CN106061923A - 陶瓷线路基板 - Google Patents

陶瓷线路基板 Download PDF

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CN106061923A
CN106061923A CN201580009679.3A CN201580009679A CN106061923A CN 106061923 A CN106061923 A CN 106061923A CN 201580009679 A CN201580009679 A CN 201580009679A CN 106061923 A CN106061923 A CN 106061923A
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copper
mass parts
silver
ceramic
mass
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CN106061923B (zh
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青野良太
和田光祐
筑地原雅夫
宫川健志
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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Abstract

本发明可得到具有高接合强度和优异的耐热循环性、在使作为电子机器的工作可靠性提高的同时放热性优异的陶瓷线路基板。本发明的陶瓷线路基板是介由银‑铜系焊料层对陶瓷基板的两个主表面和金属板进行接合而成的陶瓷线路基板，其特征在于，相对于75～98质量份的银粉末和2～25质量份的铜粉末的合计100质量份，银‑铜系焊料层由含有0.3～7.5质量份的碳纤维(carbon fiber)和1.0～9.0质量份的选自钛、锆、铪、铌、钽、钒和锡的至少一种活性金属的银‑铜系焊料构成，所述碳纤维的平均长度为15～400μm、平均直径为5～25μm、平均长径比为3～28。

Description

陶瓷线路基板
技术领域
本发明涉及兼具高接合强度和优异的耐热循环特性的陶瓷线路基板。
背景技术
作为在功率模块等中使用的线路用基板，从导热率、成本和安全性等方面考虑，使用氧化铝、氧化铍、氮化硅、氮化铝等陶瓷基板。这些陶瓷基板与铜、铝等金属线路板、放热板接合来用作线路基板。相对于将树脂基板、树脂层作为绝缘材料的金属基板，它们具有优异的绝缘性和放热性等，因而作为用于搭载高放热性电子部件的基板来使用。
在电梯、车辆、混合动力汽车等的功率模块用途中，使用了在陶瓷基板的表面上用焊料来接合金属线路板、进而在金属线路板的规定位置上搭载半导体元件而成的陶瓷线路基板。近年来，对于伴随着半导体元件的高集成化、高频化、高输出化等导致的来自半导体元件的发热量的增加，使用具有高导热率的氮化铝烧结体、氮化硅烧结体的陶瓷基板。特别是，氮化铝基板与氮化硅基板相比，导热率高，因此适合作为用于搭载高放热性电子部件的陶瓷线路基板。
但是，氮化铝基板虽然具有高导热率，但机械强度、韧性等低，因而存在在装配工序中因紧固而发生开裂、或在施加热循环时易于产生裂纹等缺点。特别是，在用于汽车、电气化铁道、工作机械、机器人等严苛的载荷、热条件下使用的功率模块中时，这样的缺点就逐渐变得明显。
因此，作为用于搭载电子部件的陶瓷基板，要求提高其机械可靠性，作为与氮化铝基板相比导热率差但机械强度、韧性优异的氮化硅基板受到了关注。
使用氮化硅基板的陶瓷线路基板例如通过如下所示的活性金属法来制作。
活性金属法是介由含有4A族元素、5A族元素这样的活性金属的焊料层、在陶瓷基板上接合金属板的方法，通常，将银-铜-钛系焊料丝网印刷到氮化硅基板的两个主表面，在该印刷面上设置金属线路板和金属放热板，通过在适当的温度下加热处理将陶瓷基板和金属板接合。
如此得到的陶瓷线路基板中，作为活性金属的Ti与氮化物系陶瓷基板的N共价结合形成TiN(氮化钛)，通过该TiN而形成接合层，因而可以得到一定程度的高接合强度。
另一方面，在车载半导体模块等中，随着高输出化、高集成化进行，对陶瓷线路基板反复施加的热应力有进一步增大的倾向。如果不能承受该热应力则会在陶瓷基板中产生微小裂纹。在产生了该微小裂纹状态下继续承受热负荷循环的情况下，金属板会从陶瓷基板上剥落，导致接合强度下降或热阻变差。其结果是，会有作为电子机器的工作可靠性下降等问题。因此，对于可耐受热应力的陶瓷线路基板的焊料的构成，提出了以下的方案。
专利文献1中，记载了以提高陶瓷线路基板的耐热循环特性为目的，在对陶瓷基板和金属板进行接合的焊料中含有碳粉末是有效的。
专利文献1：日本专利特开平9-283656
发明内容
但是，在近年的车载用半导体模块等中，迅速地进行进一步高输出化、高集成化，在陶瓷线路基板中，要求采用由以提高放热性为目的的厚金属板和以降低热阻为目的的薄陶瓷基板形成的结构。在金属板较厚的情形下，在陶瓷基板与金属板的接合界面中产生的因热膨胀率差引起的热应力会更加显著，因此在施加热循环时，在陶瓷基板中易于产生微小裂纹。
而且，用于评价热循环特性的热循环评价通常采用-40℃至125℃的温度区间，但对作为今后的下一代功率器件而被期待的搭载了SiC、GaN等的宽带隙半导体的器件而言，由于工作温度增高，热应力会变得越来越大。
这样的问题，无论是将氮化硅基板作为陶瓷基板的情形、还是如专利文献1中所公开的在焊料层中含有碳粉末的陶瓷线路基板中都是不能满足的状态。
而且，在焊料中所含有的非纤维状碳粉末即使在由相同的碳原子构成的碳成分中的石墨(Graphite)粉末、金刚石粉末等中也具有低导热率，因此有阻碍陶瓷线路基板的放热性的可能性，因而不优选。
鉴于上述课题，本发明的目的在于，得到具有高接合强度和优异的耐热循环性、在使作为电子机器的工作可靠性提高的同时放热性优异的陶瓷线路基板。
本发明的发明人为了实现上述目的而认真研究，结果发现，通过使对陶瓷基板和金属板进行接合的焊料的热膨胀率接近于陶瓷基板，能够提高线路基板的热循环特性。进而发现，通过将在焊料中含有的碳成分制成碳纤维(carbon fiber)，能够得到放热性优异的陶瓷线路基板，从而完成了本发明。
即，本发明是一种陶瓷线路基板，其为介由银-铜系焊料层对陶瓷基板的两个主表面和金属板进行接合而成的陶瓷线路基板，其特征在于，相对于75～98质量份的银粉末和2～25质量份的铜粉末的合计100质量份，银-铜系焊料层由含有0.3～7.5质量份的碳纤维(carbon fiber)和1.0～9.0质量份的选自钛、锆、铪、铌、钽、钒和锡的至少一种活性金属的银-铜系焊料构成，上述碳纤维的平均长度为15～400μm，平均直径为5～25μm以下，平均长径比为3～28。
“介由银-铜系焊料层对陶瓷基板的两个主表面和金属板进行接合”是指，分别在陶瓷基板的两个主表面上介由银-铜系焊料层接合金属板。
根据本发明，能够制造具有高接合性，而且在-40℃至150℃的热循环试验的2000个循环中裂纹率小于1％的氮化硅线路基板。
具体实施方式
作为本发明的陶瓷线路基板所使用的陶瓷基板，没有特别限定，可以使用氮化硅、氮化铝等氮化物系陶瓷，氧化铝、氧化锆等氧化物系陶瓷，碳化硅等碳化物系陶瓷，硼化镧等硼化物系陶瓷等。其中，为了通过活性金属法将金属板接合到陶瓷基板，适用氮化铝、氮化硅等非氧化物系陶瓷，进而，从优异的机械强度、破坏韧性的观点出发，优选氮化硅基板。
本发明的陶瓷基板的厚度没有特别限定，但一般为0.1～3.0mm左右，尤其在考虑到降低线路基板整体的热阻率时，优选为1.0mm以下，更优选为0.4mm以下。
本发明的金属板中所使用的金属只要是铜、铝、铁、镍、铬、银、钼、钴的单质或其合金等可适用于活性金属法的金属，就没有特别限定，尤其从导电性、放热性的观点出发，优选为铜板。
本发明的铜板的纯度优选为90％以上，在纯度低于90％的情况下，在将陶瓷基板与铜板接合时，会有铜板与焊料的反应不充分、或者铜板变硬、线路基板的可靠性下降的情形。
本发明的铜板的厚度没有特别限定，一般为0.1～1.5mm，尤其从放热性的观点出发，优选为0.3mm以上，更优选为0.5mm以上。
本发明的焊料层由含有碳纤维(carbon fiber)和选自钛、锆、铪、铌、钽、钒、锡的至少一种活性金属的银-铜系焊料构成。银-铜系焊料的组成比优选设定为易于生成共晶组成的组成比，特别优选考虑了来自线路铜板和放热铜板的铜的熔入的组成。在银粉末和铜粉末的合计100质量份中，银粉末适合为75～98质量份，铜粉末适合为2～25质量份。在银粉末的量为75～98质量份以外的情形下，焊料的熔融温度上升，因此接合时的热膨胀率差所引起的热应力增加，耐热循环性容易下降。
构成本发明的焊料层的焊料中所含有的碳纤维(carbon fiber)的量，相对于75～98质量份的银粉末和2～25质量份的铜粉末的合计100质量份，优选为0.3～7.5质量份，更优选为0.5～3.5质量份。在碳纤维(carbon fiber)的掺合量少于0.3质量份的情形下，焊料的热膨胀率的下降变小，对线路基板的热循环特性的改善的贡献变小。另一方面，在大于7.5质量份的情形下，陶瓷基板和金属板的接合强度降低，因而不优选。
碳纤维(carbon fiber)优选为15～400μm的平均长度、且5～25μm的平均直径、且3～28的平均长径比，更优选为22～160μm的平均长度、7.5～10μm的平均直径、4～10的平均长径比。在平均长度大于400μm、且平均直径大于25μm、且平均长径比大于28的情形下，难以均匀地分散于焊料糊剂中。此外，在平均长度小于15μm、且平均直径小于5μm、且平均长径比小于4的情形下，陶瓷基板和金属板的接合强度降低，因而不优选。
本发明中，“平均长度”意指利用扫描型电子显微镜观测20根以上的碳纤维、通过图像分析测量各纤维的长度得到的值的平均值。“平均直径”意指利用扫描型电子显微镜观测20根以上的碳纤维、通过图像分析测量各纤维的直径得到的值的平均值。“平均长径比”意指上述“平均长度”除以上述“平均直径”得到的值。
碳纤维(carbon fiber)的种类只要是沥青系碳纤维或聚丙烯腈系碳纤维即可。此外，即使在碳纤维(carbon fiber)、有机粘合剂、有机溶剂中所含的碳成分、碳粉末、金刚石等由相同的碳原子构成的碳成分中，其物理化学行为、机械性质也完全不同，这是众所周知的事实。但是，例如由于非纤维状碳粉末的导热率低，因此有可能阻碍陶瓷线路基板的放热性，因而不优选。进而，耐热循环特性下降，因而不优选。此外，金刚石粉末虽然导热率优异但成本升高而不优选。
构成焊料层的焊料中所含有的活性金属的量，相对于72质量份以上的银粉末和28质量份以下的铜粉末的合计100质量份，优选为1.0～9.0质量份，更优选为3.0～5.5质量份。在活性金属的掺合量小于1.0质量份的情形下，陶瓷基板与焊料的润湿性不好，易于产生接合不良。另一方面，活性金属的掺和量超过9质量份时，在接合界面形成的脆弱的活性金属的氮化物层过剩，耐热循环性下降。另外，活性金属可以选自钛、锆、铪、铌、钽、钒和锡等金属，其中合适的是钛。
用于构成焊料层所涂布的焊料的厚度，以干燥基准计优选5～40μm。焊料的厚度如果小于5μm则有时产生未反应的部分，另一方面，在超过40μm时，去除接合层的时间增加，有时会降低生产率。对涂布方法没有特别限定，可以采用能够在基板表面进行均匀涂布的丝网印刷法、辊涂法等公知的涂布方法。
陶瓷基板和金属板的接合，优选在真空中以780℃～875℃的温度且10～60分钟的时间进行接合。在接合温度低于780℃的情形下，或接合时间少于10分钟的情形下，陶瓷基板与焊料的接合性下降。另一方面，在接合温度高于875℃的情形下、或接合时间长于60分钟的情形下，接合时的热膨胀率差所导致的热应力增加，耐热循环性容易下降。
为了在线路基板上形成线路图案，在金属板上涂布抗蚀剂以进行蚀刻。对于抗蚀剂没有特别限定，例如，可以使用通常使用的紫外线固化型、热固化型的抗蚀剂。对抗蚀剂的涂布方法没有特别限定，例如可以采用丝网印刷法等公知的涂布方法。
为了形成线路图案，进行铜板的蚀刻处理。对于蚀刻液没有特别限定，可以使用通常使用的氯化铁溶液、氯化铜溶液、硫酸、过氧化氢水等，作为优选的蚀刻液，可例举氯化铁溶液、氯化铜溶液。在经过蚀刻除去了不需要的金属部分的氮化物陶瓷线路基板中，残留有涂布的焊料、其合金层、氮化物层等，通常使用卤化铵水溶液，硫酸、硝酸等无机酸，含有过氧化氢水的溶液将其除去。形成线路后进行抗蚀剂的剥离，对剥离的方法没有特别限定，通常为将其浸渍于碱水溶液的方法等。
实施例
[实施例1]
在厚度0.25mm的氮化硅基板的两个主表面上涂布活性金属焊料，在真空条件下以830℃且20分钟的条件下，在线路面上对厚度1.0mm、在背面的1.0mm的无氧铜板进行接合；所述活性金属焊料中，相对于90质量份的银粉末(福田金属箔粉工业株式会社(福田金属箔粉工業(株))制：AgC-BO)和10质量份的铜粉末(福田金属箔粉工业株式会社制：SRC-Cu-20)的合计100质量份，含有1.5质量份的平均长度为120μm、平均直径为15μm、平均长径比为8的碳纤维(carbon fiber)(日本石墨纤维株式会社(日本グラファイトファイバー(株))制：XN-100-15M)、3.5质量份的钛(大阪钛技术株式会社((株)大阪チタニウムテクノロジーズ)制：TSH-350)。
用含有氯化铜的蚀刻液对经接合的线路基板进行蚀刻，形成线路。进而，用氟化铵/过氧化氢蚀刻液对焊料层进行蚀刻，制作氮化硅线路基板。
铜板与氮化硅基板的接合性和线路基板的耐热循环评价用如下方法来进行评价。
<铜板与氮化硅基板的接合性>
铜板与氮化硅基板的接合性通过剥离强度测定来评价。测定方法如下所述。用钳子将作为与氮化硅基板接合的铜线路图案的一部分的、宽度为5mm的图案的端部剥离，将该接合基板固定于拉伸试验机的工作台，将上述图案的端部安装于剥离试验机的卡盘。此时，以使氮化硅基板的表面与剥离的上述铜线路图案的角度成为90°(垂直方向)的方式进行设置。之后，使拉伸试验机工作，介由卡盘使剥离的上述图案向上方拉伸、移动，测定此时的最大剥离载荷。将该最大剥离载荷除以宽度(0.5cm)，算出接合强度。结果示于表3。
<耐热循环性的评价>
对于制作的氮化硅线路基板进行2000个循环重复试验的耐热循环试验，其中以-40℃下30分钟、25℃下10分钟、150℃下30分钟、25℃下10分钟作为1个循环。之后，使用氯化铜液和氟化铵/过氧化氢蚀刻液将铜板和焊料层从氮化硅线路基板剥离，由图像分析软件GIMP2(阈值140)对氮化硅基板表面的水平裂纹面积进行二值化而算出后，由水平裂纹面积/回路图案的面积(即水平裂纹面积相对于线路图案面积的比例)算出裂纹率(％)。结果示于表3。
如表3所示，将铜板接合于氮化硅板时，对于如实施例1那样的相对于90质量份的银粉末和10质量份的铜粉末的合计100质量份，含有碳纤维的平均长度为120μm、平均直径为15μm以下、平均长径比为8的碳纤维(carbon fiber)1.5质量份、钛3.5质量份的配方中，通过在780℃～875℃的温度且10～60分钟的时间进行接合，得到接合性不降低且耐热循环的评价中裂纹率为0.01％的线路基板，证明了能够得到裂纹率1％以下的线路基板。
[实施例2～24、比较例1～13]
除了变为表1、表2中所示的条件以外，以与实施例1相同的方式进行。另外，比较例13中，使用了非纤维状碳粒子来代替碳纤维。以与实施例1相同的方式进行铜板与氮化硅基板的接合性以及耐热循环性的评价。结果示于表3、表4。
[表1]
[表2]
[表3]
[表4]
由表3、表4可知，将铜板接合于氮化硅板时，相对于75～98质量份的银粉末和2～25质量份的铜粉末的合计100质量份，含有碳纤维的平均长度为15～400μm、平均直径为5～25μm、平均长径比为3～28的0.3～7.5质量份的碳纤维(carbon fiber)、1.0～9.0质量的份从钛、锆、铪、铌、钽、钒和锡中选择的至少一种的活性金属的配方中，通过在780℃～875℃的温度且10～60分钟的时间进行接合，得到了接合性不降低且耐热循环的评价中裂纹率为1％以下的线路基板。

Claims (1)

1.一种陶瓷线路基板，其为介由银-铜系焊料层对陶瓷基板的两个主表面和金属板进行接合而成的陶瓷线路基板，其特征在于，相对于75～98质量份的银粉末和2～25质量份的铜粉末的合计100质量份，所述银-铜系焊料层由含有0.3～7.5质量份的碳纤维和1.0～9.0质量份的选自钛、锆、铪、铌、钽、钒和锡的至少一种活性金属的银-铜系焊料构成，所述碳纤维的平均长度为15～400μm、平均直径为5～25μm、平均长径比为3～28。
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WO2015125907A1 (ja) 2015-08-27
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EP3109222A1 (en) 2016-12-28
US20160358840A1 (en) 2016-12-08
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TWI665766B (zh) 2019-07-11
US10424529B2 (en) 2019-09-24

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