CN101919037B - 球焊用包覆铜丝 - Google Patents

球焊用包覆铜丝 Download PDF

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Publication number
CN101919037B
CN101919037B CN2009801007236A CN200980100723A CN101919037B CN 101919037 B CN101919037 B CN 101919037B CN 2009801007236 A CN2009801007236 A CN 2009801007236A CN 200980100723 A CN200980100723 A CN 200980100723A CN 101919037 B CN101919037 B CN 101919037B
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China
Prior art keywords
copper
core
ball
copper wire
wire
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CN2009801007236A
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CN101919037A (zh
Inventor
山下勉
秋元英行
桑原岳
冈崎纯一
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Tanaka Denshi Kogyo KK
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Tanaka Denshi Kogyo KK
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
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Abstract

本发明提供一种球焊用包覆铜丝，其在扯断后形成球时，能够避免由于Cu或Cu合金芯材的氧化造成的不便。该球焊用包覆铜丝的特征在于，具有由铜-磷合金构成的芯材、在该芯材上的包含钯或铂的中间层，在该中间层上的包含金或银的表层。

Description

球焊用包覆铜丝
技术领域
本发明涉及一种包覆铜丝，其用于通过球焊连接半导体元件上的电极和电路配线基板的配线。 
背景技术
现在，作为通过球焊将半导体元件上的电极和外部端子之间接合的焊丝，主要使用丝径为20～50μm左右的金丝。该金丝的接合通常采用热压接超声波并用方式，可采用通用焊接装置、将焊丝通入其内部用于连接的毛细管夹具等。第一焊接中，用弧光输入热将焊丝前端加热熔融，利用表面张力形成球后，使该球部压接在加热到150～300℃范围的半导体元件的电极上。其后，用毛细管夹具使焊丝形成规定线弧(loop)后，在第二焊接中，通过超声波压接使焊丝直接与外部引线侧接合并引出。 
近年来，半导体封装的结构、材料、连接技术迅速多样化，例如，封装结构中，除现行的使用引线框架的QFP(Quad Flat Packaging)之外，正在寻求使用基板、聚酰亚胺带的BGA(Ball Grid Array)、CSP(Chip Scale Packaging)等新方式的实用化，且线弧性(loopcharacteristics)、接合性、批量生产使用性更加提高的焊丝。 
作为焊丝的接合对象的材质也正在多样化，硅基板上的配线、电极材料中，除现有的Al合金以外，适宜更微细配线的Cu正在实用化。另外，大多是在引线框架上施行镀Ag、镀Pd等，以及在树脂基板、带等上施与Cu配线，再在其上施与金等贵金属及其合金的膜。对应于这样的各种接合对象，要求提高焊丝的接合性、接合部的可靠性。 
当初考虑代替一直以来的高纯度4N系(纯度99.99质量％以上)的金丝，利用高纯度3N～6N系(纯度99.9～纯度99.9999质量％以上) 的铜丝。但是，铜丝存在易氧化的缺点。根据引线接合技术的要求，重要的是在形成球时，形成圆球度良好的球，在其球部和电极的接合部得到充分的接合强度，但是，特别是在第一焊接中，当形成熔融球时，由于熔融铜带入大气中的氧而氧化、固化，所以存在球变硬，使半导体芯片开裂这种致命的缺陷。因此，高纯度3N～6N系的铜丝不得不在还原性气氛中使用，使球焊用包覆铜丝对半导体装置的应用范围受到限制。 
另一方面，已提出了可以在Cu或Cu-Sn等芯材的外周设置0.002～0.5μm的Pd、Pd-Ni、Pd-Co等包覆层，改善抗蚀性以及强度的设计(参照专利文献1)。另外，作为防止铜焊丝的表面氧化的方法，已提出了用金、银、铂、钯、镍、钴、铬、钛等贵金属或抗蚀性金属将铜包覆的焊丝(参照专利文献2～专利文献4)。 
专利文献1：(日本)实开昭60-160554号公报 
专利文献2：(日本)特开昭62-97360号公报 
专利文献3：(日本)特开2005-167020号公报 
专利文献4：(日本)特许4203459号公报 
发明内容
但是，即使是包覆铜丝，在第二焊接中将包覆铜丝扯断时，在前端的切断面芯材的铜也会露出，结果露出面的铜会被氧化。因此，在第一焊接中，当想使包覆铜丝形成球形时，用贵金属进行了涂覆的铜芯材不会氧化，但在熔融固化的球的底部，露出面的铜的氧化膜会作为痕迹残留，因此，存在如下问题，即：应固定在半导体芯片上的球部硬化，第一焊接的球接合时，使半导体芯片损伤。 
鉴于上述状况，本发明的目的在于提供一种球焊用包覆铜丝，该球焊用包覆铜丝能够避免扯断后形成球时，由Cu或Cu合金芯材的氧化造成的不便。 
用于解决上述课题的本发明以下述的构成为要旨。 
(1)一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和 该芯材上的两种包覆层，其特征在于，所述芯材包含铜(Cu)-1～500质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。 
(2)一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和该芯材上的两种包覆层，其特征在于，所述芯材由铜(Cu)-1～80质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。 
(3)一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和该芯材上的两种包覆层，其特征在于，所述芯材由铜(Cu)-200～400质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。 
(4)上述1～3中任一项记载的球焊用包覆铜丝，其中，磷(P)以外的芯材的成分是纯度99.999质量％以上的铜(Cu)。 
(5)上述1～3中任一项记载的球焊用包覆铜丝，其中，磷(P)以外的芯材的成分是纯度99.9999质量％以上的铜(Cu)。 
(6)上述1～3中任一项记载的球焊用包覆铜丝，其中，中间层的厚度为0.005～0.2μm。 
(7)上述1～3中任一项记载的球焊用包覆铜丝，其中，中间层的厚度为0.01～0.1μm。 
(8)上述1～3中任一项记载的球焊用包覆铜丝，其中，表层的厚度为0.005～0.1μm。 
(9)上述1～3中任一项记载的球焊用包覆铜丝，其中，表层的厚度比中间层的厚度薄。 
根据本发明，即使在第二焊接的切断时芯材的铜露出，由于第一焊接中的熔融球形成时，低熔点的表层元素金(Au)早于中间层元素熔融，由此，表层元素一直扩展到露出来的芯材的铜的氧化部分，除此之外，芯材的铜利用含有的磷(P)的脱氧效果，在表层附近，磷(P)浓缩，由此，使芯材的铜的氧化部分开除去，从而可以使熔融球形成时不存在芯材的铜的氧化部分的影响。 
具体实施方式
本发明的包覆铜丝之一，芯材由铜(Cu)-1～500质量ppm磷(P)合金构成。含有1～500质量ppm磷(P)是为了利用磷(P)的脱氧作用将形成于芯材的露出部的铜(Cu)的氧化膜分解除去。熔融球表面上存在的(P)氧化时升华。这时，磷(P)在芯材表面附近形成浓缩层，由此，能够抑制并延迟芯材表面上形成的氧化铜的发生，能够和后述的金(Au)表层互相作用，将铜(Cu)表面的氧化膜厚度抑制在最低限。 
本发明的包覆铜丝之一，芯材由铜(Cu)-1～80质量ppm磷(P)合金构成。这是因为，即使磷(P)为微量，也具有使铜丝的再结晶温度上升，使铜丝自身的强度增强的效果。另外，铜(Cu)的纯度越高，磷(P)受到的杂质的影响越小，因此，磷(P)的添加量即使少量也可以。 
本发明的包覆铜丝之一，芯材由铜(Cu)-200～400质量ppm磷(P)合金构成。这是因为，即使磷(P)以外的杂质元素存在数十质量ppm程度，也能够抑制并延迟芯材表面上形成的氧化铜的发生。 
但是，优选芯材的铜(Cu)-磷(P)合金中，尽量不含磷(P)以外的杂质元素。因为这些杂质元素与大气中的氧反应形成氧化物，使第一焊接时的熔融的铜球变硬。相反，杂质元素越少，即使磷(P)的含量多至数百质量ppm程度，熔融的铜球也不倾向于变硬。具体地说，磷(P)以外的芯材成分优选纯度99.999质量％以上的铜(Cu)，更优选纯度99.9999质量％以上的铜(Cu)。在此，所谓“纯度99.999质量％以上”是指磷(P)及铜(Cu)以外的金属杂质元素小于0.001质量％，是指除去了铜(Cu)中存在的氧、氮和碳等气体状元素的情况。 
两种包覆层中的中间层由钯(Pd)或铂(Pt)、或者钯(Pd)和铂(Pt)的合金构成。钯(Pd)的熔点(1554℃)及铂(Pt)的熔点(1770℃)都比铜(Cu)的熔点(约1085度)高。因此，在芯材的铜(Cu)形成球状的熔融球的最初阶段，钯(Pd)或铂(Pt)成为薄膜， 或者，钯(Pd)和铂(Pt)的合金成为薄膜，防止且延迟来自熔融球的侧面的氧化。 
中间层的厚度优选0.005～0.2μm，更优选0.01～0.1μm。小于0.005μm时，有作为薄膜的氧化延迟的效果变得不充分的倾向。超过0.2μm时，有使铜(Cu)的纯度下降、因铜球的合金化容易引起集成电路芯片开裂的倾向。 
但是，钯(Pd)或铂(Pt)的薄膜，或者钯(Pd)和铂(Pt)的合金的薄膜往往会被吸收到熔融铜球的内部，所以，该薄膜不能完全覆盖芯材的露出部，即在铜球的端部因电弧放电形成的铜(Cu)的氧化膜。并且，最外层的熔点更高，由于电弧放电需要更大的能量，因此会促进铜丝断面的氧化。于是，在芯材的铜(Cu)形成球状的熔融球的阶段，需要防止芯材露出部分氧化的手段。因此，在本发明中，除了使芯材中含磷(P)以外，两种包覆层中的表层采用了金(Au)。金(Au)的熔点(约1064℃)，比铜(Cu)的熔点(约1085度)低，所以，在铜(Cu)形成球状的熔融球的阶段，表层的低熔点的金(Au)比铜(Cu)提前更早地融解，迅速地包裹铜丝端面，促进铜(Cu)的熔化。接着，铜(Cu)熔化之后，中间层的钯(Pd)或铂(Pt)的薄膜或者钯(Pd)和铂(Pt)的合金的薄膜软化而形成熔融球。可以认为，这样，在形成铜(Cu)的熔融球的过程中，低熔点的金(Au)表层促进铜(Cu)的熔化，与没有金(Au)表层相比，使钯(Pd)或铂(Pt)等的薄膜迅速地被吸收到熔融铜球的内部，由此，金(Au)将露出于端部的芯材的铜(Cu)覆盖，从而可以防止熔融(Cu)球的铜(Cu)的氧化。 
两种包覆层中，优选表层的厚度比中间层的厚度薄。因为如果表层变厚，熔融需要花费时间，促进铜(Cu)的熔化的效果减弱，并且，因熔融铜球的表面由于偏析产生的合金化，熔融铜球自身变硬，容易引起半导体芯片的开裂。作为表层的厚度，只要具有使钯(Pd)或铂(Pt)等的薄膜被熔融铜球的内部迅速地吸收，且足够防止在熔融铜球芯材的露出部形成的铜(Cu)氧化的厚度就可以。具体地说，金(Au) 的表层的厚度优选0.005～0.1μm，更优选0.005～0.010.02μm以下，最优选0.005～0.01μm。 
中间层的钯(Pd)或铂(Pt)及表层的金(Au)是即使形成熔融球也不会氧化的元素。另外，这些元素像银(Ag)一样不会和大气中的硫磺(S)发生反应，所以，不会给芯材的铜(Cu)带来不良影响。并且，钯(Pd)或铂(Pt)元素也不会给芯材的铜(Cu)中所含的磷(P)带来不利影响，表层的金(Au)和芯材的铜(Cu)完全固溶。其结果是，在第一焊接中，在熔融的铜球凝固的过程中，铜(Cu)球受到的磷(P)的脱氧作用与包覆层的有无没有关系，对半导体集成电路芯片是同等的。另外，作为两种包覆层的中间层和表层由贵金属形成，所以，在第二焊接中的超声波接合时，相比于芯材的铜(Cu)直接与引线框架接合，利用包覆层可防止芯材的铜(Cu)的氧化，具有接合力提高的效果。 
在铜芯材的表面形成金(Au)的表层及钯(Pd)或铂(Pt)等的中间层时，优选镀敷法。镀敷法可以是电解镀敷、化学镀敷、熔融盐镀敷等。得到被称为冲击镀、闪镀的薄的膜厚的电解镀敷，镀敷速度快，和基底的密合性也良好，所以，进行电解镀敷时优选。化学镀敷使用的溶液分为置换型和还原型，像金(Au)表层那样膜比较薄时，仅采用置换型镀敷就可以，但形成像中间层的钯(Pd)或铂(Pt)那样有一定厚度的膜时，有效的是在置换型镀敷后实施自身催化型的还原型镀敷。对于化学法而言，装置等简便，容易实施，但比电解法花费时间。镀浴中优选含有磷酸或磷酸盐。因为金(Au)、钯(Pd)和铂(Pt)析出时，将磷(P)带入，由此在第一焊接中，在芯材的铜(Cu)熔融时，具有可以使熔融铜(Cu)球表面的磷(P)的脱氧效果更良好地发挥的效果。具体地说，因为磷(P)具有将形成于芯材的露出部的铜(Cu)的氧化膜分解除去的效果，还具有使熔融铜(Cu)的氧化更缓慢的效果。 
另一方面，对于物理气相沉积法而言，可以利用溅射法、离子镀敷法、真空淀积等的物理吸附、和等离子CVD等的化学吸附。这些方法都是干式，只要不考虑成本，则不需要膜形成后的清洗，不必担心清洗时的表面污染等。 
对于实施镀敷或气相沉积的阶段，有效的是在粗直径的芯材上形成镀敷膜或气相沉积膜之后，进行多次拉丝模拉丝直至目标丝径的方法。这是为了使镀敷或气相沉积的结晶组织通过拉丝加工变性为塑性加工后的组织。优选的包覆手段可以是在实施冲击镀后，将粗的铜(Cu)芯线浸渍于电解镀浴中，形成中间层及表层的电镀膜后，将该包覆铜丝进行拉丝使其达到最终直径的方法等。必要时，优选进行钯(Pd)或铂(Pt)的冲击镀。 
表层形成包含两种以上的金属的多层时，用镀敷法、气相沉积法、熔融法等阶段性地形成多个不同的金属层。此时，有效的是全部形成不同的金属之后进行热处理的方法、在每一层的形成中进行热处理而依次层叠的方法等。 
实施例 
下面，对实施例进行说明。 
将从含有规定量的磷(P)的纯度的铜(Cu)锭进行拉丝加工到500μm的丝径的铜丝作为芯材，在该铜丝表面实施冲击镀之后，用通常的方法进行电解镀敷。准备包覆了钯(Pd)及/或铂(Pt)作为中间层的三种丝，在该三种丝上直接包覆金(Au)作为表层。镀浴使用在半导体用途中市售的镀浴。具体地说，钯(Pd)使用在中性的二硝基二氨合钯浴中添加了10gW/l的磷酸盐的镀浴；铂(Pt)使用酸性Pt-p盐浴；金(Au)使用在中性的氰基化金浴中添加了100gW/l的磷酸盐的镀浴。其后，将该包覆铜丝进行拉丝模拉丝直到最终直径25μm，最后消除加工变形，实施热处理，以使伸长率值达到10％左右。最终的镀层厚度等如表1所示。另外，镀层厚度用奥格电子分光法(AES)进行测定。 
[表1]包覆铜丝的各层结构 
Figure GPA00001098984200081
焊丝的连接使用市售的自动丝焊器((株)新川制的超声波热压接丝焊器“UTC-1000型UTC-1000(商品名)”)，进行球/针脚接合。在氮气氛中通过电弧放电在焊丝前端制作球，将其与硅基板上的0.8μm铝(Al-0.5％Cu)电极膜接合，以频率1/200周期、2kW将焊丝另一端通过楔形针脚接合在镀敷有4μmAg的200℃的引线框架上。 
另外，第一焊接的条件如下。 
(接合温度：200℃。初始球径：40～60μm) 
试验结果示于表2。 
初始球形状的观察：观察20个接合前的球，判定形状是否为圆球、尺寸精度是否良好等。如果异常形状的球产生2个以上，则判定为不良，用符号×标记；如果异常形状的球为2个以下，但球位置相对于丝的芯偏离显著的个数为5个以上的情况，用符号△标记；如果芯偏离为2～4个，则判定为使用上没有大的问题，用符号○标记；芯偏离为1个以下且尺寸精度良好的情况，球形成良好，用符号◎标记。 
压接球部的接合形状的判定：观察500个经接合的球，对形状的圆度、尺寸精度等进行评价。球压接直径选定达到丝直径的2～3倍的范围的条件。如果从真圆偏离较大的各向异性或椭圆状等不良球形状为5个以上，则判定为不良，用符号×标记；不良球形状为2～4个或花瓣状等球压接部的外周部为8个以上，则需要改善，用符号△标记；如果不良球形状为1个以下且花瓣状变形为3～7个，则判定为实用上没有问题的水平，用符号○标记；如果花瓣状变形为2个以下，则为良好，用符号◎标记。 
对于熔融球的氧化，用50个芯片确认进行球焊时是否产生了裂纹。对铝(Al)焊盘进行碱溶解时露出的硅芯片产生了裂纹的情况，记载其个数。 
针脚接合的评价，对于在实施了镀银(Ag)的引线框架上超声波热压的焊接线弧，测量将距针脚侧其长度为20％的部分用牵引钩垂直地拉伸时，达到断裂的负荷。用mN表示50个线弧中测量的平均值。 
表2中表示了本发明的包覆铜丝的评价结果。 
[表2]包覆铜丝的实施评价 
第一包覆铜丝的焊丝(Au/Pd/CuP)为实施例1、3、6、8、10、12、15、18及21，第二包覆铜丝的焊丝(Au/Pt/CuP)为实施例2、4、5、7、9、11、14、16、17及22，第三包覆铜丝的焊丝(Au/(Pt·Pd)/CuP)为实施例11～19及20，对第三包覆铜丝的焊丝进行900℃×20秒钟热处理后的焊丝(Au/(Pt·Pd)/CuP)相当于实施例13。表1的比较例23～30表示与本发明的技术方案不符合的焊丝的结果。 
可以确认，实施例1～4、6、7、9、10、14、16、17及19的焊丝，球部的圆球度、圆度优异，无芯片损伤，针脚接合性、压接形状良好。这些性能在仅仅在表面形成有比较例23～30的与本发明的技术方案不符合的铜以外的元素的膜的Cu丝中不充分。 
可以确认，实施例5、8、15、18及20～22的5～10的焊丝，虽然比上述的实施例1～5的焊丝稍差，但球部的圆球度、圆度优异，芯片损伤也少，针脚接合性、压接形状较好。 
[0056] 可以确认，实施例11～13的焊丝，虽然比上述的实施例的焊丝稍差，但是和实施例1～5的焊丝一样，球部的圆球度、圆度优异，且芯片损伤也少，没有比较例那样的缺陷，楔形接合性、压接形状较好。另外，实施例13的焊丝表现出和实施例11、12的焊丝同样的结果。 

Claims (9)

1.一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和该芯材上的两种包覆层，其特征在于，所述芯材由铜(Cu)-1～500质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。
2.一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和该芯材上的两种包覆层，其特征在于，所述芯材由铜(Cu)-1～80质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。
3.一种球焊用包覆铜丝，具有以铜(Cu)为主成分的芯材、和该芯材上的两种包覆层，其特征在于，所述芯材由铜(Cu)-200～400质量ppm磷(P)合金构成，并且，所述包覆层包含钯(Pd)或铂(Pt)中间层及金(Au)表层。
4.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，磷(P)以外的芯材的成分是纯度99.999质量％以上的铜(Cu)。
5.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，磷(P)以外的芯材的成分是纯度99.9999质量％以上的铜(Cu)。
6.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，中间层的厚度为0.005～0.2μm。
7.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，中间层的厚度为0.01～0.1μm。
8.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，表层的厚度为0.005～0.1μm。
9.如权利要求1～3任一项所述的球焊用包覆铜丝，其中，表层的厚度比中间层的厚度薄。
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US20130175677A1 (en) * 2012-01-06 2013-07-11 Texas Instruments Incorporated Integrated Circuit Device With Wire Bond Connections
US8866298B2 (en) * 2013-01-11 2014-10-21 Infineon Technologies Ag Bonded system with coated copper conductor
TWI500788B (zh) * 2013-12-10 2015-09-21 Truan Sheng Lui 耐磨抗蝕無鍍層銅線及其製造方法
CN104778992B (zh) * 2014-01-09 2016-10-19 吕传盛 耐磨抗蚀无镀层铜线及其制造方法
KR20180105740A (ko) * 2014-04-21 2018-09-28 신닛테츠스미킹 마테리알즈 가부시키가이샤 반도체 장치용 본딩 와이어
JP5807992B1 (ja) * 2015-02-23 2015-11-10 田中電子工業株式会社 ボールボンディング用パラジウム（Ｐｄ）被覆銅ワイヤ
US10032741B2 (en) 2015-02-26 2018-07-24 Nippon Micrometal Corporation Bonding wire for semiconductor device
CN106463495B (zh) 2015-08-12 2020-09-04 日铁新材料股份有限公司 半导体装置用接合线
JP6410692B2 (ja) * 2015-08-28 2018-10-24 田中電子工業株式会社 銅合金ボンディングワイヤ
JP6898705B2 (ja) * 2015-09-02 2021-07-07 田中電子工業株式会社 ボールボンディング用銅合金細線
JP6047214B1 (ja) * 2015-11-02 2016-12-21 田中電子工業株式会社 ボールボンディング用貴金属被覆銅ワイヤ
JP2019068053A (ja) * 2017-09-28 2019-04-25 日亜化学工業株式会社 発光装置
US10622531B2 (en) * 2017-09-28 2020-04-14 Nichia Corporation Light-emitting device
CN109628780B (zh) * 2019-01-15 2021-01-26 北华大学 一种汽车轻量化铝基复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1311526A (zh) * 2000-02-22 2001-09-05 国际商业机器公司 制备用于电连接的导电座的方法及形成的导电座
CN1482264A (zh) * 2003-07-28 2004-03-17 洛阳铜加工集团有限责任公司 Ic用引线框架铜带及其制作工艺方法
CN101179061A (zh) * 2007-11-22 2008-05-14 周少平 铁合金引线整流用电子二极管及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60160554U (ja) * 1984-03-31 1985-10-25 古河電気工業株式会社 半導体用ボンディング細線
JPS6297360A (ja) * 1985-10-24 1987-05-06 Mitsubishi Metal Corp 半導体装置のボンデイングワイヤ用表面被覆高純度銅極細線
US7969021B2 (en) * 2000-09-18 2011-06-28 Nippon Steel Corporation Bonding wire for semiconductor device and method for producing the same
JP2003133364A (ja) * 2001-10-19 2003-05-09 Tanaka Electronics Ind Co Ltd 銅ボールの熱圧着方法
JP2004064033A (ja) 2001-10-23 2004-02-26 Sumitomo Electric Wintec Inc ボンディングワイヤー
JP4204359B2 (ja) * 2002-03-26 2009-01-07 株式会社野毛電気工業 ボンディングワイヤーおよびそれを使用した集積回路デバイス
JP4203459B2 (ja) 2004-08-30 2009-01-07 日東工器株式会社 電動ドライバ装置
WO2006073206A1 (ja) 2005-01-05 2006-07-13 Nippon Steel Materials Co., Ltd. 半導体装置用ボンディングワイヤ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1311526A (zh) * 2000-02-22 2001-09-05 国际商业机器公司 制备用于电连接的导电座的方法及形成的导电座
CN1482264A (zh) * 2003-07-28 2004-03-17 洛阳铜加工集团有限责任公司 Ic用引线框架铜带及其制作工艺方法
CN101179061A (zh) * 2007-11-22 2008-05-14 周少平 铁合金引线整流用电子二极管及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2005-254298A 2005.09.22

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MY154850A (en) 2015-08-14

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