CN102187749A - 用于在衬底上形成焊料沉积物的方法 - Google Patents
用于在衬底上形成焊料沉积物的方法 Download PDFInfo
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- CN102187749A CN102187749A CN2009801407084A CN200980140708A CN102187749A CN 102187749 A CN102187749 A CN 102187749A CN 2009801407084 A CN2009801407084 A CN 2009801407084A CN 200980140708 A CN200980140708 A CN 200980140708A CN 102187749 A CN102187749 A CN 102187749A
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- layer
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- tin
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- 238000000034 method Methods 0.000 title claims abstract description 100
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- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
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- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
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Abstract
本发明描述了在衬底上形成焊料沉积物的方法,其包括如下步骤:i)提供包括具有电路的表面的衬底,其包括至少一个接触区域,ii)形成置于所述衬底表面上的阻焊层,并将其图案化以暴露出所述至少一个接触区域,iii)使包括所述阻焊层和所述至少一个接触区域的所述整个衬底区域与适于在所述衬底表面上提供导电层的溶液接触,iv)在所述导电层上电镀包含锡或锡合金的焊料沉积物层,和v)将一定量的包含锡或锡合金的该焊料沉积物层蚀刻掉,所蚀刻掉的量使得足以从所述阻焊层区域除去所述焊料沉积物层,在所述至少一个接触区域上留下焊料材料层。
Description
技术领域
本发明涉及通过电镀形成焊料沉积物,特别涉及倒装芯片封装,更特别涉及通过电镀锡和锡合金的焊料形成的倒装芯片接缝和板对板焊接接缝。
背景技术
自从二十世纪60年代早期由IBM引入倒装芯片技术开始,倒装芯片装置已经安装在昂贵的陶瓷衬底上,在该硅芯片和陶瓷衬底之间的热膨胀失配较不严重处。与引线键合技术相比,倒装芯片技术更能够提供更高的封装密度(较小的装置轮廓)和较高的电学性能(较短的可能引线和较低的感应系数)。在此基础上,该倒装芯片技术已经使用高温焊料(可控坍塌芯片连接,C4)在陶瓷衬底上在工业上实践了过去的40年。然而,近年来,受到现代电子产品的小型化趋势所需要的高密度、高速度和低成本的半导体装置的驱使,该倒装芯片装置安装在具有环氧树脂底层填料的低成本有机电路板上(例如印刷电路板或衬底)以降低由该硅芯片与板结构之间的热膨胀失配引发的热应力,该倒装芯片装置经历了显著的爆炸性生长。这种低温倒装芯片接缝和有机基电路板的显著出现能使现有工业得到用于制备倒装芯片装置的廉价方案。
在现有的低成本倒装芯片技术中,该半导体集成电路(IC)芯片的上表面具有电接触焊盘的阵列。该有机电路板也具有相应的接触格栅。该低温焊料块或其它导电粘合材料放置并适当排列在该芯片和该电路板之间。将该芯片上端朝下翻转并安装在该电路板上,在其中该焊料块或导电粘合材料提供电输入/输出(I/O)以及该芯片和该电路板之间的机械互连。对于焊料块接缝,可以将有机底层填料密封剂进一步分配到该芯片和电路板之间的缝隙中以抑制该热失配并降低在该焊料接缝上的应力。
通常,为了通过焊料接缝实现倒装芯片组件,通常将金属块(例如焊料块、金块或铜块)预形成在该芯片的焊盘电极表面上,其中该块可以是任意形状,例如螺柱块、球块、柱块或其它。相应的焊料块(或称为预焊接块)通常使用低温焊料,其也形成在该电路板的接触区域上。在回流温度,通过该焊料接缝将该芯片结合到该电路板上。在分配底层填料密封剂之后,由此构造了该倒装芯片装置。这种方法也是本领域已知的,使用焊料接缝的倒装芯片装置的典型实例例如描述于美国专利号7,098,126(H.-K.Hsieh等)中。
目前,用于在电路板上形成预焊接块的最常用方法是雕版印花方法。与该雕版印花方法相关的一些现有的提议可参考美国专利号5,203,075(C.G.Angulas等)、美国专利号5,492,266(K.G.Hoebener等)和美国专利号5,828,128(Y.Higashiguchi等)。用于倒装芯片组件的焊料块技术需要在凸块间距和尺寸小型化方面的设计考虑。依照实践经验,该凸块间距降低到0.15毫米以下时,该雕版印花将变得不可行。相反,通过电镀沉积的焊料块提供了进一步将凸块间距降低到低于0.15毫米的能力。关于在用于倒装芯片结合的电路板上电镀块的现有提议能够见于美国专利号5,391,514(T.P.Gall等)和美国专利号5,480,835(K.G.Hoebener等)中。尽管在电路板上电镀焊料块提供了比雕版印花更小的凸块间距,但其最初实施提出几个挑战。
美国专利号7,098,126(H.-K.Hsieh等)中描述了在有机衬底上形成焊料的多步工艺。在该方法中,首先提供包括具有电路的表面的有机电路板,其包括至少一个接触区域。阻焊层设置在该板表面上并将其图案化以暴露出该焊盘。然后,通过物理气相沉积、化学气相沉积、使用催化铜的无电镀或使用催化铜的电镀在该板表面上沉积金属种子层。在该金属种子层上形成具有至少一个位于该焊盘上的开孔的抗蚀层。然后通过电镀在该开孔内形成焊料。最后,将该抗蚀剂和在该抗蚀剂下面的金属种子层除去。为了实施该方法,需要多个图案化步骤,从工艺效率的整体角度来讲这是不希望的。此外,如果由于电子装置的小型化使得相邻接触区域之间的距离(间距)非常小,那么该方法具有其限制。
在US 2006/0219567 A1中公开了电路板的导电块结构的制备方法。将焊料电镀在部分受到阻焊保护的衬底上,然后在该焊料层上沉积抗蚀刻剂,然后以使在随后的蚀刻步骤过程中对该涂覆有焊料的连接焊盘进行保护的方式将其图案化。然后将焊料沉积物不需要的焊料蚀刻掉,只留下有抗蚀刻剂保护的焊料沉积物在该连接焊盘上。
因此,本发明的目的是提供用于在衬底,例如电路板上形成焊料沉积物的方法,其包括减少数量的工艺步骤。此外,其目的还在于提供产生具有高均匀性的焊料的电镀方法,其适于在非常微小的结构上形成焊料沉积物。
发明概述
因此本发明的目的是采用锡和锡合金的电镀方法在衬底上制备均匀的焊料沉积物层。这种浴应当适于填充具有高纵横比的凹槽结构而不会留下空隙或凹痕。
本发明的另一目的是提供用于焊料沉积的方法,其具有减少的电镀步骤数量,且即使当该阻焊剂开孔具有不同尺寸时其也是普遍适用的。
本发明的另一目的是提供用于在非导电衬底,例如电路板上形成金属种子层的方法,其用于制备用于形成倒装芯片接缝和板对板焊接接缝的电镀焊料。
总体说来,公开了在衬底上制备电镀焊料沉积物用于形成倒装芯片接缝和板对板焊接接缝的方法。依照本发明,提供了非导电衬底,例如电路板,其包括具有电路的表面,其包括至少一个接触区域。这种接触区域可以是任何导电表面区域,例如接触焊盘或朝向衬底外的电路的顶部区域。
在该衬底的部分表面上施加阻焊之后,在整个表面区域上形成导电种子层。任选地,在沉积该种子层之前,能够通过另外的非导电层,例如抗蚀剂,提高该阻焊层的高度。这导致随后电镀的焊料沉积物的体积的增加。然后在该衬底的导电区域上电镀在该导电层上的包含锡和锡合金的焊料层以形成焊料沉积物。然后,将过量的焊料以足以从该阻焊层上除去该焊料并在该至少一个接触区域上留下焊料沉积物以形成焊料沉积物的量蚀刻掉。优选在同一工艺步骤中,还从该阻焊层区域上除去该导电种子层。
本发明的另一目的是提供在衬底上制备电镀焊料沉积物用于形成倒装芯片焊料接缝和板对板焊接接缝的方法,在其上任选地通过印刷和蚀刻方法形成电路。
任选地,在将过量的焊料蚀刻掉之后在该焊料沉积物上沉积另一层金属或金属合金。所述另一层金属在回流焊接过程中与该电镀的焊料沉积物层形成焊料合金。
附图说明
图1显示了用于得到具有平坦化电镀焊料层的阻焊限定的焊盘的方法。
图2显示了用于得到具有平坦化电镀焊料层的非阻焊限定的焊盘的方法。
图3显示了用于得到具有微盲孔(BMV)的阻焊限定的焊盘的方法,该焊盘具有平坦化的电镀焊料层。
图4显示了用于得到具有微盲孔(BMV)的非阻焊限定的焊盘的方法,该焊盘具有平坦化的电镀焊料层。
图5显示了用于得到具有个体高度的经受回流焊接工艺的电镀焊料层的阻焊限定的焊盘的方法。
图6显示了用于得到具有个体高度的经受回流焊接工艺的电镀焊料层的非阻焊限定的焊盘的方法。
图7显示了用于得到具有个体高度的经受回流焊接工艺的电镀焊料层的微盲孔(BMV)的阻焊限定的焊盘的方法。
图8显示了用于得到具有个体高度的经受回流焊接工艺的电镀焊料层的微盲孔(BMV)的非阻焊限定的焊盘的方法。
图9显示了用于得到具有施加另外的抗蚀剂以增大该焊料沉积物的体积的个体高度的电镀焊料层的非阻焊限定的焊盘的方法。
图10显示了依照图1实施方式的平面结构与包含另外的焊料体积(焊料块)的图7的实施方式的结合。
图11显示了依照图1实施方式的平面结构与包含另外的具有通过该焊料的回流焊接得到的预球形化结构的焊料体积(焊料块)的图4的实施方式的结合。
图12显示了用于得到具有微盲孔(BMV)的阻焊限定的焊盘的方法,该焊盘具有平坦化的电镀焊料沉积物。
图13显示了用于得到具有微盲孔(BMV)的阻焊限定的焊盘的方法,该焊盘具有平坦化的电镀焊料沉积物和阻挡层。
图14显示了用于得到具有堆叠的微盲孔(BMV)的阻焊限定的焊盘的方法,该焊盘具有平坦化的电镀焊料沉积物。
100 焊料沉积物层
101 导电种子层
102 任选的阻挡层
103 阻焊层
104 外层接触焊盘
105 非导电衬底
106 抗蚀刻剂
107 阻焊开孔(SRO)
108 铜层
109 光致抗蚀剂层
110 内层接触焊盘
111 开孔,形成的微盲孔(BMV)
112 共形的涂层BMV
113 堆叠的BMV
114 具有用于BMV的开孔的内层
发明详述
本发明提供了通过电镀锡或锡合金层在衬底上形成焊料沉积物的方法。该工艺特别适于在电路板上制备焊料块,其能够形成具有良好电镀均匀性的焊料快。下面更详细地描述该方法。此处所示的附图简要描述了该工艺。该附图并不按比例绘制,即其不反映该芯片封装结构中各层的实际尺寸或特征。在整个说明书中类似的编号表示类似的元件。
现在参照图1a,依照本发明的优选实施方式,提供了非导电衬底105,在其表面上具有接触焊盘104作为接触区域实施方式。该非导电衬底105能够是电路板,其可以由有机材料或纤维增强的有机材料或颗粒增强的有机材料等制成,例如环氧树脂、聚酰亚胺、双马来酰亚胺三嗪、氰酸酯、聚苯并环丁烯或其玻璃纤维复合物等。
所述接触焊盘104通常是由金属材料,例如铜,制成。任选地,在该接触焊盘104上形成阻挡层102,其能够例如是镍粘合层或金保护层。所述阻挡层102也可以由镍、钯、银、锡、镍/钯、铬/钛、钯/金或镍/钯/金等制成,其能够通过电镀、无电镀或物理气相沉积等制成。最终在所述非导电衬底105的表面上沉积阻焊层103以保护电路并提供绝缘。
为了通过电镀在非导电表面上制备包含锡或锡合金的焊料沉积物,需要在该非导电表面上形成导电种子层以引发电镀。这种种子层101示于图1b中。通常,该种子层例如是通过非导电表面的常规制造工业中的并为本领域技术人员已知的无电沉积而形成。
依照本发明,将该导电种子层沉积在包括接触焊盘区域104和阻焊区域103的该非导电衬底105的整个表面上。
该种金属层是电导性的,提供粘合,使其上表面的暴露部分可以电镀,且能够防止随后的焊料沉积物金属迁移到下面的接触区域的金属中。可选地,该种金属层可以由两个金属层构成。第二金属的实例是铜,因为其提供了适于随后电镀的表面。
该非导电的衬底能够被在例如Handbuch der Leiterplattentechnik,第4卷,2003,第292至300页中描述的各种方法激活。这些工艺包括形成包含碳颗粒、Pd胶体或导电聚合物的导电层。“Electrochemicals”公司已经开发了包括使用碳颗粒的工艺并以例如商标“Shadow”市场化。现有技术中已知的另一种工艺是已经由MacDermid公司开发的“黑孔”工艺。Shipley Ronal和Atotech公司已经开发了包括使用钯胶体的工艺且例如分别以商标“Crimson”、“Conductron”和“Neopact”已知。
OMI Enthone和Atotech公司已经开发了包括使用导电聚合物的工艺且例如分别以商标“DMSE”、“Seleo CP”和“Compact CP”已知。
专利文献中描述了这些工艺中的一些,并在下面给出实例:
欧洲专利EP 0 616 053描述了在非导电衬底上施加金属涂层的工艺(不使用无电涂覆),其包括:
a.将所述衬底与包括贵金属/第IVA族金属溶胶的活化剂接触以得到经处理的衬底;
b.将所述经处理的衬底与pH值高于11至13的自加速和补充的浸没金属组合物接触,该浸没金属组合物包括如下的溶液:
(i)Cu(II)、Ag、Au或Ni的可溶金属盐或其混合物,
(ii)第IA族金属的氢氧化物,
(iii)包括对于所述金属盐的金属具有0.73至21.95的累计形成常数log K的有机材料的络合剂。
该工艺得到能够用于随后电涂覆的薄导电层。该工艺在现有技术中已知为“Connect”工艺。
美国专利号5,503,877描述了包括使用络合物在非金属衬底上产生金属种的非导电衬底的金属化。该金属种为随后的电镀提供了足够的电导性。该工艺在现有技术中已知为所谓的“Neoganth”工艺。
美国专利号5,693,209涉及包括使用导电吡咯聚合物的非导电衬底的金属化工艺。该工艺在现有技术中已知为“Compact CP”工艺。
欧洲专利1 390 568 B1也涉及非导电衬底的直接电解金属化。其包括使用导电聚合物得到用于随后电涂覆的导电层。该导电聚合物具有噻吩单元。该工艺在现有技术中已知为“Seleo CP”工艺。
最后,该非导电衬底也能够用含胶体或无机钯离子的溶液激活,其方法描述于例如Handbuch der Leiterplattentechnik,第4卷,2003,第307至311页中。
随后可以任选地进行薄中间金属涂层的无电镀以增强该导电种子层。借助于该种子层,然后能够进行依照本发明的焊料沉积物的电镀。
依照本发明,所述导电种子层101可以由金属或合金制成或由金属多层制成,例如铜、锡、钴、锡-铅合金、铬-铜合金、钛/镍(双金属)、锡/铜、铬/铬-铜合金/铜或镍/锡/铜多层。优选铜作为种子层。
依照本发明的优选实施方案,所述种子层101也能够通过无电镀方法形成,其中该催化金属不使用贵金属而是使用铜作为催化金属。在美国专利号3,993,491和3,993,848中能够找到用于在非导电表面上形成这种催化铜的典型实例。
所述种子层101的厚度优选小于0.1毫米,更优选为0.0001毫米至0.005毫米。根据所述种子层101在该焊料中的溶解度,所述种子层101也能够完全溶解在该焊料沉积物中或在回流焊接工艺之后仍至少部分存在。
优选较薄的所述种子层101,因为较薄的种子层能够较快地在蚀刻溶液中除去,所述非导电衬底105在蚀刻溶液中浸没所需的时间能够缩短。在这种情况中,所述蚀刻溶液对所述阻焊层103的损害将会降低到可接受的低水平。
本发明方法的优点是在该焊料沉积物的电镀之前不需要在该衬底表面的选定区域上施加抗蚀层。
现在参照图1c,然后在该导电种子层101上形成包含锡或锡合金的焊料层100。
依照本发明的优选实施方式,所述焊料100是锡或由锡与选自铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、镍和镓的元素的混合物制成的锡合金。
锡和锡合金电镀浴是本领域已知的。下面描述了通常使用的锡或锡合金电镀浴组成和电镀的工艺参数。
在该浴的其它组分中,可以添加Sn2+离子源、抗氧化剂和表面活性剂。
该Sn2+离子源可以是含锡的可溶阳极,或在使用不溶阳极的情况下,可以是可溶Sn2+离子源。甲磺酸锡Sn(MSA)2是优选的Sn2+离子源,因为其具有高溶解度。一般该Sn2+离子源的浓度足以在该浴中提供约10g/L至约100g/L的Sn2+离子,优选约15g/L至约95g/L,更优选约40g/L至约60g/L。例如可以加入Sn(MSA)2以在该电镀浴中提供约30g/L至约60g/L的Sn2+离子。
优选的合金是锡银合金。在这种情况中,该电镀浴还包含可溶银盐,通常使用的是硝酸盐、乙酸盐和优选的甲磺酸盐。一般Ag+离子源的浓度足以在该浴中提供约0.1g/L至约1.5g/L的Ag+离子,优选约0.3/L至约0.7g/L,更优选约0.4g/L至约0.6g/L。例如可以加入Ag(MSA)以在该电镀浴中提供约0.2g/L至约1.0g/L的Ag+离子。
可以在本发明的浴中添加抗氧化剂以稳定该浴使得溶液中的Sn2+离子不会被氧化。能够加入约0.1g/L至约10g/L,优选约0.5g/L至约3g/L浓度的例如以下的优选的抗氧化剂:对苯二酚、邻苯二酚和任何羟基、二羟基或三羟基苯甲酸和选自以下化合物的一取代、二取代或三取代吡啶衍生物:2-氨基-3-羟基吡啶、3-氨基-2-羟基吡啶、2,3-二羟基吡啶、3,4-二羟基吡啶、2,5-二羟基吡啶、2,3,4-三羟基吡啶、3,4,5-三羟基吡啶、2,3-二氨基吡啶、3,4-二氨基吡啶、2,5-二氨基吡啶、3-氨基-4,5-二羟基吡啶、4-氨基-3,5-二羟基吡啶、4-氨基-2,5-二羟基吡啶、4-氨基-2,3-二羟基吡啶、3,4-二氨基-2-羟基吡啶、3,4-二氨基-5-羟基吡啶、2,3-二氨基-4-羟基吡啶、2,3-二氨基-5-羟基吡啶、3,4-二氨基-2-羟基-5,6-二甲基吡啶、3,4-二氨基-5-羟基-2,6-二甲基吡啶、2,3-二氨基-4-羟基-5,6-二甲基吡啶、4-氨基-2,3-二羟基-5,6-二甲基吡啶、3-氨基-4,5-二羟基-2,6-二甲基吡啶、2,5-二氨基-3,4,6-三甲基吡啶、3,4-二氨基-2,5,6-三甲基吡啶、2,3-二氨基-4,5,6-三甲基吡啶、3,4,5-三羟基-2,6-二甲基吡啶、2,3,4-三羟基-5,6-二甲基吡啶、2,5-二羟基-3,4,6-三甲基吡啶、3,4-二羟基-2,5,6-三甲基吡啶、2,3-二羟基-4,5,6-三甲基吡啶、3-氨基-2-羟基-4,5,6-三甲基吡啶、2-氨基-3-羟基-4,5,6-三甲基吡啶和相应的乙基、丙基和烷氧基衍生物。例如,可以在该浴中加入约2g/L浓度的对苯二酚。
可以加入表面活性剂以促进该衬底的润湿。该表面活性剂似乎用作温和的沉积抑制剂,其能够在一定程度上抑制三维生长,从而改进该膜的形态和形貌。其也能够有助于精制粒度,产生更均匀的块。示例性的阴离子表面活性剂包括烷基磷酸盐、烷基醚磷酸盐、烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基醚磺酸盐、羧酸醚、羧酸酯、烷基芳基磺酸盐、芳基烷基醚磺酸盐、芳基磺酸盐和磺基丁二酸盐。
本发明的电镀浴优选具有酸性pH值以抑制阳极钝化,实现更好的阴极效率,并实现更具延展性的沉积物。因此,该浴pH值优选为约0至约3。在优选实施方式中,该浴的pH值是0。因此,可使用硝酸、乙酸和烷基磺酸,例如甲磺酸(MSA),实现该优选的酸性pH值。在一种优选实施方式中,该酸是甲磺酸。该酸的浓度优选为约50g/L至约200g/L,更优选为约70g/L至约120g/L。例如,可以在该电镀浴中加入约50g/L至约160g/L的甲磺酸以实现pH值为0的浴并用作导电电解液。
本发明的电解浴还包含至少一种流平剂,其包括但不局限于芳香醛和酮,选自如下化合物:苯丁烯酮、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-萘甲醛、2-萘甲醛、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、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。该术语“芳香羰基化合物”此处用作芳香醛和芳香酮化合物的同义词,且不包括“α/β-不饱和羧酸”。所述芳香羰基化合物流平剂以0.001g/l至0.5g/l,更优选0.005g/l至0.1g/l的量加入到该电解液中。
在另一实施方式中,除了该芳香羰基化合物的该至少一种流平剂之外,该电解液还包含至少一种其它类型的流平剂,其是α/β-不饱和羧酸或其衍生物。优选地,该α/β-不饱和羧酸选自以下化合物:丙烯酸、甲基丙烯酸、丁烯酸、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-羟基乙酯、甲基丙烯酸2-羟基丙酯、甲基丙烯酸2-二甲基氨基乙酯、甲基丙烯酸酐和甲基丙烯酸甲酯。该α/β-不饱和羧酸的该至少一种流平剂以在0.05g/l至3g/l,更优选0.1g/l至0.5g/l的范围内的浓度存在于该电解液中。
在本发明的一种实施方式中,该增白剂是苯丁烯酮、1-萘甲醛和甲基丙烯酸的混合物,其中该苯丁烯酮的浓度在0.01g/l至0.3g/l,更优选0.005g/l至0.02g/l的范围内,其中该1-萘甲醛的浓度在0.001g/l至0.2g/l,更优选0.005g/l至0.02g/l的范围内,以及其中该甲基丙烯酸的浓度在0.05g/l至3g/l,更优选0.1g/l至0.5g/l的范围内。
例如在以下中公开了典型的浴组成:The Electrodeposition of Tin and its Alloys,1995,71-84页。
用于焊料沉积物电镀的锡和锡合金的电镀能够通过直流(DC)或脉冲电镀进行。脉冲电镀技术特别适用于填充在图1-15中所示的本发明的结构。脉冲电镀的优点是更好的表面分布均匀性和改进的晶体结构,其具有具有更细的粒度和因此更好的可焊接性质的锡沉积物。而且,与DC电镀相比,脉冲电镀能够得到更高的可施加电流密度和因此更高的生产量。
通常,能够使用有效电流密度为1-20A/dm2的电流脉冲。可选地,也能够用电流密度为1-3A/dm2的DC操作该浴。
例如,用3A/dm2的电流密度实施锡脉冲电镀在30min电镀时间内产生40μm的锡沉积物平均厚度。表面上的厚度变化仅为+/-15%。实施DC电镀能够得到仅1A/dm2的最大电流密度。获得40μm的锡沉淀物厚度的电镀时间为86min。表面上的变化为+/-33%,因此比脉冲电镀要高得多。
优选的脉冲参数如下:
调节至少一个正向电流脉冲的持续时间与至少一个反向电流脉冲的持续时间之比为至少1∶0-1∶7,优选至少1∶0.5-1∶4,更优选至少1∶1-1∶2.5。
可将该至少一个正向电流脉冲的持续时间调节为优选至少5ms至1000ms。
可将该至少一个反向电流脉冲的持续时间优选调节为0.2-至多5ms,更优选0.5-1.5ms。
该至少一个正向电流脉冲在该工件处的最大电流密度优选调节为1-最大30A/dm2的值。特别优选地,在水平工艺中,该至少一个正向电流脉冲在该工件处的最大电流密度为约2-8A/dm2。在垂直工艺中,该至少一个正向电流脉冲在该工件处的最优选的最大电流密度为1-最大5A/dm2。
该至少一个反向电流脉冲在该工件处的最大电流密度将优选调节为0-60A/dm2的值。特别优选地,在水平工艺中,该至少一个反向电流脉冲在该工件处的最大电流密度为约0-20A/dm2。在垂直工艺中,该至少一个正向电流脉冲在该工件处的最优选的最大电流密度为0-最大12A/dm2。
依照图1-8的结构中的开孔表示SRO(阻焊开孔),优选尺寸为约5-1000μm,优选约10-500μm,甚至更优选20-100μm。
SRO的高度为5-250μm,优选约10-50μm。相邻接触区域的中心点的距离表示为间距,对于IC衬底在90-300μm范围内,对于印刷电路在150-1000μm范围内。
因为该阻焊104也被导电种子层101覆盖,因此也在该层上电镀该焊料沉积物100。该层100的厚度应当优选不超过1-10μm,更优选不超过3-6μm。
参照图1d,从该阻焊层103上除去该焊料沉积物100以及该导电种子层101。该除去优选是通过化学蚀刻一定量的包含锡或锡合金的焊料层足以从该阻焊层区域103上除去该焊料沉积物层100和该导电种子层101并在该至少一个接触区域上留下焊料层而进行的。该锡和锡合金的蚀刻,也称作脱模,能够电解或化学进行。而且,可以仅使用机械抛光,或者可以将其与电解或化学脱模结合使用以除去该焊料沉积物层100和导电种子层101。
通常能够在单一蚀刻步骤中用相同的蚀刻溶液除去该锡或锡合金焊料沉积物100和该导电种子层101。然而,在一些情况中,使用不同的蚀刻溶液以首先除去该阻焊区域103上的焊料沉积物层并然后除去该导电种子层101可能是有利的。能够使用常规实验选择适合的蚀刻溶液。
典型的蚀刻或脱模组合物例如公开于Jordan:The Electrodeposition of Tin and its Alloys,1995,373-377页中。
在电解脱模方法过程中,将锡或其合金在70-90℃阳极溶解在10wt%的NaOH溶液中。
化学脱模通常是在包含强碱,例如NaOH,的溶液(约10wt%)中在70-90℃的高温下进行的。可以在该溶液中添加有机添加剂,特别是硝基芳香化合物,例如对硝基苯酚。
可选地,化学脱模可在以下溶液中进行:
-过氧化氢,通常添加氟化物,
-基于硝酸和硝酸盐的体系,5-40wt%硝酸盐,
-基于HCl/氯化铜的体系,包含5-20wt%HCl,氯化铜的初始浓度为2.5mg/L。
尽管对依照图1的衬底详细描述了该工艺步骤,但其并不限定于此,且可以被应用于所有类型的衬底。图2-9中显示了能够由此处理的本发明的一些其它优选实施方式。
依照本发明,所述阻焊层103并不限于覆盖所述接触焊盘104表面的一部分。如图2中所示,所述阻焊层103沉积在所述非导电表面105的表面上,而不覆盖所述接触焊盘104表面的任何部分。按顺序形成所述导电种子层101。然后,在覆盖该接触焊盘104的所述开孔中以及非导电表面105的区域上形成该焊料沉积物层100。这种结构称作非阻焊限定的焊盘结构。
依照本发明,所述接触焊盘104并不限定于平坦结构。如图3中所示,所述接触焊盘104能够是填充有焊料沉积物100的过孔或沟槽的一部分。过孔和沟槽优选具有5-250μm的深度和5-200μm的宽度。
这种结构也可以是如图4中所示的非阻焊限定的焊盘衬底。
依照本发明,该焊料沉积物层100并不限定于该开孔,而是也能够延伸到如图5中所示的开孔之上。对于该实施方式,将抗蚀刻剂106施加到位于至少该至少一个接触焊盘104之上的表面积上的该焊料沉积物层100上,如图5d所示。该焊料沉积物层100以及该导电层101以足以从该阻焊层103上除去该焊料沉积物层和该导电层并在该至少一个接触焊盘区域上留下焊料沉积物层的量蚀刻掉。然后,除去该抗蚀刻剂。图5f是在回流焊接步骤之后为焊料块的焊料沉积物100的实例。
图6是类似于图5中所示的具有非阻焊限定接触焊盘104的焊料块的实施例。
图7是焊料块实施方式的实施例,其中该接触焊盘104是过孔或沟槽的一部分。
图8是焊料块实施方式的实施例,其中该接触焊盘104是过孔或沟槽的一部分,且该接触焊盘104是非阻焊限定的。
图9是施加有另外的抗蚀剂的具有个体高度的电镀焊料层的非阻焊限定的焊盘。在该实施方式中,将另外的抗蚀剂106施加在该阻焊103的水平表面区域上。这种抗蚀剂优选不施加在该衬底表面105上。添加另外的抗蚀剂的目的是提高该衬底上焊料沉积物的量。从图9中显而易见可知,在该阻焊层103顶部施加另外的抗蚀剂层106不会改变总的电镀步骤,且特别不会影响本发明的优点。
依照本发明的优选实施方式,由依照图5-9的焊料沉积物100形成的所述焊料块100能够用于形成倒装芯片接缝。在回流焊接温度能够形成倒装芯片接缝。
依照本发明的优选实施方式,所述电镀焊料块能够用于形成在IC芯片上具有金属块的倒装芯片接缝。在回流焊接温度能够形成倒装芯片接缝。
图10是依照本发明的优选实施方式的两个衬底之间的结合工艺,例如具有印刷电路板(下部)的IC衬底(上部)。在回流焊接温度能够形成倒装芯片接缝。
图11是依照本发明的优选实施方案的两个衬底之间的结合工艺,例如具有印刷电路板(下部)的IC衬底(上部)。在该结合工艺之前,该焊料块已经通过回流焊接工艺预球体化。
在回流焊接温度能够形成倒装芯片接缝。
依照本发明的优选实施方案,所述电镀焊料块能够用于形成倒装芯片接缝和板对板焊接接缝。
该焊料块可以是任何形状,例如螺柱块、球块、柱块或其它。
在另一实施方式中,依照本发明的方法能够用于形成倒装芯片接缝和板对板焊接接缝,在其上通过印刷和蚀刻工艺形成电路。
参照图12,其中在在其表面的一侧上具有铜层108的非导电衬底105上形成具有微盲孔111的阻焊限定的焊盘。该铜层108的典型厚度为15μm,尽管厚度在3至35μm范围内的铜层108都可适用本发明的方法。尤其适用于制备高密度互连的是厚度为3-7μm的铜层108。所述铜层108通常能够以3μm、5μm或7μm的厚度使用。
通过该印刷和蚀刻方法将该附着到该非导电衬底105的至少一个表面上的至少一个铜层108构造(即转化)为电路。因此,将光致抗蚀剂层109沉积在所述铜层108上并使用现有技术已知的方法图案化。在本发明的一种实施方式中,该铜层108的表面用微蚀刻工艺处理以提高该铜层108的表面与该光致抗蚀剂层109之间的粘附力。这种用于铜表面的微蚀刻工艺描述于例如W.Jillek,G.Keller“Handbuch der Leiterplattentechnik Band 4”,E.G.Leuze Verlag Bad Saulgau,第一版2003,132页中。典型的微蚀刻工艺包括用过硫酸盐和硫酸或用包含过氧化氢和硫酸的组合物处理铜表面。
任选地,在沉积光致抗蚀剂之前将该铜层108的表面经过机械处理以提高随后在该铜层108上沉积的光致抗蚀剂的粘附力。这种机械处理是现有技术中已知的并包括刷新和浮石磨光。
也可以将用于提高铜层108的表面和光致抗蚀剂层之间的粘附力的所述化学和机械工序相结合。
能够施加液体和干膜光致抗蚀剂以将铜层108转化为构造化的铜层108。典型的光致抗蚀剂材料和沉积工序、其说明和开发都是现有技术中已知的。在本发明的一种实施方式中,使用干膜光致抗蚀剂以在该铜层108上提供电路图案。在另一实施方式中,使用液体光致抗蚀剂用于与干膜光致抗蚀剂相同的目的。
涂有图案化的光致抗蚀剂的该铜层108与蚀刻组合物接触以从不涂有该光致抗蚀剂的该铜层108的那些部分上除去所有铜,得到构造化的铜层108。为此目的,可使用不同的蚀刻组合物。在一种实施方式中,使用包括酸、过氧化物和CuCl2的酸性蚀刻组合物。在另一实施方式中,使用包括氨和CuCl2的碱性蚀刻组合物。
通过常规抗蚀剂脱模方法从该非导电衬底105上除去该光致抗蚀剂层109,其中将该涂有抗蚀剂的衬底与碱性水溶液接触。所述脱模处理的温度通常保持在50℃至55℃。通常将所述水溶液喷在具有光致抗蚀剂层的该非导电衬底105上。
在形成开孔111之后,将阻焊层103沉积在该构造化的铜层108和该非导电衬底105的相邻表面上。为此目的能够使用机械和激光钻孔。激光钻孔是用于形成开孔111、堆叠的微盲孔113和直径≤150μm的阻焊开孔107的优选方法。UV型或CO2型激光钻孔方法都适用于本发明。
在本发明的一种实施方式中,该阻焊层103是永久阻焊,且在制备印刷电路板之后保持附着在该构造化的铜层108和该非导电衬底105的表面上。
通过已知技术将该阻焊层103沉积在该非导电的衬底105的表面和该构造化的铜层108上。适用于本发明的实施例是丝网印刷和/或光刻工艺。依照本发明能够使用各种类型的阻焊:UV硬化阻焊、热固化双组分阻焊和可光成像的阻焊。
在图14中所示的本发明的一种实施方式中,与如图12和13中所示相反,在沉积该阻焊层103之后,钻出开孔111,即在沉积和构造该阻焊层103之后,通过激光钻孔除去该非导电衬底105的材料。
在本发明的另一实施方式中,如图15中所示,将堆叠的微盲孔113钻孔通过在钻孔之前沉积的该阻焊层103和非导电衬底105。
在下一步中,必须将该钻出的堆叠的微盲孔114和暴露出该内层接触焊盘110的阻焊开孔107清洁并调节其用于随后的工艺步骤。本领域中已知的方法,例如去钻污工艺,可用于本发明的方法中。
涂污与来自非导电衬底材料、阻焊和光致抗蚀剂的聚合物材料残余物有关,且是由钻孔和在钻孔过程中的热作用造成的。在对所述孔进行金属化之前必须将该涂污除去以在第一金属化层和该介电材料之间实现可靠的附着和/或保证可靠的铜/铜互连。
在本发明的一种实施方案中,该去钻污工艺是碱性高锰酸盐处理,其中从该激光钻孔111中除去该塑性材料,用包括以下的三步工艺除去堆叠的微盲孔113和阻焊开口107:a)将该塑性材料在例如基于丁二醇的溶胀剂中膨胀,b)高锰酸盐蚀刻,其导致从塑性材料上除去涂污和其它残余物,和c)还原工艺,其中除去在高锰酸盐蚀刻过程中产生的分解产物并进一步清洗和调节孔内的衬底表面。所述还原步骤c)通常是用基于H2O2的组合物进行的。任选地增加另一处理步骤以清理在一些类型的衬底材料中存在的玻璃颗粒和/或玻璃丝。
任选地,在沉积导电种子层101之前在该内层接触焊盘110上形成阻挡层102(图13)。
接下来然后在该导电种子层101上形成包含锡或锡合金的焊料层100。
从该阻焊层103上除去该焊料沉积物层100以及该导电种子层101。
任选地,在蚀刻掉过量的焊料之后在该焊料沉积物层100上沉积另一金属层。该金属是通过无电金属镀工艺沉积的,且选自如下物质:铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、金和镓。所述无电金属镀工艺包括浸镀和自催化镀。用于无电沉积铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、金和镓的工艺和组合物是本领域已知的,且能够在不进行任何进一步改进的情况下适用于本发明。用于无电金属镀在该焊料沉积物层100上的优选金属是银、铜、镍、金和钯。沉积在该焊料沉积物层100上的所述另一金属层在进行回流焊接工艺时形成金属间合金焊料。
具体实施方式
以下实施例进一步描述本发明。
实施例
实施例1
使用具有依照图1a的接触焊盘结构的IC衬底。该SRO是120μm,阻焊高度是25μm。
电镀步骤依照图1。首先在整个衬底表面上形成铜的导电种子层101。为此,首先将该表面与包含无机钯的酸性溶液接触,然后与用于化学铜沉积的溶液接触。
然后,将锡焊料沉积物100从包含45g/L Sn2+作为Sn(MSA)2、60mL/L MSA(70%溶液)、2g/L对苯二酚、7.0g/Lugalvan BNO12和100mg/L苯丁烯酮的浴中镀在该导电层上。
该浴的pH值为0,温度为25℃。镀7分钟。使用脉冲电镀,使用以下参数:
正向电流脉冲的平均电流密度:2A/dm2;
正向电流脉冲的持续时间:20ms;
反向电流脉冲的平均电流密度:0A/dm2(无反向脉冲,仅暂停脉冲);
反向电流脉冲的持续时间:4ms。
将依照图1的开孔(SRO)完全充满锡焊料沉积物,不形成任何孔隙。此外,在该阻焊区域103上沉积了锡,其厚度为3μm(图1c)。
然后通过在包含30vol%硝酸的溶液中在40℃的温度处理1min除去在该阻焊区域上的该锡焊料沉积物100以及该导电种子层101。
在该蚀刻工艺之后,锡焊料沉积物100仅剩余在该开孔中,而在该阻焊区域103上的该锡焊料沉积物100以及该铜的导电种子层101已经完全除去(图1d)。该锡焊料沉积物显示出非常均匀的表面分布且没有须状物。其适于焊接到芯片或电路上。
实施例2
重复实施例1,现在使用包含45g/l Sn2+作为Sn(MSA)2、60ml/lMSA(70%溶液)、0.5g/l 2-氨基-3-羟基-吡啶、7.0g/l LugalvanBNO12(BASF SE的产品)和由0.5g/l甲基丙烯酸和0.05g/l 1-萘甲醛构成的流平剂的锡浴。
该锡焊料沉积物显示出非常均匀的表面分布且没有须状物。其适于焊接到芯片或电路上。
Claims (20)
1.一种在衬底上形成焊料沉积物的方法,其包括如下步骤:
i)提供包括具有电路的表面的衬底,所述的表面包括至少一个接触区域,
ii)形成置于所述衬底表面上的阻焊层,并将其图案化以暴露出所述至少一个接触区域,
iii)使包括所述阻焊层和所述至少一个接触区域的整个衬底区域与适于在所述衬底表面上提供导电层的溶液接触,
iv)在所述导电层上电镀包含锡或锡合金的焊料沉积物层,
v)将如下量的包含锡或锡合金的所述焊料沉积物层和所述导电层蚀刻掉,所蚀刻掉的如下的量使得足以从所述阻焊层区域除去所述焊料沉积物层和所述导电层,在所述至少一个接触区域上留下焊料沉积物层。
2.根据权利要求1的方法,在步骤i)和步骤ii)之间包括如下步骤:
a)形成置于所述衬底的至少一个铜表面108上的光致抗蚀剂层,并将所述光致抗蚀剂层构造成电路的负像,
b)将所述至少一个铜表面108经由所述图案化的光致抗蚀剂暴露出的部分蚀刻掉,
c)除去所述光致抗蚀剂。
3.根据前述权利要求中任一项的方法,其中形成至少一个开孔以暴露出至少一个内层焊盘。
4.根据权利要求3的方法,其中所述至少一个开孔是在步骤ii)之后形成的。
5.根据权利要求3的方法,其中所述至少一个开孔是在步骤ii)之前形成的。
6.根据前述权利要求中任一项的方法,其包括如下步骤:
i)提供包括具有电路的表面的衬底,所述表面包括至少一个接触区域,
ii)形成置于所述衬底表面上的阻焊层,并将其图案化以暴露出所述至少一个接触区域,
iii)使包括所述阻焊层和所述至少一个接触区域的整个衬底区域与适于在所述衬底表面上提供导电层的溶液接触,
iv)在所述导电层上电镀包含锡或锡合金的焊料沉积物层,
iv a)至少在与所述至少一个接触区域重叠的表面区域上,在所述焊料沉积物层上提供抗蚀剂,
v)将如下量的包含锡或锡合金的所述焊料沉积物层和所述导电层蚀刻掉,所蚀刻掉的如下的量使得足以从所述阻焊层区域除去所述焊料沉积物层和所述导电层,在所述至少一个接触区域上留下焊料沉积物层,
vi)除去所述抗蚀剂。
7.根据权利要求1的方法,其包括如下步骤:
i)提供包括具有电路的表面的衬底,所述的表面包括至少一个接触区域,
ii)形成置于所述衬底表面上的阻焊层,并将其图案化以暴露出所述至少一个接触区域,
ii a)在所述阻焊层上形成另外的抗蚀剂层,
iii)使包括所述抗蚀剂和阻焊层和所述至少一个接触区域的整个衬底区域与适于在所述衬底表面上提供导电层的溶液接触,
iv)在所述导电层上电镀包含锡或锡合金的焊料沉积物层,
v)将如下量的包含锡或锡合金的所述焊料沉积物层和所述导电层蚀刻掉,所蚀刻掉的如下的量使得足以从所述抗蚀剂层区域除去所述焊料沉积物层和所述导电层,在所述至少一个接触区域上留下焊料层,
v)除去所述抗蚀剂层。
8.根据前述权利要求中任一项的方法,其中所述锡或锡合金是从如下组合物沉积的,所述组合物包括:
·至少一种锡离子的源,
·至少一种酸,
·至少一种流平剂,其选自芳香醛、芳香酮和α-/β-不饱和羧酸,以及
·至少一种抗氧化剂。
9.根据权利要求4的方法,其中所述至少一种芳香醛或酮选自:亚苄基丙酮、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-萘甲醛、2-萘甲醛、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、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。
10.根据权利要求4的方法,其中所述至少一种α-/β-不饱和羧酸选自:丙烯酸、甲基丙烯酸、丁烯酸、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-羟基乙酯、甲基丙烯酸2-羟基丙酯、甲基丙烯酸2-二甲基氨基乙酯、甲基丙烯酸酐和甲基丙烯酸甲酯。
11.根据权利要求4至6的方法,其中使用至少一种芳香醛或芳香酮和至少一种α-/β-不饱和羧酸的混合物作为流平剂。
12.根据前述权利要求中任一项的方法,其中将阻挡层镀在所述至少一个接触区域上。
13.根据前述权利要求中任一项的方法,其中所述阻挡层由如下金属构成,所述金属选自:铜、锡、镍、铬、钛、金、铜-铬合金、锡-铅合金及其任意合金。
14.根据前述权利要求中任一项的方法,其中在所述焊料沉积物层上有另外的金属层。
15.根据权利要求14的方法,其中所述另外层的金属选自:铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、金和镓。
16.根据前述权利要求中任一项的方法,其中所述接触区域包括通孔或沟槽。
17.根据前述权利要求中任一项的方法,其中使所述衬底经回流焊接工艺处理,以回流焊接所述包含锡或锡合金的焊料沉积物层。
18.根据前述权利要求中任一项的方法,其中所述导电种子层是由铜的无电沉积形成的。
19.根据前述权利要求中任一项的方法,其中所述焊料沉积物层是锡合金,所述锡合金由锡和选自铅、银、铜、铋、锑、锌、镍、铝、镁、铟、碲、镍和镓的元素的混合物制成。
20.根据前述权利要求中任一项的方法,其中所述衬底是印刷电路板、IC衬底或内插器。
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
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EP08167159.6 | 2008-10-21 | ||
EP08167159A EP2180770A1 (en) | 2008-10-21 | 2008-10-21 | Method to form solder deposits on substrates |
EP09158715.4 | 2009-04-24 | ||
EP09158725.3 | 2009-04-24 | ||
EP09158715A EP2244285A1 (en) | 2009-04-24 | 2009-04-24 | Method to form solder deposits on substrates |
EP09158725 | 2009-04-24 | ||
PCT/EP2009/063049 WO2010046235A1 (en) | 2008-10-21 | 2009-10-07 | Method to form solder deposits on substrates |
Publications (1)
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CN102187749A true CN102187749A (zh) | 2011-09-14 |
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CN2009801407084A Pending CN102187749A (zh) | 2008-10-21 | 2009-10-07 | 用于在衬底上形成焊料沉积物的方法 |
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US (1) | US8507376B2 (zh) |
EP (1) | EP2377376B1 (zh) |
JP (1) | JP2012506628A (zh) |
KR (1) | KR20110070987A (zh) |
CN (1) | CN102187749A (zh) |
MY (1) | MY158939A (zh) |
TW (1) | TWI437135B (zh) |
WO (1) | WO2010046235A1 (zh) |
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CN104620394A (zh) * | 2012-09-14 | 2015-05-13 | 安美特德国有限公司 | 用于太阳能电池基板的金属化的方法 |
CN103898570A (zh) * | 2012-12-27 | 2014-07-02 | 罗门哈斯电子材料有限公司 | 锡或锡合金电镀液 |
CN103898570B (zh) * | 2012-12-27 | 2017-03-01 | 罗门哈斯电子材料有限公司 | 锡或锡合金电镀液 |
CN105308218A (zh) * | 2013-06-26 | 2016-02-03 | 株式会社杰希优 | 锡或锡合金用电镀液及其用途 |
CN104674312A (zh) * | 2013-11-05 | 2015-06-03 | 罗门哈斯电子材料有限公司 | 镀液和镀覆方法 |
CN104928730A (zh) * | 2014-03-18 | 2015-09-23 | 上村工业株式会社 | 锡或锡合金的电镀浴以及凸点的制备方法 |
CN108493629A (zh) * | 2018-03-12 | 2018-09-04 | 福耀集团(上海)汽车玻璃有限公司 | 一种电气联接元件和汽车玻璃 |
CN108834330A (zh) * | 2018-06-29 | 2018-11-16 | 惠州市金百泽电路科技有限公司 | 一种pcb“d”字型异型焊盘的加工方法 |
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Also Published As
Publication number | Publication date |
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WO2010046235A1 (en) | 2010-04-29 |
US8507376B2 (en) | 2013-08-13 |
US20110189848A1 (en) | 2011-08-04 |
EP2377376B1 (en) | 2019-08-07 |
TWI437135B (zh) | 2014-05-11 |
EP2377376A1 (en) | 2011-10-19 |
KR20110070987A (ko) | 2011-06-27 |
TW201026910A (en) | 2010-07-16 |
JP2012506628A (ja) | 2012-03-15 |
MY158939A (en) | 2016-11-30 |
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