CN105830205A - 半导体装置用接合线 - Google Patents

半导体装置用接合线 Download PDF

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Publication number
CN105830205A
CN105830205A CN201480068797.7A CN201480068797A CN105830205A CN 105830205 A CN105830205 A CN 105830205A CN 201480068797 A CN201480068797 A CN 201480068797A CN 105830205 A CN105830205 A CN 105830205A
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China
Prior art keywords
concentration
coating
intermediate layer
core
loop
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Granted
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CN201480068797.7A
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CN105830205B (zh
Inventor
宇野智裕
萩原快朗
小山田哲哉
小田大造
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Nippon Steel & Sumitomo New Materials Co.,Ltd.
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Kanae Co Ltd
Nippon Micrometal Corp
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Publication of CN105830205A publication Critical patent/CN105830205A/zh
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Publication of CN105830205B publication Critical patent/CN105830205B/zh
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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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227—Rods, wires
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    • 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
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B23K35/302—Cu as the principal constituent
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    • 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
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    • B23K35/3033—Ni as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B32—LAYERED PRODUCTS
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Abstract

本发明提供能够减少异常环路的发生的接合线。所述接合线的特征在于，具备：芯材，其含有超过50mol％的金属M；中间层，其形成于所述芯材的表面，包含Ni、Pd、所述金属M和不可避免的杂质，所述Ni的浓度为15～80mol％；以及，被覆层，其形成于所述中间层上，包含Ni、Pd和不可避免的杂质，所述Pd的浓度为50～100mol％，所述金属M为Cu或Ag，所述被覆层的Ni浓度低于所述中间层的Ni浓度。

Description

半导体装置用接合线
技术领域
本发明涉及用于将半导体元件上的电极和电路布线基板(引线框、基板、带(tape)等)的布线连接的半导体装置用接合线。
背景技术
目前，作为将半导体元件上的电极与外部端子之间接合的半导体装置用接合线(以下称为接合线)，主要使用线径为20～50μm左右的细线(接合线)。接合线一般采用并用超声波的热压接方式来进行接合。在本方式中，可使用通用接合装置、将接合线通到其内部而用于连接的毛细管工具等。为了将接合线连接，首先，产生电弧放电而将线尖端加热熔融，利用表面张力形成球部之后，使该球部压接接合(球接合)于在150～300℃的范围内加热了的半导体元件的电极上。接着，直接将线通过超声波压接而接合(楔接合)于外部引线侧。
近年来，半导体安装的结构、材料、连接技术等快速多样化，例如在安装结构中，除了现行的使用引线框的QFP(QuadFlatPackaging：方形扁平式封装)以外，使用基板、聚酰亚胺带等的BGA(BallGridArray：球栅阵列封装)、CSP(ChipScalePackaging：芯片级封装)等新的形态已实用化，需求进一步提高了环路性、接合性、量产使用性等的接合线。
关于接合线的原材料，一直以来主要使用高纯度4N系(纯度>99.99质量％)的金。但是，金的价格昂贵，因此期望获得材料成本便宜的其它种类金属的接合线。
作为材料成本便宜、电传导性优异的接合线，专利文献1中公开了一种接合线，该接合线具有以铜为主成分的芯材、以及设置在所述芯材上的含有金属M和铜的外层，所述外层的成分和组成中的任一者或两者与所述芯材不同。
在先技术文献
专利文献1：日本特开2010-212697号公报
发明内容
但是在上述专利文献1的情况下，在形成环路时，由于芯材和外层的应变、变形阻力的差别，有可能接合线变形，产生异常环路。
因此，本发明的目的是提供能够减少异常环路的发生的接合线。
本发明的权利要求1涉及的接合线，其特征在于，具备：芯材，其含有超过50mol％的金属M；中间层，其形成于所述芯材的表面，包含Ni、Pd、所述金属M和不可避免的杂质，所述Ni的浓度为15～80mol％；以及被覆层，其形成于所述中间层上，包含Ni、Pd和不可避免的杂质，所述Pd的浓度为50～100mol％，所述金属M为Cu或Ag，所述被覆层的Ni浓度低于所述中间层的Ni浓度。
另外，本发明的权利要求3涉及的接合线，其特征在于，所述被覆层还含有Au，所述接合线具备表面层，所述表面层形成于所述被覆层上，由包含Au和Pd的合金构成，所述Au的浓度为10～70mol％，Au和Pd的合计浓度为80mol％以上，所述被覆层的Au浓度低于所述表面层的Au浓度。
根据本发明的权利要求1，通过中间层缓和芯材与被覆层的变形阻力的差别，能够减少作为异常环路的蛇形环路的发生。
根据本发明的权利要求3，通过表面层抑制线表面的硫化和氧化从而减小滑动阻力，作为异常环路除了能够减少蛇形环路以外，还能够减少下沉环路的发生。
附图说明
图1是表示由接合线的异常变形导致的不良形态的示意图，图1A是表示蛇形环路不良的图，图1B是表示下沉环路不良的图。
具体实施方式
1.实施方式
(总体构成)
以下，对本发明的实施方式进行详细说明。本实施方式涉及的接合线具备：含有超过50mol％的金属M的芯材；形成于芯材上的中间层；以及形成于该中间层上的被覆层。金属M为Cu或Ag。
中间层包含Ni、Pd、所述金属M和不可避免的杂质，所述Ni的浓度为15～80mol％。被覆层包含Ni、Pd和不可避免的杂质，所述Pd的浓度为50～100mol％。被覆层的Ni浓度低于所述中间层的Ni浓度。再者，本说明书中的浓度，单位为mol％时是除了芯材以外，基于俄歇电子能谱法(AES：AugerElectronSpectroscopy)在深度方向上测定时的、各层中的最高浓度。
构成芯材的Cu或Ag、与被覆层中所含的Pd，在强度上有2倍以上的差异，再结晶温度有400℃以上的差异。与此相对，Ni的强度和再结晶温度为Cu或Ag、与Pd的中间的程度。因此，本实施方式的情况下，中间层为含有Ni和Pd、以及、Cu或Ag的合金，Ni的浓度为15～80mol％，通过与被覆层相比含有更多的Ni，中间层的强度和再结晶温度成为芯材与被覆层的中间的程度。由此，接合线能够通过中间层缓和芯材与被覆层的变形阻力的差别，来减少异常环路的发生。
参照图1A对异常环路进行说明。图1A所示的接合线10通过球接合12和楔接合14而接合，作为异常环路发生了蛇形环路16。蛇形环路16，在靠近楔接合14的下降区域中，具有多次在接合线10上发生弯曲的形状。蛇形环路16，在球接合12与楔接合14的高低差大、跨距长的梯形环路中发生频度高。例如，在球接合12与楔接合14的高低差为500μm以上、距离(跨距)为3mm以上、下降区域的长度为800μm的情况下发生频度高。
中间层通过使Ni的浓度为15～80mol％，能够更切实地缓和芯材与被覆层的变形阻力的差别。中间层的Ni的浓度如果超过80mol％，则会在球部内产生气泡。
产生了气泡的球部如果接合到电极上，则会发生从线中心偏移而使球部变形的偏芯变形、作为偏离正圆的形状不良的椭圆变形、花瓣变形等，成为引起接合部从电极面伸出、接合强度降低、芯片损坏、生产管理上的不良情况等问题的原因。这样的初期接合的不良，有时也会诱发后述的接合可靠性的降低。
中间层的厚度优选为8～80nm。接合线通过使中间层的厚度为8～80nm，能够更切实地缓和芯材与被覆层的变形阻力的差别。中间层的厚度如果超过80nm，则在低温下连接接合线时，由于在接合界面处的扩散速度变慢，因此楔接合的强度降低。
本实施方式的情况下，在被覆层与中间层的边界上即使Ni的浓度为15mol％以上，只要Pd的浓度为50mol％以上，在本说明书中就也将该区域作为被覆层。
被覆层通过使Pd的浓度为50～100mol％，能够进一步抑制接合线表面的氧化。再者，接合线会因表面氧化而导致楔接合的强度降低，容易发生树脂密封时的线表面的腐蚀等。
另外，被覆层也可以含有金属M。接合线通过使被覆层含有金属M，可提高减少在球部与颈部的边界附近成为问题的唇状损伤的效果。
芯材，在金属M为Cu的情况下，也可以含有选自P、Ti、B、Ag之中的一种以上的元素。该情况下，选自P、Ti、B、Ag之中的一种以上的元素，通过所述元素在线整体中所占的浓度总计为0.0005～0.02质量％的范围，能够提高压接球的正圆度。再者，在近年来的最大密度安装中，要求窄间距连接。因此，球接合部的变形形状很重要，需要抑制花瓣状、偏芯等的异形、提高正圆度。
另外，芯材，在金属M为Cu的情况下，也可以含有选自Pd、Ni之中的一种以上的元素。该情况下，选自Pd、Ni之中的一种以上的元素，通过所述元素在线整体中所占的浓度总计为0.2～2.0质量％的范围，能够提高接合可靠性。
再者，接合可靠性，在如汽车用半导体等那样在高温下使用的用途的情况下，在接合线与电极的接合部成为问题的情况较多。接合可靠性是通过高温加热试验等加速试验来对上述接合部的强度的降低、电阻的上升等进行评价。
芯材，在金属M为Ag的情况下，也可以含有选自Pd、Ni、Cu之中的一种以上的元素。该情况下，选自Pd、Ni、Cu之中的一种以上的元素，通过所述元素在线整体中所占的浓度总计为0.5～5.0质量％的范围，能够提高上述接合可靠性。
进入，本实施方式涉及的接合线，也可以在上述被覆层上具备表面层，所述表面层由包含Au和Pd的合金构成。该情况下，被覆层还含有Au。另外，被覆层也可以含有少量的Ni、Cu。
表面层，其Au的浓度为10～70mol％，Au和Pd的合计浓度为80mol％以上。在其与被覆层的边界上即使Pd的浓度为50mol％以上，只要Au的浓度为10mol％以上，在本说明书中就也作为表面层。
由包含Au和Pd的合金构成的表面层，能够抑制线表面的硫化和氧化，从而减少滑动阻力。因此，接合线通过具备表面层，除了能够减少蛇形环路的发生以外，还能够减少图1B所示的下沉(sagging)环路18的发生。下沉环路18与蛇形环路16同样地，在球接合12与楔接合14的高低差大、跨距长的梯形环路中发生频度高。另外，下沉环路18具有与蛇形环路16相比缓缓地蛇行的形状。
表面层，通过其Au的浓度为10～70mol％、Au和Pd的合计浓度为80mol％以上，能够更切实地减少滑动阻力。表面层的Au的浓度如果超过70mol％，则会发生球部成为椭圆形的不良。这样的椭圆形的球部，不适合于在小的电极上进行球接合的高密度安装。
表面层、被覆层和中间层的总计厚度优选为25～200nm。通过为上述范围，接合线能够抑制楔接合部的卷缩即剥离不良、提高楔接合性。如果表面层、被覆层和中间层的总计厚度为40～150nm，则能够更切实地提高楔接合性，因而更加优选。
表面层的厚度优选为3～30nm。通过为上述范围，接合线能够更切实地减少蛇形环路和下沉环路的发生。
(制造方法)
下面，对本实施方式涉及的接合线的制造方法进行说明。在接合线的制造中，需要在芯材的表面形成中间层、被覆层、以及根据情况形成表面层的工序、形成为期望的粗细度的加工工序、热处理工序。
在铜的芯材的表面形成中间层、被覆层和表面层的方法，有镀敷法、蒸镀法、熔融法等。镀敷法可以采用电解镀敷法、无电解镀敷法的任一种方法来进行制造。被称为触击镀、闪镀的电解镀敷法，镀敷速度快，与基底的密着性也良好。用于无电解镀敷法的溶液，分类为置换型和还原型，在膜较薄的情况下仅采用置换型镀敷就足够了，但在形成厚的膜的情况下，在置换型镀敷之后阶段性地实施还原型镀敷是有效的。无电解镀敷法的装置等简便，比较容易，但比电解镀敷法需要时间。
在蒸镀法中，可以利用溅射、离子镀和真空蒸镀等物理吸附、以及等离子体CVD等化学吸附。这些方法都是干式方法，不需要形成膜之后的洗涤，不用担心洗涤时的表面污染等。
对于实施镀敷或蒸镀的阶段，以目标线径形成期望的膜的方法、和在粗径的芯材上形成膜后进行多次拉丝直到成为目标线径的方法都是有效的。前者以最终直径形成膜，在制造、品质管理等方面较为简便，而后者将膜形成与拉丝组合，在提高膜与芯材的密着性方面较为有利。作为各形成法的具体例，可举出：对于目标线径的铜线，一边使线在电解镀敷溶液中连续地扫掠通过一边形成膜的方法；或者，将粗的铜线浸渍在电解镀浴或无电解镀浴中来形成膜，然后将线进行拉丝而达到最终线径的方法等。
形成中间层、被覆层、表面层之后的加工工序中，根据目的而选择并灵活使用辊轧制、挤锻(swaging)、模拉丝等。通过加工速度、压下率或模减面率等来控制加工组织、位错、晶界的缺陷等，也会对中间层、被覆层、表面层的结构、密着性等带来影响。
在热处理工序中，在芯材与中间层、中间层与被覆层、被覆层与表面层的各界面，促进各构成中所含的金属元素的相互扩散。根据目的来实施1次或多次热处理是有效的。为了在中间层、被覆层、表面层的结构中得到期望的膜厚、组成，需求以严格的精度控制％级的浓度、nm级的膜厚等的制造技术。热处理工序分类为刚形成膜之后的退火、加工途中的退火、在最终直径下的最终退火，选择、灵活使用它们是很重要的。
只是单纯地对线进行了加热并不能控制接合线的表面和内部的各金属元素的分布。即使原样应用在通常的线制造中所采用的在最终线径下的消加工应力退火，也会由于芯材、中间层、被覆层、表面层的密着性的降低而导致环路控制变得不稳定，难以对线的长度方向的各层的均质性、线截面中的各层的分布进行控制。因此，热处理的时机、温度、速度、时间等的控制是很重要的。
通过将加工与热处理组合而控制扩散的进行度，能够控制期望的膜厚、组成、结构。进行热处理之前的加工过程，和在芯材与中间层、中间层与被覆层、被覆层与表面层的各界面中的组织等有关系，因此也会对热处理中的扩散行为带来影响。最终的各层的组成、厚度等根据在哪个加工阶段进行热处理而发生变化。
作为热处理法，通过一边将线连续地扫掠一边进行热处理，而且，不是使一般的热处理的炉内温度恒定，而是在炉内形成温度梯度，由此能够容易地量产具有带有本实施方式的特征的芯材、中间层、被覆层、表面层的接合线。在具体的事例中，有局部地导入温度梯度的方法、使温度在炉内变化的方法等。为了抑制接合线的表面氧化，一边使N2、Ar等惰性气体在炉内流动一边加热也是有效的。
在温度梯度的方式中，炉入口附近的正的温度梯度(相对于线的扫掠方向温度上升)、稳定温度区域、炉出口附近的负的温度梯度(相对于线的扫掠方向温度下降)等多个区域设置温度梯度是有效的。由此，在炉入口附近不产生各层与芯材的剥离等，使密着性提高，在稳定温度区域中促进各金属元素的扩散而形成期望的浓度梯度，而且在炉出口附近抑制表面的铜的过度氧化，从而能够改善所得到的接合线的接合性、环路控制性等。为了得到这样的效果，期望将出入口处的温度梯度设为10℃/cm以上。
在使温度变化的方法中，通过将炉内分割为多个区域、在各区域中进行不同的温度控制而形成温度的分布也是有效的。例如，将炉内分割为3处以上，独立地进行温度控制，使炉的两端的温度比中央部的温度低，由此可得到与温度梯度的情况同样的改善效果。另外，为了抑制接合线的表面氧化，使炉的出口侧成为铜的氧化速度慢的低温，由此可使楔接合部的接合强度上升。
另外，熔融法是使各层或芯材的任一者熔融而进行浇铸的方法，通过以1～50mm左右的粗径将各层与芯材连接之后进行拉丝而具有生产性优异，以及与镀敷法、蒸镀法相比各层的合金成分设计容易，强度、接合性等特性改善也容易等优点。在具体的工序中，分为在预先制作出的芯材的周围，将熔融的构成各层的金属依次浇铸而形成各层的方法，和使用预先制作出的包含中间层、被覆层、表面层的中空圆柱，通过向其中空部浇铸例如熔融的铜或铜合金而形成芯材的方法。优选后者，即向中空圆柱的内部浇铸铜的芯材，该方法能够容易地在中间层和被覆层中稳定形成铜的浓度梯度等。另外，在熔融法中，也可以省略用于使铜向中间层和被覆层扩散的热处理操作，但通过实施用于调整中间层和被覆层内的铜的分布的热处理，也能期待进一步的特性改善。
另外，在利用这样的熔融金属的情况下，也可以通过连铸来制造芯材和各层的至少一者。通过该连铸法，与上述的浇铸方法相比，工序简略化，而且能够使线径较细，提高生产性。
另外，作为形成不含金属M的被覆层的制法，为了抑制被覆层内的金属M的体扩散、晶界扩散等，期望热处理温度低。具体而言，分两次以上进行热处理，加工途中的粗线的中间热处理设为高温，最终线径的最终热处理为低温化，由此形成不含金属M的被覆层是有效的。例如期望实施两种热处理的线径之差为2倍以上，温度差为100℃以上。
在本实施方式涉及的接合线的连接中，形成球部时所使用的保护气体，除了标准的5体积％H2+N2气体以外，也可以使用纯N2气体。产生电弧放电而在线尖端形成球部时，通过吹送保护气体，能够使电弧放电稳定化，抑制熔融了的球部表面的氧化。
2.实施例
按照试样、评价内容、评价结果的顺序对实施例进行说明。
(试样)
作为接合线的原材料，芯材所用的Cu、Ag使用了纯度约为99.99质量％以上的高纯度的原材料，作为被覆层的Pd、中间层的Ni、表面层的Au，准备了纯度为99.9质量％以上的镀液。在溶解芯材的工序中，添加了适量的合金元素。
准备直径约为1～3mm的粗径的线，在该线的表面采用电解镀敷法形成了中间层、被覆层、表面层等。作为电解镀液，使用了面向电子部件、半导体的市售镀液。
在由芯材、中间层、被覆层构成的接合线的情况下，以通过Ni镀敷处理形成中间层之后再通过Pd镀敷处理形成被覆层的顺序实施了两个阶段的处理。另外，在由芯材、中间层、被覆层、表面层构成的接合线的情况下，以通过Ni镀敷处理形成中间层、通过Pd镀敷处理形成被覆层、通过Au镀敷处理形成表面层的顺序实施了三个阶段的处理。为了提高密着性，根据需要在实施最后的镀敷处理之后，实施了加热处理。加热条件设为在氮气气氛中、在150～300℃的低温进行30分钟的分批式加热。另外，根据需要在形成中间层之后实施了加热处理。其加热条件设为上述范围。
在形成中间层、被覆层、表面层等之后，通过拉丝来较细地加工直到最终线径18～20μm。拉丝速度设为10～100m/分钟的范围，拉丝模使用了每一个的减面率为3～15％的拉模。
在拉丝到最终直径之后，实施了最终退火以使得除去加工应力、拉伸率值成为5～20％的范围。根据需要在模拉丝到线径30～100μm之后，实施中间退火，进而实施了拉丝加工。
在线的最终退火或中间退火中，利用了一边将线连续地扫掠一边连续加热的连续退火。温度设定为300～700℃的范围，线扫掠速度在10～100mm/分钟的范围内进行了调整。结合温度分布，也对线扫掠速度等进行了优化。作为退火的气氛，出于抑制氧化的目的而使用了氮气。气体流量在0.0002～0.004m3/分钟的范围内进行了调整。将拉丝加工途中的中间退火、最终直径下的最终退火适当组合。中间退火是以拉丝加工的途中的线径0.1～1mm对线进行了退火。
接合线的连接，使用市售的自动焊线机(K&S公司制)，进行了球/楔接合。通过电弧放电在线尖端制作球部，将该球部与硅基板上的电极膜接合，将线的另一端楔接合到引线端子上。为了抑制球熔融时的氧化，向线尖端吹送5体积％H2+N2气体。接合温度设为通常的175℃、和低温的150℃。作为接合对象的硅基板上的电极，使用铝电极(Al-0.5％Cu膜)，其厚度为0.8μm。另一方面，楔接合的对象，使用了引线框上的Au/Pd电极。
线表面的膜厚测定，使用了通过AES进行的深度分析。利用Ar离子一边溅射一边在深度方向进行测定，深度的单位按SiO2换算进行表示。接合线中的合金元素的浓度，利用了AES或感应耦合等离子(ICP：InductivelyCoupledPlasma)分析。在芯材中所含有的元素与在线表面形成的中间层、被覆层、表面层的元素重复的情况下，芯材中所含有的元素的浓度使用了芯材截面中的利用电子探针(EPMA：ElectronProbeMicroAnalyser)、能量色散型X射线分析(EDX：EnergydispersiveX-rayspectrometry)、AES分析方法求出的浓度的平均值。与其对应的元素为Pd、Ni、Au元素。另一方面，在芯材中所含有的元素为Pd、Ni、Au以外的元素，且与中间层、被覆层、表面层的元素不同的情况下，利用线整体的由ICP分析测定出的浓度。
(评价内容)
关于接合部的高温可靠性，将接合后进行了树脂密封的试样，在处理温度为185℃、处理时间为2000小时的条件下进行加热处理之后，评价了60根接合线的电特性。在表1、2中的“高温可靠性”一栏中，电阻上升至初期的3倍以上的接合线的比例为30％以上的情况下，由于接合不良而用×标记表示，电阻上升至3倍以上的接合线的比例为5％以上且低于30％的范围的情况下，由于能够用于可靠性要求不严格的IC而用△标记表示，电阻上升至3倍以上的接合线的比例低于5％且上升到1.5倍以上的接合线的比例为10％以上且低于30％的情况下，由于在实际使用上没有问题而用○标记表示，如果电阻上升至1.5倍以上的接合线的比例低于10％，则由于良好而用◎标记表示。
关于蛇形环路不良的评价，利用中跨距高段差和长跨距高段差这两种环路进行了评价。在中跨距高段差中，线长度为3.5mm且下降区域的长度为0.5mm，将梯形环路连接以使得从楔接合部到环路最高位置的高低差成为0.7mm。在长跨距高段差中，线长度为5mm且下降区域的长度为0.7mm，将梯形环路连接以使得从楔接合部到环路最高位置的高低差成为0.8mm。线径为20μm。从上方用光学显微镜观察环路的下降区域，如果1条环路的下降区域中的弯曲为2次以上则判定为蛇形环路不良，对500条环路连接中的发生频度进行了评价。在表1、2中的“蛇形环路”一栏中，该发生频度超过10％的情况下判定为不良而用×标记表示，超过5％且为10％以下的情况下由于担心量产性而用△标记表示，超过2％且为5％以下的情况下由于比较良好而用○标记表示，0～2％的情况下判断为环路形状稳定，用◎标记表示。
关于下沉环路不良的评价，线长度为5mm且下降区域长度为1.5mm，将梯形环路连接以使得从楔接合部到环路最高位置的高低差成为0.7mm。线径为20μm。用光学显微镜从上方观察环路，环路以0.2mm以上的长周期蛇行的情况下，判断为下沉环路不良，对400条环路连接中的发生频度进行了评价。在表2中的“下沉环路”一栏中，该发生频度超过10％的情况下判定为不良而用×标记表示，超过5％且为10％以下的情况下由于担心量产性而用△标记表示，超过2％且为5％以下的情况下由于比较良好而用○标记表示，0～2％以下的情况下判断为不会发生下沉环路不良的问题，用◎标记表示。
关于楔接合性，利用将接合线接合到引线电极时的卷缩不良的发生频度进行了评价。关于接合线的制造后的保管，以放入线圈盒的状态在洁净室内的大气中常温保管了30天。在接合条件中，稍稍降低超声波输出，进而将台(stage)温设为160℃的低温，诱发了楔接合的分离。通过1000条的接合而评价了分离发生频度。在表1、2中的“楔接合性”一栏中，卷缩不良数量为10条以上的情况下，由于需要改善而用×标记表示，4～9条的情况下用△标记表示，1～3条的情况下由于大致良好而用○标记表示，不良为零的情况下判断为楔接合性优异而用◎标记表示。
在压接球部的接合形状的判定中，观察200条接合了的球部，对形状的正圆度、异常变形不良、尺寸精度等进行了评价。线径采用20μm，将初期球径/线径的比率大约设为2，通过严格的小球接合进行了评价。
在表1、2中的“压接球形状”一栏中，如果偏离正圆的各向异性、花瓣状等不良球形状为5条以上则判定为不良而用×标记表示，偏离正圆的不良球形状为2～4条的情况下分为两类，如果发生1条以上的异常变形则由于期望量产上的改善而用△标记表示，如果没有发生异常变形则由于能够使用而用○标记表示，如果不良球形状为1条以下则由于良好而用◎标记表示。
(评价结果)
实施例1～18的接合线，由芯材、中间层、被覆层构成，中间层的Ni的浓度为15～80mol％，由此确认了能够减少蛇形环路不良。另一方面，不含中间层的比较例1、2、5、或中间层的Ni的浓度为上述范围外的比较例3、4、6中，蛇形环路不良高频度发生。
实施例2～5、7～18，中间层的厚度为8～80nm，由此确认了能够减少楔接合时的卷缩不良。
实施例19～35的接合线由芯材、中间层、被覆层、表面层构成，中间层的Ni的浓度为15～80mol％，而且表面层的Au的浓度为10～70mol％、Au和Pd的合计浓度为80mol％以上，由此确认了能够减少蛇形环路不良和下沉环路不良。另一方面，不含中间层的比较例7、9、或中间层的Ni的浓度为上述范围外的比较例8、10，蛇形环路不良和下沉环路不良高频度发生。另外，表面层的Au的浓度为上述范围外的比较例11，尽管能够减少蛇形环路不良，但是发生了下沉环路不良。
实施例19～21、24～35的接合线，表面层、被覆层和中间层的总计厚度为25～200nm，由此确认了能够减少楔接合时的卷缩不良。而且，实施例19～21、24～29、31～35的接合线，表面层、被覆层和中间层的总计厚度为40～150nm，由此确认了能够更切实地减少楔接合时的卷缩不良。
实施例19～22、25～35的接合线，表面层的厚度为3～30nm，由此确认了能够更切实地减少蛇形环路不良和下沉环路不良的发生。
关于实施例3、4、6～9、20、21、23～26的接合线，芯材中的所述金属M为Cu，并含有选自P、Ti、B、Ag之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.0005～0.02质量％的范围，由此确认了压接球形状良好。
关于实施例10～12、27～29的接合线，芯材中的所述金属M为Cu，并含有选自Pd、Ni之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.2～2.0质量％的范围，由此确认了加热处理后的可靠性(高温可靠性)高。
关于实施例15～18、32～35的接合线，芯材中的所述金属M为Ag，并含有选自Pd、Ni、Cu之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.5～5.0质量％的范围，由此确认了加热处理后的可靠性高。

Claims (9)

1.一种半导体装置用接合线，其特征在于，具备：
芯材，其含有超过50mol％的金属M；
中间层，其形成于所述芯材的表面，包含Ni、Pd、所述金属M和不可避免的杂质，所述Ni的浓度为15～80mol％；和
被覆层，其形成于所述中间层上，包含Ni、Pd和不可避免的杂质，所述Pd的浓度为50～100mol％，
所述金属M为Cu或Ag，
所述被覆层的Ni浓度低于所述中间层的Ni浓度。
2.根据权利要求1所述的半导体装置用接合线，其特征在于，所述中间层的厚度为8～80nm。
3.根据权利要求1所述的半导体装置用接合线，其特征在于，
所述被覆层还含有Au，
所述半导体装置用接合线还具备表面层，所述表面层形成于所述被覆层上，由包含Au和Pd的合金构成，所述Au的浓度为10～70mol％，Au和Pd的合计浓度为80mol％以上，
所述被覆层的Au浓度低于所述表面层的Au浓度。
4.根据权利要求3所述的半导体装置用接合线，其特征在于，所述表面层、所述被覆层和所述中间层的总计厚度为25～200nm。
5.根据权利要求3或4所述的半导体装置用接合线，其特征在于，所述表面层的厚度为3～30nm。
6.根据权利要求1～5的任一项所述的半导体装置用接合线，其特征在于，所述金属M为Cu，所述芯材含有选自P、Ti、B、Ag之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.0005～0.02质量％的范围。
7.根据权利要求1～5的任一项所述的半导体装置用接合线，其特征在于，所述金属M为Cu，所述芯材含有选自Pd、Ni之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.2～2.0质量％的范围。
8.根据权利要求1～5的任一项所述的半导体装置用接合线，其特征在于，所述金属M为Ag，所述芯材含有选自Pd、Ni、Cu之中的一种以上的元素，所述元素在线整体中所占的浓度总计为0.5～5.0质量％的范围。
9.根据权利要求1～8的任一项所述的半导体装置用接合线，其特征在于，所述被覆层还含有与所述芯材的所述金属M相同的金属M。
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