CN105492661A - 银和锡合金的电镀浴 - Google Patents
银和锡合金的电镀浴 Download PDFInfo
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- CN105492661A CN105492661A CN201480031676.5A CN201480031676A CN105492661A CN 105492661 A CN105492661 A CN 105492661A CN 201480031676 A CN201480031676 A CN 201480031676A CN 105492661 A CN105492661 A CN 105492661A
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Abstract
银和锡合金电镀浴包括允许电镀富银或富锡合金的络合剂。所述银和锡合金电镀浴实质上不含铅。其可用于在诸如电连接器的电子组件、金属衬底的修整层、装饰应用和焊料凸点的制造中电镀银和锡合金。
Description
技术领域
本发明涉及银和锡合金的电镀浴,和电镀银和锡合金的方法。更具体来说,本发明涉及银和锡合金的电镀浴,和电镀银和锡合金的方法,其中电镀浴含有允许富银或富锡合金的络合剂。
背景技术
存在两种类别的银和锡合金。一种是基于银或富银的银/锡合金,其中银含量大于50%。与纯银相比此类合金拥有较高硬度和较高耐磨性并且用于修饰应用。因为其极好的导电性,其还可用于电子连接器以降低硬金的量。由于硬金具有良好的耐磨性和耐腐蚀性,硬金在电子连接器中用作接触材料修整面层。硬金提供为电荷传输所需要的低电接触电阻;然而,金价格已经增加的使得其对于低成本接触修整面层来说已变成一限制性因素。银/锡合金已用于连接器修整面层以代替或降低硬金的量。此类合金通过镀敷银和锡的一或多个交替层并且随后在非氧化气氛中扩散以形成银/锡合金来制备。美国5,438,175公开具有银/锡以及银/钯闪烁层以使得薄金修整层能够制造更低成本物件的电子连接器。
合金的第二类型是基于锡的合金,其中银含量接近共晶,诸如大约3.5%。锡/银合金是比银/锡合金更软的合金并且硬度类似于纯锡。此类合金可以用作低晶须、无铅焊料。在用于锡/银合金的各种电子应用中,目前聚焦于关于晶片级包装(WLP)的半导体制造工业。对于晶片级包装,IC互连件集体构造于晶片上,并且完整IC模块在其被切块前可建构于晶片上。使用WLP获得的益处包括(例如)提高I/O密度,改进操作速度,增强功率密度和热管理,并且减小包装大小。
对于WLP一个关键是于晶片上建立倒装芯片导电互连凸点。这些互连凸点充当半导体组件至印刷线路板的电连接和物理连接。已提出在半导体装置上形成互连凸点的若干方法,例如焊料板凸点法、蒸发凸点法、导电胶接、模板印刷焊料凸点法、立柱凸点法和球放置凸点法。在这些技术中,相信用于形成精细间距阵列的最具成本效益的技术是焊料板凸点法,其涉及临时光刻胶镀敷掩模和电镀的组合。此技术快速采纳为用于诸如微处理器、数字信号处理器和专用集成电路的高附加值组合件的全区域互连凸点技术。
通常锡/铅合金用于形成焊料凸点;然而,因铅的毒性所致,业界已经尝试寻找可易于共-沉积的可接受的无铅锡合金。当所沉积的材料具有显著不同的沉积电势时,产生与通过电镀共沉积无铅锡合金相关的困难。例如当尝试沉积锡(-0.137V)与银(0.799V)的合金时,可产生新增的困难。针对给定的应用,业界期望有效控制沉积物的组成以防止材料在过高或过低温度下的熔融。不良组成控制可导致温度过高而使所处理的组件不能耐受或在另一个极端上导致焊点的不完全形成。
在电镀凸点是凸点形态中,经常碰到另一问题。举例而言,锡/银凸点通过光刻胶定义的通孔电沉积于凸点金属下的铜或镍上。剥离光刻胶并且回焊锡/银以形成球状凸点。凸点大小的均一性至关重要,使得所有凸点在相对应的倒装芯片组件上与其电连接接触。除凸点大小均一性之外,至关重要是空隙的低密度和体积在凸点回焊期间形成。理想地,在回焊期间无空隙形成。当接合到相对应的倒装芯片组件上时,凸点中的空隙还可导致互连可靠性问题。另一与镀敷凸点相关的问题是在凸点表面上形成结节,其用许多常规扫描电子显微镜可易于检测。此类结节可引起回焊排出,并且具有结节的外观矿床商业上不可接受。
因此,需要稳定的银和锡合金电镀浴,其可提供富银的银/锡合金以代替硬金并且可提供富锡的锡/银合金以提供实质上无节结和无空隙的焊料凸点。
发明内容
电镀浴包括一或多种银离子源、一或多种锡离子源、具有下式的一或多种化合物:
X-S-Y
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'-S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1到20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾,并且R1是被取代或未被取代的直链或支链(C2-C20)烷基,被取代或未被取代的(C6-C10)芳基。
电镀方法包括:使衬底与电镀浴接触,所述电镀浴包括一或多种银离子源、一或多种锡离子源、一或多种具有下式的化合物:
X-S-Y
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'-S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1到20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾,并且R1是被取代或未被取代的直链或支链(C2-C20)烷基,被取代或未被取代的(C6-C10)芳基;和将银和锡合金电镀于衬底上。
电镀方法还包括:提供具有多个互连凸点垫的半导体裸片;在互连凸点垫上方形成晶种层;使半导体裸片与银和锡合金电镀浴接触,所述银和锡合金电镀浴包括一或多种银离子源、一或多种锡离子源、一或多种具有下式的化合物:
X-S-Y
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'-S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1到20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾并且R1是被取代或未被取代的直链或支链(C2-C20)烷基,被取代或未被取代的(C6-C10)芳基;在互连凸点垫上方电镀银和锡合金互连凸点;和回焊银和锡合金互连凸点。
银和锡合金浴不含铅并且稳定。其可沉积富银或富锡的银和锡合金。富银的银/锡合金提供可以用于修饰目的并且足够硬以代替硬金作为电连接器的修整层的光亮银/锡合金。富锡的锡/银合金浴可用以沉积是共晶或接近共晶的锡/银合金。另外,使用锡/银合金浴沉积的互连凸点具有实质上均一形态并且在回焊后提供实质上无空隙互连凸点。互连凸点还实质上无结节。
具体实施方式
如在整个说明书中所使用,除非上下文明确指示,否则以下缩写具有以下含义:℃=摄氏度;g=克;mm=毫米;cm=厘米;mL=毫升;L=升;ppm=百万分之一;DI=去离子化;nm=纳米;μm=微米;wt%=重量百分比;A=安培;A/dm2和ASD=安培每平方分米;Ah=安培小时;HV=硬度值;mN=毫牛顿;cps=厘泊;rpm=转每分钟;IEC=国际电化学委员会(InternationalElectrochemicalCommission);和ASTM=美国(American)标准测试方法。关于氢参比电极提供电镀电势。关于电镀方法,术语“沉积”、“涂布”、“电镀”和“镀敷”在本说明书通篇中可互换使用。“卤化物”是指氟化物、氯化物、溴化物和碘化物。“共晶”意谓通过改变组分比例可获得的最低熔点的合金;并且相比于相同金属的其它组合具有确定和最小的熔点。除非另外指出,否则所有百分比按重量计。所有数值范围为包括性的且可以任何顺序组合,除了合乎逻辑此类数值范围被解释成总计为100%以外。
银和锡合金电镀浴实质上不含铅。“实质上不含铅”意谓浴和银和锡合金沉积物含有50ppm或小于50ppm的铅。另外,银和锡合金电镀浴优先地不含氰化物。通过在包括CN-阴离子的浴中不使用任何银或锡盐或其它化合物基本上避免氰化物。
银和锡合金电镀浴还优选是低起泡的。在金属镀敷工业中高度需要低起泡电镀浴,因为在镀敷期间电镀浴气泡愈多,在镀敷期间每单元时间浴丢失的组分愈多。在镀敷期间组分的丢失可导致产生商业上较差的银和锡合金沉积物。因此,工作人员必须密切监测组分浓度并且将丢失组分更换到其原始浓度。在镀敷期间监测组分浓度可冗长并且困难,因为一些关键组分浓度相对低,使得其难以精确测量和置换以维持最优镀敷性能。低起泡电镀浴改进整个衬底表面中的合金组成均一性和厚度均一性并且可降低在沉积物中所捕获的有机物和气体气泡,回焊后所述沉积物在沉积中引起空隙。
电镀浴包括一或多种银离子源。银离子源可由银盐提供,所述银盐诸如(但不限于)卤化银、葡萄糖酸银、柠檬酸银、乳酸银、硝酸银、硫酸银、烷磺酸银和烷醇磺酸银。当使用卤化银时,优选地卤化物是氯化物。优选地银盐是硫酸银、烷磺酸银或其混合物,并且更优选的是硫酸银、甲磺酸银或其混合物。银盐一般可商购或可通过文献中所描述的方法制备。优选地银盐易溶于水。浴中所使用的一或多种银盐的量取决于(例如)待沉积的所需合金组成和操作条件。一般来说,浴中的银盐可介于0.01g/L到100g/L、通常0.02g/L到80g/L范围内。当需要光亮的富银合金时,电镀浴中银离子与锡离子的浓度介于1到12、优选地1-6范围内。当银是合金中的较少的金属时,银盐可介于0.01g/L到20g/L、通常0.01g/L到15g/L范围内。
电镀浴包括一个或多种锡离子源。锡离子源包括(但不限于)盐,诸如卤化锡、硫酸锡、烷磺酸锡、烷醇磺酸锡,和酸。当使用卤化锡时,典型地卤化物是氯化物。锡化合物优选是硫酸锡、氯化锡或烷磺酸锡,并且更优选地硫酸锡或甲磺酸锡。锡化合物一般可商购或可通过文献中已知的方法制备。优选地锡盐易溶于水。浴中所使用的锡盐的量取决于待沉积合金的所需组成和操作条件。一般来说,锡盐可介于1g/L到100g/L、通常5g/L到80g/L范围内。当合金富锡时,锡盐通常介于30g/L到100g/L范围内。当锡是两种金属中较少的那种时,银离子与锡离子的重量比如以上所描述。
银和锡合金电镀浴包括具有下式的一或多种化合物:
X-S-Y(I)
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'-S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1到20个碳原子的直链或支链亚烷基。酚上的取代基包括(但不限于)直链或支链(C1-C5)烷基。一般来说此类化合物以0.1g/L到25g/L,通常0.5g/L到10g/L的量包括于浴中。
变量X和Y是酚基的化合物的实例是4,4'-硫代二酚和4,4'-硫双(2-甲基-6-第三丁基酚)。优选地化合物是4,4'-硫代二酚。
当X和Y不同时化合物优选地具有以下通式:
HO-R-S-R'-S-R"-OH(II)
其中R、R'和R"相同或不同并且是具有1到20个碳原子、优选的是1到10个碳原子的直链或支链亚烷基,更优选的是R和R"具有2到10个碳原子并且R'具有2个碳原子。此类化合物称为二羟基双硫化物化合物。优选地二双硫化物化合物在含有酚化合物上包括于合金浴中。
此类二羟基双硫化物化合物的实例是2,4-二硫杂-1,5-戊二醇、2,5-二硫杂-1,6-己二醇、2,6-二硫杂-1,7-庚二醇、2,7-二硫杂-1,8-辛二醇、2,8-二硫杂-1,9-壬二醇、2,9-二硫杂-1,10-癸二醇、2,11-二硫杂-1,12-十二烷二醇、5,8-二硫杂-1,12-十二烷二醇、2,15-二硫杂-1,16-十六烷二醇、2,21-二硫杂-1,22-二十二烷二醇、3,5-二硫杂-1,7-庚二醇、3,6-二硫杂-1,8-辛二醇、3,8-二硫杂-1,10-癸二醇、3,10-二硫杂-1,8-十二烷二醇、3,13-二硫杂-1,15-十五烷二醇、3,18-二硫杂-1,20-二十烷二醇、4,6-二硫杂-1,9-壬二醇、4,7-二硫杂-1,10-癸二醇、4,11-二硫杂-1,14-十四烷二醇、4,15-二硫杂-1,18-十八烷二醇、4,19-二硫杂-1,22-十二烷二醇、5,7-二硫杂-1,11-十一烷二醇、5,9-二硫杂-1,13-十三烷二醇、5,13-二硫杂-1,17-十七烷二醇、5,17-二硫杂-1,21-二十一烷二醇和1,8-二甲基-3,6-二硫杂-1,8-辛二醇。
银和锡合金浴还包括具有下式的巯基四唑化合物:
其中M是氢、NH4、钠或钾,并且R1是被取代或未被取代的直链或支链(C2-C20)烷基,被取代或未被取代(C6-C10)芳基,优选的是被取代或未被取代的直链或支链(C2-C10)烷基和被取代或未被取代(C6)芳基,更优选的是被取代或未被取代的直链或支链(C2-C10)烷基。取代基包括(但不限于)烷氧基、苯氧基、卤素、硝基、氨基、取代氨基、磺酸基、氨磺酰基、取代氨磺酰基、磺酰基苯基、磺酰基-烷基、氟磺酰基、磺酸基氨基苯基、磺酰胺-烷基、羧基、羧酸酯、脲基氨甲酰基、氨甲酰基-苯基、氨甲酰基烷基、羰基烷基和羰基苯基。优选取代基包括氨基和取代氨基。巯基四唑的实例是1-(2-二乙氨基乙基)-5-巯基-1,2,3,4-四唑、1-(3-脲基苯基)-5-巯基四唑、1-((3-N-乙基乙二酰胺)苯基)-5-巯基四唑、1-(4-乙酰氨基苯基)-5-巯基-四唑和1-(4-羟基苯基)-5-巯基四唑。一般来说,式(III)巯基四唑化合物以1g/L到200g/L、通常5g/L到150g/L的量包括于浴中。
一或多种式(I)和式(II)的化合物与一或多种式(III)巯基四唑化合物的组合在存储期间或在电镀期间对合金浴提供稳定性以及在可应用电流密度范围内的稳定的合金组成,使得硬、光亮、富银的银/锡合金可作为硬金的替代物沉积;或富锡的锡/银合金可被沉积以提供具有良好形态、减少或不含结节焊料凸点,并且在回焊后减少或没有空隙。另外,银和锡合金沉积物比银在具有更大的抗蚀性。一般来说,式(III)化合物与式(I)化合物的重量比是3-300。当式(I)的变量X和Y相同时,式(III)巯基四唑与式(I)化合物的重量比是25-300,优选的是25-150。当式(II)化合物包括于浴中时,巯基四唑与式(II)化合物的重量比是3-30,优选的是3-15。
可使用任何水溶性酸,其不以其他方式不利地影响浴。合适的酸包括(但不限于)芳基磺酸、烷磺酸(诸如甲磺酸、乙磺酸和丙磺酸)、芳基磺酸(诸如苯磺酸和甲苯基磺酸)和无机酸,诸如硫酸、氨基磺酸、盐酸、氢溴酸和氟硼酸。通常,所述酸是烷磺酸和芳基磺酸。尽管可使用酸的混合物,但典型地使用单酸。酸一般可商购或可通过文献中已知的方法制备。
在取决于所需合金组成和操作条件时,在电解质组合物中酸的量可在0.01到500g/L或诸如10到400g/L或诸如100到300g/L范围内。当银离子和锡离子来自金属卤化物时,可需要使用相对应的酸。举例而言,当使用氯化锡或氯化银中的一或多者时,可需要使用盐酸作为酸组分。还可使用酸的混合物。
任选地,一或多种抑制剂可包括于浴中。通常其以0.5到15g/L或诸如1到10g/L的量使用。此类抑制剂包括(但不限于)烷醇胺、聚乙二亚胺和烷氧基化芳香族醇。合适的烷醇胺包括(但不限于)被取代或未被取代的甲氧基化胺、乙氧基化胺和丙氧基化胺,例如四(2-羟丙基)乙二胺、2-{[2-(二甲基氨基)乙基]-甲基氨基}乙醇、N,N'-双(2-羟基乙基)-乙二胺、2-(2-氨基乙基胺)-乙醇和其组合。
合适的聚乙二亚胺包括(但不限于)分子量是800-750,000的被取代或未被取代的直链或分支链聚乙二亚胺或其混合物。合适的取代基包括例如羧基烷基,例如羧基甲基、羧基乙基。
适用的烷氧基化芳香族醇包括(但不限于)乙氧基化双酚、乙氧基化β萘酚和乙氧基化壬基酚。
任选地,一或多种还原剂可添加至浴中以辅助锡保持可溶性、二价状态。合适的还原剂包含(但不限于)氢醌、氢醌磺酸、钾盐和羟基化芳香族化合物,诸如间苯二酚和儿茶酚。当用于组合物中时,此类还原剂以0.01到20g/L或诸如0.1到5g/L的量存在。
对于需要良好湿润能力的应用,一或多种表面活性剂可包括于浴中。合适的表面活性剂为熟习此项技术者已知,并且包括得到具有良好焊接性、良好无光泽或有光泽的修整面层沉积物(其中所需、令人满意的晶粒细化)的任何表面活性剂,并且在酸性电镀浴中稳定。优选地,使用起泡表面活性剂。可使用常规量。
任选地,可包括一或多种光亮剂。此类光亮剂为熟习此项技术者所熟知。合适的光亮剂包含(但不限于)芳香族醛,诸如氯苯甲醛或其衍生物,诸如亚苄基丙酮。合适的光亮剂的量为熟习此项技术者已知。
其它任选的化合物可添加至浴中以提供进一步的晶粒细化。此类化合物包含(但不限于):诸如聚乙氧基化胺吉夫胺(JEFFAMINE)T-403或曲拉通(Triton)RW的烷氧基化物或诸如曲拉通QS-15的硫酸化烷基乙氧基化物和明胶或明胶衍生物。还可包括烷氧基化胺氧化物。尽管已知各种烷氧基化胺氧化物表面活性剂,但优选地,使用低起泡胺氧化物。此类优选烷氧基化胺氧化物表面活性剂使用具有#2轴的布洛克菲尔德(Brookfield)LVT黏度计测量的粘度小于5000cps。通常在环境温度下测定此粘度。可使用常规量的此类晶粒细化剂。通常其以0.5g/L到20g/L的量包括于浴中。
黄酮化合物还可包括于浴中作为晶粒细化剂。此类黄酮化合物包含(但不限于)五羟基黄酮、桑色素、白杨素、槲皮素、非瑟酮、杨梅素、芸香苷和栎素。黄酮化合物可以1到200mg/L、通常10到100mg/L、更通常25到85mg/L的量存在。
通常通过向容器中添加一或多种酸、一或多种式(I)、式(II)的化合物和一或多种式(III)化合物,随后添加一或多种溶液可溶性的银和锡化合物、一或多种任选添加剂和平衡水制备电镀浴。优选地,在溶液可溶性的银和锡化合物之前,将式(I)、式(II)和式(III)的化合物添加至容器中。制备水性浴时,可去除不当材料,诸如通过过滤并且接着通常添加水以调节浴的最终体积。可通过诸如搅动、抽吸或再循环的任何已知方法搅拌浴以提高镀敷速度。浴是酸性的,pH值小于7,通常小于1,更通常小于或等于1到2。
浴适用于多种镀敷法,其中银和锡合金是所需的并且低起泡的。镀敷方法包含(但不限于)水平或垂直晶片镀敷、机筒镀敷、机架镀敷和高速镀敷,诸如卷轴到卷轴和喷射镀敷。银和锡合金可通过使衬底与浴接触并且传送电流通过浴以将银和锡合金沉积于衬底上的步骤沉积于衬底上。可被镀敷的衬底包含(但不限于)铜、铜合金、镍、镍合金、含有黄铜的材料、电子组件(诸如电连接器)和半导体晶片(诸如硅晶片)。浴可用于诸如电连接器、珠宝、装饰品的电镀电子组件,和互连凸点镀敷应用。衬底可以此项技术中已知的任何方式与浴接触。
用以镀敷银和锡合金的电流密度取决于特殊的镀敷方法。一般来说,电流密度是0.05A/dm2或大于0.05A/dm2或诸如1到25A/dm2 。通常较低的电流密度介于0.05A/dm2到10A/dm2范围内。诸如在具有高搅拌的喷射镀敷中的高电流密度超过10A/dm2并且可高达25A/dm2。
可在室温到55℃或诸如室温到40℃或诸如室温到30℃的温度下电镀银和锡合金。通常,银/锡电镀自室温到55℃进行并且锡/银自室温到40℃进行。
浴可用于沉积各种组成的银和锡合金。当合金是光亮富银的银/锡合金时,银含量可介于大于50%到95%范围内并且其余部分是合金锡,通常银含量介于60%到90%范围内。富锡合金含有大于50%的锡到99%的锡并且其余部分是银,通常富锡合金包括80%到99%锡并且其余部分是银。此类重量以通过原子吸收光谱分析(atomicadsorptionspectroscopy,“AAS”)、X射线荧光(X-rayfluorescence,“XRF”)、感应耦合等离子体(inductivelycoupledplasma,“ICP”)或差示扫描热量测定(differentialscanningcalorimetry,“DSC”)获得的测量结果计。对于多种应用,可使用合金的共晶组合物。此类锡合金实质上不含铅并且是氰化物。
一般来说,富银合金比富锡合金提供更硬的沉积。此类富银合金用以(诸如)在用于珠宝、其它装饰品的修饰应用中代替硬金修整面层并且用于需要具有耐磨性和抗蚀性的连接器上的硬修整面层。通常此类修整面层的厚度介于0.4μm到5μm范围内。
富锡的锡/银合金通常用于晶片级包装的互连凸点形成。此涉及提供具有多个互连凸点垫的半导体裸片,在互连凸点垫上方形成晶种层,通过使半导体裸片与锡/银合金浴接触将锡/银合金互连凸点层沉积于互连凸点垫上方,并且传送电流通过浴以将锡/银合金互连凸点沉积于衬底上并且将互连凸点回焊。
一般来说,装置包括形成多个导电互连凸点垫的半导体衬底。半导体衬底可以是单晶体硅晶片、蓝宝石上硅(silicon-on-sapphire,SOS)衬底或绝缘体上硅(silicon-on-insulator,SOI)衬底。导电互连凸点垫可以是通常通过诸如溅镀的物理气相沉积(physicalvapordeposition,PVD)形成的金属、复合金属或金属合金的一或多种层。典型的导电互连凸点垫材料包含(但不限于)氮化铝、氮化铜、氮化钛和其合金。
钝化层形成于互连凸点垫上方并且延伸至互连凸点垫中的开口在其中通过蚀刻方法、通常通过干式蚀刻形成。钝化层通常是绝缘材料,例如氮化硅、氮氧化硅或氧化硅,诸如磷硅酸玻璃(phosphosilicateglass,PSG)。此类材料可通过化学气相沉积(chemicalvapordeposition,CVD)方法(诸如等离子体增强CVD(plasmaenhancedCVD,PECVD))沉积。
通常由多个金属或金属合金层形成的下方凸点金属化(bumpmetallization,UBM)结构沉积于装置上方。UBM充当用于待形成的互连凸点的胶层和电接触基质(晶种层)。形成UBM结构的层可通过诸如溅镀或蒸发的PVD或CVD方法沉积。在不限制的情况下,UBM结构可以是(例如)复合结构,依序包括底部铬层、铜层和上部锡层。
将光刻胶层施用到装置上,随后是标准光刻曝光和显影技术以形成镀敷掩模。镀敷掩模界定I/O垫和UBM上方的镀敷通孔的大小和位置。在不限制的情况下,镀敷方法一般采用厚度通常是25到70μm的相对薄的光刻胶层,而在通孔镀敷方法中一般采用厚度通常是70到120μm的相对厚的光刻胶层。光刻胶材料可商购并且在此项技术中熟知。
互连凸点材料使用上文所描述的富锡的锡/银合金电镀浴通过电镀方法沉积于装置上。可需要使用提供共晶浓度的锡/银合金浴。凸点材料在通过镀敷通孔界定的区域中电镀。为此目的,例如喷镀敷系统的水平或垂直晶片镀敷系统通常与直流电(directcurrent,DC)或脉冲镀敷技术一起使用。在镀敷方法中互连凸点材料完全填充延伸在镀敷掩模的一部分顶部表面上方和上面的通孔。此确保足够体积的互连凸点材料沉积以在回焊后达到所需球大小。在通孔镀敷方法中,光刻胶厚度足够厚,使得适当体积的互连凸点材料含于镀敷掩模通孔内。在镀敷互连凸点材料前,可在镀敷通孔中电镀铜层或镍层。在回焊后,此层可充当互连凸点的可湿润基座。
沉积互连凸点材料后,使用适当溶剂剥离镀敷掩模。此类溶剂在此项技术中熟知。接着使用已知技术选择性蚀刻UBM结构,去除来自互连凸点周围和互连凸点之间的场区的所有金属。
接着任选地熔化晶片并且在回焊炉中加热到在其下互连凸点材料熔融并且流成截短的实质上球形的温度。加热技术在此项技术中已知,并且包括(例如)红外、传导和对流技术和其组合。回流互连凸点一般与UBM结构的边缘共同延伸。可在惰性气体气氛或空气中进行热处理步骤,其中特殊工艺温度和时间取决于互连凸点材料的特殊组成。
银和锡合金浴不含铅并且稳定。优选地,其不含氰化物化合物。相比于通常通过2个月闲置时间分解的常规银和锡氰化物浴,银和锡合金通常在闲置时间期间可保持稳定,持续至少8月。其可沉积富银或富锡的银和锡合金。富银的银/锡合金提供可以用于修饰目的并且足够硬以代替硬金作为电连接器的修整层的光亮银/锡合金。富锡的锡/银合金浴可用以沉积是共晶或接近共晶的锡/银合金。另外,使用锡/银合金浴沉积的互连凸点具有实质上均一形态并且在回焊后提供实质上无空隙互连凸点。互连凸点还实质上无结节。
以下实例意欲进一步说明本发明,但不意欲限制本发明范畴。
实例1
具有下表中的两种配方制备多个富银的银/锡合金电镀浴。
表1
接着进行配方I的电解。进行测试以展示浴的电化学稳定性。称量黄铜面板(7.5cm×10cm)并且接着固定在镀敷浴中。将2ASD的低电流密度施加至面板15分钟。自镀敷浴去除面板并且称量。测定在15分钟期间所镀敷的银/锡的量。还以安培小时/升浴记录电量。结果指示在2ASD下在100Ah/L浴寿命内,每安培小时/升沉积于黄铜面板上的银/锡的量实质上相同,并且浴在电镀期间稳定。在电解期间电流效率稳定并且接近100%。在电解期间未观测到浴的分解;然而,过滤出锡(IV)沉淀以保持浴的浑浊度和性能恒定。镀敷面板具有光亮的银/锡沉积物。
在2安培总电流下,在0Ah/L、30Ah/L、70Ah/L和100Ah/L的浴寿命下对配方I进行赫尔槽测试(Hullcelltest),以判定可应用的电流密度范围是否随着浴寿命保持稳定,在电流密度范围内于黄铜面板(7.5cm×10cm)上进行镀敷3分钟。电流密度介于0.05ASD到10ASD范围内。在所有情况下获得光亮的银/锡沉积物。
实例2
表1中的两种配方用以将银/锡合金电镀于黄铜面板、铜面板、铜/铍合金面板、铜/镍合金面板、铜/锡合金面板、镍涂布的黄铜面板和镍涂布的铜面板上。每一面板是7.5cm×10cm。面板厚度是0.25mm。镍涂布的黄铜面板和镍涂布的铜面板含有小于100nm的银冲击层以提升银/锡层对镍的粘附性。使用含有2g/L银离子、15g/L3,6-二硫杂-1,8-辛二醇、67g/L甲磺酸的银冲击浴将银冲击层电镀于面板上。进行电镀,维持0.5ASD到1ASD,持续10秒到30秒。
将面板放置于含有配方I或配方II的镀敷浴中。浴的温度是50℃并且阳极是氧化铱不溶性阳极。将每一电极连接到整流器上。在2ASD下进行电镀。电镀面板后,检测银/锡沉积物的物理外观。所有银/锡沉积物均具有光亮有光泽的沉积物。
实例3
将直径是12mm并且高度是8mm的黄铜圆柱体安装于电发动机的轴上并且浸没于含有表1中的配方I的镀敷浴中。将发动机设定成1000rpm的旋转速度。将不溶性氧化铱电极用作阳极。将电极连接到整流器上。通过旋转阴极搅拌电镀浴并且将浴温度维持在50℃。在0.5、1、2、4、6、8、10、12、14、16、18和20ASD下进行电镀。当自一电流密度移动到另一电流密度时更换圆柱体,并且调节镀敷时间以保持相同的膜厚度。在0.5ASD到16ASD的电流密度范围内,所有的银/锡合金沉积物具有光亮有光泽的外观。在18ASD和20ASD下观测较少的燃烧边缘。
使用来自海尔姆特菲希尔(HelmutFischer)AG的菲希尔X射线光谱仪(FISCHERSCOPEX-Ray)型号XDV-SD,通过X射线荧光(XRF)分析测定每一沉积物的银和锡含量。XRF分析展示银/锡合金层含有75重量%到80重量%的银和20重量%到25重量%的锡。测定银/锡合金的平均合金含量是78+2%的银和22+2%的锡。在可应用的电流密度范围内银和锡含量未显著变化。
实例4
电镀黄铜面板(5cm×2.5cm),其中硬金层来自含有750mL/LRONOVALTMCM-97组成配方、17.7g/L(68.2%)氰化金钾、20mL/LRONOVALTMCM钴浓缩物(购自陶氏电子材料(DowElectronicMaterials))和足够的去离子水以使浴达到所需体积的金/钴合金电镀浴,来自或上文表1中的配方I的银/锡合金电镀浴。将黄铜面板放置于或具有电镀浴的电镀槽中。不溶性镀铂钛电极用作阳极。在50℃下进行银/锡电镀并且在60℃下进行金/钴电镀。硬金浴的电流密度是4ASD并且银/锡浴的电流密度是2ASD。进行电镀直至含有0.2重量%钴的硬金或具有79重量%银和21重量%锡的银/锡合金的5μm层沉积于黄铜上。
针对每一镀敷黄铜面板,在室温下使用具有钻石尖端的CSM纳米压痕测试仪测试纳米维氏硬度(VickersHardness)。压头尖端的深度穿透率小于或等于黄铜面板上的硬金层或银/锡合金层厚度的10%。这确保下伏黄铜不影响硬度结果。测定硬金的平均硬度是175HV并且测定银/锡合金层的硬度是240HV。银/锡层比硬金层更硬。
接着在常规对流炉中在150℃下使电镀黄铜面板退火一个小时。再次测试硬金层和银/锡合金层的硬度。硬金层的硬度具有200HV的平均硬度值并且银/锡合金具有225HV的平均硬度值。尽管退火过程软化银/锡合金层,但银/锡合金层仍具有比硬金更硬的表面。银/锡合金指示超过常规硬金的改进的硬度。
实例5
在富银的银/锡合金或金/钴硬金下根据上文实例4的方法电镀黄铜面板(5cm×10cm和0.25mm厚)。进行电镀以在面板上形成3μm层。使用来自新英仪器有限公司(SHEENInstrumentsLtd.)的弯曲测试仪根据ASTM标准B489-85测试每一镀敷黄铜面板的延展性。对于硬金,测量的延展性介于4-5%范围内,并且银/锡合金的延展性大于7.8%。在银/锡合金样品的伸长期间不存在任何开裂的迹象。4%后硬金样品中的一些观测到开裂,并且其余部分在5%后开裂。银/锡层具有超过硬金样品的改进的延展性。
实例6
镀敷两个5cm×2.5cm黄铜面板(0.25mm厚),其中银来自SILVERONTMGT-101银电镀浴(购自陶氏电子材料,马尔堡(Marlborough),MA)或上文表1中的配方I的银/锡合金浴。在电镀槽中在50℃下电镀每一面板。用于银/锡浴的阳极是镀铂钛不溶性电极并且可溶性银阳极用于银浴。电流密度是0.5ASD。进行镀敷直至银或银/锡层(3μm厚)沉积于面板上。
接着将每一面板浸没于2重量%硫化钾(K2S)溶液中10分钟以测试每一涂层的抗蚀性。银涂层具有指示形成Ag2S和严重锈污的黑蓝色外观。相比于实质上纯的银涂层,银/锡涂层具有指示在硫存在下聚硫化物与银/锡涂层极其缓慢地反应的浅褐色。银/锡涂层提供比银涂层更抗蚀性的涂层。
实例7
使用配方I将富银的银/锡合金层电镀于黄铜面板(1cm×3cm)上。在电镀池中在1ASD下并且在50℃的温度下进行电镀。阳极是镀铂钛不溶性电极。进行电镀直至3μm的银/锡合金层沉积于面板上。在光亮锡下使用SOLDERONTMBT-280光亮锡电镀浴(购自陶氏电子材料)镀敷第二黄铜面板(1cm×3cm)。在30℃下在1ASD下进行电镀直至3μm的光亮锡层沉积于面板上。
接着根据IEC60068-2-69(“通过湿润平衡方法对表面安装装置(surfacemountingdevices,SMD)的电子组件的焊接性测试”)测试银/锡合金焊接性能并且与常规光亮锡的焊接性能相比。在焊接前,首先将每一样品浸没于由量电(Metronelec)(法国(France))供应的非活化焊剂C25R中以去除灰尘、油状物和氧化物。接着将样品安装于量电/梅纳斯科(MENESCO)ST50焊接性设备(购自量电)中,所述设备将其4mm驱动成速度是20毫米/秒的焊料。焊料是含有95.5重量%锡、3.8重量%银和0.7重量%铜的无铅焊料。在245℃下测试时间是10秒。当样品引入焊料中时,设备所要求的编程软件提供测量力的方法,以及当焊料使样品表面湿润时的力。所有测量结果制成为时间函数。通过软件程序自如所计算的力测量结果测定过零时间、5mN下的时间、5秒后的平均力和5秒时的角度的关键参数。测试重复五次进行。5次测试的平均结果展示于下文表2中。
表2
所得资料展示富银的银/锡合金的焊接性能类似于光亮锡的焊接性能。银/锡合金和光亮锡的过零时间以及5mN下的时间、5秒后的平均力和5秒下的角度在常规I级分类内,其中小于1.2秒的过零时间在工业中认为极其良好。II级认为良好并且具有小于1.5秒的过零,III级认为中等,其中过零时间小于2秒,并且IV级认为较差,无过零时间。银/锡合金的良好焊接性能指示其可以是可接受的硬金的替代物来作为电连接器上的涂层。
实例8
如下文表3中所展示制备三个富锡的锡/银合金电镀浴。
表3
1非离子表面活性剂,13环氧乙烷单元
三个锡/银电镀浴的pH值小于1。每一锡/银电镀浴用以在通孔中镀敷焊料凸点。将具有75μm(直径)×75μm(深度)光刻胶图案化通孔的4cm×4cm晶片片段和铜晶种层浸没于电镀槽中的镀敷浴中,并且用锡/银凸点镀敷。在每一浴中在8ASD下镀敷样品。每一浴的温度在30℃下。在每一情况下不溶性氧化铱电极用作阳极。进行电镀直至60μm的凸点被镀敷。
用日立(Hitachi)S2460TM扫描电子显微镜检验所得锡/银层的形态。沉积物均一、光滑、紧密并且无结节。
通过常规AAS方法测量用于样品的所得锡银层的银浓度。通过瓦里安公司(Varian,Inc.)(帕罗奥多,加利福尼亚)制造用于测量的AAS设备。方法包括以下步骤:1)去除光刻胶;2)测量每一锡银凸点的重量,即平均10mg;3)接着将每一锡银凸点溶解于具有10到20mL的30-40%硝酸(如果需要添加更多的硝酸以溶解锡/银)的分离容器中;4)接着将来自每一烧杯的经溶解锡/银转移到分离100mL烧瓶中并且与去离子水组成体积并且混合;和5)使用公式化:%Ag=[10×AASAg(ppm)]/重量(mg)测量每一溶液中银的量并且测定沉积物中银的浓度。所镀敷的合金中每一金属的量在下文表4中。
表4
浴1 | 浴2 | 浴3 |
Sn 99.5重量%/Ag 0.5重量% | Sn 98.8重量%/Ag 1.2重量% | Sn 98.2重量%/Ag 1.8重量% |
所有浴提供具有良好形态并且无可观测到的结节的富锡的锡/银沉积物。
Claims (7)
1.一种电镀浴,其包含一或多种银离子源、一或多种锡离子源、一或多种具有下式的化合物:
X-S-Y(I)
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1至20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾,并且R1是被取代或未被取代的直链或支链(C2-C20)烷基或被取代或未被取代的(C6-C10)芳基。
2.根据权利要求1所述的电镀浴,其中银离子与锡离子的比率介于1-12范围内。
3.根据权利要求2所述的电镀浴,其中银离子与锡离子的比率介于1-6范围内。
4.根据权利要求1所述的电镀浴,其中X和Y不同并且是HO-R-或-R'-S-R"-OH。
5.根据权利要求1所述的电镀浴,其中式(III)化合物与式(I)化合物的比率是3-300。
6.一种电镀方法,其包含:
a)使衬底与电镀浴接触,所述电镀浴包含一或多种银离子源、一或多种锡离子源、一或多种具有下式的化合物:
X-S-Y
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1至20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾并且R1是被取代或未被取代的直链或支链(C2-C20)烷基或被取代或未被取代的(C6-C10)芳基;和
b)于所述衬底上电镀银和锡合金。
7.一种电镀方法,其包含:
a)提供具有多个互连凸点垫的半导体裸片;
b)在所述互连凸点垫上方形成晶种层;
c)使所述半导体裸片与电镀浴接触,所述电镀浴包含一或多种银离子源、一或多种锡离子源、一或多种具有下式的化合物:
X-S-Y
其中X和Y可以是被取代或未被取代的酚基、HO-R-或-R'-S-R"-OH,其条件是当X和Y相同时其是被取代或未被取代的酚基,否则X和Y不同,并且其中R、R'和R"相同或不同并且是具有1至20个碳原子的直链或支链亚烷基;和一或多种具有下式的化合物:
其中M是氢、NH4、钠或钾,并且R1是被取代或未被取代的直链或支链(C2-C20)烷基或被取代或未被取代的(C6-C10)芳基;
d)在所述互连凸点垫上方电镀银和锡合金互连凸点;和
e)回焊所述银和锡合金互连凸点。
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