)(R)2-,或-NR-P(O)(R)2-;其中R各自独立地为氢、烷基或取代的烷基。
17.权利要求13所述的组合物,其中J为氧烷基、硫烷基、氨基烷基、羧基烷基、氧烯基、硫烯基、氨基烯基、羧基烯基、氧炔基、硫炔基、氨基炔基、羧基炔基、氧环烷基、硫环烷基、氨基环烷基、羧基环烷基、氧环烯基、硫环烯基、氨基环烯基、羧基环烯基、杂环基、氧基杂环基、硫基杂环基、氨基杂环基、羧基杂环基、氧芳基、硫芳基、氨基芳基、羧基芳基、氧烷基芳基、硫烷基芳基、氨基烷基芳基、羧基烷基芳基、氧芳基烷基、硫芳基烷基、氨基芳基烷基、羧基芳基烷基、氧芳基烯基、硫芳基烯基、氨基芳基烯基、羧基芳基烯基、氧烯基芳基、硫烯基芳基、氨基烯基芳基、羧基烯基芳基、氧芳基炔基、硫芳基炔基、氨基芳基炔基、羧基芳基炔基、氧炔基芳基、硫炔基芳基、氨基炔基芳基或羧基炔基芳基、氧亚烷基、硫亚烷基、氨基亚烷基、羧基亚烷基、氧亚烯基、硫亚烯基、氨基亚烯基、羧基亚烯基、氧亚炔基、硫亚炔基、氨基亚炔基、羧基亚炔基、氧亚环烷基、硫亚环烷基、氨基亚环烷基、羧基亚环烷基、氧亚环烯基、硫亚环烯基、氨基亚环烯基、羧基亚环烯基、氧亚芳基、硫亚芳基、氨基亚芳基、羧基亚芳基、氧烷基亚芳基、硫烷基亚芳基、氨基烷基亚芳基、羧基烷基亚芳基、氧芳基亚烷基、硫芳基亚烷基、氨基芳基亚烷基、羧基芳基亚烷基、氧芳基亚烯基、硫芳基亚烯基、氨基芳基亚烯基、羧基芳基亚烯基、氧烯基亚芳基、硫烯基亚芳基、氨基烯基亚芳基、羧基烯基亚芳基、氧芳基亚炔基、硫芳基亚炔基、氨基芳基亚炔基、羧基芳基亚炔基、氧炔基亚芳基、硫炔基亚芳基、氨基炔基亚芳基、羧基炔基亚芳基、含有杂原子的二或多价环状基团、含有氧杂原子的二或多价环状基团、含有硫杂原子的二或多价环状基团、含有氨基杂原子的二或多价环状基团、或含有羧基杂原子的二或多价环状基团。
18.权利要求13所述的组合物,其中,J为杂芳基、氧基杂芳基、硫基杂芳基、氨基杂芳基、羧基杂芳基、杂亚芳基、氧基杂亚芳基、硫基杂亚芳基、氨基杂亚芳基、或羧基杂亚芳基。
19.权利要求1所述的组合物,其进一步包含有机稀释剂。
20.权利要求1所述的组合物,其中所述组合物包含:
至少1wt%的所述环氧树脂,
至少6wt%的所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺,
至少4wt%的所述丙烯酸酯,和
至少30wt%的所述填料。
21.权利要求20所述的组合物,其进一步包含下述的一种或多种:
至少1wt%的助熔剂,
至少0.1wt%的粘合促进剂;和/或
至少4wt%的增韧剂。
22.权利要求1所述的组合物,其中所述组合物包含:
在1-20wt%范围内的所述环氧树脂,
在6-16wt%范围内的所述马来酰亚胺、纳特酰亚胺或衣康酰亚胺,
在4-12wt%范围内的所述丙烯酸酯,和
在30-75wt%范围内的所述填料。
23.权利要求22所述的组合物,其进一步包含下述的一种或多种:
至少1wt%的助熔剂,
至少0.1wt%的粘合促进剂;和/或
至少4wt%的增韧剂。
24.包含将权利要求1所述的组合物固化的反应产物的底部填充膜。
25.权利要求24所述的底部填充膜,其中当暴露于85%相对湿度和85℃下2天时,所述膜吸收小于2重量%的水分。
26.权利要求24所述的底部填充膜,其中所述膜为B-阶段膜,其固化后具有大于80℃的Tg,Tg通过热力学分析测定。
27.权利要求24所述的底部填充膜,其中所述膜在260℃下的裸片剪切为至少5kg/cm2,用SiN裸片/PI裸片/SiO2测试,,其尺寸为3.81×3.81×700mm3,其中所述裸片是在120℃/1kg力/5秒下附着在BT基板上,然后通过在30分钟内将温度从室温升温至175℃来固化,然后在175℃下保持5小时。
28.底部填充膜的制备方法,所述方法包括在将权利要求1所述的组合物施加至适合的基板后将其固化。
29.包含粘附至其适合的基板的根据权利要求24的底部填充膜的制品。
30.权利要求29所述的制品,其中所述适合的基板为聚乙烯、聚丙烯、环氧树脂、聚酰亚胺、聚酰胺、聚酯、玻璃、具有氮化硅钝化层的Si裸片、具有聚酰亚胺钝化层的Si裸片、BT基板、裸Si、SR4基板或SR5基板。
31.权利要求29所述的制品,其中所述适合的基板为聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯或聚碳酸酯。
32.权利要求29所述的制品,其中所述制品为覆晶封装、堆叠裸片、混合存储立方或TSV装置。
33.权利要求29所述的制品,其中所述底部填充膜对所述基板的粘合性为至少5kg/cm2,用SiN裸片/PI裸片/SiO2测试,其尺寸为3.81×3.81×700mm3,其中所述裸片在120℃/1kg力/5秒下附着在BT基板上,然后通过在30分钟内将温度从室温升温至175℃来固化,然后在175℃下保持5小时。
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PCT/US2016/055698 WO2017062586A1 (en) | 2015-10-07 | 2016-10-06 | Formulations and the use for 3d tsv packages |
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JP6927117B2 (ja) * | 2018-03-29 | 2021-08-25 | 信越化学工業株式会社 | パワーモジュール |
CN110146539B (zh) * | 2019-05-13 | 2021-09-10 | 南京理工大学 | 一种评估物质热分解反应最小分解起始温度的方法 |
KR20210070639A (ko) * | 2019-12-05 | 2021-06-15 | 주식회사 두산 | 반도체 패키지용 언더필 필름 및 이를 이용하는 반도체 패키지의 제조방법 |
KR20220160027A (ko) * | 2020-04-06 | 2022-12-05 | 쇼와덴코머티리얼즈가부시끼가이샤 | 비스말레이미드계 접착제 조성물, 경화물, 접착 시트 및 플렉시블 프린트 배선판 |
KR102485700B1 (ko) | 2020-12-23 | 2023-01-06 | 주식회사 두산 | 반도체 패키지용 언더필 필름 및 이를 이용하는 반도체 패키지의 제조방법 |
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US5646241A (en) | 1995-05-12 | 1997-07-08 | Quantum Materials, Inc. | Bleed resistant cyanate ester-containing compositions |
US5717034A (en) | 1996-07-29 | 1998-02-10 | Quantum Materials, Inc. | Perfluorinated hydrocarbon polymer-filled adhesive formulations and uses therefor |
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US6833629B2 (en) * | 2001-12-14 | 2004-12-21 | National Starch And Chemical Investment Holding Corporation | Dual cure B-stageable underfill for wafer level |
US20030170450A1 (en) * | 2002-03-05 | 2003-09-11 | Stewart Steven L. | Attachment of surface mount devices to printed circuit boards using a thermoplastic adhesive |
JP4952585B2 (ja) * | 2006-01-23 | 2012-06-13 | 日立化成工業株式会社 | 接着剤組成物、フィルム状接着剤、接着シート、並びにそれを用いた半導体装置 |
CN101595553A (zh) * | 2006-12-08 | 2009-12-02 | 汉高股份两合公司 | 涂布有凸点的半导体晶片的方法 |
US20100007018A1 (en) * | 2006-12-08 | 2010-01-14 | Derek Wyatt | Process for coating a bumped semiconductor wafer |
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US20120133061A1 (en) * | 2009-06-30 | 2012-05-31 | Kazuyuki Mitsukura | Photosensitive adhesive, and film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, and semiconductor device, which are made using same |
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US10428253B2 (en) * | 2013-07-16 | 2019-10-01 | Hitachi Chemical Company, Ltd | Photosensitive resin composition, film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, and semiconductor device |
WO2015127179A1 (en) * | 2014-02-24 | 2015-08-27 | Henkel IP & Holding GmbH | Thermally conductive pre-applied underfill formulations and uses thereof |
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KR102592641B1 (ko) | 2023-10-24 |
TWI727977B (zh) | 2021-05-21 |
US20180226313A1 (en) | 2018-08-09 |
WO2017062586A1 (en) | 2017-04-13 |
CN108137903A (zh) | 2018-06-08 |
KR20180066040A (ko) | 2018-06-18 |
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