CN105393352A - 铜接合导线以及其制造方法 - Google Patents
铜接合导线以及其制造方法 Download PDFInfo
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- CN105393352A CN105393352A CN201480037851.1A CN201480037851A CN105393352A CN 105393352 A CN105393352 A CN 105393352A CN 201480037851 A CN201480037851 A CN 201480037851A CN 105393352 A CN105393352 A CN 105393352A
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- wire
- stylet
- annealing
- diameter
- copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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Abstract
本发明涉及包括具有表面的芯的接合导线,其中所述芯包括铜作为主要成分,其中所述芯包括铜作为主要成分,其中在所述芯中的晶体颗粒的平均大小是在2.5μm与30μm之间,并且其中所述接合导线的屈服强度小于120MPa。
Description
技术领域
本发明涉及包括具有表面的芯的接合导线,其中所述芯包括铜作为主要成分,其中在所述芯中的晶体颗粒的平均大小是在2.5μm与30μm之间,并且其中所述接合导线的屈服强度是小于120MPa。
本发明进一步涉及包括第一接合焊盘、第二接合焊盘以及根据本发明的导线的模块,其中发明的导线通过球形接合的方式连接到接合焊盘中的至少一个。
本发明进一步涉及用于制造根据本发明的导线的方法。
背景技术
接合导线在半导体装置的制造中用于在半导体装置制作期间将集成电路与印刷电路板电互连。进一步地,接合导线在功率电子应用中用于将晶体管、二极管等与壳体的焊盘或管脚电连接。虽然起初接合导线由金制成,但是现在使用比较便宜的材料,诸如铜。虽然铜导线提供很好的电和热传导性,但是铜导线的球形接合以及楔形接合具有它的挑战。此外,铜导线易于氧化。
关于导线几何形状,最常见的是圆形横截面的接合导线和具有或多或少矩形横截面的接合带。两种类型的导线几何形状具有使它们对于特定的应用有用的它们的优点。因此,两种类型的几何形状在市场上具有它们的份额。例如,接合带对于给定的横截面面积具有更大的接触面积。然而,当接合时,带的弯曲被限制并且带的定向必须被观察到以便达到在带与所述带接合到的元件之间的可接受的电接触。转向接合导线,这些弯曲更灵活。然而,接合在接合工艺中包括导线的更大的变形和焊接,这能够导致伤害或者甚至毁坏接合焊盘和在下面的元件的电结构,所述元件接合到所述接合焊盘。
发明内容
对于本发明,术语接合导线包括所有形状的横截面以及所有平常的导线直径,尽管具有圆形横截面和细直径的接合导线是优选的。
一些近来的发展涉及具有铜芯的接合导线。作为芯材料,因为高电传导性所以选择铜。探索了针对铜材料的不同的掺杂剂以便优化接合性质。例如,US7,952,028B2描述了具有大量的不同掺杂剂和浓度的数个不同的基于铜的测试导线。然而关于接合导线本身以及接合工艺,不断需要进一步改进接合导线技术。
因此,本发明的目的是提供改进的接合导线。
因此,本发明的另一个目的是提供接合导线,当互连时所述接合导线具有良好的加工性质并且没有特定的需要,因此节约成本。
提供具有卓越的电和热传导性的接合导线也是本发明的目的。
本发明的进一步目的是提供展示改进的可靠性的接合导线。
本发明的进一步目的是提供展示卓越的接合性的接合导线。
本发明的另一个目的是提供关于球形接合示出改进的接合性的接合导线。
本发明的另一个目的是提供关于是球形接合的第一接合示出改进的接合性同时对于是楔形接合的第二接合的接合性能至少是足够的接合导线。
本发明的另一个目的是提供在接合之前示出导线芯的增加的柔性的接合导线。
本发明的另一个目的是提供对侵蚀和/或氧化具有改进的抵抗性的接合导线。
另一个目的是提供用于接合电子装置或模块的系统以与标准芯片和接合技术一起使用,所述系统或模块至少关于第一接合示出减少的失效率。
另一个目的是提供用于制造发明的接合导线的方法,所述方法与已知的方法相比基本上在制造成本上没有示出增加。
惊人地,发现了本发明的导线解决以上提到的目的中的至少一个。进一步地,发现了用于制造这些导线的工艺,该工艺克服了制造导线的挑战中的至少一个。进一步地,发现了包括本发明的导线的系统和模块在根据本发明的导线与其他电元件(例如,印刷电路板、焊盘/管脚等)之间的界面处更加可靠。
由类别形成的权利要求的主题提供对解决以上目的中的至少一个的贡献,由此类别形成的独立权利要求的从属子权利要求代表本发明的优选的方面,所述从属子权利要求的主题同样对解决以上提到的目的中的至少一个做出贡献。
本发明的第一方面是接合导线,所述接合导线包括:
具有表面的芯,
其中所述芯包括铜作为主要成分,
其中在所述芯中的晶体颗粒的平均大小是在2.5μm与30μm之间,并且
其中所述接合导线的屈服强度小于120MPa。
根据本发明的这样的导线关于它的机械和接合性质具有优化的晶体结构。
如果没有提供其他特定的定义,成分的所有含量或份额目前被给定为重量中的份额。特别地,以百分率给定的份额被理解为重量-%,并且以ppm(百万分率)给定的份额被理解为重量-ppm。
导线的芯被定义为在表面下面的体材料的同质区段。因为任何体材料基本上具有在某种程度上具有不同性质的表面区段,导线的芯的性质被理解为这个体材料区段的性质。体材料区段的表面能够在形态、组分(例如,氧含量)或其他特征方面有差别。在优选的实施例中,表面能够是发明的导线的外部表面。在进一步实施例中,导线芯的表面能够被提供为在导线芯与叠加在所述导线芯上的涂层之间的界面区段。
关于晶体颗粒的平均颗粒大小,通过使用标准的金相技术来确定颗粒的大小。导线芯的样品被横切片然后刻蚀。在本情况下,2gFeCl3和6ml浓缩的HCl在200mlDI水中的溶液用于刻蚀。通过线截取原理来测量和计算颗粒大小。在本文中使用的普通的定义是:颗粒的大小被定义为通过颗粒的直线的所有节段中最长的。
通常优选地,在导线芯的直径与平均颗粒大小之间的比率是在2.5与5之间。甚至更优选地,所述比率是在2.5与4之间。这允许贯穿导线的不同直径的范围的导线性质的优化。特别地,优选的比率能够对细导线的性质有益。
在分别的导线直径的考虑下,有利的平均颗粒大小的具体优化的选择被获得如下:
导线芯的直径是在15μm与28μm之间并且平均颗粒大小是在2.5μm与6μm之间;或者
导线芯的直径是在28μm与38μm之间并且平均颗粒大小是在3μm与10μm之间;或者
导线芯的直径是在38μm与50μm之间并且平均颗粒大小是在7μm与15μm之间;或者
导线芯的直径是在50μm与80μm之间并且平均颗粒大小是在10μm与30μm之间。
所述导线是特别用于在微电子中接合的接合导线。所述导线优选地是单片的物体。
成分是“主要成分”,如果这个成分的份额超过参考材料的所有进一步的成分。优选地,主要成分包括至少50%的材料的总重量。
对于屈服强度的定义,参考普通的理解。材料的“屈服强度”在工程和材料科学中被定义为材料在其处开始塑性变形的应力。在塑性变形开始之前,材料将弹性变形并且当施加的应力移除时将恢复到它的最初的形状。
通常优选地,本发明的接合导线的屈服强度小于110MPa并且更优选地小于90MPa。最优选地,屈服强度不大于80MPa。作为通常的规则,如果屈服强度被减少,对于本发明的导线的接合性质是有利的。
发明的导线的屈服强度的下限优选地大于50MPa并且最优选地大于65MPa。这特别地导致对于发明的接合导线的屈服强度的优选的和有利的范围。根据本发明的接合导线优选地具有在如下范围中的一个或多个中的屈服强度:50..120MPa、50..110MPa、65..110MPa、65..90MPa或65..80MPa。
在本发明的优选的实施例中,导线的杨氏模量小于100GPa。更优选地,杨氏模量小于95GPa。导线关于它的杨氏模量的优化对于它的机械性质并且也对于在接合工艺中它的行为是有益。
能够顾及杨氏模量的下限以便防止不利的效果。证明了优化的导线的杨氏模量不应该低于75GPa,优选地不低于80GPa。根据本发明的接合导线优选地具有在如下范围中的一个或多个中的杨氏模量:75..100GPa、75..95GPa或80..95GPa。
对于杨氏模量的定义,参考普通的理解。杨氏模量,也被认为拉伸模量或者弹性模量,是弹性材料的刚度的测量并且是用于表征材料的量。它被定义为在其中胡克定律有效的应力范围内沿着轴的应力与沿着所述轴的应变的比率。
为了维持发明的导线的良好的接合特性,通常优选的是,导线芯的铜的总量是至少97%。更优选地,铜的量是至少98%。
在本发明的一个优选的实施例中,导线芯由纯铜组成。优选地,纯度是至少3N级铜(>=99.9%Cu),最优选地4N级铜(>=99.99%Cu)。纯铜导线通常示出良好的传导性和良好的接合性质。
在优选的实施例中,在导线芯中硼的含量小于100ppm。由于已知硼会影响基于铜的导线的晶体结构,保持硼量低于某些阈值是有利的。这对于由纯铜组成的导线芯而言尤其是正确的。在另一个优选的实施例的情况下,在10ppm与100ppm之间的量中硼以控制的方式被提供。
在又一个优选的实施例中,在导线芯中的磷的含量小于200ppm。可以提供的是尽可能消除磷(痕迹量级),尽管在一些实施例中,能够提供小量的磷。在这样的情况下,磷的优选的量是在10ppm与200ppm之间。
在另一个优选的实施例中,导线芯以在0.5%与3%之间,更优选地在1.0%与2.5%之间的量含有钯。在甚至更优选的优化的实施例中,钯含量是在1.2%与2.5%之间,并且最优选地在1.2%与2.0%之间。在特别优选的实施例中,钯份额是在1.2%与1.3%之间。实验示出了钯的小份额不减少本发明的有益效果,然而这样的钯含量通常有助于导线对侵蚀的稳定性并且具有进一步的有益的效果。
进一步优选的,本发明的这样的含有Pd的导线示出在85至95HV(0.010N/5s)的范围内导线芯的微硬度。在甚至更优化的实施例中,在导线芯的硬度与钯含量之间的比率是在60与120HV(0.010N/5s)/wt.-%之间的范围内。理解的是导线芯的硬度例如能够通过退火过程的方式独立于在某些范围之内选择的钯含量而被调整。
在又一个优选的实施例中,导线芯以在45ppm与900ppm之间的量含有银。在优选的实施例中,银含量是在100ppm与900ppm之间,甚至更优选地是在100ppm与700ppm之间。在非常优选的实施例中,当导线的显著有利的性质被得到时,银含量是在100ppm至400ppm的范围中。在又一个优化的实施例中,芯的银含量是在100ppm与300ppm之间,最优选地是在200ppm与250ppm之间。通常,在导线芯中具有小份额银的这样的实施例对于球形接合示出良好的FAB(无空气焊球)形成以及大的接合窗口。
对于含有银的导线通常优选的,导线芯的除了Cu和Ag的成分的总量是小于1000ppm,甚至更优选地小于100ppm。这提供导线性质的良好的再现性。
在发明的导线的进一步优选的实施例中,Au以在45ppm与900ppm之间的量被提供为份额。更优选地,Au的量是在100ppm与700ppm之间,最优选地是在100ppm与300ppm之间。
注意的是,Pd、Au、Ag、P和B的以上提到的份额中的两个或多个能够同时被提供在发明的导线中。最优选的,在以上提到的量中之一中的Pd的份额分别与从以如以上提到的量的Au、Ag、P或B的组选择的一个份额组合。
通常优选的,对于特定元素在发明导线的导线芯中的不想要的污染物等级的有益上阈值是如下:
Ag:<35ppm;
Ni:<15ppm;
在每个情况下Pd、Au、Pt、Cr、Ca、Ce、Mg、La、Al、B、Zr、Ti:<2ppm;
P:<6ppm;
Fe:<10ppm;
S、Mn:<15ppm。
指出的是对于元素Pd、Ag、Au、B和P的以上通常的阈值仅仅对于在其中这些元素没有以其他定义的量被明确含有的本发明的实施例而言是有效的。
以上特定的污染物限制中的每个意指是本发明的单独的特征。
本发明特别地涉及细接合导线。特别地关于颗粒大小的控制,观察的效果对细导线尤其有益。在本情况下,术语“细导线”被定义为具有在8μm至80μm的范围内的直径的导线。特别优选的,根据本发明的细导线具有在12μm至55μm的范围内的直径。在这样的细导线中,发明的组分和退火特别地有助于获得有益的性质。
在发明的导线的优选的实施例中,在接合步骤之前,导线芯在至少580℃的温度下退火达至少0.1s的时间。特别是在细导线的情况下,这保证足够的退火和要求的颗粒大小的获得。甚至更优选的,退火时间是至少0.2s并且最优选地是0.25s。发明的导线的特别高的退火温度通常允许大的平均颗粒大小的调整。在最优选的情况下,在600℃之上选择退火温度。
特别地,在考虑导线直径下能够优化导线的退火。在这样的优化的实施例中,最小退火温度被选择如下:
直径[μm]最小退火温度[℃]
15-28600
28-38610
38-50625
50-80635
在本发明的通常优选的方面中,导线在退火之后的延伸值不大于最大延伸值的92%。更优选的,延伸值不大于85%,并且最优选地不大于最大延伸值的80%。在又一个优选的情况下,导线在高于在其处通过退火获得最大延伸值的温度至少10℃的温度处退火。更优选地,所述温度高于最大延伸的温度至少50℃,并且最优选的,所述温度高于最大延伸的温度至少80℃。
最大延伸值被定义如下:在基于铜的接合导线的通常情况下,能够通过最终退火步骤来调整导线的延伸。在这个方面中的“最终”意指,此后没有建立具有对导线的形态的主要影响的生成步骤。当选择退火参数时,经常选择一组参数。在对导线退火的简单的情况下,在给定长度的烘箱中调整恒定的温度,其中导线以恒定的速度通过所述烘箱。这将导线的每一个点暴露到所述温度达给定的时间,这个温度和这个退火时间是退火过程的两个相关的参数。在其他情况下,可能使用烘箱的特定温度分布,因此将进一步的参数添加到系统。
在任何情况下,参数之一能够被选择为变量。然后,依赖于这个变量的接收的导线的延伸值导致通常具有局部最大值的曲线。这被定义为在本发明的意义上的导线的最大延伸值。在变量是退火温度的情况下,这样的曲线经常被称为“退火曲线”。
在现有技术下,经常将任何导线退火到关于可变参数的这样的最大延伸值,因为局部最大值的存在提供特别稳定的制造条件。
关于本发明,惊人地证明了退火到在最大延伸值之下的不同值能够导致有益的导线性质,因为能够以积极的方式来影响导线形貌。如果退火温度被选择为可变参数并且将退火时间设置为恒定值,则如果退火温度被选择在高于最大延伸的退火温度的值处是特别有益的。特别地,这个制造原理能够用于例如将导线的平均颗粒大小调整到更大的颗粒大小。通过这个调整,能够以积极的方式影响其他性质像例如导线柔软度、球形接合行为等。
在本发明的可能进一步的发展中,涂层被叠加在芯的表面上方。理解的是,这样的涂层是可能的但是不是发明的导线的必要特征。为了最小化这样的涂层的材料对接合工艺的影响,涂层的质量优选地不大于导线芯的质量的3%。最优选地,涂层的质量不大于导线芯的质量的1%。有利地,涂层包括Pd、Au、Pt和Ag的组中的至少一个作为主要成分。
在本发明的上下文中的术语“叠加”用于描述例如铜芯的第一项关于例如涂层的第二项的相对位置。可能地,进一步的项(诸如中间层)可能被布置在第一和第二项之间。优选地,第二项至少部分地(例如关于第一项的总表面达至少30%、50%、70%或者达至少90%)被叠加在第一项的上方。最优选地,第二项被完全叠加在第一项上方。在本发明的上下文中的术语“中间层”是在铜芯和涂层之间的导线的区段。在这个区段中,如在芯中的材料以及如在涂层中的材料组合地存在。
在本发明的优选的实施例的情况下,在接合之前的导线芯的硬度是不大于95.00HV(0.010N/5s)。更优选的,硬度是不大于93HV(0.010N/5s)。导线芯的这样的柔软度有助于防止敏感的衬底在接合的进程中受到损害。实验还示出了根据本发明的这样柔软的导线展示非常良好的无空气焊球(FAB)性质。导线硬度的这样的限制是特别有帮助的,如果机械敏感结构排列在接合焊盘之下。这是特别正确的,如果接合焊盘由像铝或金的软材料组成。敏感结构例如能够包括一个或数个层的特别地具有小于2.5的介电常数的多孔二氧化硅。这样多孔的并且因此脆弱的材料正变得日益常见,因为它能够有助于增加装置性能。因此,发明的接合导线的机械性质被优化以避免脆弱层的破裂或其他损害。
使用具有维氏压头的费舍尔范围H100C测试器来测量硬度。如果没有给定不同的值,则使用136o方形金刚石压头压印,施加10mN力(F)的力达5s停留时间。硬度测试过程按照基于在横切片的样品的平坦的面上的维氏压痕的基本良好建立过程的制造者的推荐。使用扫描电子显微镜(SEM)来测量并且使用公式来计算在导线切片的表面上的压痕对角线(d),其中F的单位是kgf并且d的单位是mm。
本发明的进一步的方面是模块,该模块包括第一接合焊盘、第二接合焊盘和根据本发明的导线,其中导线通过球形焊接的方式被连接到接合焊盘之一。
这样的模块能够包括通过接合导线的方式电连接的任何特别的电子装置。特别地,所述装置能够是集成电路、发光二极管(LED)、显示装置等。
在发明的模块的优选的实施例中,在将20μm直径的导线接合到铝接合焊盘的情况下,用于球形接合的工艺窗口面积具有至少120g*mA的值。更优选的,值是至少130g*mA,并且最优选的,值是至少140g*mA。
通过标准过程来测量球形接合窗口面积的这些值。使用KNS-iConn接合器工具来接合测试导线。用于接合导线的工艺窗口面积的定义在本领域中已知并且广泛用于比较不同的导线。原则上,它是用在接合中的超声能量和用在接合中的力的乘积,其中产生的接合必须满足某些拉力测试规格例如3克的拉力、无未粘上焊盘(non-stickonpad)等。给定的导线的工艺窗口面积的实际值进一步取决于导线直径以及接合焊盘材料。为了给出发明的导线的性质的特定定义,要求的工艺窗口值是基于20μm=0.8mil的导线直径,其中接合焊盘由铝(Al、Al-0.5Cu、Al-1Si-0.5Cu等)组成。发明的系统的范围不限于这个直径的导线和由铝制成的接合焊盘,而是仅仅为了定义的目的而指定这个数据。
本发明的又一个方面是用于制造根据本发明的接合导线的方法,该方法包括如下的步骤:
a.提供具有要求的组分的铜芯前驱体;
b.牵引前驱体直到达到了导线芯的最终直径;
c.在定义的温度处将牵引的导线退火达最小的退火时间。
在特别优选的实施例中,通过连续退火(strandannealing)来执行退火,从而允许具有高再现性的导线的快速生成。连续退火意指,在导线移动通过退火烘箱并且在离开了烘箱之后卷缆到卷轴上时动态地完成退火。
附图说明
本发明的主题被例示在附图中。然而这些附图不旨在以任何方式限制本发明或权利要求的范围。
在图1中,描绘了导线1。
图2示出导线1的横截面视图。在横截面视图中,铜芯2是在横截面视图的中间。铜芯2由涂层3来包围。在铜导线2的界限上,铜芯的表面15被定位。在通过导线1的中心23的线L上,铜芯2的直径被示出为在线L与表面15的交叉点之间的末端至末端的距离。导线1的直径是在通过中心23的线L与导线1的外部界限的交叉点之间的末端至末端距离。此外,涂层3的厚度被描绘。涂层3的厚度在图2中被夸大。如果提供了涂层3,则它的典型厚度与芯直径相比是非常小的,例如小于芯直径的1%。
理解的是导线1的涂层3在本发明的情况下是可选的。对于最优选的实施例,在导线芯上没有提供涂层。
图3示出用于制造根据本发明的导线的工艺。
图4描绘以包括两个元件11和导线1的电子装置10的形式的模块。导线1电连接两个元件11。虚线意指连接元件11与围绕元件11的封装装置的外部配线的进一步的连接或电路。元件11能够包括接合焊盘,引线指、集成电路、LED等。
图5示出导线拉力测试的概图。到衬底20,导线1以45°的角度19被接合在接合部21中。拉力吊钩17拉导线1。当拉力钩17拉导线1时形成的角度22是90°。
图6示出对于本发明的第一示例的不同直径的导线的一组退火曲线。这个示例包括由4N铜芯组成而没有涂层的导线。
图7示出与传统的纯铜导线相比的第一示例的25μm导线的针拉(stitchpull)测量的图。
图8示出与分别的传统纯铜导线相比的第一示例的20μm和25μm导线的硬度测量的图。
图9示出与传统25μm的纯铜导线的接合窗口相比的第一示例的25μm导线的楔形接合的第二接合加工窗口的比较。
图10示出根据本发明的第二示例的20μm导线的退火曲线。在这个示例中,导线芯的铜含有小量的银。
图11示出第二示例的导线与比较的导线的针拉比较。
图12示出第二示例的导线与比较的导线的硬度比较。
图13a示出第一示例的导线的热老化行为。
图13b示出第二示例的导线的热老化行为。
图14示出对于本发明的第一和第二示例的不同的20μm直径导线的平均颗粒大小的比较。
图15示出连续退火装置的示意图。
图16示出根据本发明的第三示例的20μm导线的退火曲线。在这个第三示例中,导线芯的铜含有小量的钯。
图17示出显示第三示例的20μm导线的平均颗粒大小的图。在左边的数据点是在导线上测量的而在右边的数据点是在导线的无空气焊球上测量的。
图18示出以离安置在0μm处的无空气焊球不同的距离测量的导线芯的微硬度的图。颈区段在无空气焊球与未受影响的导线区段之间以及直到在未受影响的导线区段中的大约200μm。明显的是导线具有在85至95HV(0.010N/5s)的范围之内的微硬度。
图19示出对于本发明的20μm导线的球形接合加工窗口。一个加工窗口涉及本发明的第一示例的导线(命名为“4N软Cu”),并且其他加工窗口涉及本发明的第三示例的导线(命名为“Pd合金的1NCu”)。
图20示出用于本发明的20μm导线的第二接合(“针接合”)加工窗口。一个加工窗口涉及本发明的第一示例的导线(命名为“4N软Cu”),并且其他加工窗口涉及本发明的第三示例的导线(命名为“Pd合金的1NCu”)。
图21示出本发明的第三示例的20μm导线的热老化行为。
具体实施方式
测试方法
所有的测试和测量是在T=20℃以及50%的相对湿度下进行的。
当测量晶体颗粒的平均颗粒大小时,通过使用标准的金相技术来确定颗粒的大小。导线芯的样品被横切片然后刻蚀。在本情况下,2gFeCl3和6ml浓缩的HCl在200mlDI水中的溶液用于刻蚀。通过线截取原理来测量和计算颗粒大小。沿着是导线轴的方向的纵向方向来测量颗粒大小。
通过标准的过程来完成球形结合工艺窗口面积的测量。使用KNS-iConn接合器工具来接合测试导线。用于接合导线的工艺窗口面积的定义在本领域中已知并且广泛用于比较不同的导线。原则上,它是用在接合中的超声能量(USG)和力的乘积,其中产生的接合必须满足某些拉力测试规格例如3克的拉力、无未粘上焊盘等。给定的导线的工艺窗口面积的实际值进一步取决于导线直径以及接合焊盘材料。为了给出发明的导线的性质的特定定义,工艺窗口值目前基于20μm=0.8mil的导线直径,其中接合焊盘由铝(Al、Al-0.5Cu、Al-1Si-0.5Cu等)组成。通过克服如下两个主要的失效模式来得到工艺窗口的四个角:
(1)过低的力和USG的供应引起FAB的未粘上接合焊盘(NSOP),以及
(2)过高的力和USG的供应引起接合焊盘坑。
示例
本发明进一步通过示例来例示。这些示例用于本发明的示例性阐明并且不旨在以任何方式限制本发明或权利要求的范围。
示例1
至少99.99%纯度的一些铜材料(“4N铜”)在坩埚中熔化。没有进一步的物质被添加到该熔化物。然后导线芯前驱体由该熔化物铸成。
使用电感耦合等离子体(ICP)仪器(PerkinElmerICP-OES7100DV)来控制Cu导线的化学组分。铜导线溶解在浓缩的硝酸中并且溶液用于ICP分析。按照针对体Cu所采用的熟知的技术由设备制造者建立测试高纯Cu导线的方法。
导线芯前驱体然后以数个牵引步骤被牵引以形成具有规定的直径的导线芯2。为了证实对于不同直径的本发明的有益效果,制造了具有不同直径的导线的选择。以下表1示出不同导线直径的列表:
(表1:对于不同导线直径的延伸和平均颗粒大小的范围)。
表1进一步示出导线芯的延伸值和平均颗粒大小的范围。这些范围对于分别的直径的导线是优选的,其中以下进一步描述根据本发明的这些值的调整。进一步地,在右边最后两列中,添加了对于在导线芯的平均颗粒大小与延伸之间的比率计算的值,以及对于在如在标准条件生成的无空气焊球(FAB)的平均颗粒大小与延伸之间的比率计算的值。
导线芯2的横截面是基本上圆形的。导线直径不被认为是高度准确的值,由于在横截面的形状等中的浮动。在本意义下,如果导线被定义成具有例如20μm的直径,则直径被理解成在19.5至20.5μm的范围中。
导线然后在最终退火步骤中退火以便进一步调整像延伸、硬度、晶体结构等的参数。通过以定义的速度将导线1运转通过定义的长度和温度的退火烘箱24来如连续退火那样动态地执行退火(参见图15)。导线从第一卷轴25退绕并且通过滑轮26引导。在离开烘箱24之后,导线被卷缆在第二卷轴上用于封装。
在本示例中,是移动导线的给定的片保留在加热烘箱24之内的暴露时间的退火时间对于所有导线直径是大约0.3s。退火温度在20μm直径导线的情况下被选择为600℃。在烘箱区之内,恒定的温度被调整。
原则上,退火时间能够根据退火温度和/或导线直径来变化。总之,如果连续退火被选择为退火方法,需要导线的某一最小速度以便得到合理的生产量。因此,退火时间优选地在0.1秒与1秒之间的区段中选择,这允许足够长度的烘箱的容易的供给。这在另一方面需要足够高的退火温度。以下表2示出对于导线直径的不同范围的优选的最小退火温度:
导线的直径 [μm] | 平均导线颗粒大小的范围 [μm] | 优选的最小退火温度 [℃] |
15-28 | 2.5-6.0 | 600 |
28-38 | 3.0-10.0 | 610 |
38-50 | 7.0-15.0 | 625 |
50-80 | 10.0-30.0 | 635 |
(表2:推荐的最小退火温度)。
测量了选择的导线样品的平均颗粒大小。结果在以下的表3中示出:
导线的直径 [μm] | 测量的平均导线颗粒大小 [μm] | 退火温度 [℃] |
20 | 5.0 | 600 |
33 | 6.5 | 615 |
50 | 11.0 | 630 |
80 | 20 (估计的) | 635 (估计的) |
(表3:对于导线示例的平均颗粒大小)。
图6示出根据发明的示例1的4N铜导线的数个示例性退火曲线。所述导线差别仅仅是它们的直径,其中示出了20μm、33μm和50μm直径的导线。通过调整移动导线的速度来将退火时间选择为恒定的值。退火温度是x轴的可变参数。这些图示出对于作为温度的函数的导线的断裂载荷(BL)以及延伸(EL)测量的值。该延伸在每个情况下展示典型的局部最大值。
对于三个示例性导线直径,如下能够从退火曲线估计延伸的最大值:
导线直径 | 最大延伸的退火温度 [℃] | 最大延伸 [%] | 在最大延伸处的断裂载荷[g] |
20 μm | 520 | 15.8 | 6.7 |
33 μm | 520 | 18.0 | 21.2 |
50 μm | 525 | 24.1 | 47.4 |
(表4:对于不同的导线直径的最大延伸处的值)。
根据本发明的导线不在分别的最大延伸的温度处而在更高的温度处退火。
对于20μm导线,选择的退火温度是600℃,其高于根据表4的最大延伸的温度80℃。这导致大约11.8%的延伸值(参见以下的表5),其低于15.8%的最大延伸值25%。
对于33μm导线,选择的退火温度是615℃,其高于根据表3的最大延伸的温度95℃。这导致大约13.3%的延伸值,其低于18.0%的最大延伸值26%。
对于50μm导线,选择的退火温度是630℃,其高于根据表3的最大延伸的温度105℃。这导致大约18.5%的延伸值,其低于24.1%的最大延伸值23%。
在退火曲线的最大值的高温度侧处的这样的退火意指工作在材料的在工艺参数方面的相当敏感的范围内。为了具有结果的良好再现性,必须仔细监视全部的参数集。
以下表5示出来自表3的发明的导线的进一步机械和电性质的测量结果:
(表5:机械和电性质)。
来自表5的结果示出发明的导线具有与从4N铜导线典型所知的一样低的电阻率的值。
如期望的那样,屈服强度与导线直径无关。发明的导线的值在每个情况下远低于120MPa、并且甚至远低于80MPa。
在延伸值的最大值周围退火的典型的现有技术的4N铜导线具有大于160MPa的屈服强度。
杨氏模量也独立于导线直径并且具有远低于100GPa的值。典型的现有技术的4N铜导线具有大约125GPa的杨氏模量。
如期望的那样也独立于导线直径的拉伸强度是大约225MPa。注意的是典型的现有技术的4N铜导线被测量为具有大约245MPa的拉伸强度。根据本发明的导线的拉伸强度典型地低于标准导线的值几个百分点。这将是期望的,由于发明的导线的柔软度。总之,在拉伸强度中的这样小的下降将不导致对标准接合过程和/或与标准接合设备一起使用的负面影响。
使用Instron-5300仪器来测试导线的拉伸性质。对于10英寸计量长度,以1(一)英寸/分钟的速度测试导线。按照ASTM标准F219-96获得断裂载荷与延伸。通过由制造者建立的方法来得到细导线的杨氏模量和屈服载荷(屈服强度):沿着拉伸图的弹性区段绘制切线。测量所述线的斜率,其代表导线的杨氏模量。在塑性区段的开始处测量的载荷定义屈服强度。由制造者开发的“Bluehill软件”能够直接从拉伸图得到屈服载荷和杨氏模量。使用公式屈服强度=屈服载荷/导线横截面的面积来计算屈服强度(工程强度)。按照ASTM标准F205通过称重方法来测量直径。
第一示例的导线的进一步的结果和比较示出在图7、8和9中。
在图7中,25μm导线的针拉比较示出,当与现有技术导线相比时根据本发明的导线具有甚至更大的针拉值。根据示例1的发明的导线的结果示出在右边并且标记为“软铜”。
在图8中,示出了20μm导线和25μm导线的硬度比较。在每个情况下,显示了现有技术导线(“传统的”)和示例1的发明的导线(“软铜”)的测量的维氏硬度10mN/5s。明显的是发明的导线具有显著更低的维氏硬度,所述维氏硬度对于这些直径是在低于90HV10mN/5s的范围内。
在图9中,对于现有技术导线(“传统的”)和根据示例1的发明的导线(“软铜”)显示了球形接合的接合工艺窗口。导线直径被选择为20μm并且测试接合在铝接合焊盘上执行。明显的是对于发明的导线的工艺窗口显著大于传统导线的窗口。
图13a示出25μm4NCu导线样品的热老化实验。球形接合的样品的球拉值被测量,其中样品在175℃处的热暴露下老化高达1000小时。结果示出导线的非常良好的老化行为。结果还证明根据本发明的导线适于高温和/或高能量应用。
尽管以上示例涉及由纯铜(4N纯度)制成的导线,但是本发明不限于这样纯度的导线。在更大的颗粒的受控生长和更低的延伸值的调整下的高温退火的基本发明的概念能够被转移到基于铜的任何合适的导线系统。特别优选的,但是不限制本发明的范围,是以下表6的系统:
系统号 | Pd (wt%) | Au (ppm) | Ag (ppm) | P (ppm) | B (ppm) | Cu |
1 | 1-3 | - | - | - | - | 余量 |
2 | - | 45-900 | - | - | - | 余量 |
3 | - | - | 45-900 | - | - | 余量 |
4 | - | - | 10-200 | - | 余量 | |
5 | - | - | - | - | 10-100 | 余量 |
6 | 1-3 | 45-900 | - | - | - | 余量 |
7 | 1-3 | - | 45-900 | - | - | 余量 |
8 | 1-3 | - | - | 10-200 | - | 余量 |
9 | 1-3 | - | - | - | 10-100 | 余量 |
(表6:对于根据本发明的铜导线的优选的系统)。
列举的元素的所有份额被理解为存在于导线芯中。表6的系统与导线芯的可选涂层无关,所述涂层可以在每个情况中附加地提供。
如果没有给出元素的份额(“-”),则元素不应该高于可容忍的痕迹量级而存在。理解的是除了在表6中给出的那些之外的元素的进一步组合是可能的。特别地,能够想到表6的元素的份额的进一步组合,例如与金的份额组合的银的份额等。此外,添加除了在表6中指定的那些之外的进一步元素能够是有利的。
通常优选的,在导线芯中的铜的总量不比97%低得多,这提供本发明的良好的适用性。
在下面,具体描述了发明的导线的进一步示例。这些示例包括在芯中的小量的银并且因此与在表6中的建议的3号系统相关,尽管不受限于在表6中对于这个系统给出的元素的份额的特定集合。
示例2
至少99.99%纯度的一些铜材料(“4N铜”)在坩埚中熔化。小量的银(Ag)被添加到熔化物并且添加的成分在铜熔化物中的均匀分布被提供。然后导线芯前驱体由熔化物铸成。
导线芯前驱体然后以数个牵引步骤被牵引以形成具有目前20μm的规定的直径的导线芯2。导线芯2的横截面是基本上圆形的。将理解的是导线直径不被认为是高度准确的值,由于在横截面的形状等中的浮动。在本意义下,如果导线被定义成具有例如20μm的直径,则直径被理解成在19.5至20.5μm的范围内。
借助于这个过程,发明的导线和比较的导线的数个不同的样品被制造。
样品 | Ag | Ni | Pd, Au, Pt, Cr, Al, B, Zr, Ti | Ca, Ce | Mg, La | P | S | Fe | Mn |
4N Cu | <25 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
1 | 45 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
2 | 110 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
3 | 225 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
4 | 350 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
5 | 900 | <15 | <2 | <2 | <2 | <6 | <10 | <10 | <15 |
(表7:导线直径20μm,值的单位是ppm)。
以上的表7示出20μm直径的发明的导线的编号1..5的不同样品的组分。导线的银含量分别是45ppm、110ppm、225ppm、350ppm和900ppm。添加了由4N纯度的铜组成的比较的导线。
导线然后在最终退火步骤中退火以便进一步调整像延伸、硬度、晶体结构等的参数。通过以定义的速度将导线1运转通过定义的长度和温度的退火烘箱24来如连续退火那样动态地执行退火(参见图15)。导线从第一卷轴25退绕并且通过滑轮26引导。在离开烘箱24之后,导线被卷缆在第二卷轴上用于封装。
在本示例中,是移动导线的给定的片保留在加热烘箱24之内的暴露时间的退火时间是大约0.3s。退火温度在20μm直径导线的情况下被选择为640℃。在烘箱区之内,恒定的温度被调整。
图10示出银掺杂的20μm铜导线的示例性退火曲线。通过调整移动导线的速度来将退火时间选择为恒定的值。退火温度是x轴的可变参数。这些图示出对于导线的断裂载荷(BL)以及延伸(EL)测量的值。
延伸在显示的示例中展示大约14.5%的典型的局部最大值,所述最大值在大约460℃的退火温度处得到。
现在根据样品1..5的发明的导线不在最大延伸的这个温度处而在640℃处退火,所述640℃高于根据图10的最大延伸的温度180℃。这导致大约10%的延伸值,其低于最大延伸值大于30%。
如在示例1中,在退火曲线的高温度侧处的这样的退火意指工作在材料的在工艺参数方面的相当敏感的范围内。为了具有结果的良好再现性,必须仔细监视全部的参数集。
测量了1-5号导线样品的平均颗粒大小。结果是在每个情况下在3μm至6μm的范围内。对于3号样品,平均颗粒大小是5μm。
导线芯的平均颗粒大小大量地受退火步骤影响,并且存在由银含量的进一步影响。
进一步的实验示出了对于具有在15..28μm的范围内的直径的导线,在3..6μm范围内的平均颗粒大小能够被获得并且对于银含量的全部范围(即从45ppm至900ppm)是优选的。
以下的表8示出对球形接合性能的评估的结果。以上定义的发明的导线样品1..5以及纯铜导线的比较的示例针对球形接合如以上在“测试方法”下所描述的那样被测试。
(表8:对于球形接合的工艺窗口)。
工艺窗口面积被定义为在超声能量和施加的力的上和下边界之间的分别的差异的乘积。
所有发明的导线导致很好地适合于工业应用的工艺窗口。特别地,发明的导线样品2、3和4示出大于120mA*g以及以上的值,这与4NCu导线相比是特别的改进。因此球形接合工艺窗口的改进至少存在于Ag含量的100..350ppm的范围内。
理解的是根据本发明的导线的有益性质不限于像球形接合工艺窗口的单一的参数。其他性质例如是FAB形状和再现性、FAB硬度、在接合之前的导线的柔软度、在接合之后的在接合区域(球形和颈)中的导线的柔软度、导线的电传导性、针拉强度、老化行为等等。
图11示出3号导线样品(225ppm银含量)与比较的4N铜样品的针拉值的比较。发明的导线示出改进的针拉值。根据图5进行测量。
图12示出3号导线样品与发明的示例1的4N铜样品(标记为“软4NCu”)的硬度值(HV15mN/10s)的比较。第二示例的发明的导线比来自第一示例的导线具有甚至更低的硬度,尽管存在测量的误差条的一些重叠。
图13b示出3号导线样品的热老化实验。测量了球形接合的样品的球拉值,其中样品在热暴露下老化高达1000小时。结果示出导线的非常良好的老化行为。
图14示出本发明的示例2的3号样品Ag掺杂的导线与20μm4NCu导线的测量的平均颗粒大小的比较。如以上在“示例1”下描述的那样,4NCu导线根据本发明被退火。4NCu导线被标记为“软4NCu”。存在测量的误差条的强烈重叠,但是能够估计在Ag掺杂的导线的情况下更大的颗粒大小的趋势。
参考以上对于20μm直径导线所描述的示例2的结果,发明的导线的优选的和优化的版本具有在45..900ppm的范围内的银含量。这对于接合导线的所有进一步检查的直径范围也显得正确。
基于银含量的这个范围,关于导线芯的柔软度、平均颗粒大小以及球形接合行为优化了具有其他直径的导线。
对于33μm直径的导线,发现了650℃的优化的退火温度。制造导线的其他参数和方法与示例1的导线相比保持不变。
进一步的实验示出了对于具有在28..38μm范围内的直径的导线,在4..10μm的范围内的平均颗粒大小能够被获得并且对于银含量的全部变化范围(即从45ppm至900ppm)是优选的。
对于具有33μm直径和225ppm银含量的导线,通过在650℃处退火获得了6μm的平均颗粒大小。
对于50μm直径的导线,发现了670℃的优化的退火温度。制造导线的其他参数和方法与示例1的导线相比保持不变。
进一步的实验示出了对于具有在38..50μm的范围内的直径的导线,在8..15μm的范围内的平均颗粒大小能够被获得并且对于银含量的全部变化范围(即从45ppm至900ppm)是优选的。
对于具有50μm直径和225ppm银含量的导线,通过在670℃处退火获得了15μm的平均颗粒大小。
示例3
至少99.99%纯度的一些铜材料(“4N铜”)在坩埚中熔化。小量的钯(Pd)被添加到熔化物并且添加的成分在铜熔化物中的均匀分布被提供。然后,通过连续和缓慢地将熔化物铸成在2mm与25mm之间的棒来生成导线芯前驱体。
导线芯前驱体然后以数个牵引步骤被牵引以形成具有目前20μm的规定的直径的导线芯2。牵引被实施为在室温处的冷牵引。
关于导线芯2的横截面形状,参考对于以上示例的评论。
借助于这个过程,制造了发明的导线的数个不同的样品。在第一变体中,在铜中的钯的量被调整为0.89%。在第二最优选的变体中,钯的量被调整为1.25%。
关于进一步元素的杂质的阈值,参考以上本发明的第二示例,参见表7。注意到在第三示例的情况下银含量优选地低于25ppm。总之,证明了在根据本发明的含有钯的铜导线的情况下,银的甚至更高的量是可容忍的或者甚至能够具有有益的效果。特别地,参考以上第一示例的表6,其中提到了含有Pd的导线的数个示例。这样的组合被理解为根据本发明的第三示例的导线的优选的进一步变体。
导线然后在最终退火步骤中退火以便进一步调整像延伸、硬度、晶体结构等的参数。通过以定义的速度将导线1运转通过定义的长度和温度的退火烘箱24来如连续退火那样动态地执行退火(参见图15)。导线从第一卷轴25退绕并且通过滑轮26引导。在离开烘箱24之后,导线被卷缆在第二卷轴上用于封装。
在本示例中,是移动导线的给定的片保留在加热烘箱24之内的暴露时间的退火时间是大约0.3s。退火温度在20μm直径、含有Pd的导线的情况下被选择为800℃。在烘箱区之内,恒定的温度被调整。
图16示出第一变体(1.25%钯合金)的20μm铜导线的示例性退火曲线。通过调整移动导线的速度来将退火时间选择为恒定的值。退火温度是x轴的可变参数。这些图示出对于导线的断裂载荷(BL)以及延伸(EL)测量的值。该延伸在图10的显示的示例中展示大约17.9%的典型的局部最大值,所述最大值是在大约570℃的退火温度处获得的。
现在第三示例的发明的导线不在最大延伸的这个温度处而在大约750℃处退火,所述750℃高于根据图16的最大延伸温度180℃。这导致大约14%的延伸值,其低于17.9%的最大延伸值大于22%。
以下的表9示出关于本发明的第三示例的20μm导线的一些测量的值。
(表9:导线直径20μm)。
注意到添加了本发明的第一示例的比较的导线(“4NCu”),其已经列举在以上的表5中。
如期望的那样,来自表9的值示出Pd合金的导线与纯铜导线相比具有轻微更高的电阻率。另一方面,由Pd合金导致像改进的侵蚀抵抗性的有益的效果。所述表进一步示出,如果实施了根据本发明的退火过程则含有Pd的导线能够获得与纯铜导线(“4NCu”)非常相似的机械性质。在表9中,在标准的焊球形成过程之后,硬度测量被实施并且在导线芯上(左边值)和在无空气焊球(FAB)上平均。1.25%Pd合金的20μm导线的进一步具体的硬度测量能够在图18的图中看到。这个图示出在导线表面上随着离无空气焊球的距离增加的多个测量。在FAB区段的附近看到硬度的小的降低。
第三示例的导线的进一步的变体被列举在以下的表10中:
(表10:不同的导线直径,Pd含量1.25%)。
显然的是导线的延伸值随着导线直径而增加。然而,贯穿所有不同的示例和导线直径保持退火到低于分别的最大值的延伸值的发明原则。
分别对20μm直径导线的样品测量在图16至21中的数据。
能够从图17得到的是,Pd合金的并且退火的导线的平均颗粒大小与纯铜导线的颗粒大小相似。
图19示出Pd合金的导线比本发明的纯铜导线具有稍微更大的球形接合工艺窗口,其中窗口是相当可比较的。
图20示出在第二接合工艺窗口的情况下,本发明的Pd合金的样品展示关于超声能量以及力值两者显著更大的窗口。
图21示出在175℃的温度处高达2000小时的热老化行为。在导线的高温储存处在这个时间尺度下没有显著的热老化是可见的。
通常,分别的实施例的特定特征能够根据分别的要求而彼此组合。如果合适的话,进一步特征(例如导线芯的涂层)能够被添加到任何特定的实施例。
Claims (20)
1.一种接合导线,包括:
具有表面的芯(2),
其中芯(2)包括铜作为主要成分,
其中在芯中的晶体颗粒的平均大小是在2.5μm与30μm之间,并且
其中接合导线的屈服强度小于120MPa。
2.根据之前的权利要求之一的导线,其中导线的杨氏模量小于100GPa。
3.根据之前的权利要求之一的导线,其中在导线芯(2)的直径与平均颗粒大小之间的比率是在2.5与6之间。
4.根据之前的权利要求之一的导线,其中导线芯(2)的铜的总量是至少97%。
5.根据之前的权利要求之一的导线,其中导线芯以在0.5%与3%之间的量含有钯。
6.根据之前的权利要求之一的导线,其中导线芯以在45ppm与900ppm之间的量含有银。
7.根据之前的权利要求之一的导线,其中导线(1)具有在8μm与80μm的范围内的直径。
8.根据之前的权利要求之一的导线,其中在接合步骤之前导线芯在至少580℃的温度处退火达至少0.1s的时间。
9.根据之前的权利要求之一的导线,其中在退火之后的导线(1)的延伸值不大于最大延伸值的92%。
10.根据权利要求9的导线,其中导线(1)在至少比通过在其处退火获得最大延伸值的温度高10℃的温度处退火。
11.根据之前的权利要求之一的导线,特征在于涂层(3)被叠加在芯(2)的表面上方。
12.根据权利要求11的导线,其中涂层的质量不大于导线芯(2)的质量的3%。
13.根据权利要求11或12的导线,特征在于涂层(3)包括Pd、Au、Pt和Ag的组中的至少一个作为主要成分。
14.根据之前的权利要求中任一个的导线,其中在接合之前的导线芯(2)的硬度不大于95.0HV(0.010N/5s)。
15.根据之前的权利要求之一的导线,其中在导线芯中的硼的含量小于100ppm。
16.根据之前的权利要求之一的导线,其中
导线芯的直径是在15μm与28μm之间并且平均颗粒大小是在2.5μm与6μm之间;或者
导线芯的直径是在28μm与38μm之间并且平均颗粒大小是在3μm与10μm之间;或者
导线芯的直径是在38μm与50μm之间并且平均颗粒大小是在7μm与15μm之间;或者
导线芯的直径是在50μm与80μm之间并且平均颗粒大小是在10μm与30μm之间。
17.模块,包括:第一接合焊盘(11),第二接合焊盘(1)以及根据之前权利要求中任一个的导线(1),其中导线(1)通过球形接合的方式被连接到接合焊盘(11)之一。
18.根据权利要求17的模块,其中在将20μm直径的导线接合到铝接合焊盘的情况下,用于球形接合的工艺窗口面积具有至少120g*mA的值。
19.用于制造根据权利要求1至16中任一个的接合导线的方法,包括步骤:
a.提供具有要求的组分的铜芯前驱体;
b.牵引前驱体直到达到了导线芯的最终直径;
c.在定义的温度处将牵引的导线(1)退火达最小的退火时间。
20.根据权利要求19的方法,其中通过连续退火来执行退火。
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EP20130002674 EP2768019A3 (en) | 2013-02-15 | 2013-07-15 | Copper bond wire and method of making the same |
PCT/SG2014/000151 WO2014178792A1 (en) | 2013-05-03 | 2014-04-04 | Copper bond wire and method of making the same |
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CN111519227A (zh) * | 2020-03-30 | 2020-08-11 | 安徽广宇电子材料有限公司 | 一种键合线制备用铜丝材料的抗氧化处理设备 |
TWI764972B (zh) * | 2017-12-28 | 2022-05-21 | 日商日鐵新材料股份有限公司 | 半導體裝置用接合導線 |
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SG10201408586XA (en) * | 2014-12-22 | 2016-07-28 | Heraeus Materials Singapore Pte Ltd | Corrosion and moisture resistant bonding wire |
SG10201508104TA (en) * | 2015-09-29 | 2017-04-27 | Heraeus Materials Singapore Pte Ltd | Alloyed silver wire |
SG10201509634UA (en) * | 2015-11-23 | 2017-06-29 | Heraeus Oriental Hitec Co Ltd | Coated wire |
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CN111519227B (zh) * | 2020-03-30 | 2021-02-23 | 安徽广宇电子材料有限公司 | 一种键合线制备用铜丝材料的抗氧化处理设备 |
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KR20160013057A (ko) | 2016-02-03 |
WO2014178792A1 (en) | 2014-11-06 |
KR101989799B1 (ko) | 2019-06-17 |
US20160078980A1 (en) | 2016-03-17 |
CN105393352B (zh) | 2018-11-16 |
JP6462665B2 (ja) | 2019-01-30 |
TW201504460A (zh) | 2015-02-01 |
JP2016524811A (ja) | 2016-08-18 |
TWI512121B (zh) | 2015-12-11 |
SG11201508519YA (en) | 2015-11-27 |
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