CN111788337A - 锡或锡合金电镀液、凸点的形成方法及电路基板的制造方法 - Google Patents

锡或锡合金电镀液、凸点的形成方法及电路基板的制造方法 Download PDF

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Publication number
CN111788337A
CN111788337A CN201980015474.4A CN201980015474A CN111788337A CN 111788337 A CN111788337 A CN 111788337A CN 201980015474 A CN201980015474 A CN 201980015474A CN 111788337 A CN111788337 A CN 111788337A
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China
Prior art keywords
tin
acid
surfactant
bump
plating
Prior art date
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CN201980015474.4A
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English (en)
Inventor
渡边真美
薄京佳
中矢清隆
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2018052012A external-priority patent/JP6635139B2/ja
Priority claimed from JP2019040216A external-priority patent/JP6677873B2/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority claimed from PCT/JP2019/011348 external-priority patent/WO2019181905A1/ja
Publication of CN111788337A publication Critical patent/CN111788337A/zh
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
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    • C25D7/00—Electroplating characterised by the article coated
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Abstract

本发明的锡或锡合金电镀液含有：(A)至少含有亚锡盐的可溶性盐；(B)选自有机酸及无机酸中的酸或其盐；(C)表面活性剂；(D)流平剂；及(E)添加剂，所述表面活性剂为由以下通式(1)表示的化合物(C1)和/或由通式(2)表示的化合物(C2)。式(1)、(2)中，R为碳原子数7～13的烷基，m为5～11，n为1～3，m与n不同。
Figure DDA0002650647470000011

Description

锡或锡合金电镀液、凸点的形成方法及电路基板的制造方法
技术领域
本发明涉及一种锡或锡合金电镀液、使用该锡或锡合金电镀液形成凸点的方法及电路基板的制造方法，所述锡或锡合金电镀液用于在电路基板上搭载半导体集成电路芯片时在基板上制造成为锡或锡合金的突起电极的凸点。更详细而言，涉及一种即使在凸点直径或凸点间距不同的图案中，对基板上的导通孔的导通孔填充性也优异，且所形成的凸点的高度变得均匀的锡或锡合金电镀液。
本申请主张基于2018年3月20日于日本申请的专利申请2018-52012号、2018年3月26日于日本申请的专利申请2018-57551号以及2019年3月6日于日本申请的专利申请2019-40216号的优先权，并将其内容援用于此。
背景技术
在搭载半导体集成电路芯片(以下，称为半导体芯片。)的电路基板中，为了对应轻薄短小(轻型化、薄型化、小型化)，目前主要制造将封装基板面积小型化至与搭载于基板的半导体芯片大致相等的程度的CSP(Chip Size/scale Package，芯片尺寸/尺度封装)型半导体装置。为了连接该电路基板和半导体芯片，利用锡或锡合金填充基板侧的作为导通孔主体部的导通孔开口部而形成突起状的作为金属端子的突起电极的凸点，并将半导体芯片装填到该凸点。
以往，为了通过填充该锡或锡合金材料来形成凸点，将锡系焊膏等导电膏或锡系焊球填充到导通孔主体部，或者使用锡或锡合金电镀液并利用电镀法在导通孔内形成锡电镀沉积层，接着通过热处理使导电膏、焊球或锡电镀沉积层熔融。
参考图1对利用电镀法形成凸点的通常的方法进行说明。如图1的(a)所示，在设置有配线等的基板1的表面上通过使用阻焊剂的光刻形成具有开口部的阻焊剂图案。接着，在阻焊层2的表面上通过化学镀形成用于供电的铜晶种层3。接着，在铜晶种层3的表面上形成干膜抗蚀剂层4，并以与阻焊层2的开口部接合的方式形成具有开口部的干膜抗蚀剂图案。接着，通过经由上述铜晶种层3供电，在干膜抗蚀剂图案的导通孔6的内部进行电镀锡，且在铜晶种层3上的导通孔6内形成锡电镀沉积层7(镀锡皮膜)。接着，依次去除干膜抗蚀剂层4和铜晶种层3，接着通过回焊处理将残留的锡电镀沉积层7熔融，从而如图1的(b)所示，形成锡凸点8。
到目前为止，当使用电镀法形成锡或锡合金凸点时，通过改变锡或锡合金电镀液的含有成分，进行了与对基板上的导通孔的导通孔填充性或凸点内的空隙的抑制有关的改善(例如，参考专利文献1、2、3、4。)。
专利文献1中公开有一种含有特定的α,β-不饱和醛或特定的α,β-不饱和酮的化合物的锡或锡合金电镀液。该专利文献1中记载了以下事项。
该电镀液的导通孔填充性较高，若使用该电镀液，则在凹部选择性地沉积锡电镀，因此可获得实质上不具有空隙的锡电镀沉积物。
在所形成的锡电镀皮膜表面上不发生烧焦或异常析出，因此可获得焊接性或耐变色性等优异的实用且具有良好的外观的锡电镀皮膜。
该电镀液的导通孔填充性较高，因此能够形成实质上不具有空隙的柱状的锡电镀沉积物(凸点)。
并且，专利文献2中公开有一种锡或锡合金电镀液，其含有(a)含羧基化合物和(b)含羰基化合物，且成分(a)为1.3g/L以上及成分(b)为0.3g/L以上。该专利文献2中记载了以下事项。
使用该电镀液，通过对具有盲孔或通孔的被镀物进行电镀，能够在短时间内可靠性高地填充盲孔或通孔。
能够利用于半导体的三维安装、印刷电路板上的盲孔或通孔的填充工序及硅贯通电极的形成。
并且，专利文献3中公开有一种锡或锡合金电镀液，其含有无机酸及有机酸以及其水溶性盐、表面活性剂及流平剂。其中，表面活性剂为选自聚氧化烯苯基醚或其盐及聚氧化烯多环苯基醚或其盐中的至少一种非离子表面活性剂。构成聚氧化烯苯基醚的苯基及构成聚氧化烯多环苯基醚的多环苯基可以被碳原子数1～24的烷基或羟基取代。流平剂为选自脂肪族醛、芳香族醛、脂肪族酮及芳香族酮中的至少一种；及α,β-不饱和羧酸或者其酰胺或它们的盐。该专利文献3中记载了以下事项。
由于含有特定的非离子表面活性剂和特定的两种流平剂，因此凹槽填充性优异，且能够抑制空隙的产生。由此，若使用该电镀液，则能够提供没有凹槽且平滑，而且回焊后不产生空隙的良好的凸点。
而且，专利文献4中公开有一种突起电极形成用的锡或锡合金电镀液，该锡或锡合金电镀液含有：(A)由亚锡盐和、亚锡盐与选自银、铜、铋、镍、铟、金中的金属的盐的混合物中的任一个组成的可溶性盐；(B)酸或其盐；(C)选自芳香族及脂肪族醛、芳香族及脂肪族酮、不饱和羧酸类、芳香族羧酸类中的填充用有机化合物；及(D)非离子系表面活性剂。该专利文献4中记载了以下事项。
关于该电镀液，由于组合使用抑制锡系材料的析出的特定的化合物(C)和成分(D)，因此有效地抑制导通孔上部的析出，能够使锡系材料的析出优先从导通孔底部朝向导通孔上方进行。因此，能够防止空隙的产生的同时平滑地进行导通孔填充。作为结果，回焊或者不回焊而能够良好地形成突起电极，接合强度或电特性优异。
近年来，在一个电路基板上混合存在有凸点直径或凸点间距不同的配线图案。在这种复杂的配线图案中，即使在凸点直径或凸点间距不同的情况下也要求将所有的凸点以均匀的高度形成。根据上述专利文献1～4的锡或锡合金电镀液，具有如下特点:凸点内的空隙的产生得到抑制，能够在短时间内可靠性高地对基板上的导通孔进行填充，导通孔填充性或外观优异。然而，这些专利文献1～4中的基板用电镀液并非以实现凸点的高度均匀性为其课题。
具体而言，如图2所示，在凸点直径不同的图案的情况下，若使用以往的锡或锡合金电镀液进行电镀，则能够改善小径或者大径中的任一个的导通孔填充性，但另一个的导通孔填充性降低。即，当在同时存在小径及大径的导通孔6的基板上，对两个导通孔6同时进行电镀时，难以导通孔填充性良好地对两个导通孔6进行电镀。如此，当存在导通孔填充性不同的导通孔6时(图2的(b))，回焊后的凸点8高度偏差变大，无法实现凸点8的高度均匀性(图2的(d))。因此，为了实现凸点8的高度均匀性(图2的(c))，如图2的(a)所示，需要改善对小径及大径的两个导通孔6的导通孔填充性。
专利文献1：日本特开2014-125662号公报(权利要求2、第[0020]段)
专利文献2：日本特开2015-007276号公报(权利要求1、第[0011]、[0012]段)
专利文献3：日本特开2015-193916号公报(权利要求1、第[0019]段)
专利文献4：日本特开2016-074963号公报(权利要求1、第[0019]段)
发明内容
本发明的目的在于提供一种即使在凸点直径不同的图案中，对基板上的导通孔的导通孔填充性也优异，且所形成的凸点的高度变得均匀的锡或锡合金电镀液。
本发明的第一方式是一种锡或锡合金电镀液，其含有：(A)至少含有亚锡盐的可溶性盐；(B)选自有机酸及无机酸中的酸或其盐；(C)表面活性剂；(D)流平剂；及(E)添加剂，所述表面活性剂为由以下通式(1)表示的化合物(C1)和/或由通式(2)表示的化合物(C2)。
式(1)中，R为碳原子数7～13的烷基，m为5～11，n为0～3，m与n不同。并且式(2)中，R为碳原子数7～13的烷基，m为5～11，n为1～3，m与n不同。
[化学式1]
Figure BDA0002650647450000041
[化学式2]
Figure BDA0002650647450000042
本发明的第二方式是第一方式的锡或锡合金电镀液，所述添加剂含有选自表面活性剂、抗氧化剂及碳原子数1～3的醇中的两个以上，所述表面活性剂与所述两种表面活性剂(C1、C2)不同。
本发明的第三方式是凸点的形成方法，其包括如下工序：
使用第一或第二方式的锡或锡合金电镀液，在基板上形成锡或锡合金电镀沉积层；和接着进行回焊处理而形成凸点。
本发明的第四方式是一种电路基板的制造方法，其使用通过第三方式的方法形成的凸点来制造电路基板。
在本发明的第一方式的锡或锡合金电镀液中，通过表面活性剂(C1、C2)具有将通式(1)及通式(2)中的聚氧丙烯烷基的数量m及聚氧乙烯基的数量n分别设定在规定范围的特定的非离子(Non-ionic)结构，能够在电镀时抑制Sn离子的析出，并能够在电镀对象表面上良好地进行电镀。尤其根据该电镀液，在凸点直径不同的图案的情况下，即使凸点直径大或者小，对基板上的导通孔的导通孔填充性也优异，且所形成的凸点的高度变得均匀。认为这是因为极化电阻变大。
本发明的第二方式的锡或锡合金电镀液中，通过进一步含有选自与两种表面活性剂(C1、C2)不同的表面活性剂、抗氧化剂及碳原子数1～3的醇中的两个以上，发挥以下效果。与两种表面活性剂(C1、C2)不同的表面活性剂发挥电镀液的稳定化、溶解性的提高等效果。并且，抗氧化剂防止可溶性亚锡盐氧化成锡盐。而且，醇对提高表面活性剂的溶解性发挥效果。
在本发明的第三方式的方法中，使用第一或第二方式的锡或锡合金电镀液在基板上形成锡或锡合金电镀沉积层，接着进行回焊处理而形成凸点。由此，即使是凸点直径不同的图案也能够形成高度均匀的凸点。
在本发明的第四方式的方法中，使用通过第三方式的方法形成的凸点来制造电路基板。由此，能够制作无电连接不良的可靠性高的半导体装置。
附图说明
图1中(a)是在本实施方式的导通孔内形成电镀沉积层的基板的剖视图。(b)是剥离干膜及铜晶种层并加热电镀沉积层后的基板的剖视图。
图2中(a)是表示在凸点直径(导通孔直径)不同的图案中，电镀沉积层的导通孔填充性良好的例子的基板的截面结构图。(b)是表示在凸点直径(导通孔直径)不同的图案中，电镀沉积层的导通孔填充性差的例子的基板的截面结构图。(c)是表示在(a)中剥离干膜及铜晶种层，加热电镀沉积层后的状态，且所形成的凸点的高度变均匀的例子的基板的截面结构图。(d)是表示在(b)中剥离干膜及铜晶种层，加热电镀沉积层后的状态，且所形成的凸点的高度不均的例子的基板的截面结构图。
具体实施方式
接着，对用于实施本发明的方式进行说明。
本实施方式的锡或锡合金电镀液含有：(A)至少含有亚锡盐的可溶性盐；(B)选自有机酸及无机酸中的酸或其盐；(C)表面活性剂；(D)流平剂；及(E)添加剂。剩余部分是溶剂的水。该表面活性剂是由上述通式(1)表示的化合物(C1)和/或由上述通式(2)表示的化合物(C2)。
上述可溶性盐由亚锡盐和该亚锡盐与选自银、铜、铋、镍、锑、铟、锌中的金属的盐的混合物中的任一个组成。
本实施方式的锡合金为锡与选自银、铜、铋、镍、锑、铟、锌中的规定金属的合金，例如，可举出锡-银合金、锡-铜合金、锡-铋合金、锡-镍合金、锡-锑合金、锡-铟合金、锡-锌合金的二元合金、锡-铜-铋、锡-铜-银合金等三元合金。
因此，本实施方式的可溶性盐(A)是指在电镀液中生成Sn2+、Ag+、Cu+、Cu2+、Bi3+、Ni2 +、Sb3+、In3+、Zn2+等的各种金属离子的任意的可溶性盐，例如，可举出该金属的氧化物、卤化物、无机酸或有机酸的该金属盐等。
作为金属氧化物，可举出氧化亚锡、氧化铜、氧化镍、氧化铋、氧化锑、氧化铟、氧化锌等，作为金属的卤化物，可举出氯化亚锡、氯化铋、溴化铋、氯化亚铜、氯化铜、氯化镍、氯化锑、氯化铟、氯化锌等。
作为无机酸或有机酸的金属盐，可举出硫酸铜、硫酸亚锡、硫酸铋、硫酸镍、硫酸锑、硝酸铋、硝酸银、硝酸铜、硝酸锑、硝酸铟、硝酸镍、硝酸锌、乙酸铜、乙酸镍、碳酸镍、锡酸钠、氟硼酸亚锡、甲磺酸亚锡、甲磺酸银、甲磺酸铜、甲磺酸铋、甲磺酸镍、甲磺酸铟、二甲磺酸锌、乙磺酸亚锡、2-羟基丙磺酸铋等。
本实施方式的酸或其盐(B)选自有机酸及无机酸或者其盐。上述有机酸可举出链烷磺酸、链烷醇磺酸、芳香族磺酸等有机磺酸或者脂肪族羧酸等。无机酸可举出氟硼酸、氟硅酸、氨基磺酸、盐酸、硫酸、硝酸、高氯酸等。其盐为碱金属盐、碱土金属盐、铵盐、胺盐、磺酸盐等。从金属盐的溶解性和排水处理的容易性的观点考虑，该成分(B)优选为有机磺酸。
作为上述链烷磺酸，能够使用由化学式CnH2n+1SO3H(例如，n＝1～5，优选为1～3)所示的链烷磺酸，具体而言，可举出甲磺酸、乙磺酸、1-丙磺酸、2-丙磺酸、1-丁磺酸、2-丁磺酸、戊磺酸等，或己磺酸、癸烷磺酸、十二烷磺酸等。
作为上述链烷醇磺酸，能够使用由化学式CpH2p+1-CH(OH)-CqH2q-SO3H(例如，p＝0～6、q＝1～5)所示的链烷醇磺酸，具体而言，可举出2-羟基乙烷-1-磺酸、2-羟基丙烷-1-磺酸、2-羟基丁烷-1-磺酸、2-羟基戊烷-1-磺酸等，或1-羟基丙烷-2-磺酸、3-羟基丙烷-1-磺酸、4-羟基丁烷-1-磺酸、2-羟基己烷-1-磺酸、2-羟基癸烷-1-磺酸、2-羟基十二烷-1-磺酸等。
上述芳香族磺酸基本上为苯磺酸、烷基苯磺酸、苯酚磺酸、萘磺酸、烷基萘磺酸等，具体而言，可举出1-萘磺酸、2-萘磺酸、甲苯磺酸、二甲苯磺酸、对苯酚磺酸、甲酚磺酸、磺基水杨酸、硝基苯磺酸、磺基苯甲酸、二苯胺-4-磺酸等。
作为上述脂肪族羧酸，例如，可举出乙酸、丙酸、丁酸、柠檬酸、酒石酸、葡糖酸、磺基琥珀酸、三氟乙酸等。
本实施方式的表面活性剂(C)中所含的非离子系表面活性剂(C1)是由以下通式(1)表示的聚氧乙烯与聚氧丙烯烷基醚的缩合物或聚氧乙烯烷基醚。
[化学式3]
Figure BDA0002650647450000061
式(1)中，R为碳原子数7～13的烷基，m为5～11，n为0～3，m与n不同。另外，R的烷基可以是直链，也可以具有支链。若R的碳原子数小于7，则存在发生电镀的外观异常的不良情况。若R的碳原子数大于13，则存在如下不良情况：难以在电镀液中溶解，或导通孔填充性差，发生电镀的外观异常。另外，R的碳原子数优选为10～12。并且若m小于5，则存在如下不良情况：难以在电镀液中溶解，或发生电镀的外观异常。若m大于11，则存在导通孔填充性差的不良情况。另外，优选m为6～10。而且，若n大于3，则存在如下不良情况：难以在电镀液中溶解，或发生电镀的外观异常。另外，n优选为0～2。
本实施方式的表面活性剂(C)中所含的非离子系表面活性剂(C2)是由以下通式(2)表示的聚氧丙烯与聚氧乙烯烷基醚的缩合物。
[化学式4]
Figure BDA0002650647450000071
式(2)中，R为碳原子数7～13的烷基，m为5～11，n为1～3，m与n不同。另外，R的烷基可以是直链，也可以具有支链。若R的碳原子数小于7，则存在发生电镀的外观异常的不良情况。若R的碳原子数大于13，则存在如下不良情况：难以在电镀液中溶解，或导通孔填充性差，发生电镀的外观异常。另外，R的碳原子数优选为10～12。并且若m小于5，则存在如下不良情况：难以在电镀液中溶解，或发生电镀的外观异常。若m大于11，则存在导通孔填充性差的不良情况。另外，优选m为6～10。而且，若n大于3，则存在如下不良情况：难以在电镀液中溶解，或发生电镀的外观异常。另外，n优选为1～2。
含有本实施方式的流平剂(D)是为了均匀且致密地形成电镀皮膜，并且使电镀皮膜平滑。而且，为了提高导通孔填充性并抑制空隙的产生，使用第一流平剂(D-1)及第二流平剂(D-2)这两种。作为第一流平剂(D-1)，可举出选自脂肪族醛、芳香族醛、脂肪族酮及芳香族酮中的一种或两种以上，作为第二流平剂(D-2)，可举出α,β-不饱和羧酸或其酰胺或者它们的盐。
第一流平剂(D-1)为含有醛或酮的羰基化合物，且不含有第二流平剂(D-2)的α,β-不饱和羧酸。具体而言，例示以下。作为脂肪族醛，可举出甲醛、乙醛、烯丙醛等。并且，作为芳香族醛，可举出苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-氯苯甲醛、2,4-二氯苯甲醛、2,6-二氯苯甲醛、2,4,6-三氯苯甲醛、1-萘醛、2-萘醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、间茴香醛、邻茴香醛、对茴香醛等。并且，作为脂肪族酮，可举出乙酰丙酮等。而且，作为芳香族酮，可举出亚苄基丙酮(与苯甲丙酮同义)、2-氯苯乙酮、3-氯苯乙酮、4-氯苯乙酮、2,4-二氯苯乙酮、2,4,6-三氯苯乙酮等。它们可以单独使用，也可以使用两种以上。电镀浴中所占的第一流平剂(D-1)的优选含量(单独含有时为单独的量，含有两种以上时为它们的总量)为0.001g/L～0.3g/L，更优选为0.01g/L～0.25g/L。若上述成分的含量较少，则其添加效果不充分，另一方面，若上述成分的含量过多，则有可能阻碍电镀皮膜的平滑化。
作为第二流平剂(D-2)，可举出丙烯酸、甲基丙烯酸、吡啶甲酸、巴豆酸、3-氯丙烯酸、3,3-二甲基丙烯酸、2,3-二甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸2-乙基己酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸2-羟乙酯、甲基丙烯酸2-羟丙酯、甲基丙烯酸2-二甲基氨基乙酯、甲基丙烯酸酐、甲基丙烯酸甲酯等。并且，第二流平剂(D-2)中也包括α,β-不饱和羧酸的酰胺(例如，丙烯酰胺等)和α,β-不饱和羧酸的盐(例如，钾、钠、铵等的盐)。电镀浴中所占的第二流平剂(D-2)的优选含量(单独含有时为单独的量，含有两种以上时为它们的总量)为0.01g/L～50g/L，更优选为0.05g/L～10g/L。若上述成分的含量较少，则其添加效果不充分，另一方面，若上述成分的含量过多，则有可能阻碍电镀皮膜的平滑化。
本实施方式的添加剂(E)是添加到锡或锡合金电镀液中的各种添加剂。添加剂(E)优选含有选自与所述两种表面活性剂(C1、C2)不同的表面活性剂、抗氧化剂及碳原子数1～3的醇中的两个以上。
作为此时的其他表面活性剂，可举出通常的阴离子系表面活性剂、阳离子系表面活性剂、非离子系表面活性剂及两性表面活性剂。
作为阴离子系表面活性剂，可举出聚氧乙烯(1摩尔的分子中含有环氧乙烷：12摩尔)壬基醚硫酸钠等聚氧化烯烷基醚硫酸盐；聚氧乙烯(1摩尔的分子中含有环氧乙烷：12摩尔)十二烷基苯基醚硫酸钠等聚氧化烯烷基苯基醚硫酸盐；十二烷基苯磺酸钠等烷基苯磺酸盐；1-萘酚-4-磺酸钠、2-萘酚-3,6-二磺酸二钠等萘酚磺酸盐；二异丙基萘磺酸钠、二丁基萘磺酸钠等(聚)烷基萘磺酸盐；十二烷基硫酸钠、油基硫酸钠等烷基硫酸盐等。
作为阳离子系表面活性剂，可举出单烷基胺盐、二烷基胺盐、三烷基胺盐、二甲基二烷基铵盐、三甲基烷基铵盐、十二烷基三甲基铵盐、十六烷基三甲基铵盐、十八烷基三甲基铵盐、十二烷基二甲基铵盐、十八烯基二甲基乙基铵盐、十二烷基二甲基苄基铵盐、十六烷基二甲基苄基铵盐、十八烷基二甲基苄基铵盐、三甲基苄基铵盐、三乙基苄基铵盐、十六烷基吡啶鎓盐、十二烷基吡啶鎓盐、十二烷基甲吡啶鎓盐、十二烷基咪唑啉鎓盐、油基咪唑啉鎓盐、十八烷基胺乙酸酯、十二烷基胺乙酸酯等。
作为非离子系表面活性剂，可举出糖酯、脂肪酸酯、C1～C25烷氧基磷酸(盐)、山梨糖醇酐酯、硅系聚氧乙烯醚、硅系聚氧乙烯酯、氟系聚氧乙烯醚、氟系聚氧乙烯酯、环氧乙烷和/或环氧丙烷与烷基胺或二胺的缩合产物的硫酸化或者磺化加成物、聚氧乙烯枯基苯基醚(其中，EO链为10～14)等。
作为两性表面活性剂，可举出甜菜碱、羧基甜菜碱、咪唑啉甜菜碱、磺基甜菜碱、氨基羧酸等。
上述抗氧化剂用于防止可溶性亚锡盐氧化成锡盐。
作为抗氧化剂，可举出次磷酸类、抗坏血酸或其盐、苯酚磺酸(Na)、甲酚磺酸(Na)、对苯二酚磺酸(Na)、对苯二酚、α-萘酚或β-萘酚、邻苯二酚、间苯二酚、间苯三酚、肼、苯酚磺酸、邻苯二酚磺酸、羟基苯磺酸、萘酚磺酸或者它们的盐等。
上述碳原子数为1～3的醇用于提高上述表面活性剂的溶解性。作为醇，可举出甲醇、乙醇、1-丙醇、2-丙醇等。醇能够单独使用一种或组合两种以上使用。
在单独使用本实施方式的非离子系表面活性剂(C1或C2)的情况下，非离子系表面活性剂(C1或C2)在电镀液中的含量为0.5g/L～50g/L，优选为1g/L～5g/L。若含量小于下限值，则由于Sn离子的过量供给而发生枝晶等电镀不良。并且，若含量大于上限值，则存在Sn离子不易到达电镀对象表面而导通孔填充性差的不良情况。在使用非离子系表面活性剂(C1)和非离子系表面活性剂(C2)这两个的情况下，非离子系表面活性剂(C1)的含量和非离子系表面活性剂(C2)的含量的总量可以在上述范围内。
并且，作为可溶性金属盐(A)能够仅使用上述化合物的一种或两种以上，电镀液中的含量为30g/L～100g/L，优选为40g/L～60g/L。若含量少于适当范围，则生产率降低，若含量多于适当范围，则导致电镀液的成本上升。
作为无机酸、有机酸或其盐(B)能够仅使用上述化合物的一种或两种以上，电镀液中的含量为80～300g/L，优选为100～200g/L。若含量少于适当范围，则导电率低且电压上升。若含量增多，则电镀液的粘度上升且电镀液的搅拌速度降低。
电镀液中的添加剂(E)的含量为0.5g/L～50g/L，优选为1g/L～5g/L。
另一方面，本实施方式的电镀液的液温通常为70℃以下，优选为10℃～40℃。基于电镀的电镀膜形成时的电流密度在0.1A/dm2以上且100A/dm2以下的范围，优选在0.5A/dm2以上且20A/dm2以下的范围。若电流密度过低，则生产率降低，若过高，则导致凸点的高度均匀性降低。
当将作为表面活性剂单独含有本实施方式的非离子系表面活性剂(C1和/或C2)或者含有非离子系表面活性剂(C1)和非离子系表面活性剂(C2)这两个的锡或锡合金电镀液应用于作为被镀物的电路基板，将液温和电流密度设定为上述范围时，能够在该电路基板上形成规定金属皮膜(锡或锡合金电镀沉积层)。接着，若进行回焊处理，则形成凸点。
当将半导体芯片装填到如此形成的凸点时，制造出搭载有半导体芯片的电路基板。
作为电路基板，可举出印刷电路基板、挠性印刷电路基板、半导体集成电路基板等。
实施例
接着，连同比较例一起对本发明的实施例进行详细说明。
(实施例及比较例中使用的非离子系表面活性剂(C1))
将在实施例1～8、13、14及比较例1～10中使用的作为非离子系表面活性剂(C1)的聚氧乙烯与聚氧丙烯烷基醚的缩合物或聚氧乙烯烷基醚(C1-1～C1-17)的各结构式(1)中的R的碳原子数、聚氧乙烯(EO)基的m的数量、聚氧丙烯(PO)基的n的数量分别示于表1。
(实施例及比较例中使用的非离子系表面活性剂(C2))
将在实施例1、2、9～14及比较例11～16中使用的作为非离子系表面活性剂(C2)的聚氧丙烯与聚氧乙烯烷基醚的缩合物(C2-1～C2-10)的各结构式(1)中的R的碳原子数、聚氧乙烯(EO)基的m的数量、聚氧丙烯(PO)基的n的数量分别示于表2。另外，R的碳原子数、m、n的值数通过1H-NMR求出。
[表1]
Figure BDA0002650647450000111
[表2]
Figure BDA0002650647450000112
(Sn电镀液的建浴)
＜实施例1＞
在甲磺酸Sn水溶液中混合作为游离酸的甲磺酸、作为抗氧化剂的对苯二酚、作为流平剂(D-1)的1-萘醛、作为流平剂(D-2)的甲基丙烯酸，制成均匀的溶液。接着，进一步作为表面活性剂添加了上述No.C1-6的聚氧乙烯烷基醚(质量平均分子量：500、式(1)中的R的碳原子数：13、聚氧乙烯(EO)基的m的数量：6、聚氧丙烯(PO)基的n的数量：0)和上述No.C2-2的聚氧乙烯与聚氧丙烯烷基醚的缩合物(质量平均分子量：530、式(2)中的R的碳原子数：9、聚氧乙烯(EO)基的m的数量：6、聚氧丙烯(PO)基的n的数量：2)。然后，最后添加离子交换水，制成了下述组成的Sn电镀液。另外，通过使金属Sn板在甲磺酸水溶液中电解来制备了甲磺酸Sn水溶液。
(Sn电镀液的组成)
甲磺酸Sn(作为Sn2+)：50g/L
甲磺酸钾(作为游离酸)：100g/L
非离子系表面活性剂C1-6：2g/L
非离子系表面活性剂C2-2：2g/L
对苯二酚(作为抗氧化剂)：1g/L
1-萘醛(作为流平剂(D-1))：0.1g/L
甲基丙烯酸(作为流平剂(D-2))：2g/L
离子交换水：剩余部分
＜实施例3～5、7～9、11、12、14及比较例1、2、4、5、7、9、10、12、13、15、16＞
在实施例3～5、7～9、11、12、14及比较例1、2、4、5、7、9、10、12、13、15、16中，作为非离子系表面活性剂(C1)及非离子系表面活性剂(C2)，使用表1及表2所示的性状的表面活性剂，如表3及表4所示那样进行选定。除此以外，以与实施例1相同的方式，制成了实施例3～5、7～9、11、12、14及比较例1、2、4、5、7、9、10、12、13、15、16的Sn电镀液。
(SnAg电镀液的建浴)
＜实施例2＞
在甲磺酸Sn水溶液中混合作为游离酸的甲磺酸、作为抗氧化剂的邻苯二酚、作为流平剂(D-1)的苯甲醛、作为流平剂(D-2)的甲基丙烯酸甲酯并使其溶解。进一步添加甲磺酸Ag液进行混合。通过混合制成均匀的溶液。接着，进一步作为表面活性剂，添加了上述No.C1-6的聚氧乙烯与聚氧丙烯烷基醚的缩合物(质量平均分子量：500、式(1)中的R的碳原子数：13、聚氧乙烯(EO)基的m的数量：6、聚氧丙烯(PO)基的n的数量：0)和上述No.C2-3的聚氧乙烯与聚氧丙烯烷基醚的缩合物(质量平均分子量：650、式(2)中的R的碳原子数：13、聚氧乙烯(EO)基的m的数量：8、聚氧丙烯(PO)基的n的数量：2)。然后，最后添加离子交换水，制成了下述组成的SnAg电镀液。另外，通过使金属Sn板在甲磺酸水溶液中电解来制备甲磺酸Sn水溶液，通过使金属Ag板在甲磺酸水溶液中电解来制备甲磺酸Ag水溶液。
(SnAg电镀液的组成)
甲磺酸Sn(作为Sn2+)：60g/L
甲磺酸Ag(作为Ag+)：1.0g/L
甲磺酸(作为游离酸)：120g/L
非离子系表面活性剂C1-6：1g/L
非离子系表面活性剂C2-3：1g/L
邻苯二酚(作为抗氧化剂)：1g/L
苯甲醛(作为流平剂(D-1))：0.05g/L
甲基丙烯酸甲酯(作为流平剂(D-2))：3g/L
离子交换水：剩余部分
＜实施例6、13及比较例3、8、11＞
在实施例6、13及比较例3、8、11中，作为非离子系表面活性剂(C1)及非离子系表面活性剂(C2)，使用表1及表2所示的性状的表面活性剂，如表3及表4所示那样进行选定。除此以外，以与实施例2相同的方式，制成了实施例6、13及比较例3、8、11的SnAg电镀液。
(SnCu电镀液的建浴)
＜实施例10＞
在甲磺酸Sn水溶液中混合作为游离酸的甲磺酸、作为抗氧化剂的对苯二酚磺酸钾、作为流平剂(D-1)的苯甲醛、作为流平剂(D-2)的甲基丙烯酸甲酯并使其溶解。接着，进一步添加甲磺酸Cu液进行混合。通过混合制成均匀的溶液。接着，进一步作为表面活性剂添加了上述No.C2-4的聚氧乙烯与聚氧丙烯的缩合物(质量平均分子量：700、式(2)中的R的碳原子数：9、聚氧乙烯(EO)基的m的数量：8、聚氧丙烯(PO)基的n的数量：3)。然后，最后添加离子交换水，制成了下述组成的SnCu电镀液。另外，通过使金属Sn板在甲磺酸水溶液中电解来制备甲磺酸Sn水溶液，通过使金属Cu板在甲磺酸水溶液中电解来制备甲磺酸Cu水溶液。
(SnCu电镀液的组成)
甲磺酸Sn(作为Sn2+)：80g/L
甲磺酸Cu(作为Cu2+)：0.5g/L
甲磺酸(作为游离酸)：150g/L
非离子系表面活性剂C2-4：5g/L
对苯二酚磺酸钾(作为抗氧化剂)：1g/L
苯甲醛(作为流平剂(D-1))：0.2g/L
甲基丙烯酸甲酯(作为流平剂(D-2))：5g/L
离子交换水：剩余部分
＜比较例6、14＞
在比较例6、14中，作为表面活性剂，使用表2所示的性状的表面活性剂，如表4所示那样进行选定。除此以外，以与实施例10相同的方式，制成了比较例6、14的SnCu电镀液。
＜比较试验及评价＞
使用在实施例1～14及比较例1～16中制备的30种电镀液，在导通孔内形成了锡或锡合金电镀沉积层。接着，进行回焊处理而形成了凸点。评价了到形成凸点为止的导通孔内的锡或锡合金电镀沉积层的导通孔填充性、凸点形成后的凸点的外观及凸点高度偏差(均匀性)。将其结果示于表3及表4。
(1)导通孔内的锡或锡合金电镀沉积层的导通孔填充性
使用激光显微镜，观察导通孔内的锡或锡合金电镀沉积层，并测定了从电镀沉积层的最高点到最低点为止的高度差。将高度差大于5μm的情况判断为“不良”，将高度差为5μm以下的情况判断为“良好”，并示于表3及表4的“导通孔填充性”栏。
(2)导通孔内的锡或锡合金电镀沉积层的外观
使用激光显微镜，观察导通孔内的锡或锡合金电镀沉积层，并测定了表面粗糙度Ra。将电镀沉积层的表面粗糙度Ra大于2μm的情况判断为“不良”，将2μm以下的情况判断为“良好”，并示于表3及表4的“电镀沉积层的外观”栏。
(3)凸点高度偏差
使用自动外观检查装置测定了基板的凸点的高度。根据所测定的凸点高度计算出高度偏差。将高度偏差为3以下的情况判断为“均匀”，将高度偏差大于3的情况判断为“不均匀”，并将其结果示于表3及表4的“凸点高度偏差”栏。
(4)空隙产生容易性
形成了以180μm、250μm、360μm的各间距间隔排列且直径为70μm、90μm、120μm的凸点(共2000个)。对这些凸点，拍摄了透射X射线图像。目视观察所拍摄的图像，将相对于凸点的大小观察到一个以上的1％以上的大小的空隙的情况判断为“NG”，将未观察到空隙的情况判断为“OK”。将其结果示于表3及表4的“空隙”栏。
[表3]
Figure BDA0002650647450000151
[表4]
Figure BDA0002650647450000161
从表4明确可知，在比较例1中，EO基的数量m过少，为2，因此电镀沉积层的外观为不良，并且导通孔填充性也不良。而且凸点高度偏差大，为5.3，观察到空隙的产生，为NG。
在比较例2中，R的碳原子数过多，为16，且EO基的数量m过少，为3，因此导通孔填充性为不良，并且电镀沉积层的外观也为不良。而且凸点高度偏差大，为8.1，观察到空隙的产生，为NG。
在比较例3中，EO基的数量m过少，为4，因此电镀沉积层的外观为不良，并且导通孔填充性也不良。而且未观察到空隙的产生，为OK，但凸点高度偏差大，为4.3。
在比较例4中，R的碳原子数过少，为6，因此电镀沉积层的外观为不良，并且导通孔填充性也不良。而且凸点高度偏差大，为3.1，观察到空隙的产生，为NG。
在比较例5及11中，R的碳原子数过大，分别为16，因此导通孔填充性均为不良，并且电镀沉积层的外观也为不良。而且均未观察到空隙的产生，为OK，但凸点高度偏差较大，为3.2及4.1。
在比较例6及12中，EO基的数量m过多，分别为13，因此导通孔填充性均良好，但电镀沉积层的外观为不良。而且凸点高度偏差大，为4.5及3.3，均观察到空隙的产生，为NG。
在比较例7及13中，R的碳原子数过多，分别为16，且EO基的数量m也过多，为15，因此导通孔填充性均为不良，并且电镀沉积层的外观也为不良。而且凸点高度偏差大，为6.7及7.5，均观察到空隙的产生，为NG。
在比较例8及14中，EO基的数量m过多，分别为15，且PO基的数量n也过多，为4，因此电镀沉积层的外观均为不良，并且导通孔填充性也不良。而且凸点高度偏差大，为8.4及9.8，均观察到空隙的产生，为NG。
在比较例9及15中，R的碳原子数过多，分别为16，且PO基的数量n过多，为4，因此导通孔填充性均为不良，并且电镀沉积层的外观也为不良。而且凸点高度偏差大，为11.4及13.4，均观察到空隙的产生，为NG。
在比较例10及16中，PO基的数量n过多，分别为4，因此导通孔填充性均为不良，并且电镀沉积层的外观也为不良。而且凸点高度偏差大，为9.7及10.1，均观察到空隙的产生，为NG。
相对于此，在实施例1～14中，R的碳原子数在7～13的范围内，EO基的数量m在5～11的范围内，且PO基的数量n也在0～3的范围内，因此全部导通孔填充性良好，并且电镀沉积层的外观也良好。而且凸点高度偏差小，在1.0～2.6的范围内，全部未观察到空隙的产生，为OK。
产业上的可利用性
本实施方式的锡或锡合金电镀液能够利用于印刷电路基板、挠性印刷电路基板、半导体集成电路等的电路基板。
符号说明
1-基板，2-阻焊层，3-铜晶种层，4-干膜抗蚀剂层，6-导通孔，7-锡电镀沉积层(镀锡皮膜)，8-锡凸点。

Claims (4)

1.一种锡或锡合金电镀液，其特征在于，含有：
(A)至少含有亚锡盐的可溶性盐；
(B)选自有机酸及无机酸中的酸或其盐；
(C)表面活性剂；
(D)流平剂；及
(E)添加剂，
所述表面活性剂为由以下通式(1)表示的化合物C1和/或由通式(2)表示的化合物C2，
[化学式1]
Figure FDA0002650647440000011
式(1)中，R为碳原子数7～13的烷基，m为5～11，n为0～3，m与n不同，
[化学式2]
Figure FDA0002650647440000012
式(2)中，R为碳原子数7～13的烷基，m为5～11，n为1～3，m与n不同。
2.根据权利要求1所述的锡或锡合金电镀液，其中，
所述添加剂含有选自表面活性剂、抗氧化剂及碳原子数1～3的醇中的两个以上，所述表面活性剂与所述表面活性剂C1和所述表面活性剂C2不同。
3.一种凸点的形成方法，其特征在于，包括如下工序：
使用权利要求1或2所述的锡或锡合金电镀液，在基板上形成锡或锡合金电镀沉积层；和
接着进行回焊处理而形成凸点。
4.一种电路基板的制造方法，其特征在于，使用通过权利要求3所述的方法形成的凸点来制造电路基板。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114059115A (zh) * 2021-12-20 2022-02-18 中国计量大学 锡锑电镀液及其制备方法
CN116529428A (zh) * 2020-11-25 2023-08-01 三菱综合材料株式会社 锡合金镀液

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102339861B1 (ko) * 2021-07-26 2021-12-16 와이엠티 주식회사 레벨링제 및 이를 포함하는 금속박 형성용 전기도금 조성물

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417957A (en) * 1982-09-03 1983-11-29 Columbia Chemical Corporation Aqueous acid plating bath and brightener mixture for producing semibright to bright electrodeposits of tin
CN101922026A (zh) * 2010-08-18 2010-12-22 济南德锡科技有限公司 甲基磺酸系镀亚光纯锡电镀液添加剂及其电镀液
CN106414808A (zh) * 2014-06-11 2017-02-15 上村工业株式会社 锡电镀浴和锡电镀膜

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3730853A (en) 1971-06-18 1973-05-01 Schloetter M Electroplating bath for depositing tin-lead alloy plates
US4849059A (en) 1988-09-13 1989-07-18 Macdermid, Incorporated Aqueous electroplating bath and method for electroplating tin and/or lead and a defoaming agent therefor
JPH1025595A (ja) * 1996-07-12 1998-01-27 Ishihara Chem Co Ltd スズ及びスズ合金めっき浴
JP3716380B2 (ja) 1997-06-06 2005-11-16 石原薬品株式会社 スズ及びスズ合金メッキ浴、当該メッキ浴の管理方法及び調製方法
JP2006348347A (ja) 2005-06-16 2006-12-28 Nippon Mektron Ltd 電子部品の表面処理方法
JP5658442B2 (ja) 2009-06-02 2015-01-28 株式会社東芝 電子部品とその製造方法
EP2405468A1 (en) 2010-07-05 2012-01-11 ATOTECH Deutschland GmbH Method to form solder deposits on substrates
JP5033979B1 (ja) 2011-09-29 2012-09-26 ユケン工業株式会社 スズからなるめっき用酸性水系組成物
JP6133056B2 (ja) 2012-12-27 2017-05-24 ローム・アンド・ハース電子材料株式会社 スズまたはスズ合金めっき液
JP6006683B2 (ja) * 2013-06-26 2016-10-12 株式会社Ｊｃｕ スズまたはスズ合金用電気メッキ液およびその用途
JP2015193916A (ja) 2014-03-18 2015-11-05 上村工業株式会社 錫または錫合金の電気めっき浴、およびバンプの製造方法
JP6442722B2 (ja) 2014-10-08 2018-12-26 石原ケミカル株式会社 電気メッキ式の突起電極形成方法
JP7009679B2 (ja) 2015-07-29 2022-01-26 石原ケミカル株式会社 電気スズ及び電気スズ合金メッキ浴、当該メッキ浴を用いた電着物の形成方法
JP6759736B2 (ja) * 2016-06-10 2020-09-23 三菱マテリアル株式会社 めっき液
JP6834070B2 (ja) * 2016-06-13 2021-02-24 石原ケミカル株式会社 電気スズ及びスズ合金メッキ浴、当該メッキ浴を用いて電着物を形成した電子部品の製造方法
CN106222710A (zh) * 2016-08-29 2016-12-14 昆明理工大学 一种酸性半光亮镀锡溶液及其制备方法
CN106835210B (zh) * 2017-03-09 2019-02-05 昆明理工大学 一种硫酸盐光亮镀锡溶液及其制备方法
US20190198474A1 (en) * 2017-04-27 2019-06-27 International Business Machines Corporation Multiple sized bump bonds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417957A (en) * 1982-09-03 1983-11-29 Columbia Chemical Corporation Aqueous acid plating bath and brightener mixture for producing semibright to bright electrodeposits of tin
CN101922026A (zh) * 2010-08-18 2010-12-22 济南德锡科技有限公司 甲基磺酸系镀亚光纯锡电镀液添加剂及其电镀液
CN106414808A (zh) * 2014-06-11 2017-02-15 上村工业株式会社 锡电镀浴和锡电镀膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116529428A (zh) * 2020-11-25 2023-08-01 三菱综合材料株式会社 锡合金镀液
CN114059115A (zh) * 2021-12-20 2022-02-18 中国计量大学 锡锑电镀液及其制备方法

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