CN110691762A - 陶瓷电路基板和其制造方法 - Google Patents
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Abstract
提供一种耐热循环特性优异的陶瓷电路基板。一种陶瓷电路基板,其特征在于,在陶瓷基板的至少一个主面介由接合钎料接合有金属板,以金属成分计,相对于Ag93.0~99.4质量份、Cu0.1~5.0质量份、Sn0.5~2.0质量份的合计100质量份,上述接合钎料含有0.5~4.0质量份的选自钛、锆、铪、铌中的至少1种活性金属,陶瓷基板与金属板之间的接合钎料层组织中的富Cu相的平均尺寸为3.5μm以下,个数密度为0.015个/μm2以上。一种陶瓷电路基板的制造方法,其包含:在接合温度855~900℃、保持时间10~60分钟的条件下进行接合。
Description
技术领域
本发明涉及陶瓷电路基板和其制造方法。
背景技术
在电梯、车辆、混合动力汽车等之类的功率模块用途中,使用在氧化铝、氧化铍、氮化硅、氮化铝等陶瓷基板的表面用钎料接合金属电路板、再在金属电路板的规定位置搭载半导体元件而成的陶瓷电路基板。
近年来,随着半导体元件的高输出化、高集成化,来自半导体元件的放热量一直在增加。为了高效率地使该放热逸散而使用了具有高绝缘性、高热传导性的氮化铝烧结体、氮化硅烧结体的陶瓷基板。
但是,陶瓷基板与金属板的热膨胀率差异大,因此在陶瓷基板与金属板的接合界面处,由于反复的冷热循环的负荷而产生起因于热膨胀率差的热应力。特别是压缩和拉伸的残留应力作用于接合部附近的陶瓷基板侧,从而在陶瓷基板产生裂纹,招致接合不良或热阻不良,具有作为电子设备的动作可靠性下降等问题。
因此,专利文献1、2、3中提出了如下方法:通过将In、Zn、Cd、Sn添加到Ag-Cu系钎料中而使接合温度降低,从而减少热应力的产生,降低接合后的残留应力,由此来提高陶瓷电路基板的可靠性。
现有技术文献
专利文献
专利文献1:日本特开平9-283656号公报
专利文献2:日本特开2014-118310号公报
专利文献3:日本特开2015-65313号公报
发明内容
发明要解决的课题
但是,在现有技术中,为了进一步降低残留应力,通过在Ag-Cu钎料中配合5%以上的低熔点金属,从而钎料层的熔点降低,形成Ag-Cu-低熔点金属系组织的时间变长,成为不均匀的Ag-Cu-低熔点金属钎料层组织。其结果是,存在在耐热循环测试中缓和陶瓷电路基板中产生的热应力的效果下降、使陶瓷电路基板的可靠性下降之类问题。本发明的课题在于提供可靠性高的陶瓷电路基板。
用于解决课题的手段
为了实现上述目的,本发明人对接合陶瓷基板和金属电路板的钎料中所含的元素的量进行各种变更并制备陶瓷电路基板,对钎料中所含的元素的量给陶瓷电路基板的耐热循环特性造成的影响进行比较研究。其结果获知,通过减小Ag-Cu-Sn钎料层组织的富Cu相的平均尺寸和增加富Cu相的个数密度,陶瓷电路基板的耐热循环特性提高。本发明是基于这些见解完成的。
即,本发明为一种陶瓷电路基板,其特征在于,在介由Ag-Cu-Sn钎料将陶瓷电路基板的至少一个主面与金属板接合而成的陶瓷电路基板的剖面的接合界面的、由SEM得到的反射电子图像的倍率3000倍的视野中,在接合界面处连续形成的上述Ag-Cu-Sn钎料层组织中的富Cu相的平均尺寸为3.5μm以下,富Cu相的个数密度为0.015个/μm2以上。
换言之,本发明为一种陶瓷电路基板,其特征在于,在陶瓷基板的至少一个主面介由接合钎料接合有金属板,以金属成分计,相对于Ag93.0~99.4质量份、Cu0.1~5.0质量份、Sn0.5~2.0质量份的合计100质量份,所述接合钎料含有0.5~4.0质量份的选自钛、锆、铪、铌中的至少1种活性金属,陶瓷基板与金属板之间的接合钎料层组织中的富Cu相的平均尺寸为3.5μm以下,个数密度为0.015个/μm2以上。
发明的效果
根据本发明,提供一种可靠性高的陶瓷电路基板。更详细而言,提供一种陶瓷电路基板,其具有1.0%以下的接合孔隙率,而且在2000次循环的-55℃至150℃的热循环试验中裂纹率小于1.0%。
附图说明
图1为富Cu相的平均尺寸为3.0μm且富Cu相的个数密度为0.016个/μm2的Ag-Cu-Sn钎料层组织的陶瓷电路基板的一例。
具体实施方式
[陶瓷电路基板]
本发明的陶瓷电路基板的特征在于,在陶瓷基板的至少一个主面介由接合钎料接合有金属板,以金属成分计,相对于Ag93.0~99.4质量份、Cu0.1~5.0质量份、Sn0.5~2.0质量份的合计100质量份,所述接合钎料含有0.5~4.0质量份的选自钛、锆、铪、铌中的至少1种活性金属,陶瓷基板与金属板之间的接合钎料层组织中的富Cu相的平均尺寸为3.5μm以下,个数密度为0.015个/μm2以上。
作为本发明的陶瓷电路基板中所用的陶瓷基板,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于陶瓷基板,优选氮化铝、氮化硅等非氧化物系陶瓷,进而从优异的机械强度、断裂韧性的观点出发,优选氮化硅基板。
在本发明的一个实施方式中,对陶瓷基板的厚度没有特别限定,通常为0.1~3.0mm左右,特别地,若考虑到降低电路基板整体的热阻率,则优选为2.0mm以下,更优选为1.2mm以下。
在本发明的一个实施方式中,金属板接合于陶瓷基板的两个主面或一个主面,金属板所使用的金属优选为铜或铜合金。
在本发明的一个实施方式中,对金属板的厚度没有特别限定,通常为0.1~1.5mm,特别地,从放热性的观点出发,优选为0.3mm以上,更优选为0.5mm以上。
本发明人为了实现陶瓷电路基板中的优异的耐热循环特性进行了深入研究,结果发现:通过减小Ag-Cu-Sn钎料层组织的富Cu相的平均尺寸和增加富Cu相的个数密度,则陶瓷电路基板的耐热循环特性提高。还发现:通过提高作为钎料的主要成分的Ag粉末的配合量,减少Cu、Sn等元素的添加量,则Ag-Cu-Sn钎料层组织的富Cu相的平均尺寸变小,富Cu相的个数密度增加,获知能够形成具有微细且均匀的富Cu相的Ag-Cu-Sn钎料层组织。
在本实施方式中,在用扫描型电子显微镜观察陶瓷电路基板的剖面的反射电子图像时,将Ag-Cu-Sn钎料层组织中的反映组成的、看起来呈黑色的相定义为富Cu相。另外,测定所观察的富Cu相的重心直径,将其平均值定义为富Cu相的平均尺寸。
另外,在本实施方式中,作为表示上述的Ag-Cu-Sn钎料层组织的微细度和均匀度的指标,将陶瓷电路基板的任意剖面中的Ag-Cu-Sn钎料层中的富Cu相的个数除以Ag-Cu-Sn钎料层组织的面积所得的值定义为富Cu相的个数密度。
本发明的陶瓷电路基板的Ag-Cu-Sn钎料层组织中的富Cu相的平均尺寸优选为3.5μm以下,更优选为3.0μm以下,进一步优选为2.8μm以下。本发明的陶瓷电路基板的Ag-Cu-Sn钎料层组织中的富Cu相的个数密度优选为0.015个/μm2以上,更优选为0.018个/μm2以上,进一步优选为0.025个/μm2以上。通过将富Cu相的平均尺寸设为3.5μm以下和将富Cu相的个数密度设为0.015个/μm2以下,从而能够抑制下述情况:Ag-Cu-Sn钎料层组织变得不均匀,在耐热循环特性评价中缓和在陶瓷电路基板中产生的热应力的效果下降,陶瓷电路基板的耐热循环特性下降。
另外,在本发明的一个实施方式中,陶瓷电路基板的接合孔隙率优选为1.0%以下,更优选为0.8%以下,进一步优选为0.5%以下。
进而,本发明的一个实施方式的陶瓷电路基板优选2000次循环的-55℃至150℃的热循环试验中的裂纹率小于1.0%,更优选为0.8%以下,进一步优选为0.5%以下。
在本发明的一个实施方式中,钎料由在钎料层中含有选自钛、锆、铪、铌中的至少一种活性金属的Ag-Cu-Sn系钎料构成。对于Ag-Cu-Sn钎料层组织中的富Cu相的形成而言,通过主要控制铜从金属板向钎料中熔入,能够制作微细且均匀的Ag-Cu-Sn钎料层组织。关于Ag-Cu-Sn系钎料的配合比,期望设为容易形成微细的富Cu相的配合比,特别优选为考虑到铜从金属板熔入的配方(在Ag粉末、Cu粉末和Sn粉末的合计100质量份中,Ag粉末为93.0~99.4质量份,Cu粉末为0.1~5.0质量份,Sn粉末为0.5~2.0质量份)。
作为上述Ag粉末,可以使用比表面积为0.1~0.5m2/g的Ag粉末。若使用比表面积大于0.5m2/g的Ag粉末则容易发生聚集、或者氧浓度高,有导致接合不良的可能性。另外,通过使用具有0.1m2/g以上的比表面积的Ag粉末,能够抑制Ag-Cu-Sn钎料层组织变得不均匀,陶瓷电路基板的可靠性下降的情况。另外,关于比表面积的测定,能够使用气体吸附法来测定。
在本发明的一个实施方式中,钎料粉末中所含的Cu粉末是用于提高Ag-Cu-Sn系钎料的熔化性的成分,它们的配合量优选为0.1~5.0质量份。通过将Cu粉末的配合量设为0.1质量份以上,从而抑制钎料的熔化性下降、导致接合不良的可能性。另外,通过将Cu粉末的配合量设为5.0质量份以下,能够抑制以下情况:Ag-Cu-Sn钎料层组织中的富Cu相的平均尺寸变大,在耐热循环评价中缓和陶瓷电路基板中产生的热应力的效果下降,从而陶瓷电路基板的可靠性下降。
在本发明的一个实施方式中,钎料粉末中所含的Sn粉末是用于减小钎料相对于陶瓷基板的接触角、改善钎料的润湿性的成分,它们的配合量优选为0.5~2.0质量份。通过将Sn粉末的配合量设为0.5质量份以上,从而抑制与陶瓷基板的润湿性下降、导致接合不良的可能性。通过将Sn粉末的配合量设为2.0质量份以下,从而可以抑制下述情况:Ag-Cu-Sn钎料层组织中的富Cu相的平均尺寸变大,在耐热循环评价中缓和陶瓷电路基板中产生的热应力的效果下降,从而陶瓷电路基板的可靠性下降。
在本发明的一个实施方式中,钎料中所含的活性金属相对于Ag粉末、Cu粉末和Sn粉末的合计100质量份优选为0.5~4.0质量份。通过将活性金属的含量设为0.5质量份以上,从而能够抑制陶瓷基板与钎料的润湿性不良、容易发生接合不良的情况。另一方面,通过将活性金属的含量设为4.0质量份以下,从而能够抑制与低熔点金属在接合界面处产生脆弱的合金层而使耐热循环性下降的情况。需要说明的是,活性金属可以从钛、锆、铪、铌等金属和它们的氢化物中选择,这些中,优选钛、氢化钛。
在本发明的一个实施方式中,钎料的厚度以干燥基准计优选为5~40μm。通过将钎料厚度设为5μm以上,能够抑制液相的形成不充分、产生较多的接合孔隙的情况,另一方面,通过设为40μm以下,能够抑制除去接合层的时间变长、生产率下降的情况。对涂布方法没有特别限制,可以采用能够对基板表面进行均匀涂布的丝网印刷法、辊涂机法等公知的涂布方法。
[陶瓷电路基板的制造方法]
本发明的陶瓷电路基板的制造方法包含:在接合温度855~900℃、保持时间10~60分钟的条件下进行接合。在本发明的一个实施方式中,陶瓷基板与金属板的接合优选在真空中在855℃~900℃的温度下且用10~60分钟的时间接合。通过使接合温度设为855℃以上且使保持时间为10分钟以上,能够抑制Cu从金属板的熔入不足、陶瓷基板与金属板的接合性下降的情况。另一方面,通过将接合温度设为900℃以下且使保持时间为60分钟以下,能够抑制来自接合时的热膨胀率差的热应力增加、陶瓷电路基板的可靠性下降的情况。
在本发明的一个实施方式中,为了在电路基板形成电路图案,在金属板涂布抗蚀剂并进行蚀刻。关于抗蚀剂,没有特别限制,可以使用例如一般使用的紫外线固化型、热固化型的抗蚀剂。关于抗蚀剂的涂布方法,没有特别限制,可以采用例如丝网印刷法等公知的涂布方法。
在本发明的一个实施方式中,为了形成电路图案,进行金属板的蚀刻处理。关于蚀刻液,也没有特别限制,可以使用一般使用的氯化铁溶液、氯化铜溶液、硫酸、双氧水等,作为优选的蚀刻液,可列举氯化铁溶液、氯化铜溶液。在通过蚀刻除去了不需要的金属部分后的氮化物陶瓷电路基板残留有涂布的钎料、其合金层、氮化物层等,通常使用包含卤化铵水溶液、硫酸、硝酸等无机酸、双氧水的溶液将它们除去。在电路形成后进行抗蚀剂的剥离,对剥离方法没有特别限制,一般用浸渍于碱水溶液的方法等。
实施例
以下利用实施例详细说明本发明。但是,本发明的范围不受以下的实施例限定。
[实施例1]
在厚0.32mm的氮化硅基板,用丝网印刷法涂布相对于Ag粉末(福田金属箔粉工业(株)制:Ag-HWQ 2.5μm)99.0质量份、Cu粉末(福田金属箔粉工业(株)制:Cu-HWQ 3μm)0.5质量份、Sn粉末(福田金属箔粉工业(株)制:Sn-HPN 3μm)0.5质量份的合计100质量份包含3.5质量份的氢化钛粉末(TOHO TECHNICAL SERVICE CO.,LTD制:TCH-100)的活性金属钎料,使得涂布量成为8mg/cm2。然后,在氮化硅基板的一面重叠电路形成用金属板,在另一面重叠放热板形成用金属板(均为厚度0.8mm、纯度99.60%的C1020无氧铜板),在890℃且20分钟的条件下接合。在接合后的铜板印刷抗蚀剂,用氯化铜溶液蚀刻而形成电路图案。进一步用氟化铵/过氧化氢溶液除去钎料层、氮化物层。
<接合孔隙率>
关于用超声波探伤装置(Hitachi Power Solutions Co.,Ltd.制:ES5000)观察的陶瓷电路基板的接合孔隙率,计量接合孔隙的面积并除以铜电路图案的面积,从而计算。
<Ag-Cu-Sn钎料层组织中的富Cu相的观察>
关于Ag-Cu-Sn钎料层组织中的富Cu相,使用扫描型电子显微镜(日本电子JSM-6380),在陶瓷电路基板的剖面的接合界面的任意位置处,利用反射电子图像以3000倍的倍率观察3个长60μm×宽80μm的视野,从而评价。通过该方法,可以观察粒径0.1μm以上的富Cu相。若观察倍率过度提高,则视野变窄,无法观察到足够数量的富Cu相,相反,若倍率过低则无法观察到小于1μm的富Cu相,因此设为3000倍。
<Ag-Cu-Sn钎料层组织中的富Cu相的评价>
对通过上述方法得到的SEM图像进行解析、测定。关于用于图像解析的软件,使用MediaCybernetics公司制图像处理软件Image-Pro Plus。本发明的Ag-Cu-Sn钎料层组织中的富Cu相为粒径0.3μm至数μm的各种类型,以用扫描型电子显微镜可观察到的粒径0.1μm以上的富Cu相为对象来进行解析。关于富Cu相的平均尺寸,对3个视野进行观察,测定所观察的所有的富Cu相的重心直径,求出其平均值。另外,关于富Cu相的个数密度,使用图像解析软件Image-pro plus计测Ag-Cu-Sn钎料层组织的面积,由以下的式(I)求出富Cu相的个数密度。
富Cu相的个数密度(个/μm2)=富Cu相的个数/Ag-Cu-Sn钎料层组织的面积···(I)
<耐热循环性的评价>
对于制作的陶瓷电路基板,通过以-55℃下15分钟、25℃下15分钟、150℃下15分钟、25℃下15分钟为1个循环的耐热循环试验,进行2000次循环的重复试验后,用氯化铁和氟化铵/过氧化氢蚀刻将金属板和钎料层剥离,用扫描仪以600dpi×600dpi的分辨率读取在陶瓷基板的表面所产生的水平裂纹面积,用图像解析软件GIMP2(阈值140)进行二值化计算后,计算水平裂纹面积,再除以铜电路图案面积而求出水平裂纹率。
[实施例2~12]
除了设为表1中所示的条件以外,与实施例1同样地进行。
[比较例1]
除了接合中使用的钎料不含Cu粉末和Sn粉末以外,与实施例1同样地得到陶瓷电路基板。
[比较例2~6]
除了设为表1中所示的条件以外,与实施例1同样地进行。
【表1】
在将金属板接合于氮化硅基板时,通过相对于Ag粉末93.0~99.4质量份、Cu粉末0.1~5.0质量份和Sn粉末0.5~2.0质量份的合计100质量份配合0.5~4.0质量份的氢化钛、并且在855~900℃的温度且10~60分钟的保持时间下进行接合,得到了在耐热循环评价中水平裂纹率为1.0%以下的陶瓷电路基板。
附图标记的说明
1 陶瓷基板
2 金属板
3 Ag-Cu-Sn钎料层组织
4 富Cu相
5 接合界面
Claims (2)
1.一种陶瓷电路基板,其特征在于,在陶瓷基板的至少一个主面介由接合钎料接合有金属板,以金属成分计,相对于Ag93.0~99.4质量份、Cu0.1~5.0质量份、Sn0.5~2.0质量份的合计100质量份,所述接合钎料含有0.5~4.0质量份的选自钛、锆、铪、铌中的至少1种活性金属,陶瓷基板与金属板之间的接合钎料层组织中的富Cu相的平均尺寸为3.5μm以下,个数密度为0.015个/μm2以上。
2.根据权利要求1所述的陶瓷电路基板的制造方法,其包含:在接合温度855~900℃、保持时间10~60分钟的条件下进行接合。
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KR102479866B1 (ko) | 2022-12-20 |
JP7301740B2 (ja) | 2023-07-03 |
US11277908B2 (en) | 2022-03-15 |
EP3632880A1 (en) | 2020-04-08 |
WO2018221492A1 (ja) | 2018-12-06 |
JPWO2018221492A1 (ja) | 2020-03-26 |
EP3632880A4 (en) | 2020-05-20 |
EP3632880B1 (en) | 2022-02-09 |
JP2022161988A (ja) | 2022-10-21 |
CN110691762B (zh) | 2022-06-14 |
US20210176859A1 (en) | 2021-06-10 |
KR20200013677A (ko) | 2020-02-07 |
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