CN102232127B - 用于提高银表面与树脂材料粘合性的方法 - Google Patents

用于提高银表面与树脂材料粘合性的方法 Download PDF

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CN102232127B
CN102232127B CN2009801373887A CN200980137388A CN102232127B CN 102232127 B CN102232127 B CN 102232127B CN 2009801373887 A CN2009801373887 A CN 2009801373887A CN 200980137388 A CN200980137388 A CN 200980137388A CN 102232127 B CN102232127 B CN 102232127B
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silver
lead frame
silver surface
treatment
treatment solution
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CN102232127A (zh
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克里斯汀·文德利希
罗伯特·吕特尔
于尔根·巴塞尔姆斯
夏文营·科克
纳迪娜·门迪尔
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Atotech Deutschland GmbH and Co KG
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Abstract

本发明解决了提高诸如用于生产电子器件的环氧树脂与模具材料的银表面与树脂材料的粘合性的问题。本发明提出一种提高银表面与树脂材料的粘合性的方法，该方法包括一个用一种溶液电解处理该银表面的步骤，该溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述银表面为阴极。在这种方法的一个特定体现中，本发明提出一种生产表面贴装电子器件(SMD)的方法，该方法包括以下步骤：(1)提供一个具有铜表面和银表面的引线框架；(2)用一种溶液电解处理所述引线框架的银表面，该溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述引线框架为阴极；(3)利用一种树脂材料把一个电子器件连同所述引线框架一起封装。

Description

用于提高银表面与树脂材料粘合性的方法
技术领域
本发明涉及一种用于提高银表面与树脂材料(例如环氧树脂和模具材料)粘合性的方法。这种方法可用于生产电子器件，例如引线框架和表面贴装器件(SMDs)。 
背景技术
引线框架用于生产安装在印制电路板(表面贴装器件，SMDs)上的电子器件。为了保护目的，例如形成所谓的封装，生产表面贴装器件的一个步骤是在引线框架的顶部应用一种树脂(模具)材料。引线框架通常包含铜和银表面。因此，模具与引线框架的银和铜表面接合。在表面贴装器件的使用寿命期间，必须保证金属和模具之间不会发生分层，否则该表面贴装器件部分可能会失效。 
在封装的使用寿命期间，模具和引线框架的接合处可能会吸收周围的湿气。吸湿并将湿气保留在封装内的问题在于，当装置经受突如其来的高温时，例如安装电路板过程中的焊接温度，锁住的湿气蒸发同时施加巨大的内部封装应力，这可能导致分层。这种潮湿诱发的分层被称作“爆米花效应”。为了避免出现爆米花效应，在焊接前必须在无湿气条件下进行封装或者重新封装从而避免吸水，这使装配过程更昂贵，质量监控更困难。由于无铅焊接应用更高的焊接温度，所以发生爆米花效应的风险也特别高，从而就会造成更多的封装失效。 
基于各种封装类型不同程度的爆米花爆裂倾向，印制电路协会/电子器件工程联合委员会(IPC/JEDEC)定义了含铅集成电路封装的湿度敏感等级(MSLs)的标准分类。根据这个标准(J-STD-20MSL)，以数字表示湿度敏感等级，湿度敏感等级的数值越高的封装越容易发生爆米花爆裂。因此，MSL1级的产品不管暴露在湿气中多久都不会产生爆米花爆裂，而MSL5级和6级的装置最容易产生潮湿诱发的断裂。我们的目标是实现MSL1级。 
根据塑料集成电路表面贴装器件湿度敏感等级(J-STD-20MSL)标准，在一定时间内，在指定的湿度和温度条件下测试整个装置(参见表1)。 
表1.塑料集成电路表面贴装器件湿度敏感等级分类 
Figure BPA00001331837700021
为了保证实际寿命条件下的足够粘合，需根据IPC/JEDEC J-STD-20MSL标准测试含铅集成电路封装。另一种粘合强度的实际测试为普遍用于工业评定的所谓拉力测试。通过简单的剥离测试也可以获得金属表面和模具之 间的粘合强度指示。拉力试验和剥离试验都是研制和评定过程中识别提高金属表面与树脂材料粘合性很好的工具。通常在试样上而不是实际封装上进行拉力试验和剥离试验。对于在实际封装上进行的湿度敏感等级测试，可以使用超声波扫描显微镜(C-SAM)检测银和模具间接合处的分层。 
可行的湿度敏感等级不仅取决于模具与引线框架表面的粘合，还取决于封装的大小和尺寸。一般来说，由于表面贴装器件很薄，因此其断裂强度更低，从而易于发生爆米花爆裂；它们更容易吸收并保留湿气；表面贴装器件电路板安装还会使模塑封装材料受到铅的高温影响。 
多数目前生产的引线框架的表面通常由两种金属构成，即引线框架的基础材料铜或铜合金以及银。不同引线框架的铜与银的相对比例会有所不同。基础材料会影响引线框架的热稳定性和机械稳定性。引线框架表面的银需要创建引线框架与其上安装的集成片之间的导电连接。引线框架的进一步处理过程中的通常做法是超声波热焊(TSB)，涉及将一根细导线接合到集成片以及引线框架上的银。 
超声波热焊(也被称为引线键合)为一种表面焊接工艺，其中将两个清洁的金属表面(基板和引线)接合，从而紧固焊线(通常包含金，也可能包含铝)与引线框架基座上的银之间的粘合。因此，这种工艺对金属表面上的杂质非常敏感。 
就引线框架的铜和铜合金表面而言，目前在引线框架生产中通常使铜或铜合金表面变毛糙，从而提高该表面与随后用于生产表面贴装器件的树脂材料(模具)的粘合性。通常利用化学蚀刻工艺来实现粗化；也可能利用电化学方法，即将阳极电流应用于铜材料。部分化学蚀刻工艺还会在铜表面产生一层氧化层，这对粘合起到积极作用，其原因在于，金属氧化表面通常比无氧化金属表面表现出更好的对树脂的粘合性。然而与化学粗化相比，这种氧化层的作用可能很小。 
一种粗化引线框架表面的铜或铜合金进而提高树脂材料(模具)与铜或铜合金的粘合性的标准工艺是由安美特公司(Atotech)开发的MoldPrepTM工艺(参见EP 1820884A1)。MoldPrepTM工艺可以用于已镀银的引线框架。然而这种工艺并不会作用于银表面。因此，树脂材料与银的粘合不受影响。 
结果表明，无论如何粗化铜材料，仅仅提高了铜与树脂材料的粘合。任何已知的粗化铜或铜合金表面的工艺都不能显著提高银与树脂材料的粘合。因此，引线框架与树脂材料的最薄弱的连接就是银与树脂材料的接合，从而妨碍了进一步改善表面贴装器件的湿度敏感等级属性。 
在这种情况下，引线框架和表面贴装器件的制造商试图最大限度地减小银表面面积并尽量增加铜表面的相对比例，从而增加系统的稳定性。然 而，将集成片接合到引线框架表面要求确定的最小银表面面积，因此这种方法具有其局限性。 
技术水平 
许多年来，引线框架工业一直努力提高树脂材料(模具)与各种金属之间的粘合性，例如铜、铜合金、银、42合金以及镍/钯/金叠层(用于所谓的预镀框架(PPFs))。通过在沉积镍/钯/金之前粗化铜，预镀框架工艺稍微提高了粘合性。另一种提高树脂材料与预镀框架的粘合的可能性是通过适当控制电镀参数而以粗糙形式沉积镍。粗糙的镍利用机械粘固提高了与树脂材料的粘合。然而，这种方法实现的粘合仍然比不上铜和目前可以实现粘合的合金。因此，由这种方法实现的粘合性的提高还不够充分。 
崔等人(1999年《电子元件及技术会议》第837页《镀钯引线框架的粘合增强》)公开了通过在含铁碱性溶液中的引线框架应用阴极电流可以沿晶界沉积铁。作者认为，在预镀框架表面沉积铁可以提高与树脂材料的粘合性。然而却同时降低了引线可焊性。在表面沉积的铁越多，引线的可焊性越差。大概是基于这个原因和铁在空气中易于氧化的事实，这个崔等人所述的方法没有用于工业。 
美国专利US 5,343,073和US 5,449,951中描述了通过电镀铬和锌来提高与树脂材料的粘合性的引线框架。由于这些专利中描述的方法涉及六价铬的应用，因此不利于环保要求。如同铁和专利中的说明相反，金导线与锌的可焊性很差，所以锌的应用也不具备优势。 
美国专利US 5,300,158中描述了为了防腐蚀保护并且提高与含铜或铜合金基座的粘合性而使用六价铬。 
美国专利US 6,852,427公开了一种包含至少一种金属(例如锌)的溶液可以用于防止腐蚀铜并且同时改善粘合性。该专利主要涉及避免使用六价铬。 
美国专利申请US 2005/0121330A1(为上述美国专利US 6,852,427的分案申请)也仅仅涉及了铜表面。该专利中没有考虑到银以及金导线与银表面的可焊性。 
发明内容
因此，本发明的目标是提高诸如那些用于生产电子器件的模具材料的树脂材料与银表面的粘合性，特别是引线框架的银表面，从而使电子封装生产具备良好的湿度敏感等级，更理想是实现MSL1级的湿度敏感等级。同时，必须具备无故障粘接引线和银表面的可能性。此外，不能恶化同时存在的粗化铜或铜合金表面的良好粘合属性。 
该发明人有选择地蚀刻银以便增加其粗糙性的尝试并未成功。放弃这种方法的原因是：首先，银的蚀刻非常不均匀从而导致形成气孔。其次，由于测试的银腐蚀溶液的选择性不足，铜也被不均匀地蚀刻，导致树脂材料与铜表面的粘合性变差。 
该发明人还尝试通过沉积粗糙形式的银来提高与树脂材料的粘合性。然而，可能实现的粗糙度值并不足以提高粘合性，或者银以粉末状沉淀，这也不能使粘合性得到提高。不过，粗银对于粘接工艺可能至关重要。 
类似于上述的预镀框架方法，该发明人还试图在沉积银之前粗化铜，然后在粗化的铜上镀银。然而结果表明，特别显著增长的粗糙度没有产生所需的粘合度提高。直到发明人找到根据本发明所述的方法，银表面与特别是用于模具材料的树脂材料的粘合性差的问题才得到解决。 
因此，为了实现上述目标，本发明提出一种提高银表面与树脂材料的粘合性的方法，该方法包括一个用一种溶液电解处理所述银表面的步骤，所述溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述银表面为阴极。 
根据本发明所述的方法，树脂材料最终要粘接的银表面与一种包含上述指定的氢氧化物的溶液接触。该溶液还至少与一个阳极接触，并且在作为阴极的银表面和至少一个阳极之间施加电压，从而使电流穿过该溶液。如此处理的银表面显示出与树脂材料的粘合性有所提高，特别是对于那些用作制造诸如表面贴装器件(SMDs)的电子元件的模具材料。 
在上述方法的一个特定体现中，本发明提出一种生产表面贴装电子器件(SMD)的方法，该方法包括以下步骤：(1)提供一个具有至少一个银表面的引线框架，(2)用一种溶液电解处理所述引线框架的银表面，该溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述引线框架为阴极，(3)利用一种树脂材料把一个电子器件连同所述引线框架一起封装。所述引线框架可能还包括至少一个铜表面。若存在，任何铜表面将会受到与所述至少一个银表面相同的处理和条件。据发明人表明，对铜表面没有显著的影响。 
电解处理银表面的步骤通常会在任何引线粘接到银表面之前进行。然而，原则上，也可能在粘接步骤之后进行电解处理银表面的步骤。 
因此，本发明还提出一种按上述方法获取的电子器件，其中一种树脂材料与银接合。 
电解处理银表面的步骤可以间歇或连续进行。在间歇模式中，每次至少处理一个网架式或鼓式应用的工件。在连续模式中，处理盘式应用的工件(特别是引线框架)。如此，在连续过程中，可以在生产的产品的板卷或基座材料的卷轴分成不同部分之前进行电镀。 
用于处理银表面的溶液温度不受特别限定。一般来说，该温度为15至75摄氏度，优选为20至50摄氏度，更优选为35至45摄氏度。 
银表面的电解处理的持续时间不受特别限定。一般来说，该持续时间为5至300秒，优选为25至60秒。一般来说，较长时间的处理会更加提高银表面和树脂材料的粘合性。然而，较长的时间可能产生不利影响，特别是在连续模式中进行处理，待处理的工件穿过电解槽，较长的处理时间因此可能要求电解槽的一端到另一端的距离过长。通过相应地增大阴极电流密度可能实现较短的处理时间。这可能要求适当增加阳极尺寸从而防止过电压。 
在电解处理银表面步骤中应用的电流密度不受特别限定。一般来说，阴极电流密度可能为2至40安培/平方分米，优选为4至32安培/平方分米。当处理液只含有一种氢氧化物(例如只有氢氧化钠)时，阴极电流密度通常为8至24安培/平方分米，优选为12至16安培/平方分米。当处理液同时还含有一种硅酸盐时，阴极电流密度通常为4至16安培/平方分米，优选为8至12安培/平方分米。一般来说，较高的电流密度使粘合性得到更好的改善。原则上来说，只有阴极和阳极之间的电压会限定电流密度。 
在电解处理银表面步骤中应用的电压不受特别限定。其特别取决于阴极与阳极表面面积的比例、电解质浓度以及电流密度。电压通常低于7伏特。 
在电解处理银表面步骤中使用的至少一个阳极除了实质上应该为惰性，即该阳极不应出现任何明显程度的溶解之外，其材料不受特别限定。由此，该阳极可以由不锈钢制成，如钢V4A或钢SS316/319，或者例如由镀铂钛制成。控制电压，即防止过高电压，可以避免阳极的溶解。 
阳极与阴极表面面积的比例不受特别限定。一般来说，阳极与阴极表面面积的比为至少2∶1，优选为至少4∶1，更优选为至少8∶1。 
电解处理银表面中使用的溶液包含一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物。优选的碱金属氢氧化物是氢氧化钠(NaOH)和氢氧化钾(KOH)。适合的氢氧化铵是分子式为NR4-nHnOH的氢氧化铵，其中各个R分别表示一个含有1至12个碳原子的烷基，优选为含有1至6个碳原子。优选的氢氧化物是氢氧化钠和氢氧化钾。 
处理液中氢氧化物的浓度通常为10至500克/升，优选为100至200克/升，例如大约150克/升。如果处理液包含任何以下描述的加强电导或增进粘合的盐，则需要的氢氧化物的浓度通常更低。 
处理液还可以另外包含一种硅酸盐，如偏硅酸钠、偏硅酸钾或偏硅酸铵。也可能使用所谓的倍半硅酸盐，例如Na3HSiO4·5H2O或相应的碱和铵盐。优选的硅酸盐是聚硅酸盐，更优选为可溶性碱金属或聚硅酸铵(分子 式可写为M2O·nSiO2)，其中n大约为1至4，M是碱金属或一般分子式为NR4-nHn +的铵离子，其中各个R分别表示一个含有1至12个碳原子的烷基，优选为含有1至6个碳原子。 
结果表明，在处理液中应用这种硅酸盐使处理的银表面和树脂间的粘合得到更大的改善。处理液中如果使用硅酸盐，其浓度通常为1至100克/升，优选为10至50克/升。 
作为选择，处理液可能包含一种或多种加强电导的盐。优选的加强电导的盐是硫酸盐和聚磷酸盐，优选为含有碱、铵或碱土阳离子，例如硫酸钠或硫酸钾(Na2SO4或K2SO4)或者三聚磷酸钠或三聚磷酸钾(Na5P3O10或K5P3O10)；也可能使用相应的铵盐((NH4)2SO4或(NH4)5P3O10)。这种加强电导的盐可以用于降低阴极与阳极之间的电压并增加电流密度。处理液中如果使用加强电导的盐，其浓度通常为1至100克/升，优选为10至50克/升。单独使用时未发现这种盐具有加强粘合的作用。 
处理液的酸碱度大于7，优选为大于10。 
作为选择，处理液可能包含一种或多种表面活性剂。该表面活性剂可能是离子型或非离子型。适合的离子型表面活性剂包括阴离子表面活性剂，如硫酸基、磺酸基或羧酸基表面活性剂(例如，十二烷基硫酸钠、十二烷基硫酸铵、其它烷基硫酸盐、烷基苯磺酸盐和脂肪酸盐，如十二烷基苯磺酸钠)以及阳离子表面活性剂，如烷基三甲基铵盐(例如十六烷基三甲基溴化铵)、氯化十六烷基吡啶和氯化苄烷铵。适合的非离子型表面活性剂包括聚烷基(环氧乙烷)、环氧乙烷和环氧丙烷的共聚物、脂肪醇(例如十六醇和油醇)、聚乙二醇(例如聚乙二醇10000)以及乙二醇醚(例如乙二醇丁醚)。这种表面活性剂促进待处理银表面的润湿。 
进行电解处理银表面步骤的过程中没有在所述银表面沉积任何金属。因此，处理液中除了碱或碱土金属离子之外基本上不含金属离子。特别地，该处理液基本上不含铁、锌或铬离子，尤其是Fe2+，Fe3+，Zn2+，Cr3+和Cr(VI)离子。关于这一点，用语“基本上不含”的意思是，除了构成几乎不能避免的杂质的范围，该溶液不含特定的离子。硅离子(作为硅酸盐)当然不包括在内(参见上文)。 
根据本发明所述的方法通常可以用于提高任何银表面和树脂材料的粘合性，特别地，在制造电子器件中用作模具材料的树脂材料，例如所谓的表面贴装器件(SMDs)。根据本发明所述的方法可以特别应用于具有银表面的引线框架。根据本发明所述的方法可以结合已知的粗化引线框架同时存在的铜或铜合金表面的方法。特别地，根据本发明所述的方法可以结合安美特公司(Atotech)的商品MoldPrepTM工艺(如EP 1820884A1所述)。在这种情况下，照常首先进行粗化铜工艺，然后应用根据本发明所述的方 法处理银表面。 
根据本发明处理的银表面可以通过已知工艺与金导线粘接，特别是通过超声波热焊(TSB)。银表面可以由基本上纯银或银含量特别高的银合金构成。 
根据本发明处理的银表面显示出与树脂材料的粘合性更加有所提高，特别是制造电子封装中通常用作模具材料的树脂材料。特别地，在本发明的情况下，树脂材料可以是环氧树脂或环氧模塑料，例如由75-95wt.-％石英、2-8wt.-％环氧树脂、1-3wt.-％环氧甲酚酚醛、2-8wt.-％酚醛树脂以及0.1-0.5wt.-％碳黑组成的商用产品Sumikon EME-G600TM，或者由大约86wt.-％硅石粉、大约1.0wt.-％三氧化锑、大约11wt.-％环氧树脂、大约1.0wt.-％溴化树脂以及大约1.0wt.-％催化剂、增韧剂、脱模剂、颜料和底漆组成的模塑料Sumikon EME 7351TQTM。模塑料也可以是无溴(“绿色”)的成型材料，其成分是大约80wt.-％石英、柔性环氧树脂和硬化剂、过渡金属氧化物/氮系阻燃剂、橡胶或热塑性增韧剂以及硅烷。 
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具体实施方式
下面将参照下列非限制性实例说明本发明。 
测试方法 
实例中使用的测试方法如下： 
实验室剥离试验 
在层压在环氧玻璃纤维基板上的银箔上，通过测量箔片剥离环氧层所需要的力进行实验室剥离试验。更具体地说，用有机溶剂对银箔(99.97％银，长度：130毫米，宽度：30毫米，厚度：50微米)除油，然后将其层压到Isola Duraver DE104MLTM环氧玻璃纤维预浸料(玻璃型号2125，玻璃化温度：135摄氏度，尺寸：25x25厘米)，同时利用压力机(HML制造；型号：MP20-2-VK)高达175摄氏度的加压使环氧树脂预浸料硬化，下表具体说明了其温度及压力方案： 
Figure BPA00001331837700091
之后，使银/环氧树脂层压板冷却到室温。然后，利用Zwick制造的测量装置(型号：Z010)在90°剥离角以50毫米/分钟的速度通过100毫米的距离测量相对于银箔宽度将银箔剥离环氧基板所需要的力。 
实验室拉力试验 
在实验室拉力试验中使用银面积为等边三角形(约7平方毫米)的铜引线框架。在银表面上应用一种模具(Sumikon EME-G600TM)并将其硬化。然后对该模具实施拉力。测量使模具从银表面分离所需的力(以公斤表示)。 
粘合力试验 
用下列设备、材料和参数进行粘合力试验： 
粘合器(装置)：              Delvotec 5410(半自动球型/楔型焊接) 
超声波频率：                60千赫 
功率设置(依照惯例)：        球型焊：40；楔型焊：140 
时间设置(依照惯例)：        球型焊：30；楔型焊：60 
力设置(依照惯例)：          20 
焊线：                      Au HD2(Heraeus)，直径：25微米， 
                            断裂载荷：＞7克 
毛管：                      UTS-41KJ-CM-1/16-16毫米 
温度：                      150摄氏度 
拉力测试仪：                 DAGE 4000；WP100 cartridge， 
                            拉速度：500微米/秒 
拉力号：                    30 
处理液 
这些实例中使用的处理液是具有表2中详述成分的水溶液： 
表2.根据本发明所述的处理液的成分 
Figure DEST_PATH_GSB00001068674100011
例1 
用有机溶剂对银箔除油。然后将其浸入40摄氏度的处理液A中60秒并同时施加直流电，对其进行根据本发明所述的电解提高粘合性处理。银箔与阴极相连。阳极由钢制成。阴极的电流密度为9安培/平方分米。 
然后对银箔实施上述的实验室拉力试验。为了进行对照，在仅仅除油过却没有受到根据本发明所述的电解提高粘合性处理的银箔进行这项试验。 
表3说明了该实验室拉力试验的结果。 
表3.例1中进行的实验室拉力试验的结果。 
Figure BPA00001331837700111
例2 
将一个标准的引线框架(用于实验室拉力试验，参见上文)浸入表4中详述的溶液，该表说明了浸渍时间及温度(参见表4，步骤1至5)，以此对其进行MoldPrep LFTM预处理。 
然后将该引线框架浸入40摄氏度的处理液C中60秒并同时施加直流电(表4，步骤6)，对其进行根据本发明所述的电解提高粘合性处理。引线框架与阴极相连。阳极由钢制成。阴极的电流密度为9安培/平方分米。 
然后用去离子水(小于2微秒)冲洗该引线框架(30秒，60摄氏度)，在65摄氏度下干燥10分钟(表4，步骤7和8)。 
表4中总结了本实例中的步骤和工艺条件。(请注意：针对引线框架的表面上存在铜(合金)的情况进行步骤3至5；这些步骤对于提高银表面的粘合性并不是必需的，而且也不是根据本发明所述方法的主要部分。) 
表4.例2中进行的工艺步骤 
Figure BPA00001331837700121
然后将一个模具应用于喷射模塑法并使引线框架经受各种烘烤条件。之后对其进行上述的实验室拉力试验和粘合力试验。为了进行对照，对已经同样处理过而没有进行根据本发明所述的电解提高粘合性处理的引线框架也进行这个试验。 
表5和表6分别说明了实验室拉力试验以及粘合力试验的结果。 
表5.例2中进行的实验室拉力试验的结果。 
Figure BPA00001331837700131
表6.例2中进行的粘合力试验的结果。 
Figure BPA00001331837700132
表6中的结果显示根据本发明所述的电解提高粘合性处理没有对粘合强度产生显著的影响(即无不利影响)。更具体地说，在粘合力试验中，所有粘合显示导线的破损不是发生在颈口就是发生在楔跟，却没有球形或楔形隆起(即导线两端发生脱离)。 
例3 
重复例1的过程并做以下修改：在电解提高粘合性处理步骤中，用处理液B代替处理液A；阳极由V4A不锈钢制成；阴极电流密度为16安培/平方分米；处理时间为30秒。表7说明了由此获得的银箔的实验室剥离试验的结果。 
表7.例3中进行的实验室剥离试验的结果。 
Figure BPA00001331837700141
例4 
重复例1的过程并做以下修改：按照MoldPrep LFTM工艺对银箔进行预处理(表4，步骤1至5)。在电解提高粘合性处理步骤中，用处理液C代替处理液A；阳极由不锈钢制成；温度为45摄氏度；处理时间为30秒。表8说明了由此获得的银箔的实验室剥离试验的结果。 
表8.例4中进行的实验室剥离试验的结果。 
Figure BPA00001331837700142
例5 
重复例2的过程并做以下修改：在电解提高粘合性处理步骤中，用处理液D代替处理液A；温度为45摄氏度；处理时间为35秒；阴极电流密度为12安培/平方分米。 
表9和表10分别说明了实验室拉力试验以及粘合力试验的结果。 
表9.例5中进行的实验室拉力试验的结果。 
Figure BPA00001331837700143
表10.例5中进行的粘合力试验的结果。 
例6 
研究两个具有22个独立表面贴装器件(四面扁平封装)的引线框架。所述引线框架局部镀银，即它们包含基本材料为铜的表面积以及由银构成的表面积。第一个引线框架未经过任何银表面的处理就应用模具并对其进行测试，也就是说，仅仅对其进行加强模具与铜表面粘合的工艺步骤1至5(参见表4)。第二个引线框架外加一个以溶液A(参见表2；电流密度：9安培/平方分米，温度：40摄氏度，时间：60秒)进行处理的如表4中所示的工艺步骤。使用超声波扫描显微镜(C-SAM)对1至3级(见表1)的湿度敏感等级测试后的模具剥离进行了研究。表11中总结了每个引线框架上失效器件的数量。使用溶液A对银表面积进行处理后的1至3级的湿度敏感等级测试中未见失效。 
表11.例6中进行的湿度敏感等级测试(MSL)的结果(总共22个器件中失效的器件数目)。 
Figure BPA00001331837700152
例7 
用有机溶剂对银箔除油。然后将其浸入含有下表12所述化学成分的溶液中对其进行根据本发明所述的电解提高粘合性处理。在45摄氏度的温度下的浸渍时间是60秒并同时施加直流电。银箔与阴极相连。阳极由钢制成。阴极的电流密度为16安培/平方分米。 
然后对银箔实施上述的实验室拉力试验。表12显示该试验结果。为了进行对照，在仅仅除油过却没有受到根据本发明所述的电解提高粘合性处理的银箔进行这项试验。 
表12.例7中进行的实验室剥离试验的结果。 

Claims (13)

1.一种提高银表面与树脂材料的粘合性的方法，其特征在于该方法包括一个用一种溶液电解处理所述银表面的步骤，所述溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述银表面为阴极，其中所述处理液中氢氧化物的浓度为10至500克/升。 
2.一种生产表面贴装电子器件的方法，该方法包括按此顺序进行的下列步骤： 
(1)提供一个具有铜表面和银表面的引线框架， 
(2)选择性地粗化所述铜表面， 
(3)用一种溶液电解处理所述引线框架的银表面，该溶液包括一种选自碱金属氢氧化物、碱土金属氢氧化物、氢氧化铵及其混合物的氢氧化物，其中所述引线框架为阴极， 
(4)利用一种树脂材料把一个电子器件连同所述引线框架一起封装； 
其中，所述处理液中氢氧化物的浓度为10至500克/升。 
3.根据权利要求1或2所述的方法，其中进行电解处理所述银表面步骤的过程中没有在所述银表面沉积任何金属。 
4.根据权利要求1或2所述的方法，其中所述处理液中除了碱或碱土金属离子之外不含金属离子。 
5.根据权利要求1或2所述的方法，其中用于处理所述银表面的溶液的温度为20至50摄氏度。 
6.根据权利要求1或2所述的方法，其中所述电解处理的持续时间为5至300秒。 
7.根据权利要求1或2所述的方法，其中电解处理银表面步骤中应用的电流密度为2至40安培/平方分米。 
8.根据权利要求1或2所述的方法，其中所述氢氧化物为氢氧化钠或氢氧化钾。 
9.根据权利要求1或2所述的方法，其中所述处理液还包含一种硅酸盐。 
10.根据权利要求9所述的方法，其中所述处理液中硅酸盐的浓度为1至100克/升。 
11.根据权利要求1或2所述的方法，其中所述处理液包含一种或多种加强电导的盐。 
12.根据权利要求11所述的方法，其中所述处理液中加强电导的盐的浓度为1至100克/升。 
13.根据权利要求1或2所述的方法，其中所述处理液包含一种或多种表面活性剂。 
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US20120020047A1 (en) 2012-01-26
CN102232127A (zh) 2011-11-02
KR20110073552A (ko) 2011-06-29
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KR101603619B1 (ko) 2016-03-15
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