CN104854260B - 在贵金属电极上制造可线接合和可焊接表面的方法 - Google Patents

在贵金属电极上制造可线接合和可焊接表面的方法 Download PDF

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CN104854260B
CN104854260B CN201380063125.2A CN201380063125A CN104854260B CN 104854260 B CN104854260 B CN 104854260B CN 201380063125 A CN201380063125 A CN 201380063125A CN 104854260 B CN104854260 B CN 104854260B
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安德烈亚斯·沃尔特
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Abstract

本发明涉及一种在贵金属电极上制造可线接合和可焊接表面的方法。所述贵金属电极是通过在60℃到90℃下无电电镀来沉积钯或钯合金层的晶种层而被活化。接着,将中间层沉积到所述晶种层上,然后将可线接合和/或可焊接表面处理层沉积到所述中间层上。这一方法尤其适用于生产光电子装置,如发光二极管LED。

Description

在贵金属电极上制造可线接合和可焊接表面的方法
技术领域
本发明涉及包含贵金属电极的光电子装置(如发光二极管)的制造和位于其上的可线接合和可焊接表面加工的形成。
背景技术
如发光二极管(LED)的光电子装置含有由当施加电流时发光的半导体物质所构成的区域。目前的LED是基于化合物半导体,尤其是所谓的III-V化合物半导体,如Ga-N、Ga-P以及Ga-As或如Ga-N/In-Ga-N的多层组件,其沉积在如蓝宝石晶片和硅晶片的衬底材料上。
所述化合物半导体需要通过电极电连接到电源上。由于电极与化合物半导体层之间不合要求的扩散过程,常规电极材料(如铝或铜)不可用于LED中。取而代之地,由如铂或金的贵金属制成的电极用作电极材料。
电极是通过将如铜线的导体焊接或接合到电极上而连接到电源上。因此,需要将可焊接和/或可线接合的表面附接到贵金属电极上,从而获得导体与电极之间的充分电接触和机械可靠性。此外,在电极与导体之间形成的连接点必须可靠。
本发明的目的
本发明的一个目的在于提供一种用于在制造(光)电子装置时在由例如铂或金制成的贵金属电极上形成可线接合表面和/或可焊接表面的方法。
发明内容
这一目的是通过一种在贵金属电极上制造可线接合和/或可焊接表面的方法解决,其按照如下顺序包含以下步骤:
i.提供其上附接有至少一个贵金属电极的衬底,
ii.清洁所述至少一个贵金属电极,
iii.通过无电电镀由含水电镀浴在所述至少一个贵金属电极上沉积选自钯和钯合金的晶种层,其中所述电镀浴在所述晶种层沉积期间具有在60℃到90℃范围内的温度,
iv.通过无电电镀在所述晶种层上沉积选自包含镍合金和钴合金的群组的中间层,
v.通过无电电镀在所述中间层上沉积至少一个表面处理层,其中所述至少一个表面处理层是选自由钯、钯合金、金以及金合金组成的群组。
根据本发明的方法提供用于由贵金属制成的电极的表面加工,其提供充分的可焊接性和/或可线接合性。此外,沉积在电极与表面处理层之间的中间层为整个组件提供高机械耐久性。因此,在向整个组件施加机械力的焊接和/或线接合操作期间保护LED的底部化合物半导体层和衬底材料。
具体实施方式
如LED的(光)电子装置中的化合物半导体层需要通过电导体(如与附接到该等化合物半导体层的电极接触的导线)与电源电连接。电导体优选地通过焊接和/或线接合与电极接触。电极和化合物半导体层附接到优选地选自包含蓝宝石晶片、硅晶片以及氧化铟锡晶片的群组的衬底。
因为如铝或铜的常规电极材料在与通常用作LED和相关装置中的电致发光材料的化合物半导体材料接触时倾向于不合要求的扩散过程,所以附接到化合物半导体层的电极需要由贵金属制成。
合适的电极包含一或多种优选地选自包含铂、金以及钯的群组的贵金属。
连续的焊接和/或线接合需要沉积在贵金属电极上的表面加工,通过所述方法,电极与电源电接触。
优选地,表面加工是仅通过无电电镀和/或浸没型电镀沉积,所述方法在原理上允许将金属和金属合金层选择性地沉积到充分活化的金属表面上。因此,在所述情形下,表面加工将不会沉积在未通过例如晶种层充分活化的衬底表面的其它区域上。
在制造印刷电路板等中已知的常规表面加工的沉积(其中电极材料为铜并且较不常见为铝)不适用于由优选地选自包含铂、金以及钯的群组的贵金属制成的电极。
在铝作为电极材料的情形下,锌酸盐预处理允许在其上无电沉积选自镍合金和钴合金的中间层。
在铜作为电极材料的情形下,浸没电镀的贵金属层(如浸没电镀的钯层)允许在其上无电沉积选自镍合金和钴合金的中间层。
浸没电镀贵金属层(如浸没电镀的钯层)不充分地活化如铂或金电极的贵金属电极的表面(比较实例2和3)。
优选地,在沉积表面处理层之前清洁电极表面以去除有机残余物等。优选地,使用包含酸并且任选地进一步包含表面活性剂和/或氧化剂的蚀刻清洁剂组合物以清洁贵金属电极的表面。尤其合适的蚀刻清洁剂组合物包含水、硫酸以及过氧化氢。
任选地,在蚀刻清洁后,在如硫酸的酸水溶液中冲洗。
在本发明的另一实施例中,应用等离子处理以清洁贵金属电极的表面。
可以应用蚀刻清洁与等离子处理的组合以清洁贵金属电极的表面。
任选地,除蚀刻清洁和/或等离子处理以外,应用用于从贵金属电极表面去除不合要求的颗粒的处理。一种这种类型的尤其合适的处理是标准清洁1(SC1)处理,其包含用包含氢氧化铝和过氧化氢的水溶液处理贵金属电极表面的步骤。这种类型的组合物和处理条件在所属领域已知。
通过例如将包含至少一个电极的衬底浸于清洁剂中或将清洁剂喷洒到电极上来使电极与清洁剂接触。在本发明的一个实施例中,通过施加超声波来支持清洁处理。
接着,通过使电极与包含钯离子源、还原剂以及用于钯离子的络合剂的无电(自动催化)钯电镀浴接触来活化电极的清洁表面。从而将钯或钯合金薄层(取决于所用还原剂的类型)沉积在清洁电极上并且其充当连续电镀操作的晶种层。
本申请人发现,用于在所述电极的表面上沉积钯或钯合金的无电电镀浴应保持在60℃到90℃范围内的温度下以在所述电极上沉积钯或钯合金。更优选地,在将钯或钯合金沉积到所述电极上期间,无电电镀浴维持在60℃到80℃之间的温度范围内。最优选地,温度在沉积期间维持在60℃到70℃范围内。所述钯或钯合金层在本文中称为晶种层。
需要60℃的最低电镀浴温度以获得用于连续沉积中间层的电极的充分活化,即通过在其上沉积钯或钯合金晶种层(比较实例4)。因为用于晶种层的所述沉积的无电电镀浴优选是含水电镀浴,因此最高温度主要由于水的沸点(在大气压下为100℃)而受限。出于根据本发明的方法的工业应用的实际原因,在晶种层沉积期间,无电电镀浴的最高温度优选是90℃、更优选是80℃并且最优选是70℃以限制在使用期间从加热的无电电镀浴蒸发的水量。
用于将晶种层沉积到贵金属电极的清洁表面上的无电电镀浴中的钯离子源优选地选自水可溶钯化合物,如硫酸钯、氯化钯以及乙酸钯。钯离子的替代来源为钯盐与一或多种含氮络合剂(如阳离子钯-乙二胺络合物)和例如硫酸盐或氯化物反离子的反应产物。
用于将晶种层沉积到贵金属电极上的无电电镀浴中的钯离子浓度优选地在0.5mmol/l到500mmol/l,更优选地1mmol/l到100mmol/l范围内。
用于沉积钯的还原剂优选地选自包含甲酸、其衍生物或盐的群组。合适的甲酸衍生物为例如甲酸酯,如甲酸甲酯、甲酸乙酯以及甲酸丙酯。其它合适的甲酸衍生物为例如经取代或未经取代的酰胺,如甲酰胺和N,N-二甲基甲酰胺。甲酸盐的合适的反离子例如选自锂、钠、钾以及铵。
纯钯层是由所述电镀浴沉积。
用于沉积钯合金的还原剂优选地选自由如次磷酸钠的次磷酸盐化合物(Pd-P合金的沉积)和如二烷基胺硼烷的硼烷化合物(Pd-B合金的沉积)组成的群组。
最优选地,用于沉积钯合金的还原剂为次磷酸钠。
无电电镀浴中的还原剂的浓度优选地在10mmol/l到1000mmol/l范围内。
在用于将晶种层沉积到贵金属电极上的无电电镀浴中的钯离子的至少一种络合剂优选为含氮络合剂。更优选地,钯离子的络合剂是选自由伯胺、仲胺以及叔胺组成的群组。合适的胺为例如乙二胺、1,3-二氨基-丙烷、1,2-双(3-氨基-丙基-氨基)-乙烷、2-二乙基-氨基-乙基-胺、二亚乙基三胺、二亚乙基三胺-五乙酸、硝基-乙酸、N-(2-羟基-乙基)-乙二胺、乙二胺-N,N-二乙酸、2-(二甲基-氨基)-乙基-胺、1,2-二氨基-丙基-胺、1,3-二氨基-丙基-胺、3-(甲基-氨基)-丙基-胺、3-(二甲基-氨基)-丙基-胺、3-(二乙基-氨基)-丙基-胺、双-(3-氨基-丙基)-胺、1,2-双-(3-氨基-丙基)-烷基-胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺以及其混合物。
无电电镀浴中的至少一种络合剂与钯离子的摩尔比在2:1到50:1范围内。
无电钯或钯合金电镀浴的pH值优选地在4到7范围内,因为所述电镀浴在低于4的pH值下倾向于不稳定。更优选地,电镀浴的pH值在5到6范围内。
在本发明的一个实施例中,无电电镀浴进一步包含优选为0.001mol/l到0.1mol/l,更优选为0.001mol/l到0.01mol/l量的至少一种其它稳定剂。
所述其它稳定剂可在升高的电镀浴温度下延长用于将晶种层沉积到贵金属电极上的无电钯或钯合金电镀浴的寿命。
所述其它稳定剂优选是磺酰亚胺。一种优选的磺酰亚胺为糖精和其衍生物。最优选的磺酰亚胺为糖精。
无电钯或钯合金电镀浴中的其它任选添加剂是选自包含聚苯基硫化物、嘧啶、多元醇以及无机络合剂(如硫氰化物)的群组。优选的嘧啶为烟酰胺、嘧啶-3-磺酸、烟酸、2-羟基吡啶以及烟碱。优选的多元醇为聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物以及其衍生物。
接着,通过无电电镀将中间层沉积到晶种层上。所述中间层优选地选自由镍合金和钴合金组成的群组。合适的镍合金为二元镍合金(如Ni-P合金和Ni-B合金)和三元镍合金(如Ni-Mo-P合金和Ni-W-P合金)。合适的钴合金为例如二元钴合金(如Co-P合金和Co-B合金)和三元钴合金(如Co-Mo-P和Co-W-P合金)。
用于将中间层沉积到晶种层上的合适的无电电镀浴包含镍或钴离子源、任选的第二金属离子源、还原剂(如在沉积含磷合金的情形下的次磷酸钠或在沉积含硼合金的情形下的硼烷化合物,如烷基胺硼烷)。
包含镍离子和次磷酸根离子源的无电电镀浴适用于沉积Ni-P合金。同样地,钴离子和次磷酸根离子源导致Co-P合金的沉积。在硼烷化合物代替次磷酸根离子用作还原剂的情形下,分别获得Ni-B或Co-B合金。向电镀浴中添加第二金属离子源允许沉积相应的三元合金。
合适的无电电镀浴进一步包含至少一种络合剂,如多羧酸和/或羟基羧酸,以及任选的至少一种稳定剂,如锑离子、铅离子、铋离子和/或含硫有机化合物,如硫脲或其衍生物。
所属领域已知用于将中间层沉积到晶种层上的适合的无电电镀浴组合物和电镀参数,如沉积期间的电镀浴温度。
选自镍合金和钴合金的中间层比由贵金属制成的电极层和电镀在所述中间层上的表面处理层显著地更硬。因此,中间层在焊接和/或线接合操作期间为LED装置的敏感部件(如衬底材料和发光二极管本身)提供机械稳定性。在线接合到中间层顶部上的表面处理层期间,以相当大的力挤压导线,由于充当中间层的镍合金或钴合金的固有硬度,所述中间层分配/获得大部分的所述力。
所述中间层的厚度优选地在0.1μm到5μm,更优选地0.15μm到3μm范围内。
接着,将可焊接和/或可线接合层(本文中表示为“表面处理层”)沉积到中间层上。
取决于此后用于将电极与电源连接的技术和/或所述连接的稳定性/可靠性要求,表面处理层可由沉积到中间层上的单一层或两个各别层组成。
单一表面处理层为通过浸没型电镀沉积到中间层上的金层。作为表面加工的所述金层可用于将例如金线焊接和接合到电极上。金层的厚度优选地在0.01μm到0.5μm,更优选地0.05μm到0.3μm的范围内。
另一类型的适合单一表面处理层是通过无电电镀沉积到中间层上的钯或钯合金层。与用于活化由贵金属制成的电极的电镀浴组合物相同类型的电镀浴组合物可以用于这一任务。因此,如Pd-P和Pd-B合金的钯或钯合金是由包含钯离子源、还原剂以及至少一种钯离子络合剂的电镀浴沉积。
最优选地,电镀浴为用于沉积钯的含水电镀浴,其包含钯离子源(如硫酸钯)、选自甲酸、其盐和衍生物的还原剂以及至少一种含氮络合剂。
作为单一表面处理层的钯或钯合金尤其适用于将由铜、钯或经钯涂布的铜线制成的导线接合到电极上。
充当单一表面处理层的钯或钯合金的厚度优选地在0.02μm到1μm,更优选地0.2μm到0.5μm的范围内。
根据本发明的合适的多层表面加工是由通过无电电镀沉积到中间层上的钯或钯合金层和通过浸没型电镀或无电电镀沉积到所述钯或钯合金层上的金层或金合金层组成。
钯或钯合金层可由上述无电电镀浴组合物沉积。
沉积在中间层与金层之间的钯或钯合金层的厚度优选地在0.1μm到0.5μm,更优选地0.15μm到0.3μm范围内。
沉积到所述钯或钯合金层上的金层厚度优选地在0.01μm到0.5μm,更优选地0.05μm到0.3μm的范围内。
为这一目的,可使用从现有技术已知的浸没型或无电金电镀电解质。所述电镀浴组合物也适用于将金直接沉积到中间层上。
用于将金沉积到中间层或钯或钯合金层上的适合的浸没型电镀浴包含金离子源和至少一种络合剂,如亚硫酸根离子。在所属领域中已知电镀参数(如电镀浴在使用期间的温度和电镀时间)并且其可以调整到常规实验中要实现的所需电镀速率和金层厚度。
用于沉积金的浸没型电镀浴优选是含水组合物。
用于将金沉积到中间层上或钯或钯合金层上的适合的无电电镀浴包含金离子源、还原剂以及至少一种络合剂。
用于沉积金的电镀浴最优选是含水浸没型电镀浴。
实例
现将通过参考以下非限制性实例来说明本发明。
在所有实例中都使用附接到作为衬底材料的硅晶片并且由直径为100μm的铂制成的电极。个别电极之间的距离为400μm。
用包含表面活性剂和酸的水溶液清洁电极的表面。
接着,测试在沉积Ni-P合金(作为中间层)前活化电极表面的不同方法。
用于将钯层沉积到Ni-P合金层上的含水无电钯电镀浴包含硫酸钯、作为还原剂的甲酸钠和作为钯离子络合剂的乙二胺。
用于将金层沉积到钯层上的含水浸没型电镀浴包含金离子和亚硫酸根离子源。
比较实例1
在用水清洁和冲洗后,立即将包含铂电极的硅晶片浸到无电镍电镀浴中。
在清洁电极表面上未引发Ni-P合金(中间层)的电镀。
比较实例2
在包含硫酸钯和硫酸的浸没型钯电镀浴中清洁后,将包含铂电极的硅晶片活化。浸没型电镀浴在使用期间维持在20℃下。
在清洁电极表面上未引发Ni-P合金(中间层)的电镀。
比较实例3
在包含硫酸钯和硫酸的浸没型钯电镀浴中清洁后,将包含铂电极的硅晶片活化。浸没型电镀浴在使用期间维持在70℃下。
在清洁电极表面上未引发Ni-P合金(中间层)的电镀。
比较实例4
在包含硫酸钯、作为还原剂的甲酸钠以及含氮络合剂的无电钯电镀浴中清洁后,将包含铂电极的硅晶片活化。电镀浴在使用期间维持在55℃下。
在清洁电极表面上未引发Ni-P合金(中间层)的电镀。
实例1
在包含硫酸钯、作为还原剂的甲酸钠以及含氮络合剂的无电钯电镀浴中清洁后,将包含铂电极的硅晶片活化。电镀浴在使用期间维持在65℃下。
如所需要的,在清洁电极表面上引发Ni-P合金(中间层)的电镀。
实例2
在包含硫酸钯、作为还原剂的甲酸钠以及含氮络合剂的无电钯电镀浴中清洁后,将包含铂电极的硅晶片活化。电镀浴在使用期间维持在85℃下。
如所需要的,在清洁电极表面上引发Ni-P合金(中间层)的电镀。

Claims (12)

1.一种在贵金属电极上制造可线接合和/或可焊接表面的方法,其按照如下顺序包含以下步骤:
i.提供其上附接有至少一个贵金属电极的衬底,
ii.清洁所述至少一个贵金属电极,
iii.通过无电电镀由含水电镀浴在所述至少一个贵金属电极上沉积选自钯和钯合金的晶种层,其中所述电镀浴在所述晶种层沉积期间具有在60℃到90℃范围内的温度,并且其中所述电镀浴包含钯离子源、还原剂以及钯离子络合剂,
iv.通过无电电镀在所述晶种层上沉积选自由镍合金和钴合金组成的群组的中间层,
v.通过无电电镀或浸没电镀在所述中间层上沉积至少一个表面处理层,其中所述至少一个表面处理层是选自由钯、钯合金、金以及金合金组成的群组,限制条件为由金组成的单一表面处理层是通过浸没型电镀沉积而多个表面处理层中的金层是通过浸没型电镀或无电电镀沉积到钯或钯合金层上。
2.根据权利要求1所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述至少一个贵金属电极包含铂、金以及钯中的一或多者。
3.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中在步骤iii.中所应用的所述含水电镀浴进一步包含磺酰亚胺化合物。
4.根据权利要求3所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述磺酰亚胺化合物为糖精。
5.根据权利要求3所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述磺酰亚胺化合物的浓度在0.001mol/l到0.1mol/l范围内。
6.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述电镀浴在所述晶种层沉积期间具有在60℃到80℃范围内的温度。
7.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述晶种层是由钯制成。
8.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中用于沉积所述晶种层的所述电镀浴中的还原剂是选自由甲酸、甲酸的衍生物以及甲酸的盐组成的群组。
9.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述包含至少一个贵金属电极的衬底是选自由蓝宝石晶片、硅晶片以及氧化铟锡晶片组成的群组。
10.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述至少一个表面处理层为钯层。
11.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述至少一个表面处理层为金层。
12.根据权利要求1或2所述的在贵金属电极上制造可线接合和/或可焊接表面的方法,其中所述表面处理层是由钯层和通过浸没型电镀或无电电镀在所述钯层顶部上电镀的金层组成。
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