CN107210085A - 导电性铜浆料、导电性铜浆料固化膜和半导体装置 - Google Patents

导电性铜浆料、导电性铜浆料固化膜和半导体装置 Download PDF

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CN107210085A
CN107210085A CN201680009284.8A CN201680009284A CN107210085A CN 107210085 A CN107210085 A CN 107210085A CN 201680009284 A CN201680009284 A CN 201680009284A CN 107210085 A CN107210085 A CN 107210085A
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electric conductivity
composition
copper slurry
conductivity copper
mass parts
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梶田昌志
坂本孝史
今野滋子
高桥友之
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Namics Corp
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Namics Corp
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    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
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Abstract

本发明的目的在于提供导电性铜浆料，其能在大气气氛中固化，适用期长，即使在高温短时间的固化条件下电阻率也低，固化后的电阻率不因铜粉的含量不同而大幅变化。所述导电性铜浆料包含(A)铜粉、(B)热固性树脂、(C)常温下液态的脂肪酸以及(D)三乙醇胺。优选的是，(B)成分为甲阶酚醛树脂，更优选的是，相对于(A)成分和(B)成分的合计100质量份，(B)成分为10～20质量份。

Description

导电性铜浆料、导电性铜浆料固化膜和半导体装置
技术领域
本发明涉及导电性铜浆料、导电性铜浆料固化膜和半导体装置，尤其涉及在大气气氛下能烧成的导电性铜浆料、所述导电性铜浆料的固化膜、以及具有所述导电性铜浆料固化膜的半导体装置。
背景技术
半导体元件的电极部与基板的导电部粘接的半导体装置被非常广泛地使用，在半导体元件的电极部与基板的导电部的粘接中，使用导电性粘接剂和焊料粘接。导电性粘接剂尽管有能够在比焊料粘接更低的温度下粘接的优点，但是由于体积电阻比焊料的体积电阻高，所以对导电性粘接剂的低电阻化进行了研究。
以往的导电性粘接剂，使用银作为导电性填料。可是，由于银的迁移性和价格昂贵，所以研究了将铜作为导电性填料使用。此外，针对使用所述铜的导电性粘接剂，要求将容易氧化的铜在大气气氛中固化。
作为将铜作为导电性填料使用的浆料，公开有以规定的粒度分布和振实密度的铜粉、热固性树脂、有机羧酸以及螯合剂、聚丁二烯为必要成分的导电性铜浆料(专利文献1的权利要求1、第0013、0022段)。
所述导电性铜浆料能够进行丝网印刷，具有能和导电性银浆料匹敌的良好导电性，并且目的是兼具抗迁移性并且适用于对应细间距的通孔用(专利文献1的第0008段)，作为有机羧酸，具体的例子可以举出水杨酸、苯甲酸、酒石酸、柠檬酸、马来酸、琥珀酸、富马酸、丙二酸等(专利文献1的第0018段)。另外，这些有机羧酸在常温下都是固体。
此外，公开有包含含铜的金属粉、至少具有2个(甲基)丙烯酸基的化合物以及β-二羰基化合物且实质上不含偶氮化合物和过氧化物的电路基板用导电性浆料(专利文献2的权利要求1)。记载有所述电路基板用导电性浆料可以包含具有熔剂活性的化合物(专利文献2的第0014段)，作为具有熔剂活性的化合物，可以列举油酸等脂肪族羧酸(专利文献2的第0038、0046段)。
此外，公开有在一个分子中至少具有2个以上的羟基、含有包含1个以上的叔胺的预聚物、铜粉、氨基树脂和还原剂且能被酸性蚀刻液蚀刻的导电性铜浆料组合物(专利文献3的权利要求1)，作为还原剂，可以列举油酸、亚油酸等碳原子数12～23的不饱和一元羧酸(专利文献3的第0016段)。
可是，在固化条件为高温短时间(例如，210℃、10分钟)的情况下，发现所述导电性铜浆料存在下述问题：电阻率变高，因铜粉的含量导致固化后的导电性铜浆料的电阻率大幅改变等。
现有技术文献
专利文献
专利文献1：日本专利公开公报特开2008-130301号
专利文献2：日本专利公开公报特开2009-295895号
专利文献3：日本专利公开公报特开平10-064333号
发明内容
本发明要解决的技术问题
本发明的发明人专心研究的结果发现了，通过并用铜粉、常温下液态的脂肪酸、三乙醇胺，能够得到能在大气气氛中固化、适用期长、在高温短时间的固化条件下电阻率也低、固化后的导电性铜浆料的电阻率不会因铜粉的含量大幅变化的导电性铜浆料。即，本发明的目的是提供一种导电性铜浆料，其能在大气气氛中固化、适用期长、固化后电阻率低、固化后的电阻率不会因铜粉的含量不同而大幅变化。
解决技术问题的技术方案
本发明涉及通过具有以下的构成而能够解决所述问题的导电性铜浆料、导电性铜浆料固化膜、导电性铜浆料固化膜的制造方法和半导体装置。
(1)一种导电性铜浆料，其包含(A)铜粉、(B)热固性树脂、(C)常温下液态的脂肪酸以及(D)三乙醇胺。
(2)根据(1)所述的导电性铜浆料，其中，(C)成分是从油酸、亚油酸和亚麻酸中选择的至少1种。
(3)根据所述(1)或(2)所述的导电性铜浆料，其中，(B)成分是甲阶酚醛树脂。
(4)根据所述(1)～(3)中任意一项所述的导电性铜浆料，其中，相对于(A)成分和(B)成分的合计100质量份，(B)成分为10～20质量份。
(5)根据所述(1)～(4)中任意一项所述的导电性铜浆料，其中，相对于(A)成分和(B)成分的合计100质量份，(C)成分是0.8～3质量份。
(6)根据所述(1)～(5)中任意一项所述的导电性铜浆料，其中，相对于(A)成分和(B)成分的合计100质量份，(D)成分是1～5质量份。
(7)根据所述(1)～(6)中任意一项所述的导电性铜浆料，其中，初期粘度为8～12Pa·s。
(8)根据所述(1)～(7)中任意一项所述的导电性铜浆料，其中，在25℃下保持时，到成为初期粘度的1.2倍以上的粘度为止的时间为1星期以上。
(9)一种导电性铜浆料固化膜，其是所述(1)～(8)中任意一项所述的导电性铜浆料的固化物。
(10)一种导电性铜浆料固化膜的制造方法，将所述(1)～(8)中任意一项所述的导电性铜浆料丝网印刷到基板上后，在大气气氛下，在200～220℃下加热5～15分钟。
(11)一种半导体装置，其具有所述(9)所述的导电性铜浆料固化膜。
发明效果
按照本发明(1)，能够提供能在大气气氛中固化、适用期长、在高温短时间的固化条件下电阻率也低、固化后的电阻率不会因铜粉的含量不同而大幅变化的(电阻率小于1×10-4Ω·cm)导电性铜浆料。
按照本发明(9)，能够提供用于得到高可靠性的半导体装置的导电性铜浆料固化膜。按照本发明(10)，能够通过大气气氛下的加热简单地得到用于获得高可靠性的半导体装置的导电性铜浆料固化膜。按照本发明(11)，能够得到例如半导体元件的电极部与基板的导电部之间的连接电阻值小的、高可靠性的半导体装置。
具体实施方式
[导电性铜浆料]
本发明的导电性铜浆料包含(A)铜粉、(B)热固性树脂、(C)常温下液态的脂肪酸以及(D)三乙醇胺。
作为(A)的铜粉赋予固化后的导电性铜浆料导电性。作为(A)成分，可以列举棒状、片状、球状的铜粉，从固化后的导电性铜浆料的电阻率的观点出发，优选的是棒状、片状。(A)成分更优选的是将颗粒形状的树枝状铜粉(电解铜粉)粉碎后得到的棒状的铜粉，进一步优选的是用脂肪酸、特别是用油酸进行了表面处理的棒状的铜粉。作为(A)成分的市售产品，可以列举三井金属矿业(株)制的电解铜粉(ECY)，更优选的是用脂肪酸、特别是用油酸进行了表面处理的电解铜粉(10％粒径：3.4μm；50％粒径：8.1μm；90％粒径：15.2μm；振实密度：4.4g/cm3)。在此，粒径使用激光衍射·散射式粒子分布测定装置进行了测量，振实密度使用振荡比重测量仪(振实机)进行了测量。(A)成分可以单独使用，也可以并用2种以上。
作为(B)成分的热固性树脂对导电性铜浆料赋予粘接性、固化性。作为(B)成分，从热固化收缩性、贴合性的观点出发，优选的是酚醛树脂，更优选的是甲阶酚醛树脂。作为(B)成分的市售产品，可以列举昭和电工(株)制的甲阶酚醛树脂(品名：CKM-918A)。(B)成分可以单独使用，也可以并用2种以上。另外，甲阶酚醛树脂这样的固态的树脂，在制作浆料时，可以与后述的作为(E)成分的溶剂加热混合形成为液状后使用。
(C)成分作为使铜粉表面的氧化层溶出的熔剂成分发挥功能。在此，常温指25℃。由于(C)成分为液态，所以认为导电性铜浆料中的均匀性变好，向作为(A)成分的铜粉的表面的润湿性也变好。优选的是，(C)成分为包含碳＝碳双键的不饱和脂肪酸。作为(C)成分，可以列举
油酸(CH3(CH2)7CH＝CH(CH2)7COOH，顺式-9-十八碳烯酸)，
亚油酸(CH3-(CH2)4-CH＝CHCH2CH＝CH(CH2)7COOH，顺式-9,顺式-12-十八碳二烯酸)，
亚麻酸(CH3CH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)7COOH，顺式-9,顺式-12,顺式-15-十八碳三烯酸)，更优选的是油酸。(C)成分可以单独使用，也可以并用2种以上。
作为(D)成分的三乙醇胺(TEA，N(CH2CH2OH)3)，使因(C)成分的熔剂效果溶出的铜离子固定，并且抑制室温下(25℃)下的脂肪酸的羧基的作用。
从导电性铜浆料的固化性、固化后的导电性铜浆料的电阻率的观点出发，相对于(A)成分(B)成分的合计100质量份，(A)成分优选的是80～90质量份，特别优选的是87.5质量份。
此外，在导电性铜浆料的固化物的情况下，相对于(A)成分和(B)成分的合计100质量份，(A)成分优选的是80～90质量份，特别优选的是87.5质量份。在此，由于导电性铜浆料在固化时的质量减少很少，小于1％，所以固化物中的优选的(A)成分的含量，与固化前的(A)成分的含量相同。在此，用热重量分析装置进行(A)成分的定量分析。
从导电性铜浆料的固化性、固化后的导电性铜浆料的电阻率的观点出发，相对于(A)成分和(B)成分的合计100质量份，(B)成分优选的是10～20质量份，特别优选的是12.5质量份。
此外，在导电性铜浆料的固化物的情况下，相对于(A)成分和(B)成分的合计100质量份，(B)成分优选的是10～20质量份，特别优选的是12.5质量份。在此，用离子色谱-质量分析装置进行(B)成分的定量分析。
相对于(A)成分和(B)成分的合计100质量份，(C)成分优选的是0.8～3质量份，更优选的是1质量份。如果(C)成分少于0.8质量份，则铜浆料固化膜的电阻率容易变高，如果多于3质量份，则铜浆料的适用期容易变短。
此外，在导电性铜浆料的固化物的情况下，相对于(A)成分和(B)成分的合计100质量份，(C)成分优选的是0.8～3质量份。在此，用离子色谱-质量分析装置进行(C)成分的定量分析。
相对于(A)成分和(B)成分的合计100质量份，(D)成分优选的是1～5质量份，更优选的是3质量份。如果(D)成分少于1质量份，则铜浆料的适用期容易变短，如果多于5质量份，则铜浆料固化膜的电阻率容易变高。
另外，从(B)成分为固态时的熔融·液状化和导电性铜浆料的粘度调整的观点出发，导电性铜浆料可以使用溶剂作为(E)成分。可以考虑热固性树脂的溶解性和固化条件来适当选择(E)成分，具体地说，可以列举乙基卡必醇、乙基卡必醇醋酸酯、丁基卡必醇、丁基卡必醇醋酸酯、萜品醇、二氢萜品醇、乙基溶纤剂、丁基溶纤剂、乙基溶纤剂醋酸酯、丁基溶纤剂醋酸酯等。当(B)成分为酚醛树脂时，(E)成分优选的是使用丁基卡必醇。
相对于导电性铜浆料100质量份，(E)成分优选的是10～20质量份。
在不损害本发明的目的的范围内，还可以根据需要，在本发明的导电性铜浆料中混合均化剂、着色剂、离子捕捉剂、消泡剂、阻燃剂、其他的添加剂等。
例如，可以通过对(A)成分～(D)成分和其他添加剂等同时或分别边根据需要实施加热处理边进行搅拌、熔融、混合、分散，来得到本发明的导电性铜浆料。作为所述的混合、搅拌、分散等的装置，没有特别的限定，可以使用具备搅拌、加热装置的擂溃机、三辊磨机、球磨机、行星式搅拌器、珠磨机等。此外，也可以适当组合使用这些装置。
从丝网印刷性的观点出发，优选的是导电性铜浆料的初期粘度处于8～12Pa·s的范围。在此，在制备导电性铜浆料后，在1小时以内采用博勒飞型(B型)粘度计，在25℃、50转下测定了导电性铜浆料的初期粘度。
优选的是，导电性铜浆料的适用期在室温(25℃)下保持时到成为初期粘度的1.2倍以上的粘度为止的时间为6天以上。
本发明的导电性铜浆料通过丝网印刷、分配器等，形成·涂布在基板的导电部、半导体元件的电极部等电子零部件的所希望的位置上。
本发明的导电性铜浆料的固化条件，在大气气氛下，优选的是150～300℃、5～30分钟的高温短时间，特别优选的是200～220℃、5～15分钟的高温短时间。作为导电性铜浆料的固化物的导电性铜浆料固化膜是低电阻率的。在此，本发明的导电性铜浆料固化膜的制造方法为：将导电性铜浆料丝网印刷到基板上后，在大气气氛下，在200～220℃下加热5～15分钟。
本发明的导电性铜浆料，适合作为半导体元件的电极部和基板的导电部等电子零部件用粘接剂。
[半导体装置]
本发明的半导体装置具有导电性铜浆料固化膜。半导体装置例如包含具有导电部的基板以及具有电极部的半导体元件，通过作为所述导电性铜浆料的固化物的导电性铜浆料固化膜，粘接基板的导电部与半导体元件的电极部。
本发明的半导体装置的半导体元件的电极部与基板的导电部之间的连接电阻值小、可靠性高。
实施例
通过实施例对本发明进行说明，但是本发明不限于这些实施例。另外，在以下的实施例中，只要没有特别说明，份、％分别表示质量份、质量％。
在实施例、比较例中，
作为(A)成分，使用了三井金属矿业(株)制的油酸表面处理电解铜粉(10％粒径：3.4μm，50％粒径：8.1μm，90％粒径：15.2μm，振实密度：4.4g/cm3)，
作为(B)成分，使用了昭和电工(株)制的甲阶酚醛树脂(品名：CKM-918A)，
作为(C)成分，使用了和光纯药工业(株)制的油酸、亚油酸、亚麻酸，
作为(C)成分的替代成分(室温下固体)，使用了和光纯药工业(株)制的棕榈酸(CH3(CH2)14COOH(十六烷酸)，硬脂酸(CH3(CH2)16COOH(十八烷酸)，
作为(D)成分，使用了和光纯药工业(株)制的三乙醇胺(TEA：品名：2,2’,2”-次氮基三乙醇，
作为(D)成分的替代成分，使用了四国化成工业(株)制的咪唑(2-苯基-4,5-二羟基甲基咪唑，品名：2PHZ-PW)，和光纯药工业(株)制的乙醇胺(MEA，NH2CH2CH2OH，品名：2-氨基乙醇)，二乙醇胺(DEA，NH(CH2CH2OH)2，品名：2,2’-亚氨基二乙醇)，
作为(E)成分，使用了シェルケミカルズジャパン(株)制的丁基卡必醇(CH3(CH2)3O(CH2)2O(CH2)2OH，2-(2-丁氧基乙氧基)乙醇或二甘醇单丁醚)。
[评价方法]
<初期粘度测定>
制备了导电性铜浆料后，在1小时以内，使用博勒飞型(B型)粘度计，在25℃、50转下测定了导电性铜浆料的初期粘度。
<适用期的测定>
将导电性铜浆料在25℃下保持，每24小时使用博勒飞型(B型)粘度计，在25℃、50转下测定粘度，测定了到成为初期值的1.2倍(增加20％)以上为止的时间。
<电阻率测定>
在氧化铝基板上，用丝网印刷机将导电性铜浆料印刷为宽度1mm、长度71mm的图案，用送风定温干燥机在大气气氛中加热处理210℃×10分钟，使其固化。使用(株)东京精密制的表面粗糙度形状测量仪(型号：サーフコム1500SD-2)，测定了得到的导电性铜浆料固化膜的膜厚，使用(株)TFFケースレーインスツルメンツ制的数字万用表(型号：2001)测定了电阻值，计算出体积电阻率作为电阻率。
[实施例1]
将把作为(A)成分的油酸表面处理电解铜粉87.5质量份、作为(B)成分的甲阶酚醛树脂12.5份加热溶解在作为(E)成分的丁基卡必醇10.2份中得到的物质、作为(C)成分的油酸1份以及作为(D)成分的三乙醇胺3份，用三辊磨机均匀混炼，制备出导电性铜浆料。所述导电性铜浆料的适用期为8天。此外，所述导电性铜浆料固化膜的电阻率为5.6×10-5Ω·cm。
[实施例2]
除了使用了将油酸表面处理电解铜粉85质量份、甲阶酚醛树脂15份加热溶解到丁基卡必醇12.3份中得到的物质以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料固化膜的电阻率为9.6×10-5Ω·cm。另外，未进行适用期的测定。
[实施例3]
除了使用了将油酸表面处理电解铜粉90质量份、甲阶酚醛树脂10份加热溶解到丁基卡必醇8.2份中得到的物质以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料固化膜的电阻率为6.4×10-5Ω·cm。另外，未进行适用期的测定。
[实施例4]
除了作为(C)成分使用了油酸3份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为7天。此外，所述导电性铜浆料固化膜的电阻率为5.9×10-5Ω·cm。
[实施例5]
除了作为(D)成分使用了三乙醇胺1份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为6天。此外，所述导电性铜浆料固化物的电阻率为8.6×10-5Ω·cm。
[实施例6]
除了作为(C)成分使用了亚油酸1份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为7天。此外，所述导电性铜浆料固化膜的电阻率是6.0×10-5Ω·cm。
[实施例7]
除了作为(C)成分使用了亚麻酸1份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为8天。此外，所述导电性铜浆料固化膜的电阻率是5.9×10-5Ω·cm。
[比较例1]
除了未添加油酸和三乙醇胺以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为8天。此外，所述导电性铜浆料固化膜的电阻率是7.1×10-4Ω·cm。
[比较例2]
除了未添加三乙醇胺以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期小于1天。此外，所述铜浆料固化膜的电阻率是2.9×10-4Ω·cm。
[比较例3]
除了未添加油酸以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为12天。此外，所述铜浆料固化膜的电阻率是4.7×10-4Ω·cm。
[比较例4]
除了代替(D)成分使用了咪唑(2-苯基-4,5-二羟基甲基咪唑，品名：2PHZ-PW)以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期小于1天。此外，所述铜浆料固化膜的电阻率为1.8×10-4Ω·cm。
[比较例5]
除了代替(C)成分使用了作为室温下固体状的脂肪酸的棕榈酸1份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为4天。此外，所述导电性铜浆料固化膜的电阻率是7.5×10-5Ω·cm。
[比较例6]
除了代替(C)成分使用了作为室温下固体状的脂肪酸的硬脂酸1份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为2天。此外，所述导电性铜浆料固化膜的电阻率是6.7×10-5Ω·cm。
[比较例7]
除了代替(D)成分使用了乙醇胺(MEA)3份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期小于1天。此外，所述导电性铜浆料固化膜的电阻率是1.4×10-4Ω·cm。
[比较例8]
除了代替(D)成分使用了二乙醇胺(DEA)3份以外，和实施例1同样地制备了导电性铜浆料。所述导电性铜浆料的适用期为1天。此外，所述导电性铜浆料固化膜的电阻率是9.2×10-5Ω·cm。
[表1]
[实施例8～10，比较例9～11]
进行了本发明与专利文献1所公开的发明的比较试验。除了表2所示的组成以外，和实施例1同样地制备了导电性铜浆料。测定了制备出的导电性铜浆料固化膜的电阻率。结果表示在表2中。
[表2]
1)三井金属矿业(株)制的油酸表面处理电解铜粉(50％粒径：8.1μm)
2)昭和电工(株)制的甲阶酚醛树脂(品名：CKM-918A)
3)和光纯药工业(株)制的油酸
4)东京化成工业(株)制的苯甲酸
5)和光纯药工业(株)制的三乙醇胺(品名：2,2’,2”-次氮基三乙醇)
6)和光纯药工业(株)制的乙酰丙酮
7)日本曹达(株)制的环氧化聚丁二烯(品名：JP-100，环氧当量：190～210g/eq)
[实施例11～14]
除了表3所示的组成以外，和实施例1同样地制备了导电性铜浆料，并进行了评价。实施例14的(A)成分-2使用了纳美仕制的液相还原球状铜粉(用日本专利公开公报特开平9-165606号所公开的方法制作，平均粒径：6μm)。表3中表示了电阻率和适用期的结果。
[表3]
从表1判明了，按照实施例1～7的全部实施例，在大气气氛中、高温短时间固化时的电阻率小于1×10-4Ω·cm，适用期为6天以上。与此相对，不含(C)成分和(D)成分的比较例1，电阻率高。不含(D)成分的比较例2，电阻率高且适用期短。不含(C)成分的比较例3，电阻率高。作为(D)成分的替代使用了咪唑的比较例4，电阻率高且适用期短。作为(C)成分的替代使用了棕榈酸的比较例5，适用期短。作为(C)成分的替代使用了硬脂酸的比较例6，适用期短。作为(D)成分的替代使用了MEA的比较例7，电阻率高且适用期短。作为(D)成分的替代使用了DEA的比较例8，适用期短。
从表2判明了，在实施例8～10中，相对于(A)成分和(B)成分的合计100质量份，(A)成分为85～90份的全部实施例，电阻率都小于1×10-4Ω·cm。与此相对，比较例9～11中，由于(A)成分的含量不同，电阻率大幅变化，即使电阻率最小的比较例10，电阻率也为2.438×10-4Ω·cm。
从表3判明了，实施例11～14的全部实施例，在大气气氛中、高温短时间固化时的电阻率，都小于1×10-4Ω·cm，适用期都为6天以上。
如上所述，本发明的导电性铜浆料，能在大气气氛中固化、适用期长、即使在高温短时间的固化条件下电阻率也低、固化后的电阻率不会因铜粉的含量不同而大幅变化，因此非常有用。

Claims (11)

1.一种导电性铜浆料，其特征在于，所述导电性铜浆料包含(A)铜粉、(B)热固性树脂、(C)常温下液态的脂肪酸以及(D)三乙醇胺。
2.根据权利要求1所述的导电性铜浆料，其特征在于，(C)成分是从油酸、亚油酸和亚麻酸中选择的至少1种。
3.根据权利要求1或2所述的导电性铜浆料，其特征在于，(B)成分为甲阶酚醛树脂。
4.根据权利要求1～3中任意一项所述的导电性铜浆料，其特征在于，相对于(A)成分和(B)成分的合计100质量份，(B)成分为10～20质量份。
5.根据权利要求1～4中任意一项所述的导电性铜浆料，其特征在于，相对于(A)成分和(B)成分的合计100质量份，(C)成分为0.8～3质量份。
6.根据权利要求1～5中任意一项所述的导电性铜浆料，其特征在于，相对于(A)成分和(B)成分的合计100质量份，(D)成分为1～5质量份。
7.根据权利要求1～6中任意一项所述的导电性铜浆料，其特征在于，初期粘度处于8～12Pa·s的范围。
8.根据权利要求1～7中任意一项所述的导电性铜浆料，其特征在于，在25℃下保持时，到成为初期粘度的1.2倍以上的粘度为止的时间为1星期以上。
9.一种导电性铜浆料固化膜，其特征在于，所述导电性铜浆料固化膜是权利要求1～8中任意一项所述的导电性铜浆料的固化物。
10.一种导电性铜浆料固化膜的制造方法，其特征在于，将权利要求1～8中任意一项所述的导电性铜浆料丝网印刷到基板上后，在大气气氛下，在200～220℃下加热5～15分钟。
11.一种半导体装置，其特征在于，所述半导体装置具有权利要求9所述的导电性铜浆料固化膜。
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Application publication date: 20170926