CN106914710B - 树脂助焊剂焊膏和安装结构体 - Google Patents
树脂助焊剂焊膏和安装结构体 Download PDFInfo
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- CN106914710B CN106914710B CN201611183827.6A CN201611183827A CN106914710B CN 106914710 B CN106914710 B CN 106914710B CN 201611183827 A CN201611183827 A CN 201611183827A CN 106914710 B CN106914710 B CN 106914710B
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- H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
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Abstract
本发明提供无需底部填充工序、并且具有优良的焊料凸块的加强效果的树脂助焊剂焊膏和安装结构体。树脂助焊剂焊膏具备包含焊料粉末和无机粉末的非树脂系粉末、以及包含第一环氧树脂和固化剂和有机酸的助焊剂,并且非树脂系粉末为整体的30~90wt%,无机粉末的表面被有机树脂覆盖。
Description
技术领域
本发明主要涉及将半导体部件、电子部件等钎焊到电路基板上时使用的焊膏中,具有包含环氧树脂的助焊剂成分的树脂助焊剂焊膏和安装结构体。
背景技术
近年来,移动电话、PDA(Personal Digital Assistant)等移动设备的小型化、高功能化不断发展。作为能够应对该发展的安装技术,大多使用BGA(Ball Grid Array)、CSP(Chip Scale Package)等安装结构。移动设备容易遭受到掉落冲击等机械负荷。对QFP(Quad Flat Package)而言,由其引线部分吸收冲击。但是,对不具有缓和冲击的引线的BGA、CSP等而言,确保耐冲击可靠性变得重要。
以往的作为代表性的焊料的Pb共晶焊料的熔点为183℃。另一方面,对如今的无铅焊料的代表性的Ag-Sn-Cu系焊料而言,其熔点比Pb共晶焊料高30℃左右。因此,回焊炉的温度分布(profile)的最高温度高达220~260℃。将高温耐性弱的部件安装在电路基板上时,仅该部件由额外工序进行点焊接合,因此生产率显著降低。
因此,开始使用克服了Sn-Ag-Cu系焊料(以下称为“SAC焊料”。)的熔点高这一缺点的Sn-Zn系、Sn-Ag-In系、Sn-Bi系等低熔点无铅焊料。但是,对使用了Sn-Zn系、Sn-Ag-In系、Sn-Bi系焊料的BGA连接而言,其焊料连接部的连接可靠性、尤其是耐冲击可靠性等尚未充分确立。
作为其对策,提出了为提高连接部的耐冲击可靠性,而使用了助焊剂中包含热固性树脂的焊膏(以下,称为“树脂助焊剂焊膏”)的半导体安装结构体及其制造方法(例如,参照专利文献1)。
需要说明的是,作为树脂助焊剂焊膏的组成的一例,可举出包含助焊剂以及焊料粉末的膏剂,该助焊剂由环氧树脂、固化剂、有机酸、增粘材料构成。
另外,作为安装结构体的耐掉落可靠性的第二个对策,提出了用通常的SAC焊料55将CSP等半导体部件51的端子52连接到基板53的电极54后,使用称作底部填充材的液态密封材57,进行连接的强度加强的方法(例如,参照专利文献2)。图4是以往的通过焊料球进行连接后,通过底部填充材57进行了加强的情况的示意截面图。底部填充材57是,例如,包含液态环氧树脂、固化剂和二氧化硅等无机粉末58的低粘度液态树脂组合物。底部填充材57中包含二氧化硅等无机粉末58,因此固化物的热膨胀系数变小、弹性模量也变高。由此,可使CSP的焊料凸块55与底部填充材57的树脂的热膨胀的差变小。其结果,可通过底部填充材57的硬树脂加强凸块55的周围,因此可以确保非常高的耐掉落可靠性。
底部填充材57自CSP芯片的周围通过毛细管现象渗透至CSP芯片与布线电路基板的微小的间隙并填充。该工序在将CSP通过焊料球55安装至基板53后,进一步追加助焊剂清洗、底部填料填充、底部填料固化这样的长的工序而成。因此,在稍微降低制造成本也好的电子设备的制造中,该工序成为成本上升的主要原因。
作为其成本对策之一,实施了用前述的树脂助焊剂焊膏代替通常的SAC焊料,将CSP的焊料球与电路基板连接,同时进行树脂加强的对策。即,通过回焊加热,树脂助焊剂焊膏的焊料与CSP的焊料球熔融连接时,树脂被挤压至焊料的周围,形成对焊料的周围进行加强的结构,因此即使没有底部填料也进行了树脂加强。由此,无需助焊剂清洗、底部填料填充、底部填料固化这样的工艺,可进行工序的缩短。
现有技术文献
专利文献
专利文献1:日本特开2009-283453号公报
专利文献2:日本特开2011-142119号公报
发明内容
发明要解决的技术问题
但是,该使用树脂助焊剂焊膏的对策与以往的底部填料填充相比,存在耐掉落可靠性稍有不良这样的技术问题。其理由可以举出2个。第一,树脂助焊剂焊膏所含Sn-Bi系的低熔点焊料与SAC焊料相比具有脆的特性。因此,将使用该树脂助焊剂焊膏的对策用于移动设备等的情况下,在掉落试验中比SAC焊料更容易损坏。第二,对于利用树脂助焊剂焊膏的焊料连接而言,确实用树脂加强了焊料连接部,但对于该加强树脂而言,其仅是不含底部填料所含的二氧化硅等填料的树脂。因此,与底部填料相比,树脂固化物的热膨胀系数较大,而弹性模量较小。由于这样的特性,CSP的焊料凸块的加强效果也变小,其结果是,耐掉落可靠性也变低。
本发明的目的在于提供无需底部填充工序,并且具有优良的焊料凸块的加强效果的树脂助焊剂焊膏和安装结构体。
用于解决课题的手段
本发明所涉及的树脂助焊剂焊膏具备:
包含焊料粉末和无机粉末的非树脂系粉末、
以及包含第一环氧树脂、固化剂和有机酸的助焊剂,
所述非树脂系粉末为整体的30~90wt%,
所述无机粉末的表面被有机树脂覆盖。
本发明所涉及的安装结构体具备:
具有电极的电路基板、
具有端子的电子部件、
包含将所述电路基板的所述电极与所述电子部件的所述端子之间连接的焊料的导电部、以及
覆盖所述焊料周围的至少一部分、并且包含分散有无机粉末的固化后的第一环氧树脂的加强部,
所述加强部的所述无机粉末的表面被有机树脂覆盖。
发明效果
根据本发明的树脂助焊剂焊膏,在用于电子部件向电路基板的焊料接合的情况下,由于包含无机粉末,因此可以不使用底部填充材,而通过焊料接合部的树脂更牢固地对加强部进行加强。因此可以提高安装结构体的耐掉落性。另外,由于无机粉末的表面被有机树脂所覆盖,因此在焊料粉末熔融时可以抑制妨碍助焊剂的还原作用的作用。因此,可以改善焊料粉末的熔融性。
附图说明
图1是表示使用实施方式1的树脂助焊剂焊膏而接合的安装结构体的截面结构的截面图。
图2是表示实施方式1的树脂助焊剂焊膏所含的表面被有机树脂覆盖的无机粒子的截面结构的截面图。
图3A是表示制作实施方式的安装结构体的制造工艺中,在电路基板的电极之上涂布树脂助焊剂焊膏的工序的示意截面图。
图3B是表示使用贴片机等以半导体部件1的端子与电路基板的电极对置的方式将半导体部件与电路基板重叠的工序的示意截面图。
图3C是表示在回焊炉内将树脂助焊剂焊膏加热至规定的加热温度的工序的示意截面图。
图3D是表示将树脂助焊剂焊膏中的焊料粉末、和设置在半导体部件的端子上的焊料球加热至熔融温度的工序的示意截面图。
图4是以往通过焊料球进行连接后,通过底部填充材进行了加强的情况的安装结构体的示意截面图。
具体实施方式
<完成本发明的历程>
本发明人对通过使树脂助焊剂焊膏中预先包含上述底部填充材所含的二氧化硅等无机粉末,则是否可以不需要底部填充工序进行了研究。其结果,发现:若对无机粉末与焊料粉末共存的树脂助焊剂焊膏进行加热,则产生原本发生熔融而进行金属接合的焊料粉末几乎不熔融,而无法进行金属接合这样严重的问题。后述的比较例中示出,作为无机粉末,二氧化硅、氧化铝、滑石等与焊料粉末共存的情况下,焊料几乎不熔融。尤其是氧化铝的情况下,焊料完全不熔融。推测这是因为作为金属氧化物的无机粉末阻碍助焊剂中的有机酸的助焊剂作用(除去焊料表面的氧化膜的还原反应)。为了增强助焊剂作用,也进行了增加有机酸的量的研究,但即使添加通常量的10倍量也没有发现大的改善。可知作为无机粉末的二氧化硅、氧化铝、滑石等金属氧化物等的助焊剂作用的阻碍效果非常强。
因此,本发明人进行了对无机粉末的二氧化硅的表面进行包覆,来抑制阻碍助焊剂的还原作用的初步研究。需要说明的是,二氧化硅使用了熔融二氧化硅(粒径0.6μm,Micron公司制)。
首先,作为(1)二氧化硅表面的包覆方法,研究了金属膜涂敷。作为金属,选择了银。利用无电解镀覆处理在二氧化硅的表面上形成了银包覆膜。将该银包覆二氧化硅添加至树脂助焊剂焊膏,制成膏剂。若用其进行通常的涂布、加热熔融,则焊料粉末发生熔融,但银包覆二氧化硅粒子在环氧树脂固化后的部分的外侧表面上以浮起的形状出现。即,形成了中心的焊料接合部、其周围的环氧树脂固化的部分、以及最外侧的银包覆二氧化硅的层。若是该构造,则银包覆二氧化硅从环氧树脂分离而形成层,环氧树脂与二氧化硅的复合化困难,因此无法期待低热膨胀化、高强度化。
接着作为(2)二氧化硅表面的包覆,研究了环氧树脂(第二环氧树脂)包覆。原本树脂助焊剂焊膏在液态的第一环氧树脂中包含有焊料粉末。另外,第一环氧树脂与包覆着二氧化硅表面的第二环氧树脂的相容性非常好。需要说明的是,向二氧化硅表面包覆第二环氧树脂的方法可以提出各种方法,这里没有特别限定。不过,未固化的第二环氧树脂直接以树脂助焊剂焊膏的形式分散于第一环氧树脂时,有未固化的第二环氧树脂与第一环氧树脂发生溶合,二氧化硅的包覆膜受损的可能。因此,覆盖二氧化硅的表面的第二环氧树脂必须进行固化反应而3维交联。通过进行固化,可以防止树脂助焊剂焊膏的第二环氧树脂的溶胀、膜被破坏的情形。
因此,发现通过将无机粉末的二氧化硅的表面预先用环氧树脂包覆再使之分散在树脂助焊剂焊膏中,可以减少阻碍焊料粉末的熔融的作用,从而完成了本发明。
第一方式的树脂助焊剂焊膏具备:
包含焊料粉末和无机粉末的非树脂系粉末、以及
包含第一环氧树脂和固化剂和有机酸的助焊剂,
所述非树脂系粉末为整体的30~90wt%,
所述无机粉末的表面被有机树脂覆盖。
关于第二方式的树脂助焊剂焊膏,在上述第一方式中,相对于所述非树脂系粉末的总量100wt%,所述焊料粉末的含有率可以是60~95wt%,所述无机粉末的含有率可以是5~40wt%。
关于第三方式的树脂助焊剂焊膏,在上述第一或第二方式中,包含覆盖表面的有机树脂的所述无机粉末的平均粒径可以是1.0μm~25μm的范围。
关于第四方式的树脂助焊剂焊膏,在上述第一至第三中的任一方式中,所述无机粉末可以是二氧化硅,
所述有机树脂可以是第二环氧树脂。
关于第五方式的树脂助焊剂焊膏,在上述第一至第四中的任一方式中,所述焊料粉末可以是42Sn58Bi、42Sn57Bi1.0Ag、16Sn56Bi28In中的任一种。
第六方式的安装结构体具备:
具有电极的电路基板、
具有端子的电子部件、
包含将所述电路基板的所述电极与所述电子部件的所述端子之间连接的焊料的导电部、以及
覆盖所述焊料周围的至少一部分、并且包含分散有无机粉末的固化后的第一环氧树脂的加强部,
所述加强部的所述无机粉末的表面被有机树脂覆盖。
第七方式的安装结构体的制造方法包含以下工序:
在电路基板上的电极、和安装于所述电路基板的电子部件的端子中的至少一者之上,设置第一至五方式中的任一项所述的树脂助焊剂焊膏的工序;
经由所述树脂助焊剂焊膏来配置所述电路基板上的所述电极和所述电子部件的所述端子的工序;以及
将所述树脂助焊剂焊膏加热至所述焊料粉末的熔点以上的温度,使所述树脂助焊剂焊膏分离为将所述电极与所述端子之间连接的焊料、和固化环氧树脂,从而将所述电路基板上的所述电极和所述电子部件的所述端子焊料接合的工序,其中,所述固化环氧树脂覆盖所述焊料周围的至少一部分,通过使分散有表面被有机树脂覆盖的无机粉末的所述第一环氧树脂固化而成。
以下,参照附图对实施方式的树脂助焊剂焊膏和安装结构体进行说明。需要说明的是,对于图中实质上相同的构件使用相同的符号。
(实施方式1)
<树脂助焊剂焊膏>
实施方式1的树脂助焊剂焊膏具备包含焊料粉末和无机粉末的非树脂系粉末、以及包含第一环氧树脂、固化剂和有机酸的助焊剂。非树脂系粉末为整体的30~90wt%。另一方面,剩余部分的10~70wt%由包含第一环氧树脂、固化剂和有机酸的助焊剂构成。无机粉末的表面被有机树脂覆盖。无机粉末可以是例如,二氧化硅。有机树脂可以是例如,第二环氧树脂。
根据该树脂助焊剂焊膏,在用于电子部件向电路基板的焊料接合的情况下,由于包含无机粉末,可以不使用底部填充材,而通过焊料接合部的树脂更牢固地对加强部进行加强。因此可以提高安装结构体的耐掉落性。另外,由于无机粉末的表面被有机树脂所覆盖,因此在焊料粉末熔融时可以抑制妨碍助焊剂的还原作用的作用。因此,可以改善焊料粉末的熔融性。
接下来,对树脂助焊剂焊膏的组成以及评价方法进行说明。
该树脂助焊剂焊膏的树脂成分以第一环氧树脂和固化剂为主成分。
<第一环氧树脂>
第一环氧树脂在相对低温下发生固化且粘接性高,因此即使在比以往的焊料回焊处理更低的温度下也能发挥充分的固化性,能够进行部件安装,同时可以发挥充分的加强效果。第一环氧树脂通过配合在常温下为液态的环氧树脂,从而可以容易地分散焊料粒子等其他成分。需要说明的是,本说明书中的“在常温下为液态”意味着在大气压下的5~28℃的温度范围,尤其是室温18℃前后具有流动性的情况。作为在常温下为液态的环氧树脂,只要是在1分子内具有2个以上的环氧基的环氧树脂,其分子量、分子结构就没有特别限定,可以使用各种环氧树脂。具体来说,例如能够使用缩水甘油基醚型、缩水甘油基胺型、缩水甘油基酯型、烯烃氧化型(脂环式)等的各种液态的环氧树脂。更具体而言,可以使用例如:双酚A型环氧树脂、双酚F型环氧树脂等双酚型环氧树脂、氢化双酚A型环氧树脂、氢化双酚F型环氧树脂等氢化双酚型环氧树脂、联苯型环氧树脂、含萘环的环氧树脂、脂环式环氧树脂、双环戊二烯型环氧树脂、苯酚酚醛型环氧树脂、甲酚酚醛型环氧树脂、三苯甲烷型环氧树脂、脂肪族系环氧树脂、三缩水甘油基异氰脲酸酯等。这些可以1种单独使用,也可以并用2种以上。在这些当中,若考虑半导体密封用的液态环氧树脂组合的低粘度化和固化物的物性提高,则作为常温下为液态的环氧树脂而优选双酚型环氧树脂、氢化双酚型环氧树脂。另外,可以并用常温下为固态的环氧树脂。作为常温下为固态的环氧树脂,例如,能够使用联苯型环氧树脂、双环戊二烯型环氧树脂、三嗪骨架环氧树脂等。
<固化剂>
另外,作为固化剂,作为一般的环氧树脂固化剂,可以使用酸酐、苯酚酚醛、各种硫醇化合物、各种胺类、双氰胺、咪唑类、金属络合物以及它们的加成化合物,例如多胺的加成改性物等。特别是,各种咪唑类在兼顾单液性(日文:一液性)和焊料熔融性方面优异。作为咪唑类,可举出例如:2-甲基咪唑(制品名2MZ:四国化成工业株式会社制)、2-十一烷基咪唑(制品名C11Z:四国化成工业株式会社制)、2-苯基咪唑(制品名2PZ:四国化成工业株式会社制)、2-乙基-4-甲基咪唑(制品名2E4MZ:四国化成工业株式会社制)、2-苯基-4-甲基咪唑(制品名2P4MZ:四国化成工业株式会社制)、1-苄基-2-甲基咪唑(制品名1B2MZ:四国化成工业株式会社制)、1-苄基-2-苯基咪唑(制品名1B2PZ:四国化成工业株式会社制)、1-氰基乙基-2-甲基咪唑(制品名2MZ-CN:四国化成工业株式会社制)、1-氰基乙基-2-乙基-4-甲基咪唑(制品名2E4MZ-CN:四国化成工业株式会社制)、1-氰基乙基-2-苯基咪唑(制品名2PZ-CN:四国化成工业株式会社制)、1-氰基乙基-2-十一烷基咪唑(制品名C11Z-CN:四国化成工业株式会社制)、1-氰基乙基-2-苯基咪唑鎓偏苯三酸盐(制品名2PZ-CNS:四国化成工业株式会社制)、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸盐(制品名C11Z-CNS:四国化成工业株式会社制)、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪(制品名2MZ-A:四国化成工业株式会社制)、2,4-二氨基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪(制品名C11Z-A:四国化成工业株式会社制)、2,4-二氨基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪(制品名2E4MZ-A:四国化成工业株式会社制)、2-苯基-4-甲基-5-羟基甲基咪唑(制品名2P4MHZ:四国化成工业株式会社制)、2-苯基-4,5-二羟基甲基咪唑(制品名:2PHZ(四国化成工业株式会社制))、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪异氰脲酸加成物(制品名2MA-OK:四国化成工业株式会社制)、2-苯基咪唑异氰脲酸加成物(制品名2PZ-OK:四国化成工业株式会社制),以及使这些咪唑类与环氧树脂加成的化合物。另外,也可以使用将这些固化剂用聚氨酯系、聚酯系的高分子物质等被覆而微胶囊化后的物质。
固化剂的使用量适当设定,但相对于第一环氧树脂的环氧当量,固化剂的化学计量上的当量比优选为0.8~1.2的范围。
需要说明的是,在树脂成分中,除了第一环氧树脂以及固化剂以外,也可以进一步根据需要配合固化促进剂。
<固化促进剂>
作为固化促进剂,除了上述咪唑类以外,可以使用例如叔胺类、1,8-二氮杂二环(5.4.0)十一烯-7、1,5-二氮杂二环(4.3.0)壬烯-5等环状胺类以及它们的四苯基硼酸盐、三丁基膦等三烷基膦类、三苯基膦等三芳基膦类、四苯基硼四苯基膦或四苯基硼四(正丁基)膦等季鏻盐、乙酰丙酮合Fe等金属络合物以及它们的加成化合物。这些固化促进剂的配合量考虑凝胶化时间、保存稳定性进行适当设定。
<有机酸>
树脂助焊剂焊膏中配合的有机酸没有特别限定,可以使用例如:松香酸所代表的松香成分材料、各种胺及其盐、癸二酸、己二酸、戊二酸、琥珀酸、丙二酸、柠檬酸、庚二酸等有机酸。特别是,有机酸具有优良的助焊剂作用(这里,助焊剂作用是指:除去焊膏所涂布的金属表面产生的氧化被膜这样的还原作用,以及降低熔融焊料的表面张力从而促进焊料向接合金属表面的浸润性的作用)。
这些有机酸可以是一种成分,也可以将二种以上的成分进行混合。而且这些有机酸中,己二酸、戊二酸的助焊剂活性高、作为化合物的稳定性高,故优选。
另外,在本发明的树脂助焊剂焊膏中,上述必须成分之外,也可以含有通常使用的改性剂、添加剂等。另外,以降低树脂助焊剂焊膏的粘度、赋予流动性为目的,也可以添加低沸点的溶剂、增塑剂。此外,作为用于保持印刷形状的触变性赋予剂,添加硬化蓖麻油、硬脂酸酰胺等也是有效的。
<焊料粉末>
作为焊料粉末,使用熔点240℃以下的焊料粉末。焊料粉末的熔点的下限没有特别限定,但优选为130℃以上。BGA,CSP半导体的焊料球使用锡-银-铜(SAC)焊料粉末,通过使用比其熔点(240℃)更低的焊料,可以防止SAC焊料粉末发生再熔融。作为该焊料粉末的组成,没有特别限定,例如,可以使用以Sn为基础的合金等。具体而言,优选SnBi系的Sn42/Bi58(Sn0.42Bi0.58),Sn42/Bi57/Ag1.0、Sn16/Bi56/In28等。
另外,该树脂助焊剂焊膏的特征在于,焊料粉末和无机粉末所构成的非树脂系粉末的比率为整体的30~90wt%,余量的10~70wt%为包含第一环氧树脂、固化剂和有机酸的助焊剂。若该非树脂系粉末的比率少于30wt%,则由于焊料量变少,因此得不到充分的电连接。另外,若非树脂系粉末的比率大于90wt%,则粘度过高从而印刷性变难。
<无机粉末(无机填料)>
本发明的树脂助焊剂焊膏的特征在于,除焊料成分以外,还包含无机粉末(以下有时称为“无机填料”。)。无机填料为低热膨胀,通过包含在树脂成分中,可以降低热膨胀率,并提高弹性模量。
作为无机填料的种类,与在半导体密封材等中通常使用的填料相同,可以使用二氧化硅、氧化铝、滑石等。在该树脂助焊剂焊膏中,焊料粉末和无机填料与树脂成分一起共存。
树脂助焊剂焊膏中的由焊料粉末和无机粉末构成的非树脂系粉末中,相对于非树脂系粉末的总量,焊料粉末的比率(含有率)优选为60~95%,无机粉末的比率(含有率)优选为5~40%。若在该范围内,则可以充分地发挥树脂助焊剂焊膏的固化物所带来的半导体部件的电接合性以及树脂成分的低热膨胀率化和高弹性模量化所带来的对焊料部分的加强效果,也可以抑制高粘度化导致的涂布作业性的低下。
图2是表示该树脂助焊剂焊膏中的无机粉末8的截面结构的截面图。芯的无机粉末8a的表面被有机树脂8b覆盖。作为该有机树脂8b,例如,可以使用环氧树脂。需要说明的是,覆盖芯的无机粉末8a的表面的有机树脂8b不限于环氧树脂。作为有机树脂8b,例如,可以使用酚醛树脂、环氧树脂等,若考虑向第一环氧树脂的分散性、相容性等,则优选环氧树脂等。覆盖无机粉末的表面的环氧树脂不限于与第一环氧树脂相同的环氧树脂,因此设为“第二环氧树脂”。
<第二环氧树脂>
为了防止与树脂的溶胀破坏,在该无机粉末的表面上第二环氧树脂所形成的膜的膜厚优选为0.1~25μm。若第二环氧树脂反应固化后的膜的膜厚比0.1μm更薄,则膜的强度弱,由于环氧粘合剂自身的溶胀,而导致包覆膜被破坏,从而出现无机粉末的被覆变得不充分的情形,因此,有焊料粉末的熔融变差的倾向。另外,若第二环氧树脂发生反应固化后的膜的膜厚比25μm更厚,则无机粉末的低热膨胀化的效果变小。
此外,树脂助焊剂焊膏所含的、被第二环氧树脂反应固化后的膜覆盖的无机粉末的平均粒径优选在1.0μm~25μm的范围。被该第二环氧树脂反应固化后的膜覆盖的无机粉末的平均粒径比1.0μm更小时,树脂助焊剂焊膏组合物的粘度变高,操作性变差。另外,若无机粉末的平均粒径大于25μm,则焊料发生金属化而凝聚时,无机粉末发生移动,无法在树脂成分内均匀地分散,无法发挥第一环氧树脂降低热膨胀的效果。
<树脂助焊剂焊膏的制造方法>
接下来,示出树脂助焊剂焊膏的制造方法的一例。
(1)首先,混合熔点为240℃以下的焊料粉末、第一环氧树脂的一部分或全部、固化剂、以及助焊剂成分。
(2)接着,将之前使用了部分第一环氧树脂的情况下的残余部分、和表面被有机树脂所形成的膜覆盖的无机粉末添加至该混合物中并混合。
通过以上,得到树脂助焊剂焊膏。
通过这样的制造,可以得到使助焊剂成分融合(日文:馴染)在焊料粉末的周围的树脂助焊剂焊膏,并且可以有效地表现出室温下的保存稳定性、并高效地表现出加热时的焊料粉末的熔融。
这样得到的树脂助焊剂焊膏如上所述作为树脂成分而含有第一环氧树脂和固化剂,因此室温下的粘度上升受到抑制。因此,是保存稳定性高的树脂助焊剂焊膏。
另外,由于无机粉末的表面被有机树脂所覆盖,因此在焊料粉末熔融时可以抑制妨碍作为助焊剂的有机酸的还原作用的作用。因此,可以改善焊料粉末的熔融性。
<安装结构体>
图1是使用实施方式1的树脂助焊剂焊膏10为接合的安装结构体20的截面图。该安装结构体20具有如下结构:将电子部件1的端子2和设置在电路基板3上的电极4之间,例如用SAC焊料凸块5和SnBi低温焊料6进行接合,并通过将该焊料5、6的周围固化的第一环氧树脂7进行加强的结构。第一环氧树脂7中分散有无机粉末8,无机粉末8中,芯的无机粉末8a的表面被树脂膜(例如,固化的第二环氧树脂所形成的膜)8b覆盖。
根据该安装结构体20,通过使用上述树脂助焊剂焊膏10,作为电子部件的CSP芯片1的端子2上的SAC焊料5与电路基板3的电极4用低温焊料6进行接合,且树脂7将其周围覆盖。即,形成了焊料5、6所形成的导电部通过第一环氧树脂7进行了加强的结构(加强部)。此外,该第一环氧树脂7所形成的加强部可成为如下结构:分散有芯的无机粉末(二氧化硅)8a的表面被有机树脂(第二环氧树脂)8b覆盖的无机粉末(二氧化硅)8的结构。加强部包含具有低热膨胀率和高弹性模量的二氧化硅8,因此具有优良的加强结构。其结果,安装结构体20可具有高的耐掉落可靠性。
该安装结构体如下得到:例如,将电子部件的端子和电路基板的电极之间,用分散有上述表面被有机树脂覆盖的无机粉末的树脂助焊剂焊膏接合而得到。
<安装结构体的制造方法>
图3A至图3D是表示实施方式1的安装结构体20的制造方法的各工序的截面图。使用上述树脂助焊剂焊膏,将作为电子部件的半导体部件安装至具有导体布线的电路基板等从而可以得到安装结构体。作为安装结构体的半导体装置20具备使用上述树脂助焊剂焊膏10将半导体部件1的端子2与电路基板3的电极4接合的接合部。
(1)首先,在电路基板3的电极4上涂布树脂助焊剂焊膏10(图3A)。该树脂助焊剂焊膏10包含树脂助焊剂7、SnBi粉末6a、和芯的无机粉末8a的表面被有机树脂8b覆盖的无机粉末8。使用了树脂助焊剂焊膏10的安装工序中,使用金属掩膜(未图示)从而将树脂助焊剂焊膏10印刷至电路基板3的布线电极4等规定的位置。例如,将在与电极4相同的位置上设置了贯通孔的金属掩膜(未图示)重叠至电路基板3。接着,将供给至金属掩膜的表面的树脂助焊剂焊膏10用刮刀填充至贯通孔。其后,将金属掩膜从电路基板3剥离,可以得到各电极4上涂布了树脂助焊剂焊膏10的电路基板3。
(2)然后,在树脂助焊剂焊膏10未固化状态下,使用贴片机等以半导体部件1的端子2与电路基板3的电极4对置的方式将半导体部件1与电路基板3重叠(图3B)。这里,作为半导体部件1,可以使用设置焊料球5作为端子2而形成的CSP、BGA,设置引线作为端子而形成的QFP等半导体封装体。另外,作为半导体部件1,可以使用未收容于封装体且设置端子2而形成的半导体元件(裸芯片)。
(3)上述状态下,将配置了半导体部件1的电路基板3通过焊料回焊工艺等在回焊炉11内将树脂助焊剂焊膏10加热至规定的加热温度(图3C)。对该树脂助焊剂焊膏10而言,通过加热,在焊料发生熔融的工序中,树脂成分的树脂助焊剂7与焊料粉末6a自树脂助焊剂7与焊料粉末6a的混合体发生分离,从而可以形成树脂将熔融的焊料6的周边覆盖这样的加强结构。该加强的结果是可使焊料接合部的强度变高、并提高耐冲击可靠性。另外,将该加热温度设为焊料粉末6a充分熔融、并且树脂成分的固化反应充分进行的适当的温度。需要说明的是,该加热温度优选被设为:在焊料粉末6a完全熔融之前,第一环氧树脂的固化反应进行从而焊料粉末6a的凝聚不会受到阻碍的温度。因此优选的加热温度为比焊料粉末的熔点高10℃~60℃的温度以上。
(4)接着,通过回焊方式,加热至树脂助焊剂焊膏10中的焊料粉末6a、和设置在半导体部件1的端子2上的焊料球5发生熔融温度(图3D)。树脂助焊剂起到将被钎焊的电极2表面的氧化膜和焊料粉末6a表面的氧化膜通过还原反应而化学地除去的作用、即助焊剂作用,使焊料的熔融连接成为可能。在这种情况下,二氧化硅等无机粉末8由于表面被第二环氧树脂等有机树脂8b所覆盖,因此可以抑制对有机酸的助焊剂作用的阻碍。另外,通过利用该加热使树脂助焊剂焊膏10发生固化,而设置将半导体部件1与电路基板3电连接的焊料接合部。即,经加热而熔融的焊料6与焊料球5一体化从而形成焊料接合部。焊料粉末发生熔解,通过金属的凝聚力而聚集于电极4时,树脂助焊剂焊膏10所包含的无机粉末8均匀地分散在覆盖着熔融的焊料6周围的树脂成分7的内部,通过树脂成分7的固化而固化。即,电路基板3的布线电极4与半导体部件1的端子2的焊料接合部的形成、以及通过环氧树脂的固化的加强部的形成,通过一次加热回焊工序来进行。
这样,接合部由熔融的焊料6和焊料球5熔融一体化的焊料接合部(导电部),以及覆盖该焊料接合部周围、包含无机粉末分散并固化的第一环氧树脂的固化部(加强部)形成。
这样,制作出半导体部件1与电路基板3的电气接合通过焊料接合部而实现、并且以加强部含有无机粉末8而被机械加强的结构来安装半导体部件1的安装结构体即半导体装置20。
<实施例>
接下来,使用实施例、比较例说明本发明。以下,通过实施例对本发明作进一步详细说明,但本发明并不限于这些实施例。需要说明的是,表1以及表2所示的配合量以质量份(重量份)表示。作为表1以及表2所示的配合成分,使用了以下成分。
[第二环氧树脂包覆的二氧化硅的制作]
(1)将液态环氧树脂和固化剂以当量1比1配合作为环氧树脂组合物在容器中称量。
(2)这里,相对于环氧树脂组合物90份,添加IPA(异丙醇)与丙酮的重量比为1比1的混合溶剂10份,制作环氧树脂组合物的溶剂稀释液。
(3)作为各种粒径的熔融二氧化硅,准备了(a)粒径1μm(SO-25R:Micron公司)、(b)粒径5μm(FB-5D:Denka(株))、(c)粒径11μm(FB-12D:Denka(株))、和(d)粒径22μm(FB-20D:Denka(株))。将它们当中的任一种熔融二氧化硅添加至上述的溶剂稀释液,使得以重量比计二氧化硅∶溶剂稀释液=80∶20。
(4)将该添加了二氧化硅的混合液盖上盖子使之成为密闭状态,用行星式混合装置充分搅拌,使得混合溶液均匀地覆盖在二氧化硅的表面。
(5)其后,在干燥机中于70℃下用1小时除去溶剂,进一步在120加热30分钟,从而使二氧化硅表面的环氧树脂膜固化。
(6)由于加热处理后的环氧树脂(第二环氧树脂)所包覆的二氧化硅存在凝聚物,因此使用粉碎机来消除凝聚。
(7)其后,通过100目(网眼149μm)的筛,除去粗粒子。
需要说明的是,在70℃下用1小时除去溶剂后,在120℃加热30分钟时,通过每隔几分钟进行搅拌,可以减少凝聚,得到即使通过其后的粉碎工序,二氧化硅表面也较少从环氧树脂膜露出的环氧树脂包覆的二氧化硅。
这样得到的环氧树脂覆盖的二氧化硅的平均粒径为5.0μm~25μm的范围。
[树脂助焊剂焊膏的制作]
1)焊料粉末:使用了JIS H42B:58A所规定的焊料组成的焊料粉末(Sn42Bi58)。焊料粉末根据常规方法制作。该焊料粒子的平均粒径为15μm,熔点为139℃。
2)第二环氧树脂包覆的二氧化硅:使用了用前述的方法制作的二氧化硅。
3)第一环氧树脂:第一环氧树脂:双酚F型环氧树脂(EPOCOAT 806:日本环氧树脂株式会社制)。
4)固化剂:咪唑系固化剂:2-苯基-4-甲基-5-羟基甲基咪唑(商品名2P4MHZ:四国化成工业株式会社制)。
5)有机酸:戊二酸(关东化学株式会社制)。
6)触变性赋予材:ThixcinR(三氧硬脂酸甘油酯:Elementis Japan公司制)。
关于使用以上材料、而由含有有机酸的粘接剂和SnBi系焊料粉末构成的导电性粘接剂,利用以下配方来制作。
将上述3)~6)的成分用行星式混合机均匀地分散。其后,添加1)2)并混炼,制作树脂助焊剂焊膏。
〔评价元件的制作〕
然后,使用金属掩膜将该树脂助焊剂焊膏通过印刷以厚度达到0.1mm的方式供给至电路基板(FR-4基板)上的镀Au的电极。
然后,使用倒装芯片接合机将大小为11mm×11mm、焊料凸块为0.5mm的间隔、凸块数为441个、基板材质为玻璃环氧材的CSP半导体封装体正确地安装在3cm×7cm的大小、厚度0.8mm、电极材质为铜的电路基板上。其后,用回焊装置进行加热(160℃,6分钟)从而连接。
〔评价方法〕
(1)印刷性:将树脂助焊剂焊膏印刷至上述电路基板,进行从掩膜转印的转印性、以及在印刷物上有无滴下(ダレ)或电桥(ブリツジ)的评价。
将从掩膜的转印可以进行、并且可保持形状的评价元件设为◎,将形状上稍有问题但可转印的设为○,将形状非常差的设为×。
(2)焊料熔融性:目视评价将涂布了树脂助焊剂焊膏的基板通过回焊而使焊料熔融时,焊料能否熔融。
将焊料没有未熔融的设为○,有少量未熔融成分的设为Δ,将不发生熔融的设为×。
(3)耐掉落性:对如上所述得到的评价用CSP封装体进行CSP封装体的掉落试验。具体而言,使安装结构体从100cm的高度掉落,测定CSP封装体的连接性、包含球连接部的菊链图案有没有导通。将其变为导通不良的掉落次数多于100次的情况设为◎,将50次以上且100次以下的情况设为○,将少于50次的情况设为×。
(4)综合判定:上述(1)~(3)的评价中,○为2个以上的话将综合判定设为◎,○为1个的情况下将综合判定设为○,×只要有1个就将综合判定设为×。
接着,说明实施例1。焊料的种类使用了Sn42/Bi58。使用的熔融二氧化硅是(d)粒径22μm的二氧化硅(FB-20D:Denka(株))。另外,关于膏剂组成,由焊料粉末、与用第二环氧树脂形成了膜的二氧化硅构成的非树脂系粉末的比率为整体的90wt%,包含第一环氧树脂、固化剂、以及有机酸的助焊剂成分为整体的10wt%。另外,二氧化硅的表面用第二环氧树脂的膜进行了表面处理。另外,关于相对于非树脂系粉末整体的、焊料粉末与形成了二氧化硅的膜的二氧化硅的比率,是二氧化硅为40%的配合。关于该树脂助焊剂焊膏的配合在表中示出。
使用该树脂助焊剂焊膏,进行(1)印刷性评价、(2)焊料熔融性评价、(3)耐掉落性评价的结果在表2中示出。印刷性中,掩膜转印性方面存在些许难点,但焊料熔融性、耐掉落性优异。
[表1]
[表2]
实施例2与实施例1同样地,非树脂系粉末的比率为90wt%。另外,熔融二氧化硅使用了(a)粒径1μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为5%的配合。
实施例3的非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(c)粒径11μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。
实施例4的非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(b)粒径5μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为20%的配合。
实施例5的非树脂系粉末的比率为30wt%。另外,熔融二氧化硅使用了(a)粒径1μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。
实施例6与实施例3相同,非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(c)粒径11μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。
实施例7与实施例3同样地,非树脂系粉末的比率为70wt%。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为20%的配合。另外,熔融二氧化硅使用了(b)粒径5μm的二氧化硅。
实施例8与实施例3同样地,非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(d)粒径22μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。焊料粉末的种类使用了Sn42/Bi57/Ag1.0(简称为SBA)。
实施例9与实施例3同样地,非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(b)粒径5μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。焊料粉末的种类使用了Sn16/Bi56/In28(简称为SBI)。
比较例1与实施例3同样地,非树脂系粉末的比率为70wt%。非树脂系粉末全部是焊料粉末。
比较例2与实施例3同样地,非树脂系粉末的比率为70wt%。另外,熔融二氧化硅使用了(b)粒径5μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合,但未进行二氧化硅的表面处理。
比较例3的非树脂系粉末的比率为10wt%。另外,熔融二氧化硅使用了(a)粒径1μm的二氧化硅。相对于非树脂系粉末整体,焊料粉末与二氧化硅的比率是二氧化硅为40%的配合。
若从表1和表2的结果进行考察,则非树脂系粉末的比率为30~90wt%的样品耐掉落性优异。此外,已知由于第二环氧树脂包覆的二氧化硅的添加,其耐掉落性大大提高。
另外,如比较例2所示,已知若添加未实施第二环氧树脂包覆的二氧化硅,则焊料的熔融性变差而无法连接。
此外,第二环氧树脂包覆的二氧化硅的粒径对耐掉落性而言影响不大。另一方面,已知在印刷性的方面,粗粒子对印刷后滴下的发生有影响,微小粒子使印刷时的掩膜抽出(マスク抜け)变差,会对印刷作业性造成影响。
另外,如实施例8和9所示,可知就焊料粉末的种类而言,不仅Sn42/Bi58,使用Sn42/Bi57/Ag1.0、Sn16/Bi56/In28也能得到优良的耐掉落性。
需要说明的是,本公开中包含将前述的各种实施方式和/或实施例当中的任意实施方式和/或实施例的适当组合而成的方案,且可以实现各个实施方式和/或实施例具有的效果。
产业上的可利用性
本发明所涉及的树脂助焊剂焊膏和安装结构体可用于电气/电路形成技术领域的广泛用途。例如,可以用于CCD元件、全息元件、芯片部件等电子部件的连接用以及将它们接合至基板的用途,并且可以用于内置这些元件、部件、或基板的产品,例如,DVD、移动电话、便携AV设备、数码相机等。
附图说明
1 半导体部件(电子部件)
2 端子(电极)
3 电路基板
4 电极
5 SAC焊料凸块
6 SnBi低温焊料
6a 焊料粉末
7 环氧树脂
8 无机粉末(被有机树脂覆盖的无机粉末)
8a 无机粉末(芯)
8b 有机树脂(第二环氧树脂)
10 树脂助焊剂焊膏
11 回焊炉
51 电子部件
52 端子
53 电路基板
54 电极
55 焊料球
57 底部填充材
58 无机粒子
Claims (7)
1.一种树脂助焊剂焊膏,其具备:
包含焊料粉末和无机粉末的非树脂系粉末、以及
包含第一环氧树脂、固化剂和有机酸的助焊剂,
所述非树脂系粉末为树脂助焊剂焊膏的30wt%~90wt%,
所述无机粉末的表面被膜厚为0.1μm~25μm的第二环氧树脂覆盖。
2.根据权利要求1所述的树脂助焊剂焊膏,就所述非树脂系粉末的总量100wt%而言,所述焊料粉末的含有率为60wt%~95wt%,所述无机粉末的含有率为5wt%~40wt%。
3.根据权利要求1所述的树脂助焊剂焊膏,其特征在于,包含覆盖表面的第二环氧树脂的所述无机粉末的平均粒径为1.0μm~25μm的范围。
4.根据权利要求1所述的树脂助焊剂焊膏,
所述无机粉末为二氧化硅。
5.根据权利要求1所述的树脂助焊剂焊膏,所述焊料粉末为42Sn58Bi、42Sn57Bi1.0Ag、16Sn56Bi28In中的任一种。
6.一种安装结构体,具备:
具有电极的电路基板、
具有端子的电子部件、
包含将所述电路基板的所述电极与所述电子部件的所述端子之间连接的焊料的导电部、以及
覆盖所述焊料周围的至少一部分、并且包含分散有无机粉末的固化后的第一环氧树脂的加强部,
所述加强部的所述无机粉末的表面被膜厚为0.1μm~25μm的第二环氧树脂覆盖。
7.一种安装结构体的制造方法,包含以下工序:
在电路基板上的电极、和安装于所述电路基板的电子部件的端子中的至少一者之上,设置权利要求1所述的树脂助焊剂焊膏的工序;
经由所述树脂助焊剂焊膏来配置所述电路基板上的所述电极和所述电子部件的所述端子的工序;以及
将所述树脂助焊剂焊膏加热至所述焊料粉末的熔点以上的温度,使所述树脂助焊剂焊膏分离为将所述电极与所述端子之间连接的焊料、和固化环氧树脂,从而将所述电路基板上的所述电极和所述电子部件的所述端子焊料接合的工序,其中,所述固化环氧树脂覆盖所述焊料周围的至少一部分,通过使分散有表面被膜厚为0.1μm~25μm的第二环氧树脂覆盖的无机粉末的所述第一环氧树脂固化而成。
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