CN107922709B - 树脂组合物、铜浆料及半导体装置 - Google Patents

树脂组合物、铜浆料及半导体装置 Download PDF

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CN107922709B
CN107922709B CN201680047365.7A CN201680047365A CN107922709B CN 107922709 B CN107922709 B CN 107922709B CN 201680047365 A CN201680047365 A CN 201680047365A CN 107922709 B CN107922709 B CN 107922709B
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高桥友之
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Abstract

本发明的目的在于提供能够在大气气氛中固化、粘度为适当范围内、在固化后电阻率低、适合于铜浆料的树脂组合物。本发明的树脂组合物，其特征在于，其含有(A)铜粉、(B)热固性树脂、(C)脂肪酸、(D)胺及(E)4－氨基水杨酸。优选使(B)成分为甲阶酚醛树脂，更优选使(C)成分为选自油酸、亚油酸、亚麻酸、硬脂酸、棕榈酸、月桂酸、丁酸及丙酸中的至少1种。

Description

树脂组合物、铜浆料及半导体装置
技术领域
本发明涉及一种树脂组合物、铜浆料及半导体装置，尤其涉及能够在大气气氛化中烧成的树脂组合物、铜浆料及半导体装置。
背景技术
将半导体元件的电极部与基板的导电部粘接而得的半导体装置，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，一般使用导电性粘接剂、软钎焊。导电性粘接剂具有可以使其在比软钎焊更低温下粘接的优点，但是，具有体积电阻比焊料高的缺点，因此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。然而，由于银的迁移性和价格高涨，因此对于将铜用作导电性填料的情况进行了研究。另外，从制造工艺的简便性、低成本化等出发，对于该使用铜的导电性粘接剂还要求使容易氧化的铜在大气气氛中固化。
作为将铜用作导电性填料的浆料，公开了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、螯合剂及聚丁二烯为必须成分的导电性铜浆料(专利文献1的权利要求1、第0013、0022段)。
该导电性铜浆料以能够网板印刷、具有与导电性银浆料相匹敌的良好导电性、且兼具耐迁移性的适合作为与细间距对应的通孔用的导电性铜浆料为目标(专利文献1的第0008段)，作为有机羧酸，就具体例而言，可列举水杨酸、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)。予以说明，这些有机羧酸均在常温下为固体。
另外，公开了一种电路基板用导电性浆料，其特征在于，其包含含铜的金属粉、含有至少2个(甲基)丙烯酰基的化合物和β－二羰基化合物，实质上不含有偶氮化合物及过氧化物(专利文献2的权利要求1)。记载了在该电路基板用导电性浆料中包含具有熔剂活性的化合物即可(专利文献2的第0014段)，作为具有熔剂活性的化合物，可列举油酸等脂肪族羧酸(专利文献2的第0038、0046段)。
此外，还公开了一种导电性铜浆料组合物，其含有在一分子中具有至少2个以上羟基且包含1个以上叔胺的预聚物、铜粉、氨基树脂及还原剂，能够利用酸性蚀刻液进行蚀刻(专利文献3的权利要求1)，作为还原剂，可列举油酸、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)。
然而，可知：在这些导电性铜浆料中，在固化条件为高温短时间(例如在210℃下为10分钟)的情况下，存在电阻率变高的问题。
现有技术文献
专利文献
专利文献1：日本特开2008－130301号公报
专利文献2：日本特开2009－295895号公报
专利文献3：日本特开平10－064333号公报
发明内容
发明要解决的课题
本发明人等进行深入了研究，结果发现一种树脂组合物，其通过并用铜粉、脂肪酸、胺和4－氨基水杨酸，从而能够在大气气氛中固化，使粘度为适当范围内，即使在高温短时间的固化条件下电阻率也低，适合于铜浆料。即，本发明的目的在于提供能够在大气气氛中固化、粘度为适当范围内、在固化后电阻率低、适合于铜浆料的树脂组合物。
用于解决课题的手段
本发明涉及通过具有以下的构成而解决了上述问题的树脂组合物、铜浆料、铜浆料的固化物、铜浆料的固化物的制造方法及半导体装置。
〔1〕一种树脂组合物，其特征在于，其含有(A)铜粉、(B)热固性树脂、(C)脂肪酸、(D)胺、(E)4－氨基水杨酸及(F)溶剂，其中，相对于(A)成分及(B)成分的合计100质量份，含有0.5～3质量份的(E)成分。
〔2〕根据上述〔1〕所述的树脂组合物，其中，(B)成分为选自甲阶酚醛树脂、线型酚醛清漆型酚醛树脂及环氧树脂中的至少1种。
〔3〕根据上述〔1〕或〔2〕所述的树脂组合物，其中，(C)成分为选自油酸、亚油酸、亚麻酸、硬脂酸、棕榈酸及月桂酸中的至少1种。
〔4〕根据上述〔1〕～〔3〕中任一项所述的树脂组合物，其中，(D)成分含有选自三乙醇胺、二乙醇胺及乙醇胺中的至少1种。
〔5〕一种铜浆料，其使用上述〔1〕～〔4〕中任一项所述的树脂组合物。
〔6〕一种固化物，其是上述〔5〕所述的铜浆料的固化物。
〔7〕一种上述〔1〕～〔4〕中任一项所述的树脂组合物的制造方法，其将(A)成分、被溶解于(F)成分的(B)成分、(C)成分、(D)成分及(E)成分混合。
〔8〕一种半导体装置，其包含上述〔1〕～〔4〕中任一项所述的树脂组合物的固化物。
发明效果
根据本发明〔1〕，可以提供能够在大气气氛中固化、粘度为适当范围内、在固化后电阻率值低、适合于铜浆料的树脂组合物。
根据本发明〔5〕，可以提供能够在大气气氛中固化、粘度为适当范围内、在固化后电阻率值低的铜浆料。
根据本发明〔6〕，可以提供用于得到高可靠性的半导体装置的铜浆料的固化物。根据本发明〔7〕，可以简便地得到用于获得高可靠性的半导体装置的树脂组合物。根据本发明〔8〕，可以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
〔树脂组合物〕
本发明的树脂组合物，其特征在于，其含有(A)铜粉、(B)热固性树脂、(C)脂肪酸、(D)胺、(E)4－氨基水杨酸及(F)溶剂，其中，相对于(A)成分及(B)成分的合计100质量份，含有0.5～3质量份的(E)成分。
作为(A)的铜粉会对固化后的树脂组合物赋予导电性。作为(A)成分，可列举棒状、球状、树枝状、片状、球状的铜粉，从固化后的树脂组合物的电阻率的观点出发，优选球状、树枝状、片状。作为(A)成分的市售品，可列举三井金属矿业(株)制的电解铜粉、纳美仕(株)制还原球状铜粉，优选三井金属矿业(株)制电解铜粉(品名：ECY、平均粒径：5～10μm)、纳美仕(株)制还原球状铜粉(平均粒径：6μm)、将上述纳美仕(株)制还原球状铜粉粉碎得到的片状粉末(平均粒径：6μm)。在此，平均粒径利用激光衍射-散射式粒子分布测定装置来测定。(A)成分可以单独使用，也可以并用2种以上。
作为(B)成分的热固性树脂会对树脂组合物赋予粘接性、固化性。作为(B)成分，可列举环氧树脂、酚醛树脂等，从热固化收缩性、密合性的观点出发，优选酚醛树脂，更优选选自甲阶酚醛树脂、线型酚醛清漆型酚醛树脂及环氧树脂中的至少1种。作为(B)成分的市售品，可列举昭和电工(株)制的甲阶酚醛树脂(品名：CKM－918A)、群荣化学工业制线型酚醛清漆型酚醛树脂(品名：Resitop PSM4324)、日本化药制环氧树脂(品名：EPPN－501HY)、三菱化学制环氧树脂(品名：JER 1031S)。(B)成分可以单独使用，也可以并用2种以上。予以说明，在制作浆料时，甲阶酚醛树脂之类的固体树脂可以与后述的(E)成分即溶剂加热混合而制成液状后再使用。
作为(C)成分的脂肪酸，作为使铜粉表面的氧化层溶出的焊剂成分发挥功能。作为(C)成分，优选为选自油酸、亚油酸、亚麻酸、硬脂酸、棕榈酸、月桂酸、丁酸及丙酸中的至少1种。认为：若(C)成分在制作树脂组合物时为液状，则在树脂组合物中的均匀性变得良好，优选向作为(A)成分的铜粉的表面的润湿性也良好。作为(C)成分，可列举：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－9－十八碳二烯酸，顺式－12－十八碳二烯酸)、亚麻酸(CH3CH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)7COOH、顺式－9－十八碳三烯酸，顺式－12－十八碳三烯酸，顺式－15－十八碳三烯酸)、硬脂酸(CH3(CH2)16COOH、十八烷酸)、棕榈酸(CH3(CH2)14COOH、十六烷酸)、月桂酸(CH3(CH2)10COOH、十二烷酸)，更优选油酸。在此，油酸、亚油酸、亚麻酸在常温(25℃)下为液体，硬脂酸、棕榈酸、月桂酸在常温下为固体。(C)成分可以以液体来使用，也可以以固体来使用。(C)成分可以单独使用，也可以并用2种以上。
作为(D)成分的胺会将在(C)成分的焊剂效果下溶出的铜离子固定化且抑制在室温下(25℃)的脂肪酸的羧基的作用。作为(D)成分，可列举三乙醇胺(TEA、N(CH2CH2OH)3)、二乙醇胺(DEA、NH(CH2CH2OH)2)、乙醇胺(MEA、NH2(CH2CH2OH))，优选含有选自三乙醇胺、二乙醇胺及乙醇胺中的至少1种。
作为(E)成分的4－氨基水杨酸(4－氨基－2－羟基苯甲酸)以化学式(1)来表示，抑制(A)成分的氧化。
[化1]
Figure GDA0002701327090000051
认为：在(E)成分中的苯酚部具有自由基吸收能力，因此吸收(A)成分表面的活性氧，且在(E)成分中的羟基部具有还原作用，因此(E)成分具有氧化抑制和还原两个作用。另外，(E)成分通过(C)成分、(D)成分的相互作用而促进固化后的树脂组合物的低电阻化。
从(B)成分为固态时的(B)成分的熔融-液状化及调整树脂组合物的粘度的观点出发，树脂组合物还使用溶剂作为(F)成分。(F)成分可以考虑热固性树脂的溶解性或固化条件进行适当选择，具体而言，可列举：乙基卡必醇、乙基卡必醇乙酸酯、丁基卡必醇、丁基卡必醇乙酸酯、萜品醇、二氢萜品醇、乙基溶纤剂、丁基溶纤剂、乙基溶纤剂乙酸酯、丁基溶纤剂乙酸酯、二醇醚、二乙二醇、乙二醇单苯基醚等。在(B)成分为酚醛树脂的情况下，优选使用丁基卡必醇。
从树脂组合物的固化性和固化后的树脂组合物的电阻率的观点出发，相对于(A)成分与(B)成分的合计100质量份，(A)成分优选为80～98质量份，更优选为85～96质量份，进一步优选为88～95质量份。
从树脂组合物的固化性和固化后的树脂组合物的电阻率的观点出发，相对于(A)成分与(B)成分的合计100质量份，(B)成分优选为2～20质量份。
另外，在树脂组合物的固化物的情况下，相对于(A)成分与(B)成分的合计100质量份，(B)成分也优选为2～20质量份。在此，(B)成分的定量分析利用离子色谱－质量分析装置来进行。
相对于(A)成分与(B)成分的合计100质量份，(C)成分优选为0.5～5质量份，更优选为1～3质量份，特别优选为1质量份。若(C)成分低于1质量份，则固化后的树脂组合物的电阻率值容易变高，若(C)成分多于3质量份，则树脂组合物的适用期容易变短。
另外，在树脂组合物的固化物的情况下，相对于(A)成分与(B)成分的合计100质量份，(C)成分也优选为0.5～5质量份，更优选为1～3质量份，特别优选为1质量份。在此，(C)成分的定量分析利用离子色谱－质量分析装置来进行。
相对于(A)成分与(B)成分的合计100质量份，(D)成分优选为1～10质量份，更优选为1～5质量份。若(D)成分低于1质量份，则树脂组合物的适用期容易变短，若(D)成分多于10质量份，则固化后的树脂组合物的电阻率值容易变高。
另外，在树脂组合物的固化物的情况下，相对于(A)成分与(B)成分的合计100质量份，(D)成分也优选为1～10质量份，更优选为1～5质量份。在此，(D)成分的定量分析利用离子色谱－质量分析装置来进行。
相对于树脂组合物100质量份，(E)成分为0.5～3质量份，优选为1质量份。若(C)成分低于1质量份，则固化后的树脂组合物的电阻率值容易变高，若(C)成分多于3质量份，则树脂组合物的适用期容易变短。
另外，在树脂组合物的固化物的情况下，相对于(A)成分与(B)成分的合计100质量份，(E)成分也优选为0.5～3质量份。在此，(E)成分的定量分析利用离子色谱－质量分析装置来进行。
相对于树脂组合物100质量份，(F)成分优选为8～22质量份，更优选为10～20质量份。
在本发明的树脂组合物中，可以在不损害本发明目的的范围内根据需要进一步配合均化剂、着色剂、离子捕捉剂、消泡剂、阻燃剂、防锈剂、表面活性剂、其他添加剂等。
本发明的树脂组合物例如可以通过边将(A)成分～(F)成分及其他添加剂等同时或分别根据需要施加加热处理，边使其搅拌、熔融、混合、分散而得到。在此，从树脂组合物的均匀性的观点出发，(B)成分优选被溶解于(F)成分。作为这些成分的混合、搅拌、分散等的装置，并无特别限定，但是可以使用具备搅拌、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。另外，也可以将这些装置适当组合使用。
从网板印刷性的观点出发，树脂组合物的初始粘度优选为10～500Pa·s的范围。在此，在制作树脂组合物后，在1小时以内使用博勒飞型(B型)粘度计并且在25℃、旋转10次下测定树脂组合物的初始粘度。
〔铜浆料〕
本发明的铜浆料使用上述的树脂组合物。利用网板印刷、分配器等将该铜浆料形成、涂布于基板的导电部、半导体元件的电极部等电子零部件的所期望的位置。
本发明的铜浆料的固化物为低电阻，与以往所使用的银浆料的固化物相比，耐迁移更优异，因此可以提供高可靠性的半导体。
本发明的铜浆料的固化条件优选为大气气氛下、150～300℃、5～60分钟，特别适合在200～220℃下固化5～30分钟。铜浆料的固化物为低电阻率。在此，本发明的铜浆料的固化物可以通过以下方式来制造，即，将铜浆料网板印刷于基板后，在大气气氛下且200～220℃下加热5～60分钟。
本发明的铜浆料适合作为半导体元件的电极部与基板的导电部等的电子零部件用粘接剂。
〔半导体装置〕
本发明的半导体装置包含上述的树脂组合物的固化物。另外，半导体装置包含例如具有导电部的基板和具有电极部的半导体元件，在使用上述的树脂组合物的铜浆料的固化物中，基板的导电部与半导体元件的电极部接合。
就本发明的半导体装置而言，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，耐迁移性优异，因此为高可靠性。
实施例
利用实施例对本发明进行说明，但本发明不受这些实施例的限定。予以说明，在以下的实施例中，只要没有特别说明，“份”、“％”表示质量份、质量％。
〔评价方法〕
《粘度测定》
制作树脂组合物后，在1小时以内使用博勒飞型(B型)粘度计并且在25℃、旋转1次及旋转10次下测定树脂组合物的初始粘度。粘度以旋转1次的粘度计时20～700Pa·s为适当范围内，20～60Pa·s为更佳的适当范围内。以旋转10次的粘度计，10～500Pa·s为适当范围内，10～15Pa·s为更佳的适当范围内。另外，由〔(旋转1次的粘度)/(旋转10次的粘度)〕求得触变比。就触变比而言，1.0～5.0为适当范围内。
《电阻率测定》
在氧化铝基板上利用网板印刷机以宽度：1mm、长度：71mm的图案印刷树脂组合物，将其在送风恒温干燥机中且大气气氛中或氮气氛中进行200℃×30分钟加热处理，使其固化。所得的树脂组合物的固化物的膜厚使用(株)东京精密制表面粗糙度形状测定机(型号：SURFCOM 1500SD－2)来测定，电阻值使用(株)TFF KEITHLEY INSTRUMENTS制数字万用表(型号：2001)来测定，计算体积电阻率，作为电阻率。
《剪切强度测定》
在20mm见方的氧化铝基板上，使用250目的不锈钢制丝网对各树脂组合物以1.5mm见方进行5×5块图案印刷，在10个部位放置3216尺寸的氧化铝芯片，进行200℃×30分钟加热处理，使其固化。在固化后，使用AIKOH ENGINEERING制台式强度试验机(型号：1605HTP)，测定在加权速度12mm/分钟下的剪切强度。
〔实施例1〕
利用三辊磨机将作为(A)成分的电解铜粉93.0质量份、使作为(B)成分的甲阶酚醛树脂7.0份加热溶解于(F)成分的丁基卡必醇17.5份而得的溶液、作为(C)成分的油酸1.0份、作为(D)成分的三乙醇胺3.0份及作为(E)成分的4-氨基水杨酸2.0份均匀地混炼，制备树脂组合物。对该树脂组合物的固化物的电阻率进行了测定。在表1中示出结果。
〔实施例2～23、比较例1～10〕
除使其成为表1～4所示的配方以外，与实施例1同样地制备树脂组合物，进行粘度、电阻率的评价。在表1～4中示出结果。
Figure GDA0002701327090000091
1)三井金属矿业制电解铜粉(品名：ECY-4、平均粒径：7μm)
2)纳美仕制液相还原球状铜粉(利用日本特开平9-165606号公报中记载的方法来制作、平均粒径：6μm)
3)将上述纳美仕制液相还原球状铜粉用球磨机粉碎后的碎片状粉末(平均粒径：6μm)
4)昭和电工制甲阶酚醛树脂(品名：shownol CKM918A)
5)和光纯药工业制油酸
6)和光纯药工业制硬脂酸
7)和光纯药工业制棕榈酸
8)和光纯药工业制月桂酸
9)和光纯药工业制三乙醇胺
10)和光纯药工业制二乙醇胺
11)和光纯药工业制单乙醇胺
12)和光纯药工业制4-氨基水杨酸
13)和光纯药工业制5-氨基水杨酸
14)Shell Chemicals Japan制丁基卡必醇
Figure GDA0002701327090000101
Figure GDA0002701327090000102
15)群荣化学工业制线型酚醛清漆型酚醛树脂(品名：Resitop PSM4324)
16)日本化药制环氧树脂(品名：EPPN-501HY)
17)三菱化学制环氧树脂(品名：JER 1031S)
18)米山药品工业制丁基卡必醇乙酸酯(品名：BCA)
19)东邦化学工业制乙二醇单苯基醚(品名：Hisolve EPH)
20)和光纯药制二乙二醇(品名：DEG)
a
Figure GDA0002701327090000111
由表1、表2可知：在全部的实施例1～23中，使其在氮气氛中固化时的电阻率不足7.0×10－5Ω·cm，使其在大气气氛中固化时的电阻率不足2.1×10－4Ω·cm，粘度及触变比为适当范围内，剪切强度也高。尤其是使实施例1～4、6～10、13～15在氮气氛中固化时的电阻率不足5.0×10－5Ω·cm，为与银浆料的固化体同样的水平。尤其是在实施例2、10中，使其在大气气氛中固化时的电阻率也不足5.0×10－5Ω·cm不足，为与银浆料的固化体同样的水平。与此相对，在(E)成分过少的比较例1、(E)成分过多的比较例2中，在大气气氛中固化时的电阻率值高。在不包含(C)成分、(D)成分及(E)成分的比较例3、不包含(C)成分及(D)成分的比较例5、不包含(C)成分及(E)成分的比较例7、不包含(D)成分的比较例8、不包含(C)成分的比较例9、包含美沙拉嗪(mesalazine)来代替(E)成分的比较例10中，在氮气氛中的固化、大气气氛中的固化时均使电阻率值非常高。在不包含(E)成分的比较例4、不包含(D)成分及(E)成分的比较例6中，在大气气氛中固化时的电阻率值非常高。
产业上的可利用性
本发明的树脂组合物能够在大气气氛中固化，粘度为适当范围内，在固化后电阻率值低，因此非常有用。

Claims (8)

1.一种树脂组合物，其特征在于，其含有(A)铜粉、(B)热固性树脂、(C)脂肪酸、(D)胺、(E)4－氨基水杨酸及(F)溶剂，其中，相对于(A)成分及(B)成分的合计100质量份，含有0.5～3质量份的(E)成分。
2.根据权利要求1所述的树脂组合物，其中，(B)成分为选自甲阶酚醛树脂、线型酚醛清漆型酚醛树脂及环氧树脂中的至少1种。
3.根据权利要求1或2所述的树脂组合物，其中，(C)成分为选自油酸、亚油酸、亚麻酸、硬脂酸、棕榈酸及月桂酸中的至少1种。
4.根据权利要求1或2所述的树脂组合物，其中，(D)成分含有选自三乙醇胺、二乙醇胺及乙醇胺中的至少1种。
5.一种铜浆料，其使用权利要求1～4中任一项所述的树脂组合物。
6.一种固化物，其是权利要求5所述的铜浆料的固化物。
7.一种权利要求1～4中任一项所述的树脂组合物的制造方法，其将(A)成分、被溶解于(F)成分的(B)成分、(C)成分、(D)成分及(E)成分混合。
8.一种半导体装置，其包含权利要求1～4中任一项所述的树脂组合物的固化物。
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