CN111344844A - 钎焊接头和钎焊接头的形成方法 - Google Patents

钎焊接头和钎焊接头的形成方法 Download PDF

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CN111344844A
CN111344844A CN201880070809.8A CN201880070809A CN111344844A CN 111344844 A CN111344844 A CN 111344844A CN 201880070809 A CN201880070809 A CN 201880070809A CN 111344844 A CN111344844 A CN 111344844A
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intermetallic compound
solder alloy
layer
solder
substrate
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CN111344844B (zh
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上岛稔
立花芳惠
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B5/00—Joining sheets or plates, e.g. panels, to one another or to strips or bars parallel to them
    • F16B5/08—Joining sheets or plates, e.g. panels, to one another or to strips or bars parallel to them by means of welds or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • 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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
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    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/008—Soldering within a furnace
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    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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Abstract

提供：形成钎焊接头时的背面金属与软钎料合金的剥离被抑制、且通过抑制软钎料合金的不润湿、熔融软钎料的飞散、和芯片裂缝所导致的电子部件的破损从而可靠性优异的钎焊接头；和，钎焊接头的形成方法。钎焊接头以软钎料合金接合具备背面金属的电子部件与基板。软钎料合金具备：软钎料合金层、Sn‑Sb金属间化合物相、背面金属侧金属间化合物层、基板侧金属间化合物层，所述软钎料合金层具有以质量％计Ag：2～4％、Cu：0.6～2％、Sb：9.0～12％、Ni：0.005～1％和余量由Sn组成的合金组成。在Sn‑Sb金属间化合物相与背面金属侧金属间化合物层之间、和Sn‑Sb金属间化合物相与基板侧金属间化合物层之间中的至少一者中夹设有软钎料合金层。

Description

钎焊接头和钎焊接头的形成方法
技术领域
本发明涉及抑制电子部件的背面金属的剥离的钎焊接头、和钎焊接头的形成方法。
背景技术
近年来，电子设备要求高集成化、大容量化、高速化。为了应对该要求，使用以QFP(四面扁平封装(Quad Flat Package))为代表的半导体封装体，实现了半导体芯片水平下的高集成化、高功能化。QFP的制造中，采用了如下封装工艺：将从硅晶圆切出的硅芯片芯片接合于引线框。
QFP中，通过该封装工艺，以软钎料合金将硅芯片与引线框芯片接合而形成钎焊接头。硅芯片中，为了改善与软钎料的润湿性、改善密合强度，形成Ni层等背面金属。但是，熔融软钎料时的热会导致Ni扩散到Si而降低半导体芯片的功能，因此，在硅芯片与Ni层之间可形成Ti层等阻隔层。如此，背面金属层如果成为多层，则有时产生背面金属层间的剥离、背面金属与软钎料合金的剥离。因此，为了抑制它们的剥离，关于背面金属层，进行了各种研究。
专利文献1中，为了抑制空隙的发生、且改善软钎料合金的润湿性而得到良好的接合特性，硅芯片中具备由包含Cr、V的层与Ni层构成的第1金属覆膜、和包含Sn、Sb的第2金属覆膜(金属层)，作为接合硅芯片与基板的软钎料合金，公开了使用如下合金：其以Sn为主成分，含有10重量％以上的Sb。
另外，专利文献2中，为了防止金属间化合物的生成所导致的界面的破坏，提出了一种半导体装置，其在硅芯片上设有Cr、Ti等的金属层(阻隔层)，具有阻隔层与以Sn和Sb为主成分的焊料直接固着而成的粘接结构。另外，专利文献2中记载了如下内容：为了改善与软钎料合金的密合强度，在阻隔层与软钎料合金之间设置Ni层、Ag层等中间层，该中间相也消失，不生成与Sn的金属间化合物相，不产生金属间化合物相的生成和选择性的破坏。
如此，以往的芯片接合中，在使用Sn-Sb系软钎料合金的情况基础上，还进行了涉及背面金属的各种研究。这些研究中，使用Sn-Sb合金是由于该合金的液相线温度高，用于芯片接合的软钎料合金安装于印刷基板等时不会熔融。但是，即使通过大量添加Sb来改善软钎料合金的液相线温度，在将硅芯片安装于印刷基板时，加热温度也达到软钎料合金的液相线温度附近的温度域，因此，存在软钎料合金软质化，钎焊接头的电阻值变化的情况。
因此，例如专利文献3中，为了在接合后的电极部接合中，通过改善耐热疲劳性能而抑制加热时的电阻变化，公开了如下技术：使用在Sn中、含有Fe和Ni的至少1种0.005～5.0质量％、进一步Ag：0.1～20质量％和Cu：0.005～9质量％的至少1种，且含有Sb0.1～15质量％的软钎料合金。
现有技术文献
专利文献
专利文献1：日本特开2001-196393公报
专利文献2：日本特开平6-244226公报
专利文献3：日本特开2001-144111公报
发明内容
发明要解决的问题
然而，如专利文献1和专利文献2记载的那样，即使使用液相线温度高的Sn-Sb系软钎料合金，如果Ni层层叠于阻隔层，则软钎料合金熔融时Ni也有时扩散到软钎料合金中而消失。上述情况下，阻隔层与软钎料合金变得接触，软钎料合金不易浸润阻隔层，因此，存在在阻隔层与软钎料合金的界面处发生剥离的情况。而且，这是在芯片接合时可能引起的问题。另一方面，专利文献3中记载的发明的目的在于，抑制在接合后的电极部接合中的加热时的电阻变化。因此，专利文献1和2中记载的发明与专利文献3中记载的发明中，课题的产生时期原本不同，因此，无法避免在芯片接合时发生上述剥离。
另外，专利文献1和2中记载的发明中，如前述，为了改善背面金属与软钎料合金的润湿性，抑制造成不良影响的金属间化合物相的生成，使硅芯片的背面金属形成层叠结构。然而，各个层的线膨胀系数不同，因此，使软钎料合金熔融并凝固时，在各层间产生应力，有界面剥离的可能性。在剥离区域的面积小的情况下，应力集中在该剥离区域，该剥离区域成为各层的裂纹的起点并且传送至硅芯片，硅芯片有时破坏。特别是专利文献2中记载了0.6μm的Ni层在芯片接合时消失，在上述情况下，存在在阻隔层与软钎料合金的界面处发生剥离的情况。这是由于，如专利文献2中记载的那样，Ni如果消失则软钎料合金与Ti变得接合，但软钎料合金对Ti的润湿性非常差，Ti使软钎料合金润湿回弹。Ti的润湿差的理由如以下所述。Sn-Ti合金的制作条件如下：加热温度为1200℃以上，且在非活性气体气氛下需要几小时的加热。因此，在作为通常的软钎焊条件的400℃以下的加热温度、且30分钟以内的短时间加热下，难以使Sn与Ti完全浸润。
进一步假定即使Ni层部分地残留，Ti也变得露出。此时，软钎料合金难以润湿Ti，因此认为，空隙增加。
此处，专利文献2中记载的Ni层的消失在完全不含Ni、Ti、和Sn以外的气体、原子的理想的环境下进行的情况下，Ni完全溶解后，Ti与Sn能发挥良好的润湿。然而，在现实的环境下，在Ni与Ti的界面中形成某种氧化物，即使为真空气氛，也包含大量的氧原子。进一步软钎焊工序中，在熔融软钎料中肯定形成有空隙，在该空隙中，包含成为污染物的氧原子、其他有机成分。对于Ti来说，氧气成为污染气体。随着Ni层消失，污染气体与Ti接触，使其表面劣化，因此，与软钎料合金的润湿愈发变差，变得容易产生剥离。
通常，软钎料合金根据组成而液相线温度、固相线温度变化。因此，根据软钎焊时的条件而有时产生软钎料合金的不润湿、熔融软钎料的飞散、芯片裂缝。
此外，随着电子设备的用途多样化而使用环境也恶化。软钎料合金凝固时不发生剥离的情况下，温差急剧的环境下，以应力所产生的重复应变为原因而发生剥离。不润湿区域、剥离区域为局部的情况下，如前述，剥离区域成为裂纹的起点，硅芯片中有时产生裂纹。在空隙明显膨胀的情况下、不润湿区域和剥离区域的面积大的情况下，硅芯片与软钎料合金的界面处的放热性明显降低，会导致半导体装置着火等重大的事态。
如此，电子设备的高集成化、大容量化、高速化、应用范围的宽域化所导致的使用环境的恶化对电子部件造成大的负荷。为了抑制硅芯片的源自剥离的裂纹、体现高的放热性，需要进一步研究。具体而言，需要用于不使作为背面金属的一部分的Ni层消失的研究。
本发明的课题在于提供：形成钎焊接头时的背面金属与软钎料合金的剥离被抑制，且抑制软钎料合金的不润湿、熔融软钎料的飞散、和芯片裂缝所导致的电子部件的破损从而可靠性优异的钎焊接头；和，钎焊接头的形成方法。
用于解决问题的方案
本发明人首先对Ni扩散和凝固时的应力、以及背面金属与软钎料合金的剥离的原因进行了调查。以往，剥离的原因的调查如前述是着眼于背面金属层而进行的，但尚未解决这些课题。与此相对，本发明人着眼于源自软钎料合金的组织的情况而不是源自背面金属层的情况。另外，必须避免芯片接合中的软钎料合金的熔融、软质化，因此，本发明人等认为：必须使用Sn-Sb系软钎料合金中、特别是同时含有Sn、Ag、Cu、Sb和Ni的软钎料合金。
因此，本发明人着眼于使用了Sn-Ag-Cu-Sb-Ni软钎料合金的钎焊接头，对剥离后的样品详细进行了调查，结果获得如下见解：背面金属与软钎料合金的剥离不仅源自Ni的扩散、凝固时的应力，还源自软钎料合金的组织。另外，对要剥离的部位进行截面观察，结果还获得如下见解：在背面金属与软钎料合金的界面形成金属间化合物层，该金属间化合物层与背面金属的界面发生剥离。其如以下推定。
以芯片接合形成的钎焊接头中，在背面金属与软钎料合金的接合界面、且软钎料合金中形成有金属间化合物层。另外，与此同时地，在基板与软钎料合金的接合界面、且软钎料合金中形成有金属间化合物层。而且，在软钎料合金中，Sn-Sb金属间化合物越与两金属间化合物层相接触越粗大化的情况下，背面金属与基板部分地仅借助金属间化合物层和Sn-Sb金属间化合物相被接合。在这样的部分，变得难以缓和对接合界面施加的应力，在背面金属与金属间化合物层之间发生剥离。
本发明人如上述推定，结果在软钎料合金中的Sn-Sb金属间化合物相中，通过控制钎焊接头的板厚方向的粒径，可以抑制背面金属与软钎料合金的剥离。但是，由于金属间化合物层不平坦，因此，除非Sn-Sb金属间化合物相的粒径极端小的情况，否则不能断言Sn-Sb金属间化合物相不会与两金属间化合物层接触。
因此，本发明人等着眼于：构成软钎料合金的组织中，使除形成于两界面的金属间化合物层和Sn-Sb金属间化合物相之外的部分形成软钎料合金层时，控制体现应力缓和作用的软钎料合金层，进一步反复进行了研究。其结果获得如下见解：如果将软钎料合金层夹设于至少一者的金属间化合物层与Sn-Sb金属间化合物相之间，则通过软钎料合金层缓和对接合界面施加的应力，因此，可以抑制剥离，完成了本发明。换言之，Sn-Sb金属间化合物如果贯通软钎料合金层，则可以抑制剥离。
而且，本发明人设想：这种粗大的Sn-Sb金属间化合物相的生成原因在于制造工序，对各工序详细地进行了调查。其结果获得如下见解：原因存在于将软钎料合金冷却的工序中。通常已知，冷却速度越慢，晶相的粒径越粗大化。以往的钎焊接头的形成中，存在有大量的只不过单纯地着眼于冷却速度的例子。另外，以往关注的冷却速度表示使冷却开始后直至室温的冷却速度。与此相对，本发明人认为：即使仅管理以往关注的温度域中的冷却速度，也无法抑制Sn-Sb金属间化合物相的粗大化。这是由于，从加热工序转移至冷却工序时，存在无法进行温度管理的时间域，Sn-Sb金属间化合物相已经粗大化。
此处，Sn-Sb系软钎料合金在冷却时经过以下的相的析出过程。首先，冷却温度如果低于SnSb相的析出开始温度，则液相和SnSb相这2相共存。而且，本发明中，使用含有Ag的Sn-Ag-Cu-Sb-Ni软钎料合金，因此，冷却温度如果低于230℃，则从剩余的接近90％的液相中，SnSb相、Sn相、SnAg相和SnCu相这4相共存。
因此，本发明人着眼于Sn-Ag-Cu-Sb-Ni软钎料合金冷却时的相的析出过程。其结果获得如下见解：控制Sn-Sb金属间化合物相的析出开始的温度至Sn-Sb系金属间化合物相的析出结束的230℃为止的冷却时间，从而可以抑制Sn-Sb金属间化合物相的粗大化。另外，伴随于此，获得如下见解：软钎料合金层夹设于至少一者的金属间化合物层与Sn-Sb金属间化合物相之间。
进一步，本发明人等认为：作为剥离的原因之一的Ni层消失源自峰温度和保持时间。控制峰温度和保持时间时需要通过软钎料合金的浸润铺开、Ni不消失的程度的扩散来抑制剥离的发生。因此，不仅对加热条件还对加热气氛的减压条件详细地进行了调查，结果偶然地获得了如下见解：加热温度、加热保持时间、加热时的峰温度和减压条件为规定的范围内，Ni层残留而背面金属与金属间化合物层的剥离被抑制。
另外获得了如下见解：加热温度、加热保持时间、加热时的峰温度和减压条件为规定的范围内时，Ni残留，从而抑制剥离，此外，也可以抑制软钎料合金的不润湿、熔融软钎料的飞散、和芯片裂缝。
由这些见解得到的本发明如下所述。
(1)一种钎焊接头，其特征在于，其为用于以软钎料合金接合具备背面金属的电子部件与基板的钎焊接头，
软钎料合金具备：软钎料合金层、Sn-Sb金属间化合物相、形成于背面金属与软钎料合金的界面的背面金属侧金属间化合物层、和形成于基板与软钎料合金的界面的基板侧金属间化合物层，所述软钎料合金层具有以质量％计Ag：2～4％、Cu：0.6～2％、Sb：9.0～12％、Ni：0.005～1％和余量由Sn组成的合金组成，
在Sn-Sb金属间化合物相与背面金属侧金属间化合物层之间、和Sn-Sb金属间化合物相与基板侧金属间化合物层之间中的至少一者中夹设有软钎料合金层。
(2)根据技术方案1或2所述的钎焊接头，其中，对于Sn-Sb金属间化合物相，在钎焊接头的截面中，以与基板平行的2条平行线夹持Sn-Sb金属间化合物相，作为2条平行线的间隔的Sn-Sb金属间化合物相的Feret径为电子部件的背面金属与基板的平均间隔的60％以下。
(3)根据技术方案1或2所述的钎焊接头，其中，合金组成还含有以质量％计Co：0.2％以下和Fe：0.1％以下的至少1种。
(4)根据技术方案1～3中任一项所述的钎焊接头，其中，背面金属与基板的间隔的平均为50～400μm。
(5)根据技术方案1～4中任一项所述的钎焊接头，其中，背面金属从电子部件侧起依次由以Ti、Cr和V的至少1种为主成分的阻隔层、以及以Ni和Cu的至少1种为主成分的第一金属层构成。
(6)根据技术方案5所述的钎焊接头，其中，在电子部件与阻隔层之间，具备以Au和Al的至少1种为主成分的第二金属层。
(7)根据技术方案5或6所述的钎焊接头，其中，在第一金属层与软钎料合金之间，具备以Au、Ag、Sn、Ni和Cu的至少1种为主成分的第三金属层。
(8)根据技术方案7所述的钎焊接头，其中，在第三金属层与软钎料合金之间，具备以Au、Ag、Ni和Sn的至少1种为主成分的第四金属层。
(9)一种技术方案1～8中任一项所述的钎焊接头的形成方法，其特征在于，所述形成方法以软钎料合金接合具备背面金属的电子部件与基板，
所述形成方法具备如下工序：
加热工序，将借助软钎料合金载置有电子部件的基板加热至比软钎料合金的液相线温度高10℃以上的加热温度域的温度，以加热温度域中的保持时间成为30秒～5分钟、保持时间下的峰温度成为270～330℃的方式进行加热；
减压工序，在基板的加热温度达到227℃前，将加热气氛减压至100Pa以下，或基板的加热温度达到加热温度域后20秒以及其后开始减压，将加热气氛减压至100Pa以下，开始减压后将加热气氛恢复至0.8个大气压以上的气压域为止的时间即减压时间为30秒～4分钟；和，
冷却工序，在加热工序后，将Sn-Sb金属间化合物相的析出开始温度～230℃的温度域在5秒以上且2分钟以内冷却。
(10)根据技术方案9所述的钎焊接头的形成方法，其中，加热工序具备如下预加热工序：在基板的加热温度达到227℃前，以150～220℃的温度域加热2～10分钟。
(11)根据技术方案9或10所述的钎焊接头的形成方法，其中，减压工序中，在开始冷却工序之前的5秒～2分钟，使加热气氛恢复至0.8个大气压以上的压力。
(12)根据技术方案9～11中任一项所述的钎焊接头的形成方法，其中，在基板的加热温度达到加热温度域后的20秒～3分钟之后，开始减压工序。
(13)根据技术方案9～12中任一项所述的钎焊接头的形成方法，其中，减压工序在减压时间内进行多次。
附图说明
图1为层叠有阻隔层、第一～第四金属层的钎焊接头的示意图，图1的(a)为从电子部件侧起依次层叠有阻隔层和第一金属层的示意图，图1的(b)为从电子部件侧起依次层叠有第二金属层、阻隔层和第一金属层的示意图，图1的(c)为从电子部件侧起依次层叠有第二金属层、阻隔层、第一金属层和第三金属层的示意图，图1的(d)为从电子部件侧起依次层叠有第二金属层、阻隔层、第一金属层、第三金属层和第四金属层的示意图。
图2为示出本发明的钎焊接头的形成方法的温度与时间和气氛压力与时间的曲线的一例。
图3为钎焊接头的截面示意图，图3的(a)为发明例1的示意图，图3的(b)为发明例8的示意图，图3的(c)为发明例9的示意图，图3的(d)为发明例10的示意图。
图4为发明例1和比较例1的截面SEM照片，图4的(a)和图4的(b)为发明例1的SEM照片，图4的(c)和图4的(d)为比较例1的SEM照片。
具体实施方式
1.钎焊接头
本发明的钎焊接头用于以软钎料合金接合电子部件与基板。以下对电子部件、基板和软钎料合金进行详述。
(1)电子部件
构成本发明的钎焊接头的电子部件例如为芯片，所述芯片是在晶圆上形成电阻、晶体管、电容器、集成电路等半导体元件、并且从晶圆切出各半导体元件的区段。作为晶圆，可以举出Si、SiC、GaN。电子部件作为半导体封装体搭载于基板时，以软钎料合金进行芯片接合。
电子部件中，为了改善与软钎料合金的密合强度，至少在与软钎料合金的接合界面侧的面上形成有背面金属。对电子部件的两面进行软钎焊的情况下，可以在电子部件的两面形成背面金属。
本发明的背面金属优选从电子部件侧起依次由以Ti、Cr和V的至少1种为主成分的阻隔层、以及以Ni和Cu的至少1种为主成分的第一金属层构成。以下，对能构成背面金属的阻隔层、第一金属层～第四金属层进行详述。
(1-1)阻隔层
本发明中，为了抑制构成第一金属层的元素扩散至电子部件侧，期望在电子部件的基板侧的面与第一金属层之间，具备以Ti、Cr和V的至少1种为主成分的阻隔层。阻隔层的膜厚没有特别限定，从抑制扩散的观点出发，期望为0.01～0.2μm。
需要说明的是，本发明中，阻隔层的主成分不应是Ag。这是由于，Ag在芯片接合时比第一金属层的Ni、Cu还快地扩散而阻隔层消失。另外，Ag中的氧的扩散急剧，阻隔层氧化而成为剥离的原因。
(1-2)第一金属层
本发明中，为了改善与软钎料合金的润湿性，期望具有以Ni和Cu的至少1种为主成分的第一金属层。第一金属层的膜厚优选0.3～1.7μm。该膜厚是指，在扩散基于芯片接合进行到某种程度而残留的第一金属层的膜厚。芯片接合前的第一金属层的膜厚期望为0.5～2μm。本发明的钎焊接头不同于以往的钎焊接头，如前述，在形成钎焊接头后第一金属层也维持前述膜厚，因此，可以抑制背面金属与软钎料合金的剥离。
另外，第一金属层与软钎料合金接触的情况下，优选第一金属层不是单独的Cu。
(1-3)第二金属层
本发明中，在电子部件的基板侧的面与阻隔层之间，期望具备以Au和Al的至少1种为主成分的第二金属层。如果在该位置具备第二金属层，则可以改善电子部件与阻隔层的密合强度。第二金属层的芯片接合后的膜厚没有特别限定，期望为0.02～1μm。
(1-4)第三金属层
本发明中，在第一金属层与软钎料合金的金属间化合物层之间，期望具备以由Au、Ag、Sn、Ni和Cu组成的组中的至少1种、以及Ni的至少1种为主成分的第三金属层。如果在该位置具备第三金属层，则可以改善软钎料合金的润湿性。第三金属层的芯片接合后的膜厚没有特别限定，期望Au为0～0.1μm、Ag为0～2μm、Sn为0～5μm、Cu为0～5μm。第三金属层有时在芯片接合后消失。
另外，第一金属层不含有Ni的情况、且第三金属层与软钎料合金接触的情况下，通过避免阻隔层的露出，从而维持背面金属与软钎料合金的润湿性，因此，第三金属层优选含有Ni。使用Ni时的第三金属层的芯片接合后的膜厚没有特别限定，可以为0.3～1.7μm。
(1-5)第四金属层
本发明中，在第三金属层与软钎料合金之间，期望具备以Au、Ag、Ni和Sn的至少1种为主成分的第四金属层。如果在该位置具备第四金属层，则可以抑制第三金属层的氧化，可以维持优异的润湿性。第四金属层的芯片接合后的膜厚没有特别限定，期望Au为0～0.1μm、Ag为0～2μm、Sn为0～5μm。第四金属层有时在芯片接合后消失。在第三金属层为Ag时第四金属层的主成分可以选择Au，在第三金属层为Cu时第四金属层的主成分可以选择Ag、Sn或Au。
另外，第一金属层和第三金属层不含有Ni的情况下，通过避免阻隔层的露出，从而维持背面金属与软钎料合金的润湿性，因此，第四金属层优选含有Ni。使用Ni时的第三金属层的膜厚没有特别限定，可以为0.3～1.7μm。
(1-6)钎焊接头的层叠结构
利用图1对本发明的钎焊接头的层叠结构进行说明。图1为层叠有阻隔层、第一～第四金属层的钎焊接头的示意图，图1的(a)为从电子部件侧起依次层叠有阻隔层、和第一金属层的示意图，图1的(b)为从电子部件侧起依次层叠有第二金属层、阻隔层、和第一金属层的示意图，图1的(c)为从电子部件侧起依次层叠第二金属层、阻隔层、第一金属层、和第三金属层的示意图，图1的(d)为从电子部件侧起依次层叠第二金属层、阻隔层、第一金属层、第三金属层、和第四金属层的示意图。如图1的(a)～图1的(d)所示那样，本发明的钎焊接头中，由于难以与用于本发明的软钎料合金润湿的Al仅用于第二金属层，因此，Al层与软钎料合金不接触。另一方面，能与软钎料合金接合的第一金属层、第三金属层、和第四金属层均存在与软钎料合金接触的可能性，因此，可以选择不含有Al，如上述用于本发明的软钎料合金容易润湿的构成元素。
各层的形成方法没有特别限定，可以应用蒸镀法、溅射法、镀覆等。
上述阻隔层以及第一～第四金属层中，均限定主成分的元素，但本发明中的“主成分”是指，各层的50质量％以上。这些层更期望由单独的元素构成。除主成分以外也可以含有不可避免的杂质。含不可避免的杂质的情况下，也不对前述效果造成影响。不可避免的杂质中，也可以包含从背面金属扩散的元素。另外，本发明中不含有的元素以不可避免的杂质含有，也不对前述效果造成影响。
(2)基板
构成本发明的钎焊接头的基板表示高耐热的FR4等玻璃纤维增强环氧系印刷基板、聚酰亚胺系的基板、DBA(Direct Bonded Aluminum)、DBC(Direct Bonded Copper)等陶瓷基板、Cu等的金属基板、Cu引线框等。在基板上借助软钎料合金搭载有电子部件。可以对基板本身实施金属镀。金属镀层可以形成于基板的两面，而且可以为多层。
电子部件的背面金属与基板的间隔的平均没有特别限制，作为实际能形成的间隔，通常为50～400μm。
本发明中，电子部件的背面金属与基板的间隔的平均可以如下求出：在电子部件的4角，用例如聚焦显微镜、激光位移计测定从基板的上表面至电子部件的上表面的高度，算出各高度的加权平均与包含背面金属的电子部件的高度之差，从而可以求出。
(3)软钎料合金
本说明书中，关于软钎料合金组成的“％”只要没有特别指定就是“质量％”。构成本发明的钎焊接头的软钎料合金由以下的元素构成。
(3-1)Ag：2～4％
Ag是用于改善可靠性的元素。Ag如果低于2％，则无法缓和凝固时的应力。Ag的下限为2％以上、优选2.5％以上、特别优选2.9％以上。
另一方面，Ag如果超过4％，则Ag3Sn等粗大的金属间化合物相局部地生成，成为剥离的原因。该Ag3Sn金属间化合物相的生成不同于Sn-Sb系金属间化合物相，非常难以用曲线控制。Ag的上限为4％以下、优选3.5％以下、特别优选3.1％以下。
(3-2)Cu：0.6～2％
Cu为如下元素：调整软钎料合金的熔点，且阻隔层中具有第一金属层的情况下，控制Ni层的扩散，抑制背面金属的剥离。Cu如果低于0.6％，则Ni的扩散进行而有时产生剥离。Cu的下限值为0.6％以上、优选0.7％以上、特别优选0.95％以上。
另一方面，Cu如果超过2％，则软钎料合金的熔点明显上升，芯片接合时，形成于电子部件的硅芯片上的IC等的性能有时劣化。Cu的上限为2％以下、优选1.5％以下、特别优选1.05％以下。
(3-3)Sb：9.0～12％
Sb为控制Sn-Sb金属间化合物相的粒径、且改善可靠性的元素。Sb如果低于9.0％，则Sn中的Sb浓度不变高，软钎料合金的可靠性差。因此，Sb的含量需要为Sn-Sb金属间化合物相析出的程度的量。Sb的下限为9.0％以上、优选10.0％以上。
另一方面，Sb如果超过12％，则Sn-Sb金属间化合物相的粒径变得容易粗大化，成为剥离的原因。Sb的上限为12％以下、优选11％以下、特别优选10.5％以下。
(3-4)Ni：0.005～1％
Ni为如下元素：调整软钎料合金的熔点，且背面金属中具有Ni层的情况下，抑制Ni层的扩散，改善与软钎料合金的密合强度，抑制剥离。Ni如果低于0.005％，则与电子部件的密合强度降低，有时产生剥离。Ni的下限为0.005％以上、优选0.010％以上、特别优选0.015％以上。
另一方面，Ni如果超过1％，则软钎料合金的熔点过度变高，芯片接合时有时给半导体元件造成热损伤。Ni的上限为1％以下、优选0.1％以下、特别优选0.025％以下。
(3-5)Co：0.2％以下和Fe：0.1％以下的至少1种
这些元素是由于抑制Ni的溶解而可以抑制背面金属的剥离的任意元素。这些元素如果为上限以下，则软钎料合金的熔点不过度变高，芯片接合时不给半导体元件造成热损伤。Co的上限优选0.2％以下、更优选0.1％以下。Fe的上限优选0.1％以下、更优选0.05％以下。
另一方面，为了发挥这些元素的添加效果，Co的下限优选0.005％以上、更优选0.01％以上。Fe下限优选0.005％以上、更优选0.01％以上。
(3-6)余量为Sn
构成本发明的钎焊接头的软钎料合金的余量为Sn。除前述元素之外还可以含有不可避免的杂质。含有不可避免的杂质的情况下，也不对前述效果带来影响。本发明中，不可避免的杂质中还包含从背面金属扩散的元素。另外，如后述，本发明中不含有的元素以不可避免的杂质含有，也不对前述效果带来影响。
(3-7)合金组织
构成本发明的钎焊接头的软钎料合金具有背面金属侧金属间化合物层、基板侧金属间化合物层、Sn-Sb金属间化合物相、和软钎料合金层。以下中，对它们进行详述。
(3-7-1)背面金属侧金属间化合物层
本发明的软钎料合金含有Sn和Cu，因此，在背面金属与软钎料合金的界面，形成Cu6Sn5、Cu3Sn等背面金属侧金属间化合物层。另外，背面金属中，与软钎料合金接触的金属层含有Ni的情况下，也形成(Cu，Ni)6Sn5、(Cu，Ni)3Sn等背面金属侧金属间化合物层。
本发明中的背面金属侧金属间化合物层为形成于背面金属与软钎料合金的界面的“一系列的金属间化合物层”，即使构成元素相同，也不含从“一系列的金属间化合物层”游离的“游离金属间化合物相”。亦即，在“一系列的金属间化合物层”与“游离金属间化合物相”之间，夹设后述的软钎料合金层的情况下，“游离金属间化合物相”不属于“一系列的金属间化合物层”。这是由于，如果夹设软钎料合金层，则假定即使Sn-Sb金属间化合物与“游离金属间化合物相”接触，通过夹设软钎料合金层，从而也可以缓和对接合界面施加的应力。
(3-7-2)基板侧金属间化合物层
对于本发明的钎焊接头，在基板与软钎料合金的界面，形成有Cu6Sn5、Cu3Sn等基板侧金属间化合物层。另外，在基板上形成有Ni镀层时，也形成(Cu，Ni)6Sn5、(Cu，Ni)3Sn等基板侧金属间化合物层。
本发明中的基板侧金属间化合物层与背面金属侧金属间化合物层同样地，为形成于基板与软钎料合金的界面的“一系列的金属间化合物层”，即使构成元素相同，也不包含从“一系列的金属间化合物层”游离的“游离金属间化合物相”。这是由于，如果夹设软钎料合金层，则假定即使Sn-Sb金属间化合物与“游离金属间化合物相”接触，通过夹设软钎料合金层，从而也可以缓和对接合界面施加的应力。
(3-7-3)Sn-Sb金属间化合物相
本发明的Sn-Sb金属间化合物需要在Sn-Sb金属间化合物相与背面金属侧金属间化合物层之间、和Sn-Sb金属间化合物相与基板侧金属间化合物层之间中的至少一者中夹设软钎料合金层。
对于本发明的钎焊接头，采用Sb的含量还含有9.0％以上的软钎料合金，因此，Sn-Sb金属间化合物相容易粗大化。Sn-Sb系金属间化合物相越局部地贯通位于背面金属侧金属间化合物层与基板侧金属间化合物层之间的软钎料合金，越粗大化的情况下，变得与两金属间化合物层接触。上述情况下，Sn-Sb金属间化合物相为高强度，且不变形，因此，无法缓和周边的应力。另外，上述两金属间化合物层比软钎料合金还硬，同样地无法缓和应力。其结果，在从背面金属至基板之间能缓和应力的部位消失，在背面金属与软钎料合金的金属间化合物层的界面产生剥离。该剥离成为电子部件的脱落、导通不良的原因。
本发明中，优选Sn-Sb金属间化合物相的粒径较小。本发明中，在钎焊接头的截面中，以与基板平行的2条平行线夹持Sn-Sb金属间化合物相，将作为2条平行线的间隔的Sn-Sb金属间化合物相的直径作为Feret径。该Feret径优选为电子部件的背面金属与基板的平均间隔的60％以下，更优选为低于50％、进一步优选为33.3％以下。
Sn-Sb金属间化合物相的Feret径取决于电子部件的背面金属与基板的间隔，优选10～350μm以下、更优选10～150μm以下、进一步优选15～30μm。
本发明中，Sn-Sb金属间化合物相的粒径如下：用显微镜以150～1000倍进行观察，在目视下从大者起抽出2～5个颗粒，拍摄照片，测量抽出的2～5个颗粒的Feret径，将抽出的2～5个颗粒中的最大值作为Feret径。本发明中，Feret径是指，以夹持颗粒的2条平行切线间的距离定义的恒定方向切线直径(粉体工学会編“颗粒测量技术”日刊工业新闻社，P7(1994))。本发明中，以与基板平行的2条平行线夹持Sn-Sb金属间化合物相，将2条平行线间的距离作为Feret径。
需要说明的是，本发明中，Sn-Sb金属间化合物相的一个晶粒或多个晶粒可以经连接。多个晶粒经连接的情况下，将连接的一组作为Sn-Sb金属间化合物相。同样地，多个晶粒经连接时的Feret径为连接的一组的晶粒中的直径。另外，本发明中的“Sn-Sb金属间化合物相”是指，SnSb相。进一步，由于金属间化合物层不平坦，因此，即使在两金属间化合物层的最短间隔小于Feret径的情况下，Sn-Sb金属间化合物相不与两金属间化合物层接触时也可以充分。
(3-7-4)软钎料合金层
本发明中，软钎料合金层是指，由软钎料合金形成的，除背面金属侧金属间化合物层、基板侧金属间化合物层、和Sn-Sb金属间化合物相之外的部分。进一步，存在有前述的“游离金属间化合物相”的情况下，“游离金属间化合物相”也从软钎料合金层中被排除。
本发明中的软钎料合金层与这些相比，硬度低，可以缓和对接合界面施加的应力。亦即，本发明中的软钎料合金层具有作为本发明的钎焊接头的缓冲材料的功能。
软钎料合金层中，有时包含：具有与这些金属间化合物层、Sn-Sb金属间化合物相等同以上的硬度的Ag3Sn等晶相。然而，其结晶量为微量，因此，不对本发明的效果造成影响。
从发挥上述效果的观点出发，夹持于Sn-Sb金属间化合物相与背面金属侧金属间化合物层之间、和Sn-Sb金属间化合物相与基板侧金属间化合物层之间中的至少一者的软钎料合金层的膜厚优选1μm以上、更优选5μm以上。
2.钎焊接头的形成方法
本发明的钎焊接头的形成方法为以软钎料合金接合具备背面金属的电子部件与基板的方法。以下，对各工序进行详述。
(1)加热工序
本发明的加热工序如下：将借助前述软钎料合金载置有电子部件的基板加热至比软钎料合金的液相线温度高10℃以上的加热温度域的温度，以加热温度域中的保持时间成为30秒～5分钟、保持时间下的峰温度成为270～330℃的方式进行加热。
(1-1)加热条件
本发明的钎焊接头的形成方法中，在基板上依次载置软钎料合金、电子部件。载置电子部件的朝向为电子部件的背面金属与软钎料合金抵接的朝向。在电子部件的两面具备背面金属的情况下，根据电子部件的功能等而选择适合的面。
本发明的加热工序中，需要将基板加热至比软钎料合金的液相线温度高10℃以上的加热温度域的温度。这是由于，加热温度如果为该温度域的范围内，则软钎料合金从半熔融状态成为熔融状态，熔融软钎料在电子部件的背面金属和基板电极中充分地浸润铺开。
本发明中，为了防止能成为与软钎料合金接触的层的第一金属层、第三金属层、和第四金属层的消失，需要使前述加热温度域中的保持时间为30秒～5分钟。下限如果低于30秒，则润湿性恶化。下限优选1分钟以上、更优选2分钟以上。另一方面，上限如果超过5分钟，则第一金属层消失，有在软钎料合金的背面金属侧金属间化合物层与背面金属的界面发生剥离的担心。上限优选4.5分钟以下。
接着，将搭载有软钎料合金和电子部件的基板在加热炉中进行加热。加热时的峰温度为270～330℃的温度域。为了促进Sn-Sb金属间化合物相的溶解、发挥良好的润湿性，本发明的峰温度必须设为270℃以上。液相线温度根据软钎料合金组成而变动，因此，根据软钎料合金的液相线温度，将峰温度在上述温度域的范围内进行调整。另一方面，峰温度如果过高，则电子部件受到热损伤，另外，第一金属层等的扩散变快，第一金属层等有时消失。另外，因此，将上限设为330℃以下。
(1-3)其他条件
本发明的加热工序中，升温速度优选0.5～5℃/s。如果为该范围，则可以充分地抑制空隙的发生，改善润湿性。
另外，对于加热工序以及其后的工序中的气氛，使用助焊剂或包含助焊剂的软钎料制品的情况下，优选形成大气、氮气、非活性气体、氢气、甲酸、其他还原气体的气氛。不使用助焊剂而仅供给软钎料合金的情况下，优选形成氢气、甲酸等还原气体与氮气等非活性气体的混合气体的气氛。需要说明的是，如后述，在减压工序中，将加热气氛恢复至0.8MPa以上的气压时，优选导入大气以外的气氛气体，恢复至前述气压。
(1-4)预加热工序
本发明的加热工序中，将基板均匀地加热，使基板上的氧化物清洁化，将助焊剂或包含助焊剂的软钎料制品供给至基板的情况下，为了去除有机溶剂，可以设置如下预加热工序：在基板的加热温度达到227℃前，以150～220℃的温度域加热2～10分钟。
(1-5)软钎料合金的使用形态
另外，本发明中，可以使用助焊剂、含有前述软钎料合金的糊剂。助焊剂、糊剂中使用的软钎料合金以外的成分没有特别限定，可以使用以往的物质。
本发明中的软钎料合金的形状只要为球、条、垫圈、粒料、线、芯片等预成型坯就对形状没有特别限定。
(2)减压工序
本发明的减压工序必须如下：在基板的加热温度达到227℃前，将加热气氛减压至100Pa以下，或基板的加热温度达到加热温度域后20秒以及其后开始减压，将加热气氛减压至100Pa以下，开始减压后将加热气氛恢复至0.8个大气压以上的气压域为止的时间即减压时间为30秒～4分钟。
本发明中，为了避免软钎料合金的半熔融状态下的急剧的气压变化，减压至100Pa以下的时刻可以在2种情形中的任意情形下进行。对两情形进行详述。
(2-1)在基板的加热温度达到227℃前，将加热气氛减压至100Pa以下
如果在该条件下进行减压，则软钎料合金变得不在半熔融状态下减压，软钎料合金在熔融开始前成为减压的状态，因此，可以抑制软钎料合金的飞散，降低安装不良。另一方面，在基板的加热温度达到227℃后，将加热气氛减压至100Pa以下时，软钎料合金在半熔融状态下引起急剧的气压变化，软钎料合金会飞散。
设为227℃是由于，特别是本发明中使用的软钎料合金的固相线温度或接近于其的温度。
本发明中，只要将加热气氛压减压至100Pa以下就是充分的。优选50Pa以下、更优选10Pa以下。
(2-2)在基板的加热温度达到加热温度域后20秒以及其后开始减压，将加热气氛减压至100Pa以下
软钎料合金在熔融状态下润湿结束前开始减压时，由于急剧的气压差而空隙会膨胀，因此，无法发挥软钎料合金本身的原本的润湿性，会发生不润湿。因此，至少需要在达到前述加热温度域并经过20秒以上后开始减压工序。减压开始时间优选达到加热温度域后20秒～3分钟之后进行、特别优选达到加热温度域后1分钟～2分钟之后进行。如果为该范围，则可以抑制不润湿。
本发明的减压工序中，优选在开始冷却工序之前的5秒～2分钟，恢复至0.8个大气压以上的压力。容易产生空隙的时间域根据第一金属层的膜厚、加热温度、升温速度、加热气氛等各种因素而变动，但大概在开始冷却之前的5秒至2分钟，进行最后的减压处理，以使在减压时膨胀了的空隙收缩，可以在去湿前向空隙部填充软钎料而抑制不润湿。恢复至0.8个大气压以上的压力的时间优选为开始冷却工序之前的10秒～1分钟。
从避免填充到空隙部的软钎料量的不足、抑制不润湿的观点出发，减压后恢复的压力的下限为0.8个大气压以上、更优选0.9个大气压以上、特别优选1个大气压以上。上限没有特别限定，只要为3个大气压以下即可。
(2-3)减压时间
本发明中，为了软钎料合金熔融时抑制空隙的发生，发挥软钎料合金本身的优异的润湿性，且还抑制第一金属层的消失，开始减压后将加热气氛恢复至0.8个大气压以上的气压域为止的时间即减压时间为30秒～4分钟。减压时间低于30秒时，减压时空隙膨胀，空隙中的气体、失去了活性的助焊剂成分残留，几乎不会从软钎料接合部排出，因此，即使恢复至0.8个大气压以上，也无法较大地期待空隙降低效果。另外，软钎料合金在熔融状态下润湿结束前进行减压时，想要收缩的空隙会扩张，因此，无法发挥软钎料合金本身的原本的润湿性，空隙反而残留，会发生不润湿。因此，需要至少达到比软钎料合金的液相温度高10℃以上的温度，经过30秒以上后，开始减压工序。
另一方面，减压时间如果超过4分钟，则减压时与扩展了的空隙接触的电极部中较薄地残留的熔融软钎料随着反应层的成长被消耗，部分的反应层在空隙中露出，所谓去湿现象在作为接合接合部的电子部件的背面金属与软钎料合金的界面、软钎料合金与基板电极的界面发生。经过一次去湿的电极的润湿非常差，在减压时软钎料合金不会再润湿，从而发生不润湿。另外，长时间的减压导致熔融时间变长，因此，第一金属层有时消失。
另外，本发明的减压工序中，将基板重复暴露于减压至0.8个大气压以上的压力的环境下，从而熔融软钎料流动，对于不润湿部分，可以以物理的方式使软钎料浸润铺开。因此，本发明中，优选在4分钟以内进行多次减压工序。如果考虑减压时间等，则优选2～3次。例如2次减压的曲线可以在以下的时刻下进行。第1次如下：加热工序中达到230℃前以加热气氛成为100Pa以下的方式开始减压，在液相线温度下暂时结束减压，恢复压力。第2次如下：达到峰温度后在20秒～3分钟之后再次开始减压，在开始冷却工序之前的5秒～2分钟，恢复压力。
本发明的减压工序中，使用旋转泵的简易的减压手段是充分的。
(4)冷却工序
本发明的冷却工序如下：在加热保持工序后，将Sn-Sb金属间化合物相的析出开始温度～230℃的温度域在5秒以上且2分钟以内冷却。
本发明中，通过进行软钎料合金凝固时的冷却控制，从而可以抑制软钎料合金中的Sn-Sb系金属间化合物相的粗大化。本发明中使用的含有Ag和Cu的Sn-Sb系软钎料合金中，如果低于230℃，则SnSb相、Sn相和SnAg相、SnCu相这4相结晶。本发明中，通过控制Sn-Sb金属间化合物相的生成温度域即Sn-Sb金属间化合物相的析出开始温度～230℃的温度域中的冷却速度，从而可以抑制Sn-Sb系金属间化合物相的粗大化，可以抑制背面金属与软钎料合金的剥离。另外，伴随于此，可以以软钎料合金层夹设于至少一者的金属间化合物层与Sn-Sb金属间化合物相之间的方式控制合金组织。因此，本发明中，可以控制Sn-Sb金属间化合物相的析出开始温度～230℃的冷却速度，优选可以控制270～230℃的冷却速度。
另外，对于冷却时间，从抑制Sn-Sb金属间化合物相的粗大化的观点出发，只要将上述温度域中的冷却时间设为5秒以上且2分钟以内即可。冷却时间如果低于5秒，则基板上的冷却的不均变大，进一步施加热冲击，因此，Si芯片中产生不均匀的应力，导致Si芯片破坏。冷却时间的下限优选10秒以上、更优选30秒以上。另一方面，冷却时间如果超过2分钟，则Sn-Sb系金属间化合物相粗大化，因此，成为剥离的原因。冷却时间的上限优选1.5分钟以下、更优选1分钟以下。
实施例
1.发明例1
(1)钎焊接头的形成
以下中对发明例1的钎焊接头的形成方法、和各评价项目的评价方法进行说明。
将板厚为100μm的Sn-3Ag-1Cu-10Sb-0.02Ni软钎料合金(液相线温度：256℃)的预成型坯搭载于实施了Ni镀覆的Cu制引线框(基板)。之后，在为5mm×5mm×200μmt的硅芯片的基板接合面侧具备背面金属的IC芯片(电子部件)搭载于软钎料合金上。背面金属是依次层叠作为阻隔层的膜厚为0.05μm的Ti层、作为第一金属层的膜厚为1μm的Ni层而成的。搭载的朝向设为具备该背面金属的IC芯片中，Ni层与软钎料合金的预成型坯抵接的朝向。将搭载有软钎料合金的预成型坯和IC芯片的基板导入至加热炉，在表1所示的条件下进行加热和冷却，进行芯片接合。表1的发明例1所示的条件成为图2所示的温度曲线。
加热气氛使用的是，甲酸与氮气的混合气体。将基板导入至加热炉，基板温度达到270℃1分钟后，用旋转泵减压至10Pa，开始减压后经过100秒前，导入前述混合气体进行排气，开始减压后经过100秒为止，恢复至大气压。排气结束后经过10秒后，以270℃～230℃的冷却时间成为60秒的方式将加热炉冷却，形成发明例1的钎焊接头。
(2)评价
对于形成的钎焊接头，针对硅芯片的背面金属，为了确认“Ni层的残留”、“SnSb相的贯通”、和“剥离”、“不润湿”、“飞散”、“芯片破坏”，进行了以下的观察。
对于硅芯片的背面金属的截面，用日本电子株式会社制JSM-6610LV，以300倍和10000倍的倍率，用SEM的监视器，根据对比度的差异，分类各相，基于定量分析和金属学见解，鉴定SnSb相(Sn-Sb金属间化合物相)、Ni层、Ti层、Si、和形成于接合界面的金属间化合物层(形成于电子部件与软钎料合金的界面的背面金属侧金属间化合物、形成于基板与软钎料合金的界面的基板侧金属间化合物)。
·“Ni层的残留”、“SnSb相的贯通”、“剥离”、“不润湿”、“飞散”、“芯片破坏”
对于硅芯片的背面金属的截面，在SEM的监视器上放大至10000倍，对于任意的10处，确认Ni层的残留。另外，由用SEM拍摄到的图像，确认了SnSb相是否贯通软钎料合金。而且，Ni层消失的情况下，确认了Ti层与软钎料合金的剥离的有无。另外，Ni层残留的情况下，确认了Ni层与软钎料合金的不润湿的有无。
对于“Ni层的残留”，Ni层残留的情况下记作“○”、Ni层不残留的情况下记作“×”。
对于“SnSb相的贯通”，SnSb相不贯通软钎料合金层，与背面金属侧金属间化合物层、或基板侧金属间化合物层接触，或不与任意金属间化合物层接触的情况下，记作“无”、SnSb相贯通软钎料合金层，与两金属间化合物接触的情况下，记作“有”。
对于“剥离”，在任意部位均无法确认到Ti层与软钎料合金的剥离的情况下，记作“无”、在任意部位存在剥离的情况下，记作“有”。
对于“不润湿”，在Ni层与软钎料合金之间，无间隙而不产生不润湿的情况下，记作“无”、在任意部位存在间隙而发生不润湿的情况下，记作“有”。
对于“飞散”的有无，在得到的钎焊接头的基板周边软钎料不飞散的情况下，记作“无”、软钎料飞散的情况下，记作“有”。
对于“芯片破坏”，对于形成的钎焊接头的外观，以目视，观察硅芯片的破坏的有无。硅芯片未破坏的情况下，记作“无”、在任意部位硅芯片破坏的情况下，记作“有”。
2.发明例2～24、比较例1～12
这些也与发明例1同样地进行评价。需要说明的是，为了钎焊接头的层叠状态明确，图3中记载了钎焊接头的截面示意图。图3的(a)为发明例1的示意图，图3的(b)为发明例8的示意图，图3的(c)为发明例9的示意图，图3的(d)为发明例10的示意图。
将结果示于表1。
[表1]
Figure BDA0002473240410000251
下划线表示为本发明的范围之外。
根据表1，发明例中Ni层残留，无SnSb相的贯通，均未见背面金属与软钎料合金的剥离、不润湿、飞散和芯片裂缝。
另一方面，对于比较例1，加热时间长，加热时的峰温度也高，因此，Ni层消失，发生了剥离。另外，冷却时间长，因此，SnSb相贯通了软钎料合金层。因此，可见背面金属与背面金属侧金属间化合物层的剥离。
对于比较例2，加热时的峰温度低，因此，呈现不润湿的外观。
对于比较例3，加热时的峰温度高，因此，Ni层消失而可见剥离。
对于比较例4，加热时的保持时间短，因此，发生了不润湿。
对于比较例5，加热时的保持时间长，因此，呈现不润湿的外观。
对于比较例6，加热温度达到270℃前的266℃下开始减压，因此，润湿不充分。
对于比较例7，加热温度达到227℃后的230℃下开始减压，因此，软钎料飞散。
对于比较例8，减压时间短，因此，呈现不润湿的外观。
对于比较例9，减压时间过长，因此，Ni层消失而发生了剥离。
对于比较例10，排气后的压力低，因此，呈现不润湿的外观。
对于比较例11，冷却时间短，因此，由于骤冷而凝固收缩大，发生了Si芯片破坏。
对于比较例12，冷却时间长，因此，SnSb相贯通软钎料合金层而发生了剥离。
为了证明这些，图4中示出截面SEM照片。图4为发明例1和比较例1的截面SEM照片，图4的(a)和图4的(b)为发明例1的SEM照片，图4的(c)和图4的(d)为比较例1的SEM照片。图4的(b)和图4的(d)是分别将图4的(a)和图4的(c)的白色四角部分放大而得到的。另外，图4的(a)中，1点虚线所围成的区域表示为SnSb相。图4的(c)中，1点虚线、背面金属侧金属间化合物相、和基板侧金属间化合物相所围成的区域表示为SnSb相。
由图4的(a)和图4的(b)表明，对于发明例1的钎焊接头，SnSb相仅与任意金属间化合物层接触，且背面金属的Ni层残留，未见背面金属与背面金属侧金属间化合物层的剥离。另一方面，图4的(c)和图4的(d)中，存在有贯通软钎料合金层的Sn-Sb相，背面金属的Ni层消失，且可见背面金属与金属间化合物层的剥离。需要说明的是，图4的(a)中，可见为与背面金属侧金属间化合物层相同的组成、且从形成于背面金属与软钎料合金的界面的一系列的背面金属侧金属间化合物层游离的游离金属间化合物相。该游离金属间化合物相不被视为背面金属侧金属间化合物层。
上述发明例和比较例的电子部件的背面金属与基板的引线框的平均间隔如下求出：在电子部件的4角，用聚焦显微镜测定从基板的上表面至电子部件的上表面的高度，算出各高度的加权平均与包含背面金属的电子部件的高度之差，从而求出。
引线框与背面金属的平均间隔在发明例1和比较例1中均为约90μm。比较例的SnSb相的Feret径最大为82μm。发明例的SnSb相的Feret径最大为30μm，可知小于引线框与硅芯片的间隔的平均。另外，发明例的Feret径为引线框与背面金属的平均间隔的33.3％以下，而比较例的Feret径为引线框与背面金属的平均间隔的91％以上。
进一步，图4的(a)中观察到的背面金属侧金属间化合物层与基板侧金属间化合物层的最短间隔为25μm左右。由此还表明，发明例1的钎焊接头的两金属间化合物层的最短间隔小于Feret径。而且，还表明，即使在这样的情况下，除非SnSb相贯通软钎料合金层，否则仍发挥效果。
附图标记说明
11、21、31、41、51、61、71、81 电子部件(硅芯片)
12、22、32、42、52、62、72、82 基板
13、23、33、43、53、63、73、83 软钎料合金
14、24、34、44、54、64、74、84 阻隔层
15、25、35、45、55、65、75、85 第一金属层
26、36、46、66，86 第二金属层
37、47、77、87 第三金属层
48、88 第四金属层
19、29、39、49、59、69、79、89 背面金属

Claims (13)

1.一种钎焊接头，其特征在于，其为用于以软钎料合金接合具备背面金属的电子部件与基板的钎焊接头，
所述软钎料合金具备：软钎料合金层、Sn-Sb金属间化合物相、形成于所述背面金属与所述软钎料合金的界面的背面金属侧金属间化合物层、和形成于所述基板与所述软钎料合金的界面的基板侧金属间化合物层，所述软钎料合金层具有以质量％计Ag：2～4％、Cu：0.6～2％、Sb：9.0～12％、Ni：0.005～1％和余量由Sn组成的合金组成，
在所述Sn-Sb金属间化合物相与所述背面金属侧金属间化合物层之间、和所述Sn-Sb金属间化合物相与所述基板侧金属间化合物层之间中的至少一者中夹设有所述软钎料合金层。
2.根据权利要求1或2所述的钎焊接头，其中，对于所述Sn-Sb金属间化合物相，在所述钎焊接头的截面中，以与所述基板平行的2条平行线夹持所述Sn-Sb金属间化合物相，作为所述2条平行线的间隔的所述Sn-Sb金属间化合物相的Feret径为所述电子部件的背面金属与所述基板的平均间隔的60％以下。
3.根据权利要求1或2所述的钎焊接头，其中，所述合金组成还含有以质量％计Co：0.2％以下和Fe：0.1％以下的至少1种。
4.根据权利要求1～3中任一项所述的钎焊接头，其中，所述背面金属与所述基板的间隔的平均为50～400μm。
5.根据权利要求1～4中任一项所述的钎焊接头，其中，所述背面金属从所述电子部件侧起依次由以Ti、Cr和V的至少1种为主成分的阻隔层、以及以Ni和Cu的至少1种为主成分的第一金属层构成。
6.根据权利要求5所述的钎焊接头，其中，在所述电子部件与所述阻隔层之间，具备以Au和Al的至少1种为主成分的第二金属层。
7.根据权利要求5或6所述的钎焊接头，其中，在所述第一金属层与所述软钎料合金之间，具备以Au、Ag、Sn、Ni和Cu的至少1种为主成分的第三金属层。
8.根据权利要求7所述的钎焊接头，其中，在所述第三金属层与所述软钎料合金之间，具备以Au、Ag、Ni和Sn的至少1种为主成分的第四金属层。
9.一种权利要求1～8中任一项所述的钎焊接头的形成方法，其特征在于，所述形成方法以软钎料合金接合具备背面金属的电子部件与基板，
所述形成方法具备如下工序：
加热工序，将借助所述软钎料合金载置有所述电子部件的所述基板加热至比所述软钎料合金的液相线温度高10℃以上的加热温度域的温度，以所述加热温度域中的保持时间成为30秒～5分钟、所述保持时间下的峰温度成为270～330℃的方式进行加热；
减压工序，在所述基板的加热温度达到227℃前，将加热气氛减压至100Pa以下，或所述基板的加热温度达到所述加热温度域后20秒以及其后开始减压，将加热气氛减压至100Pa以下，开始所述减压后将所述加热气氛恢复至0.8个大气压以上的气压域为止的时间即减压时间为30秒～4分钟；和，
冷却工序，在所述加热工序后，将所述Sn-Sb金属间化合物相的析出开始温度～230℃的温度域在5秒以上且2分钟以内冷却。
10.根据权利要求9所述的钎焊接头的形成方法，其中，所述加热工序具备如下预加热工序：在所述基板的加热温度达到227℃前，以150～220℃的温度域加热2～10分钟。
11.根据权利要求9或10所述的钎焊接头的形成方法，其中，所述减压工序中，在开始所述冷却工序之前的5秒～2分钟，使所述加热气氛恢复至0.8个大气压以上的压力。
12.根据权利要求9～11中任一项所述的钎焊接头的形成方法，其中，在所述基板的加热温度达到所述加热温度域后的20秒～3分钟之后，开始所述减压工序。
13.根据权利要求9～12中任一项所述的钎焊接头的形成方法，其中，所述减压工序在所述减压时间内进行多次。
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