CN107709418A - 可烧结的膜和膏及其使用方法 - Google Patents
可烧结的膜和膏及其使用方法 Download PDFInfo
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- CN107709418A CN107709418A CN201680033792.XA CN201680033792A CN107709418A CN 107709418 A CN107709418 A CN 107709418A CN 201680033792 A CN201680033792 A CN 201680033792A CN 107709418 A CN107709418 A CN 107709418A
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Classifications
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Abstract
本发明提供了可烧结的膜和膏作为具有优越性能用于半导体封装中的导电芯片贴装材料。还提供了用于制备这种膜和膏的配制品,以及制备这种配制品的方法。在本发明的其它方面,提供了由根据本发明的组合物制备的导电网络。在某些方面,本发明涉及包含粘附在适当基底上的这种烧结膜和膏的制品。
Description
技术领域
本发明涉及可烧结的膜和膏以及用于制备这种膜和膏的组合物。一方面,本发明涉及制备这种组合物的方法。另一方面,本发明还涉及由基于本发明的组合物制备的导电网络及其制造方法。此外另一方面,本发明涉及将导电膜层压到基底上的方法和将导电膏分配到基底上的方法。
背景技术
由于环境法规要求在电子设备中使用无铅材料,所以芯片贴装行业聚焦于软焊料替代材料。另外,芯片贴装材料必须具有合适的导热性和导电性,特别是对于电路密度越来越高的较小半导体器件而言。烧结膜之前不能满足这个目的,因为用半导体工业中常规使用的层压机难以层压该膜。具体而言,烧结膜具有高的金属含量,这造成烧结膜的表面干燥并妨碍了膜的层压和粘合性能。此外,需要高温和高压将烧结膜层压到晶片上,以及随后将芯片和膜粘合到基底上。烧结膜层压和粘合所需的高温和高压超过了半导体工业中常用的半导体工艺设备所提供的能力。
发明内容
根据本发明,提供了可烧结(即烧结的)膜和膏作为导电芯片贴装材料,其在电子工业和其它工业应用(例如,芯片贴装半导体封装)中具有优越使用性能。例如,此处描述的烧结膜和膏可用于功率分立器件中引线框上的芯片贴装应用,作为引线接合替代用于高性能分立器件的线夹黏着应用,用于用来冷却带有裸露焊盘的功率分立器件的散热片黏着应用,用于单芯片和多芯片器件,以及在芯片和框架之间需要高导电性和/或高导热性的其它器件。还提供了用于制备这种膜和膏的配制品,以及制备这种配制品的方法。
根据本发明的另一方面,提供了由基于本发明的组合物制备的导电网络。在某些方面,本发明涉及包含粘附在适当基底上的这种烧结膜和膏的制品。
此处所述的烧结膜组合物可以使用常规的低温低压层压机层压到晶片上。此外,烧结膜与基底之间的润湿能力得到保持,并且在粘合和固化之后实现适当的烧结形态。
此外,由根据本发明的组合物制备的烧结膜可以以柔性卷或预切割形式进行加工,分别如图1和2所示。在柔性卷或预切割形式中,膜可以以这些形式夹在合适的基底之间,包括离型膜、切割带等。举例来说,烧结膜(在图1和图2中标记为“芯片贴装膜”)如图1所示,以柔性卷的形式被夹在两个离型膜之间,以及如图2所示,以预切割形式被夹在离型膜和切割带之间。
附图说明
图1A-B是以柔性卷形式制造的可烧结膜的示意图。
图2A-B是以预切割形式制造的可烧结膜的示意图。
图3A是由此处所述的组合物制备的可烧结膜的示意图。
图3B是图3A的放大图。
具体实施方式
此处描述的是制备具有超出预期的低温低压层压性能的烧结膜的组合物和方法。具体而言,此处所述的组合物包含形成低温低压层压膜的粘合剂、填料和其它组分。该膜表现出改进的可加工性能和润湿能力,而不牺牲作为半导体芯片贴装材料的膜的烧结能力。此外,特别是由此处所述的组合物得到的烧结膜是柔性的并且可以通过生产涂布机制成卷。
根据本发明,此处提供了用于烧结膜的组合物,所述组合物包含:
至少一种热固性树脂或热塑性树脂组分,其包括一种或多种环氧单体、低聚物或聚合物,丙烯酸单体、低聚物或聚合物,酚醛树脂,酚醛清漆树脂,聚氨酯,氰酸酯,聚乙烯醇,聚酯,聚脲,聚乙烯醇缩醛树脂,苯氧基树脂,马来酰亚胺,双马来酰亚胺,聚酰亚胺或其混合物;
一种或多种导电填料;和
任选存在的有机稀释剂,
其中所述组合物在100℃或更低的温度和40psi或更低的压力下被层压到晶片上;和
其中所述组合物在固化或烧结后,使用钛-镍-银金属化的芯片和银引线框基底测得的在260℃下的芯片剪切强度(die shear strength)为至少1.0kg/mm2。
在一些实施方案中,所述组合物帖装到芯片上后,在0.2kg/mm2至1kg/mm2的压力下粘合至基底上。芯片不受尺寸的限制,例如,可以是1×1mm或更小,直到8×8mm或更大。
根据本发明,此处还提供了用于烧结膏的组合物,所述组合物包含:
至少一种热固性树脂或热塑性树脂组分,其包括一种或多种环氧单体、低聚物或聚合物,丙烯酸单体、低聚物或聚合物,酚醛树脂,酚醛清漆树脂,聚氨酯,氰酸酯,聚乙烯醇,聚酯,聚脲,聚乙烯醇缩醛树脂,苯氧基树脂,马来酰亚胺,双马来酰亚胺,聚酰亚胺或其混合物;
一种或多种导电填料;和
任选存在的颗粒填料;和
有机稀释剂,
其中所述组合物在固化或烧结后,使用钛-镍-银金属化的芯片和银引线框基底测得的在260℃下的芯片剪切强度为至少1.0kg/mm2。
此处所述的组合物包含至少一种热固性树脂或热塑性树脂组分。在此处所述的组合物中加入所述热固性树脂或热塑性树脂组分以改善由所述组合物制备的膜的质量、粘性、润湿能力、柔韧性、工作寿命、高温粘合性、树脂-填料相容性和烧结能力。另外,在此处所述的组合物中加入所述热固性树脂或热塑性树脂组分以改善由组合物制备的膏的流变性、分散性、工作寿命和烧结能力。热固性树脂或热塑性树脂组分可以是能够为组合物提供上述性能的任何树脂,包括但不限于环氧树脂、酚醛树脂、酚醛清漆树脂(例如酚醛树脂和甲酚醛树脂)、丙烯酸树脂、聚氨酯、氰酸酯、聚乙烯醇、聚酯、聚脲、聚乙烯醇缩醛树脂、苯氧基树脂、马来酰亚胺、双马来酰亚胺和聚酰亚胺,如下面进一步所描述的。
这里考虑使用的一种或多种环氧单体、低聚物或聚合物,在此处也称为环氧树脂,可以包括具有脂肪族主链或芳香族主链的环氧化合物、改性环氧树脂或其混合物。在某些实施方案中,所述一种或多种环氧单体、低聚物或聚合物包括官能化环氧单体、低聚物或聚合物。环氧树脂中的环氧官能度为至少1。在一些实施方案中,环氧树脂的环氧官能度为1(即,环氧树脂是单官能环氧树脂)。在其它实施方案中,环氧树脂含有至少两个或更多个环氧官能团(例如2,3,4,5或更多个)。
用于本发明的环氧树脂不限于具有特定分子量的树脂。作为示例的环氧树脂可以具有约50或更低至约1,000,000的分子量。在某些实施方案中,可考虑任选使用的环氧树脂具有约200,000-约900,000的分子量。在其它实施方案中,可考虑任选使用的环氧树脂具有约10,000-约200,000的分子量。在其它实施方案中,可考虑任选使用的环氧树脂具有约1,000-约10,000的分子量。在其它实施方案中,可考虑任选使用的环氧树脂具有约50-约10,000的分子量。
在一些实施方案中,环氧树脂可以是含有芳香族和/或脂肪族主链的液体环氧树脂或固体环氧树脂,例如双酚F的二缩水甘油醚或双酚A的二缩水甘油醚。环氧树脂可以任选是柔性环氧树脂。柔性环氧树脂可以具有不同长度的链长(例如,短链或长链),例如短链或长链的聚乙二醇双环氧液体树脂。示例性短链聚乙二醇双环氧液体树脂包括D.E.R.736,示例性长链聚二醇双环氧液体树脂包括D.E.R.732,它们均可从Dow Chemical Company(Midland,MI)购得。
在一些实施方案中,环氧树脂可以是增韧的环氧树脂,例如环氧化羧基封端的丁二烯-丙烯腈(CTBN)低聚物或聚合物,环氧化聚丁二烯二缩水甘油醚低聚物或聚合物,杂环环氧树脂(例如异氰酸酯改性的环氧树脂)等。
在某些实施方案中,环氧化CTBN低聚物或聚合物是具有以下结构的低聚物或聚合物前体的含环氧基衍生物:
HOOC[(Bu)x(ACN)y]mCOOH
其中:
每个Bu都是丁烯部分(例如1,2-丁二烯基或1,4-丁二烯基),
每个ACN都是丙烯腈部分,
Bu单元和ACN单元可以随机分布或以嵌段的形式分布,
x和y中的每一个均大于零,且满足x+y=1,
x:y的比率为约10:1-1:10,
m为约20至约100。
正如本领域技术人员容易认识到的,环氧化CTBN低聚物或聚合物可以由例如(1)羧基封端的丁二烯/丙烯腈共聚物,(2)环氧树脂和(3)双酚A,通过CTBN的羧酸基团与环氧化物之间的反应(通过链增长反应)等以多种方法制备得到。
在一些实施方案中,环氧树脂可以包括由如上所述的(1)羧基封端的丁二烯/丙烯腈共聚物,(2)环氧树脂和(3)双酚A制备得到的环氧化CTBN低聚物或聚合物;HyproTM环氧官能丁二烯-丙烯腈聚合物(之前名为ETBN)等。
在某些实施方案中,可考虑用于此处的环氧树脂包括橡胶或弹性体改性的环氧树脂。橡胶或弹性体改性的环氧树脂包括下述物质的环氧化衍生物:
(a)如美国专利号4,020,036(该专利的全部内容通过引用并入本发明)中所述的重均分子量(Mw)为30,000-400,000或更高的共轭二烯烃的均聚物或共聚物,其中共轭二烯烃每分子含有4-11个碳原子(例如1,3-丁二烯,异戊二烯等);
(b)如美国专利号4,101,604(该专利的全部内容通过引用并入本发明)中所述的表卤代醇均聚物,两种或更多种表卤代醇单体的共聚物,或表卤代醇单体与数均分子量(Mn)为约800至约50,000的氧化物单体的共聚物;
(c)如美国专利号4,161,471中所述的烃类聚合物,其包括乙烯/丙烯共聚物和乙烯/丙烯与至少一种非共轭二烯的共聚物如乙烯/丙烯/己二烯/降冰片二烯的共聚物;或者
(d)共轭二烯丁基弹性体,例如由85-99.5重量%的C4-C5烯烃与约0.5-约15重量%的具有4-14个碳原子的共轭多烯烃组成的共聚物,异丁烯和异戊二烯的共聚物,其中结合在分子中的大部分异戊二烯单元具有共轭二烯不饱和(参见例如美国专利号4,160,759;其全部内容通过引用并入本发明)。
在某些实施方案中,环氧树脂是环氧化聚丁二烯二缩水甘油醚低聚物或聚合物。
在某些实施方案中,可考虑用于此处的环氧化聚丁二烯二缩水甘油醚低聚物具有如下结构:
其中:
R1和R2各自独立地为H或低级烷基,
R3是H、饱和或不饱和的烃基、或环氧基,
每个低聚物中存在至少一个上述含环氧基的重复单元和至少一个上述烯烃类重复单元,以及,当存在时,每个重复单元的数量为1-10,以及,
n为2-150。
在某些实施方案中,可考虑用于实施本发明的环氧化聚丁二烯二缩水甘油醚低聚物或聚合物具有以下结构:
其中R是H、OH、低级烷基、环氧基、环氧乙烷取代的低级烷基、芳基、烷芳基等。可考虑用于此处的环氧树脂的其它例子包括具有柔性主链的环氧树脂。例如,环氧树脂可以包括:
等。
在一些实施方案中,本发明的配制品中可以包含其它的环氧材料。当包含在本发明的配制品中时,可以考虑使用多种环氧官能化树脂,例如基于双酚A的环氧树脂(例如Epon Resin 834),基于双酚F的环氧树脂(例如RSL-1739或JER YL980),基于酚醛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,以及其中任何两种或更多种的混合物。
考虑用于此处的环氧官能化树脂的例子包括脂环醇的双环氧化物,氢化双酚A(可购得的商品Epalloy 5000),六氢邻苯二甲酸酐的双官能脂环族缩水甘油酯(可购得的商品Epalloy 5000),Epiclon EXA-835LV和Epiclon HP-7200L等,以及其中任何两种或更多种的混合物。
适合用作本发明配制品的任选存在的额外组分的常规环氧材料的其它例子包括:
等。
此处考虑使用的环氧官能化树脂的例子包括环氧化CTBN橡胶561A、24-440B,和EP-7(购自Henkel Corporation;Salisbury,NC & Rancho Dominguez,CA);脂环族醇氢化双酚A的二环氧化物(可购得的商品Epalloy5000);六氢邻苯二甲酸酐的二官能脂环族缩水甘油酯(可购得的商品Epalloy 5000);ERL 4299;CY-179;CY-184等,以及其中任何两种或更多种的混合物。
任选地,环氧树脂可以是主链为多个单体单元混合物(即,杂化主链)的共聚物。环氧树脂可以包含直链或支化链段。在某些实施方案中,环氧树脂可以是环氧化有机硅单体或低聚物。任选地,环氧树脂可以是柔性的环氧–有机硅共聚物。考虑用于此处的柔性环氧–有机硅共聚物的例子包括均购自Evonik Industries(德国)的ALBIFLEX 296和ALBIFLEX348。
在一些实施方案中,组合物中存在一种环氧单体、低聚物或聚合物。在某些实施方案中,组合物中存在多种环氧单体、低聚物或聚合物的混合物。例如,组合物中存在两种或更多种,三种或更多种,四种或更多种,五种或更多种,或者六种或更多种的环氧单体、低聚物或聚合物。可以选择多种环氧树脂的组合用于实现由该组合物制备的膜或膏的所需性质。例如,可以选择多种环氧树脂的组合,使得由该组合物制备的膜表现出改善的膜质量、粘性、润湿能力、柔韧性、工作寿命、高温粘合性、树脂-填料相容性和烧结能力。可以选择多种环氧树脂的组合,使得由该组合物制备的膏表现出改善的流变性、可分配性、工作寿命和烧结能力。
所述一种或多种环氧单体、低聚物或聚合物在组合物中的量可以是组合物总固体含量(即除稀释剂以外的组合物)的至多约10重量%。例如,所述一种或多种环氧单体、低聚物或聚合物在组合物中的量可以是约0.1重量%至约10重量%,约0.5重量%至约8重量%,或约1重量%至约6重量%。在一些实施方案中,基于组合物的总固体含量,所述一种或多种环氧单体、低聚物或聚合物的在组合物中的量可以为约10重量%或更少,约9重量%或更少,约8重量%或更少,约7重量%或更少,约6重量%或更少,约5重量%或更少,约4重量%或更少,约3重量%或更少,约2重量%或更少或约1重量%或更少。
此处所述的组合物还可以包含丙烯酸单体、聚合物或低聚物。考虑用于实施本发明的丙烯酸酯类在本领域中是熟知的。参见,例如,美国专利号5,717,034,其全部内容通过引用并入本发明。用于本发明的丙烯酸单体、聚合物或低聚物不限于特定的分子量。作为示例的丙烯酸树脂可以具有约50或更低至约1,000,000的分子量。在一些实施方案中,考虑任选使用的丙烯酸聚合物可具有约100至约10,000的分子量和约-40℃至约20℃的Tg。在某些实施方案中,考虑任选使用的丙烯酸聚合物的分子量为约10,000至约900,000(例如,约100,000至约900,000或约200,000至约900,000),Tg为约-40℃至约20℃。用于此处所述组合物的丙烯酸共聚物的实例包括Teisan树脂SG-P3和Teisan树脂SG-80H(都可从NagaseChemtex Corp.;Japan购得)。任选地,用于此处所述组合物中的丙烯酸聚合物或低聚物可以是可降解的丙烯酸聚合物或低聚物或环氧改性的丙烯酸树脂。
所述丙烯酸单体、低聚物或聚合物在组合物中的量可以是组合物总固体含量的至多约10重量%。例如,所述丙烯酸单体、低聚物或聚合物在组合物中的量可以为约0.05重量%至约7重量%,或约0.1重量%至约3重量%。在一些实施方案中,基于组合物的总固体含量的含量,所述丙烯酸单体、低聚物或聚合物在组合物中的量为约10重量%或更少,约9重量%或更少,约8重量%或更少,约7重量%或更少,约6重量%或更少,约5重量%或更少,约4重量%或更少,约3重量%或更少,约2重量%或更少或约1重量%或更少。
用于此处所述组合物中的其它的热固性树脂或热塑性树脂组分可包括聚氨酯、氰酸酯、聚乙烯醇、聚酯、聚脲、聚乙烯醇缩醛树脂和苯氧基树脂。在一些实施方案中,组合物可以包括含酰亚胺的单体、低聚物或聚合物,例如马来酰亚胺、降冰片烯酰亚胺(nadimide)、衣康酰亚胺、双马来酰亚胺或聚酰亚胺。
热固性树脂或热塑性树脂组分,包括所述一种或多种环氧单体、聚合物或低聚物;所述丙烯酸单体、聚合物或低聚物;酚醛树脂;酚醛清漆树脂;聚氨酯;氰酸酯;聚乙烯醇;聚酯;聚脲;聚乙烯醇缩醛树脂;苯氧基树脂;和/或含酰亚胺的单体、聚合物或低聚物(例如马来酰亚胺,双马来酰亚胺和聚酰亚胺),可以组合形成粘合剂。所述粘合剂可以是固体、半固体或液体。任选地,粘合剂具有小于350℃的分解温度。
此处所述的组合物还包含一种或多种导电填料,所述填料包括银。在一些实施方案中,组合物中存在的导电填料是银。在其它实施方案中,除了银以外,还可以包括一种或多种其它的导电填料。考虑用于实施本发明的其它导电填料包括镍、钴、铜、镀银金属、镀镍金属、镀银石墨、涂覆银的聚合物、镀镍石墨、镀镍聚合物、金、钯、铂、炭黑、碳纤维、石墨、碳纳米管、铝、铟锡氧化物、涂覆银的铜、涂覆银的铝、涂覆银的石墨、涂覆镍的石墨、铋、锡、铋锡合金、涂覆金属的玻璃球、涂覆银的纤维、涂覆银的球体、掺杂锑的氧化锡、碳纳米管、导电纳米填料和这些金属的合金等,以及其中任何两种或更多种的混合物。这些以及类似的金属和金属合金是市场上可以购得的。
导电填料可以具有适合用于此处所述方法的尺寸,并且不限于任何特定的范围。作为示例的导电填料如银可具有约0.1μm-约20μm的平均粒径。在一些实施方案中,导电填料的平均粒径可以为约1μm-约10μm。在其它实施方案中,导电填料的平均粒径可以为约1μm-约3μm。
在一些实施方案中,存在银作为主要的导电填料(即,占组合物中所有导电填料的至少50重量%,至少60重量%,至少70重量%,至少80重量%或至少90重量%),此外还有一种或多种其它的导电填料。
导电填料在组合物中的量为组合物中总固体含量的至少65重量%。例如,导电填料在组合物中的含量可以为约65重量%至约95重量%,或约75重量%至约85重量%。在一些实施方案中,导电填料在组合物中的量可以为组合物总固体含量的至少约65重量%,至少约70重量%,至少约75重量%,至少约80重量%,至少约85重量%,或至少约90重量%。
此处所述的组合物可以任选包含一种或多种颗粒填料。所述颗粒填料可以包括例如二氧化硅、镍基合金、铁基合金、钨酸锆或其混合物。例如,颗粒填料可以是镍/铁组合物或硅酸铝锂。作为示例的颗粒填料具有10ppm/℃或更低(例如,5ppm/℃或更低,0ppm/℃或更低,或者-5ppm/℃或更低)的热膨胀系数(CTE)。在一些实施方案中,颗粒填料可以包括以下材料:合金42、碳纳米管、β-锂霞石、α-ZrW2O8、β-ZrW2O8、Cd(CN)2、ReO3、(HfMg)(WO4)3、Sm2.75C60、Bi0.95La0.05NiO3、因瓦合金(Fe-36Ni)、因瓦合金(Fe3Pt)、Tm2Fe16Cr、CuO纳米颗粒、Mn3Cu0.53Ge0.47N、Mn3ZN0.4Sn0.6N0.85C0.15、Mn3Zn0.5Sn0.5N0.85C0.1B0.05,及其混合物。
颗粒填料在组合物中的量可以为组合物总固体含量的约20重量%或更少(即至多20重量%)。例如,颗粒填料在组合物中的量可以为组合物总固体含量的小于约20重量%,小于约19重量%,小于约18重量%,小于约17重量%,小于约16重量%,小于约15重量%,小于约14重量%,小于约13重量%,小于约12重量%,小于约11重量%,小于约10重量%,小于约9重量%,小于约8重量%,小于约7重量%,小于约6重量%,小于约5重量%,小于约4重量%,小于约3重量%,小于约2重量%或小于约1重量%。
此处所述的组合物还可以包含稀释剂,所述稀释剂包括例如有机稀释剂。所述有机稀释剂可以是反应性有机稀释剂、非反应性有机稀释剂或其混合物。作为示例的稀释剂包括例如芳香族烃(例如苯、甲苯和二甲苯等);脂肪族烃(如己烷、环己烷、庚烷和十四烷等);氯代烃(如二氯甲烷、氯仿、四氯化碳、二氯乙烷和三氯乙烯等);醚(如乙醚、四氢呋喃、二噁烷、乙二醇醚和乙二醇的单烷基或二烷基醚等);酯(例如乙酸乙酯、乙酸丁酯和乙酸甲氧基丙酯等);多元醇(例如聚乙二醇、丙二醇和聚丙二醇等);酮(例如丙酮和甲基乙基酮等);酰胺(例如二甲基甲酰胺和二甲基乙酰胺等);杂芳香族化合物(例如N-甲基吡咯烷酮等);和杂脂肪族化合物。
考虑用于本发明的非反应性稀释剂的量可以在很宽的范围内变化,只要使用足够的量以溶解和/或分散本发明组合物的组分即可。当存在时,所使用的非反应性稀释剂的量通常为组合物的约2重量%-约30重量%。在某些实施方案中,非反应性稀释剂的量为组合物整体的约5重量%-20重量%。在一些实施方案中,非反应性稀释剂的量为组合物整体的约10重量%-约18重量%。考虑用于本发明的反应性稀释剂的量可以是组合物的至多5重量%(例如5重量%或更少,4重量%或更少,3重量%或更少,2重量%或更少或1重量%或更少)。
如本领域技术人员容易认识到的,在某些实施方案中,本发明组合物中基本上不含非反应性稀释剂。即使在某一时间点存在非反应性稀释剂,也可以如下面进一步描述的,在B阶段工艺中成膜期间将其除去。
此处所述的组合物可以任选包含一种或多种固化剂。所述固化剂可以任选起到组合物中的导电促进剂和/或还原剂的作用。考虑用于实施本发明的固化剂包括脲、脂肪族和芳香族胺、聚酰胺、咪唑、双氰胺、酰肼、脲-胺混合固化体系、自由基引发剂、有机碱、过渡金属催化剂、酚、酸酐、路易斯酸和路易斯碱等。参见,例如美国专利号5,397,618,全部内容通过引用并入本发明。
固化剂可任选以组合物总固体含量的至多4重量%的量存在于组合物中。在一些实施方案中,组合物中不存在固化剂(即,组合物总固体含量的0重量%)。在其它实施方案中,固化剂在组合物中的含量可以为约0.05重量%-约4重量%,或约0.1重量%-约3重量%。任选地,固化剂在组合物中的量可以为约4重量%或更少,约3重量%或更少,约2重量%或更少,或约1重量%或更少。
此处所述的组合物可以任选包含一种或多种助熔剂,例如羧酸。任选地,用于组合物中的所述助熔剂可以为在烧结过程中重排以释放作为助熔剂的羧酸的潜在助熔剂。适用于此处所述组合物中的潜在助熔剂的实例包含以下结构,在此处也称为Diacid 1550-VEGE加合物:
所述助熔剂在组合物中的量可以为组合物总固体含量的至多约10重量%。例如,助熔剂在组合物中的量可以为约0.1重量%-约10重量%,约0.2重量%-约8重量%,或约1重量%-约5重量%。在一些实施方案中,助熔剂在组合物中的量为约10重量%或更少,约9重量%或更少,约8重量%或更少,约7重量%或更少,约6重量%或更少,约5重量%或更少,约4重量%或更少,约3重量%或更少,约2重量%或更少,或约1重量%或更少。在一些实施方案中,组合物中不含助熔剂(即,0重量%)。
此处所述的组合物还可任选包含一种或多种其它组分:流动添加剂、助粘剂、流变改性剂、导电促进剂(例如过氧化物)、表面活性剂、增韧剂、薄膜增韧剂、环氧固化催化剂、固化剂、自由基聚合调节剂、自由基稳定剂或其混合物。
本发明组合物的每种组分的量可以在很宽的范围内变化。作为示例的组合物包含:
至多10重量%的一种或多种环氧单体、低聚物或聚合物,
至多10重量%的所述丙烯酸单体、低聚物或聚合物,
任选存在的至多4重量%的所述含酰亚胺的单体、低聚物或聚合物,
至少65重量%的所述导电填料,
任选存在的至多5重量%的选自促粘剂、导电促进剂和表面活性剂的其它组分,和
任选存在的至多20重量%的颗粒填料,
以上均为基于组合物总固体含量的重量百分比。
任选地,所述组合物可以包含至多30重量%的有机稀释剂。
在一些实施方案中,本发明组合物的每种组分的量范围大约为:
1-10重量%的所述一种或多种环氧单体、低聚物或聚合物,
1-10重量%的所述丙烯酸单体、低聚物或聚合物,
65-95重量%的所述导电填料,
任选存在的至多5重量%的一种或多种选自促粘剂、导电促进剂和表面活性剂的其它组分,
任选存在的3-20重量%的颗粒填料,
以上均为基于组合物总固体含量的重量百分比。
任选地,所述组合物可以包含至多5重量%的有机稀释剂。
在一些实施方案中,本发明组合物的每种组分的量范围大约为:
1-6重量%的所述一种或多种环氧单体、低聚物或聚合物,
任选存在的至多3重量%(即0-3重量%)的所述丙烯酸单体、低聚物或聚合物,
65-95重量%的所述导电填料,
任选存在的至多5重量%的选自促粘剂、导电促进剂和表面活性剂的其它组分,
3-20重量%的颗粒填料,
以上均为基于组合物总固体含量的重量百分比。
任选地,所述组合物可以包含至多30%的有机稀释剂。
此处所述的组合物具有很多有用的使用性能。例如,当固化或烧结时,组合物在260℃下具有至少1.0kg/mm2的芯片剪切强度(例如在260℃下至少1.5kg/mm2)。此外,组合物在100℃或更低的温度和40psi或更低的压力下被层压到晶片上。此外,薄膜形式的组合物可以进行切割和拾取工艺,以得到能够在约110℃-350℃的温度和约0.2至1kg/mm2的压力下与基底粘合的芯片/膜。芯片尺寸可以为约1×1mm或更小至约8×8mm或更大。粘合时间可以短于3秒。这些使用性能将在下面进一步描述。
在本发明的某些实施方案中,提供了制备此处所述组合物的方法。本发明组合物可以以烧结膜的形式或以烧结膏的形式制得。
用于形成烧结膜的本发明方法包括将预期的组分组合物进行高剪切混合足够长的时间以获得基本均匀的共混物。在一些实施方案中,可将组分混合至多约3小时(例如约1小时至3小时)的时间。组分的组合可以在室温下混合。
在组合物将以烧结膜形式存在的实施方案中,将组合物涂覆到合适的基底(例如离型膜)上,然后在升高的温度下加热以除去基本上所有的非反应性稀释剂(即,溶剂)。例如,可以除去至少65%,至少75%,至少80%,至少85%,至少90%,至少95%或至少99%的溶剂。加热烧结膏以将其干燥成膜的过程在此处被称为B阶段。所得的膜可具有约5微米至约50微米的厚度。
在本发明的某些实施方案中,提供了烧结膜,其包含从上述B阶段组合物中除去基本上所有溶剂/稀释剂后得到的反应产物。该膜可以卷在辊上。
如此处所述的薄膜可以使用半导体工业中常规的层压机来层压到基底(例如晶片)上。例如,可以使用辊式层压机将薄膜层压到晶片上。可以使用的层压机的例子包括DFM2700(Disco Corporation;Japan),Leonardo 200LD(Microcontrol Electronic;Italy)和Western Magnum XRL-120(El Segundo,CA)。如上所述,可以在低于100℃(例如,95℃或更低,90℃或更低,85℃或更低,80℃或更低,75℃或更低,70℃或更低,或者65℃或更低)的温度下进行层压。层压可以在40psi或更低(例如,35psi或更低,或30psi或更低)的压力下进行。
如果使用离型膜的话,可以将其从薄膜上剥下来。然后可以将薄膜层压到切割带上,所述切割带在切割过程中起到支撑的作用。可以在室温下将膜层压到切割带上。层压工艺的结果是,薄膜保持在切割带和晶片之间并与它们直接接触。在切割过程中,可以将晶片和薄膜切割成单独的芯片,其中薄膜粘附到芯片上。可以在拾取过程中将单独的芯片和粘附膜从切割带上移除,然后可以在粘合/芯片贴装步骤中将其帖装到基底上。粘合/芯片贴装步骤可以在约110℃-350℃的温度下进行短于3秒的粘合时间。对于各种芯片尺寸(例如,对于小于1×1mm至8×8mm或以上的芯片尺寸),可以使用0.2kg/mm2至1kg/mm2的粘合/芯片贴装压力。所得到的芯片/膜/基底组件接下来可以在至少一步热操作中加工,例如在烘箱中固化,引线接合之后模塑等。
此处考虑的烧结膜的例子包括将所述组合物在约160-300℃的温度下在不加压的情况下固化约10分钟-2小时所生成的膜。固化步骤的气氛可以是任何合适的固化气氛,例如氮气或空气气氛。在一些实施方案中,固化步骤在氮气气氛下进行。如本领域技术人员已知的,可以基于进行固化步骤所用的气氛调整固化步骤的持续时间。
用于形成烧结膏的本发明方法包括将预期的组分组合处理足够长的时间获得基本上均匀的共混物。在一些实施方案中,可将组分混合至多约3小时(例如约1小时-3小时)的时间。组分的组合可以在室温下混合。
在本发明的某些实施方案中,提供了包含所述组分的组合混合一段时间后的烧结膏。然后将烧结膏涂覆到基底(例如,引线框)上,然后进行将芯片贴装到基底过程。可以使用本领域技术人员已知的方法来进行芯片贴装工艺。例如,芯片贴装可以在室温下低于500mg的压力下进行。所得到的材料可以接着进行固化。
此处考虑的烧结膏的例子包括当所述组合物在约160-300℃的温度下固化约10分钟-2小时产生的烧结膏。固化可以在烘箱中,在加压或者不加压下进行。例如,固化可以在压力烘箱中或在无压烘箱中进行。固化步骤的气氛可以是任何合适的固化气氛,例如氮气或空气气氛。在一些实施方案中,固化步骤在氮气气氛下进行。如本领域技术人员已知的,可以基于进行固化步骤所用的气氛调整固化步骤的持续时间。
可以设计出各种固化方案以适应从业者的需要。较低温度和较长时间的烧结温度曲线可以用于大尺寸芯片,以便溶剂逐渐被去除,从而确保无空隙的接合线。此处提供了典型的烧结温度曲线,但需要理解的是,其它类似的烧结温度曲线也可以同样有效。作为示例的烧结温度曲线包括从室温至175℃斜线上升30分钟,然后在175℃下保持60分钟;从室温至200℃斜线上升30分钟,然后在200℃下保持60分钟;从室温至220℃斜线上升30分钟,然后在220℃下保持60分钟;从室温至110℃斜线上升15分钟,然后在110℃下保持60分钟,然后在240℃保持下60分钟;或从室温至250℃斜线上升30分钟,接着在250℃下保持60分钟。任选地,烧结温度曲线可包括较高的温度,例如从室温到300C斜线上升60分钟,接着在300℃下保持两小时。
在固化时根据本发明的烧结芯片贴装膜和膏也可以参照其热芯片剪切强度来进行表征。如此处所用,“热芯片剪切强度”是指在260℃下固化膜或膏的芯片剪切强度。在一些实施方案中,所述固化膜或膏在260℃下的热芯片剪切强度为至少1.0kg/mm2。在一些实施方案中,所述膜或膏的热芯片剪切强度为至少约1.50kg/mm2。在某些实施方案中,所述膜或膏的热芯片剪切强度为1.0kg/mm2–4kg/mm2。如上所述,使用钛-镍-银金属化的芯片和涂银引线框基底在芯片剪切测试机上测量芯片剪切强度。
在固化时根据本发明的烧结芯片贴装膜和膏还可以用将其在85%相对湿度下暴露于85℃下约3天之后在260℃下的热湿芯片剪切强度来进行表征;在一些实施方案中,暴露于这种条件之后,所述膜或膏的热湿芯片剪切强度为至少1.0kg/mm2;在一些实施方案中,所述膜或膏在暴露于这样的条件之后的热湿芯片剪切强度为至少1.0kg/mm2。
根据本发明的另一个实施方案,提供了用于制备烧结芯片贴装膜和膏的方法,所述方法包括在将上述组合物涂覆到合适的基底上之后,从该组合物中基本除去所有的非反应性稀释剂或溶剂。
考虑用于此处的合适基底包括引线框。此处所使用的“引线框”包括由铜或铜合金构成的基板以及在所述基板的上(或两个)表面上形成的保护涂层。所述保护涂层由选自金、金合金、银、银合金、钯或钯合金中的至少一种金属构成,并且具有约10-500埃的厚度。保护涂层通过合适的方法形成,例如通过气相沉积。通过气相沉积或湿法电镀可以在基板的表面和保护涂层之间形成镍或镍合金的中间层。所述中间层的合适厚度为约50-20,000埃。参见,例如美国专利号5,510,197,其全部内容通过引用并入本发明。
任选地,用于本发明的基底包括设计用于半导体封装的层压基底(例如BT基底和FR4基底等)、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、聚酯和玻璃等。
根据本发明的又一个实施方案,提供了用于制备烧结芯片贴装膜和膏的方法。对于膏,如上所述,该方法可以包括在将上述组合物涂覆到合适的基底上之后将其固化。在该固化过程中,所述膏可以经历烧结。对于膜,如上所述,该方法可以包括将芯片和膜高温粘合到合适的基底上。在该粘合过程中,膜可以经历烧结。任选地,用于制备烧结芯片贴装膜的方法可以包括固化过程以优化烧结形态并且用于器件应力稳定化。固化过程可以在烘箱中进行。
如上所述,根据本发明的烧结膜和膏可以用于芯片贴装。芯片表面可以任选涂覆有金属,例如银。
根据本发明的又一个实施方案,提供了一种制品,其包含粘合到合适的基底上的如此处所述的烧结芯片贴装膜和膏。
基于本发明的制品可以根据固化的烧结芯片贴装膜或者膏与基底的粘合性来进行表征;通常在260℃下粘合力为至少约1.0kg/mm2(例如,在260℃下至少约1.5kg/mm2);在一些实施方案中,260℃下的粘合力为至少约2.5kg/mm2。如上所述,使用钛-镍-银金属化的芯片和涂银引线框基底在芯片剪切测试机上测量芯片剪切强度。
如本领域技术人员容易认识到的,本发明制品的尺寸可以在很宽范围内变化。制品的实例包括例如芯片。用于本发明的芯片的表面积可以变化。在一些实施方案中,用于本发明的芯片可以为1×1mm或更小至8×8mm或更大。
根据本发明的又一个实施方案,提供了将烧结膜层压到晶片上的方法,所述方法包括下述步骤:
将如此处所述的用于烧结膜的组合物涂覆到晶片上;和
在100℃或更低的温度和40psi或更低的压力下将所述组合物层压到晶片上。
根据本发明的又一实施方案,提供了用于制备导电网络的方法,所述方法包括下述步骤:
将如此处所述的用于烧结膜的组合物涂覆到晶片上;
在100℃或更低的温度和40psi或更低的压力下将所述组合物层压到晶片上以得到附着于晶片上的膜;
切割附着在晶片上的薄膜以产生芯片和薄膜;和
在0.2kg/mm2至1kg/mm2的压力下将所述芯片和膜粘合至基底上。
根据本发明的又一实施方案,提供了用于制备导电网络的方法,所述方法包括:
将如此处所述的用于烧结膏的组合物以预定的图案涂覆到基底(例如,引线框)上;
将所述组合物芯片帖装到芯片和所述基底上;和
固化组合物。
任选地,可以涂覆所述组合物使得所得的膜或膏的厚度为至少5微米。例如,膜的厚度可以为约5微米-约50微米(例如约5微米-约30微米),并且膏的厚度可以为约5微米-约50微米。
根据本发明的另一个实施方案,提供了如此处所述制备的导电网络。
此处所述的烧结膜和膏可用于电子工业和其它工业应用中。例如,此处描述的烧结膜和膏可用于功率分立器件中引线框上的芯片贴装应用,作为引线接合替代用于高性能分立器件的线夹附着应用,用于用来冷却带有裸露焊盘的功率分立器件的散热片附着应用,用于单芯片和多芯片器件,以及在芯片和框架之间需要高导电性和/或高导热性的其它器件。
图1A-B和2A-B展示了以柔性卷形式(10)或预切割形式(20)制造的由本发明的组合物制备的烧结膜(也称为“芯片贴装膜”)。在柔性卷形式或预切割形式中,膜可以以下述形式夹在合适基底之间,包括离型膜和切割带等。离型膜可以是约50μm,膜可以是约15-30μm。在图1A中,柔性卷形式(10)包括夹在两个离型膜:易剥离型膜(16)和紧密离型膜(18)之间的烧结膜(14)。还展示了前导离型膜(12),其是不夹在烧结膜上的离型膜的一部分。图1B是图1A沿线A-A的截面图,显示夹在离型膜(16)和(18)之间的烧结膜(14)。图2A展示了预切割形式(20),图2B代表了图2A沿着线B-B的截面图,显示了夹在切割带(24)和离型膜(26)之间的烧结膜(22)。
通过以下非限制性实施例来说明本发明的各个方面。这些实施例是为了阐释的目的,而不对本发明的任何实践进行限制。应该理解的是,在不脱离本发明的精神和范围的情况下可以对其做出改变和调整。本领域普通技术人员容易知道如何合成或购得此处所述的试剂和组分。
实施例1
烧结膜
如下所示通过组合表1中所列出的组分来制备基于本发明的配制品。
表1
1环氧树脂1是脂肪族环氧树脂和芳香族环氧树脂的加成物。
2环氧树脂2是环氧树脂和CTBN橡胶的加成物。
3丙烯酸聚合物是分子量(Mw)为850,000,玻璃化转变温度为12℃的丙烯酸聚合物。
4潜在助熔剂是乙烯基醚和羧酸的加成物。
对于表1所示的配制剂A、B和C的每一种,通过以高剪切速度混合表1中所示的组分和溶剂(组合物的约30重量%)以生成涂布浆料,来制备烧结膜。将涂布浆料施涂在离型膜上,在约120-150℃的温度下加热5分钟,以除去溶剂,并使组合物稳定成烧结膜。接着,在烧结膜上施涂保护膜,在110℃和30psi下进行层压,以使B阶膜粘贴在保护膜上,将所得材料卷绕成烧结膜卷。通过以下步骤实现芯片贴装:剥离保护膜;在约90-95℃和约30-40psi下将膜层压到晶片上;剥离离型膜;将膜层压到切割带上;切割膜和晶片;从切割带上取下切割好的芯片和膜;将切割的芯片和膜附着到引线框上;在升高的温度和压力下,在此处所述的用于芯片贴装接合条件的时间条件下,将芯片、膜和引线框粘合在一起;以及任选地,根据此处所述的固化条件进行芯片贴装器件的固化或烧结过程。测试所得材料的热芯片剪切强度,如下文进一步所述。为了制备用于封装内性能和可靠性测试的测试材料,在芯片帖装接合和固化之后进行引线接合和成型工艺。
图3A是TiBiAg芯片表面(32)和涂银引线框(46)之间的烧结膜(30)在聚焦离子束(FIB)研磨后的横截面的扫描电子显微镜(SEM)成像示例。图3B是膜(30)的一部分的放大视图。烧结膜(30)包含颗粒填料(36)、烧结银(38)、树脂(48)以及孔或多孔区域(42)。此外,可烧结膜包括存在于材料中的金属间层(例如,在钛-镍-银芯片表面和烧结膜之间形成的金属间层,以及在烧结膜和涂银引线框之间形成的金属间层)。第一金属间层(44)形成在TiNiAg芯片表面(32)和烧结膜(30)之间的界面处。第二金属间层(46)形成在涂银引线框(46)和烧结膜(30)之间的界面处。
测量了芯片剪切强度、热导率和电阻率以及电导率,在下文展开详述。结果如表2中所示。
热芯片剪切强度(HDSS)是使用钛-镍-银金属化的硅芯片和涂银铜基底在Dage系列4000芯片剪切测试机上测量的。
使用热导率测试仪(LFA 447NanoFlash,可从NETZSCH-Geratebau GmbH,Germany购得)测量整体固化材料的热导率,并使用T3Ster瞬态温度测量系统(Mentor Graphics;Wilsonville,OR)测量热阻率。
电导率是以体积电阻率来测量的,其使用Megohm桥上的四点探针进行测试。
表2
表2中所示的结果表明了本发明组合物的热芯片剪切强度、热导率和电阻率以及电导率得到改善。
实施例2
烧结膏
如下所示通过组合表3列出的组分来制备基于本发明的配制品。
表3
5环氧树脂1是脂肪族环氧树脂和芳香族环氧树脂的加成物。
6环氧树脂2是环氧树脂和CTBN橡胶的加成物。
7丙烯酸聚合物是分子量(Mw)为850,000,玻璃化转变温度为12℃的丙烯酸共聚物。
对于表3中所示的配制品D、E和F的每一种,通过在室温下混合各组分制备烧结膏。将这些膏分配到引线框基底上,并在如上所述的条件下进行芯片贴装工艺。根据此处所述的固化条件固化芯片贴装器件。测试所得材料的热芯片剪切强度。为了制备用于性能和可靠性测试的测试材料,在芯片贴装接合和固化之后进行引线接合和成型工艺。
根据实施例1中所述的方法测量芯片剪切强度、热导率和电导率。结果示于表4中。
表4
表4中所示的结果表明本发明组合物具有合适的和/或改进的热芯片剪切强度、热导率和电导率。
除了此处所展示和描述的之外,本发明的各种修改对于本领域技术人员将是显而易见的。这样的修改也意图落入所附权利要求的范围内。
说明书中提及的专利和出版物表明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并入本发明,其程度等同每个单独的专利或出版物被具体和单独地作为参考引入此处。
以上描述是对本发明的特定实施方案的说明,但并不意味着对本发明的实践进行限制。所附权利要求书,包括其所有等同项意在限定本发明的范围。
Claims (23)
1.一种用于烧结膜的组合物,所述组合物包含:
热固性树脂或热塑性树脂组分,其选自以下组:一种或多种环氧单体、低聚物或聚合物,丙烯酸单体、低聚物或聚合物,酚醛树脂,酚醛清漆树脂,聚氨酯,氰酸酯,聚乙烯醇,聚酯,聚脲,聚乙烯醇缩醛树脂,苯氧基树脂,马来酰亚胺,双马来酰亚胺,聚酰亚胺,或其混合物;
一种或多种导电填料;和
任选存在的有机稀释剂,
其中所述组合物在100℃或更低的温度和40psi或更低的压力下被层压到晶片上;和
其中所述组合物在固化或烧结时,在260℃下具有至少1.0kg/mm2的芯片剪切强度。
2.根据权利要求1所述的组合物,其中所述组合物在附着至芯片上时,在0.2kg/mm2至1kg/mm2的压力下粘合到基底上。
3.根据权利要求1所述的组合物,其还包含助熔剂、流动添加剂、助粘剂、流变改性剂、导电促进剂、表面活性剂、增韧剂、薄膜增韧剂、环氧固化催化剂、固化剂、自由基聚合调节剂、自由基稳定剂或其混合物中的一种或多种。
4.根据权利要求1所述的组合物,其中所述热固性树脂或热塑性树脂组分包括一种或多种环氧单体、低聚物或聚合物,所述一种或多种环氧单体、低聚物或聚合物包含具有脂肪族主链、芳香族主链或其混合的环氧化合物。
5.根据权利要求1所述的组合物,其中所述热固性树脂或热塑性树脂组分包括一种或多种环氧单体、低聚物或聚合物,所述一种或多种环氧单体、低聚物或聚合物包括官能化的环氧单体、低聚物或聚合物。
6.根据权利要求1所述的组合物,其中所述热固性树脂或热塑性树脂组分包括丙烯酸单体、低聚物或聚合物。
7.根据权利要求1所述的组合物,其中所述热固性树脂或热塑性树脂组分在所述组合物中的量为组合物总固体含量的至多10重量%。
8.根据权利要求1所述的组合物,其中所述一种或多种导电填料包括银。
9.根据权利要求8所述的组合物,其中所述一种或多种导电填料还包括镍、铜、镀银金属、镀镍金属、镀银石墨、涂覆银的聚合物、镀镍石墨、或镀镍聚合物中的一种或多种。
10.根据权利要求1所述的组合物,其中所述一种或多种导电填料在所述组合物中的量为组合物总固体含量的至少65重量%。
11.根据权利要求1所述的组合物,其还包含颗粒填料。
12.根据权利要求11所述的组合物,其中所述颗粒填料包括镍基合金、铁基合金、钨酸锆、二氧化硅或其混合物。
13.根据权利要求11所述的组合物,其中所述颗粒填料具有10ppm/℃或更低的热膨胀系数。
14.根据权利要求11所述的组合物,其中所述颗粒填料在所述组合物中的量为组合物总固体含量的至多20重量%。
15.根据权利要求1所述的组合物,其中所述有机稀释剂是反应性有机稀释剂、非反应性有机稀释剂或其混合物。
16.由根据权利要求1所述的组合物形成的膜。
17.一种将导电膜层压到晶片上的方法,所述方法包括:
将根据权利要求1所述的组合物施涂到晶片上;和
在100℃或更低的温度和40psi或更低的压力下将所述组合物层压到所述晶片上。
18.一种制备导电网络的方法,所述方法包括:
将根据权利要求1所述的组合物施涂到晶片上;
在100℃或更低的温度和40psi或更低的压力下将所述组合物层压到所述晶片上,以得到附着于晶片上的膜;
切割所述附着于晶片上的膜,以得到芯片和膜;和
在0.2kg/mm2至1kg/mm2的压力下将所述芯片和膜粘合至基底上。
19.一种用于烧结膏的组合物,所述组合物包含:
热固性树脂或热塑性树脂组分,其选自一种或多种环氧单体、低聚物或聚合物,丙烯酸单体、低聚物或聚合物,酚醛树脂,酚醛清漆树脂,聚氨酯,氰酸酯,聚乙烯醇,聚酯,聚脲,聚乙烯醇缩醛树脂,苯氧基树脂,马来酰亚胺,双马来酰亚胺,聚酰亚胺或其混合物;
一种或多种导电填料;
颗粒填料,其含量为所述组合物总固体含量的至多20重量%;和
有机稀释剂,
其中所述组合物在固化或烧结时,在260℃下具有至少1.0kg/mm2的芯片剪切强度。
20.根据权利要求19所述的组合物,其中所述颗粒填料选自镍基合金、铁基合金、钨酸锆、二氧化硅及其混合物。
21.根据权利要求19所述的组合物,其中所述颗粒填料具有10ppm/℃或更低的热膨胀系数。
22.由根据权利要求19所述的组合物形成的膏。
23.一种制备导电网络的方法,所述方法包括:
将根据权利要求19所述的组合物施涂到基底上;
将所述组合物芯片贴装到芯片和所述基底上;以及
固化所述组合物。
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CN110232986A (zh) * | 2019-06-21 | 2019-09-13 | 上海本诺电子材料有限公司 | 一种柔性电子纸用导电银浆及其制备方法 |
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CN113102914A (zh) * | 2021-04-15 | 2021-07-13 | 浙江机电职业技术学院 | 一种高强度耐老化复合焊料片及其制备方法 |
CN113102914B (zh) * | 2021-04-15 | 2022-06-28 | 浙江机电职业技术学院 | 一种高强度耐老化复合焊料片及其制备方法 |
CN113831876A (zh) * | 2021-09-24 | 2021-12-24 | 深圳市南科康达科技有限公司 | 一种导电胶、固态导电胶膜及其制备方法和应用 |
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CN107709418B (zh) | 2021-04-27 |
JP2018524415A (ja) | 2018-08-30 |
US20180056449A1 (en) | 2018-03-01 |
WO2016182663A1 (en) | 2016-11-17 |
TWI721979B (zh) | 2021-03-21 |
US11745294B2 (en) | 2023-09-05 |
EP3294799A1 (en) | 2018-03-21 |
JP2023153928A (ja) | 2023-10-18 |
EP3294799A4 (en) | 2018-11-21 |
US20230321765A1 (en) | 2023-10-12 |
TW201703056A (zh) | 2017-01-16 |
KR102360575B1 (ko) | 2022-02-09 |
KR20180004746A (ko) | 2018-01-12 |
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