CN104379689A - 粘接剂组合物及使用其的半导体装置 - Google Patents

粘接剂组合物及使用其的半导体装置 Download PDF

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CN104379689A
CN104379689A CN201380031406.XA CN201380031406A CN104379689A CN 104379689 A CN104379689 A CN 104379689A CN 201380031406 A CN201380031406 A CN 201380031406A CN 104379689 A CN104379689 A CN 104379689A
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adhesive composite
equal
zinc
silver
composite according
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CN104379689B (zh
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中子伟夫
田中俊明
名取美智子
石川大
松本博
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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Abstract

本发明提供一种粘接剂组合物,其为包含含有银原子的银粒子和含有金属锌的锌粒子的粘接剂组合物,相对于该粘接剂组合物的固体成分中的全部过渡金属原子,银原子的含量大于或等于90质量%,锌原子的含量大于或等于0.01质量%且小于或等于0.6质量%。

Description

粘接剂组合物及使用其的半导体装置
技术领域
本发明涉及粘接剂组合物及使用其的半导体装置。进一步详细而言,涉及适合将功率半导体、LSI、发光二极管(LED)等半导体元件粘接于引线框、陶瓷配线板、玻璃环氧配线板、聚酰亚胺配线板等基板上的粘接剂组合物及使用其的半导体装置。
背景技术
作为在制造半导体装置时使半导体元件与引线框(支撑构件)粘接的方法,有使银粉等填充剂分散于环氧系树脂、聚酰亚胺系树脂等树脂中而制成糊状(例如,银糊),将其用作粘接剂的方法。在该方法中,使用分配器(dispenser)、印刷机、压印机(stamping machine)等将糊状粘接剂涂布于引线框的芯片焊盘(die pad)上后,对半导体元件进行芯片接合(die bonding),通过加热固化进行粘接,从而制成半导体装置。
近年来随着半导体元件的高速化、高集成化进展,为了确保半导体装置的工作稳定性,要求高散热特性。
作为实现比以前的通过金属粒子彼此接触起作用的导电性粘接剂更高的散热性的方法,提出了高填充热导率高的银粒子的粘接剂组合物(专利文献1~3)、使用了焊料粒子的粘接剂组合物(专利文献4)、使用烧结性优异的平均粒径小于或等于0.1μm的金属纳米粒子的粘接剂组合物(专利文献5)。
另外,作为与这些组合物相比热导率和高温下的连接可靠性更优异的组合物,提出了通过使用实施了特殊表面处理的微小尺寸的银粒子,利用大于或等于100℃且小于或等于400℃的加热使银粒子彼此被烧结那样的粘接剂组合物(专利文献6)。关于专利文献6所提出的银粒子彼此被烧结那样的粘接剂组合物,可认为:由于银粒子形成金属键,因此与其它方法相比热导率和高温下的连接可靠性更优异。
现有技术文献
专利文献
专利文献1:日本特开2006-73811号公报
专利文献2:日本特开2006-302834号公报
专利文献3:日本特开平11-66953号公报
专利文献4:日本特开2005-93996号公报
专利文献5:日本特开2006-83377号公报
专利文献6:日本专利第4353380号公报
发明内容
发明要解决的问题
另外,在半导体元件的被粘面上,有时从防锈方面出发而通过镀敷、溅射等施加金。由此,半导体元件安装前的性能试验变得容易,而且能够抑制由于氧化被膜的形成而导致的粘接性的变动。
本发明人等发现,如果将专利文献6中所提出的粘接剂组合物适用于被粘面由金形成的半导体元件的安装,则粘接力差。
因此,本发明的目的在于提供一种即使为适用于被粘面由金形成的半导体元件的安装的情况,也具有充分高的粘接力的粘接剂组合物及使用其的半导体装置。
解决问题的方法
鉴于上述情况,本发明提供一种粘接剂组合物,其为包含含有银原子的银粒子和含有金属锌的锌粒子的粘接剂组合物,相对于该粘接剂组合物的固体成分中的全部过渡金属原子,银原子的含量大于或等于90质量%,锌原子的含量大于或等于0.01质量%且小于或等于0.6质量%。
上述粘接剂组合物优选进一步包含分散介质。
上述粘接剂组合物优选卡森(Casson)粘度大于或等于0.05Pa·s且小于或等于2.0Pa·s。
上述锌粒子的一次粒子的平均粒径优选大于或等于50nm且小于或等于150000nm。另外,上述锌粒子优选为片状(薄片状)。另外,所谓片状,是包含板状、盘状、鳞片状等形状的概念。
上述银粒子的一次粒子的平均粒径优选大于或等于0.1μm且小于或等于50μm。
上述分散介质优选包含从具有大于或等于300℃沸点的醇、羧酸和酯中选择的至少1种以上。另外,本发明中的沸点是指在1个气压下的沸点。
将上述粘接剂组合物热固化而成的固化物的体积电阻率和热导率优选分别为小于或等于1×10-4Ω·cm、大于或等于30W/m·K。
上述粘接剂组合物优选在100~300℃、5秒钟~10小时、更优选150~300℃、30分钟~5小时、进一步优选150~250℃、1~2小时、特别优选200℃、1小时的条件下进行固化。
本发明提供一种具有通过上述粘接剂组合物将半导体元件与半导体元件搭载用支撑构件粘接而成的结构的半导体装置。
发明的效果
根据本发明,能够提供一种即使为适用于被粘面由金形成的半导体元件的安装的情况,也具有充分高的粘接力的粘接剂组合物及使用其的半导体装置。
附图说明
图1是实施例2的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。
图2是比较例2的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。
图3是比较例2的粘接剂组合物固化物的截面形态观察结果的倍率5000倍的SEM照片。
图4是实施例2的芯片剪切强度试验后的基板侧断裂面的倍率1000倍的SEM照片。
图5是比较例1的芯片剪切强度试验后的基板侧断裂面的倍率1000倍的SEM照片。
图6是实施例7的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。
图7是比较例10的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。
图8是表示对于使用实施例8和比较例11的粘接剂组合物制作的芯片剪切强度用的样品,测定芯片剪切强度的结果的图表。
图9是表示本实施方式的半导体装置的一例的示意截面图。
图10是表示本实施方式的半导体装置的另一例的示意截面图。
具体实施方式
本说明书中的“工序”一词,不仅是独立的工序,即使在与其它工序不能明确区别的情况下,若能实现该工序的期望作用,则也包含在本用语中。
另外,本说明书中使用“~”所表示的数值范围表示包含“~”前后所记载的数值分别作为最小值和最大值的范围。
进一步,本说明书中谈及组合物中的各成分的量的情况下,在组合物中存在多种与各成分相当的物质的情况下,只要没有特别说明,就是指在组合物中存在的该多种物质的合计量。
<粘接剂组合物>
本实施方式的粘接剂组合物包含银粒子和锌粒子。本实施方式的粘接剂组合物可以进一步包含分散介质。
在本实施方式的粘接剂组合物中,银原子的含量相对于固体成分中的全部过渡金属原子大于或等于90质量%,更优选大于或等于95质量%。由此,能够表现充分高的粘接力。
在本实施方式的粘接剂组合物中,锌原子的含量相对于固体成分中的全部过渡金属原子大于或等于0.01质量%,优选大于或等于0.05质量%,更优选大于或等于0.08质量%,进一步优选大于或等于0.1质量%。另外,在本实施方式的粘接剂组合物中,锌原子的含量相对于固体成分中的全部过渡金属原子小于或等于0.6质量%,优选小于或等于0.5质量%。
如果将锌原子的含量设为上述范围,则能够抑制后述的粘接界面附近的空隙偏集,同时能够抑制由于过剩的锌粒子在烧结后继续残存所导致的粘接力降低,能够防止粘接力的降低。
粘接剂组合物中的银原子和锌原子的含量可以通过XRD、SEM-EDX、荧光X射线测定进行测定。以下表示通过SEM-EDX测定银原子和锌原子含量的方法的例子。
首先,在浅底盘上将粘接剂组合物铺展成厚度小于或等于1mm,使用减压干燥机在70℃、小于或等于100Pa、大于或等于40小时的条件下干燥而得到干燥粘接剂组合物。将干燥粘接剂组合物在SEM试样台上按照大于或等于2μm的厚度且平坦的方式成型,制成SEM用样品。按照后述的通过SEM-EDX的定量方法的例子对该SEM用样品进行定量分析,从而得到粘接剂组合物中的各过渡金属原子的比例。
另外,关于固化后的粘接剂组合物,银原子和锌原子不挥发,它们的含量实质上不发生变化,因此也可以对固化后的粘接剂组合物测定银原子和锌原子的含量,将其作为粘接剂组合物的银原子和锌原子的含量。具体而言,也可以在玻璃板上以0.1~0.5mm厚度均匀地涂布粘接剂组合物之后,在大气中、200~300℃进行1小时固化处理,将对固化后的粘接剂组合物通过后述的方法测定的银原子和锌原子的含量作为粘接剂组合物的含量。
就本实施方式的粘接剂组合物而言,固体成分中也可以含有除银原子和锌原子以外的过渡金属原子,其含量相对于固体成分中的全部过渡金属原子例如优选为小于10质量%,更优选为小于5质量%。
(银粒子)
银粒子为含有银原子的粒子,更优选为含有银原子作为主要成分(例如,固体成分中的银含量大于或等于90质量%,以下同样)的粒子。作为以银原子为主要成分的组成,可列举金属银、氧化银,优选金属银。
作为银粒子的形状,例如可列举球状、块状、针状、片状。银粒子的一次粒子的平均粒径优选大于或等于0.001μm且小于或等于500μm,更优选大于或等于0.01μm且小于或等于100μm,进一步优选大于或等于0.1μm且小于或等于50μm。
银粒子的一次粒子的平均粒径(体积平均粒径)可以通过激光散射法粒度分布测定装置进行测定。以下表示测定法的一例。
将银粒子0.01g和十二烷基苯磺酸钠(和光纯药工业制)0.1g以及蒸馏水(和光纯药工业制)99.9g混合,使用超声波清洗机处理5分钟而得到水分散液。使用安装了具有超声波分散单元的通用液体模块(Universal LiquidModule)的激光散射法粒度分布测定装置LS13320(贝克曼库尔特制),为了稳定光源,接通主体电源并放置30分钟。接着,通过测定程序中的冲洗(Rinse)指令向液体模块导入蒸馏水,进行测定程序中的去泡沫(De-bubble)、测量补偿(Measure Offset)、校正(Align)、测量空白(Measure Background)。接下来,进行测定程序中的测定加样(Measure Loading),将该水分散液振动混合变得均匀时,使用玻璃吸管(spuit)添加至液体模块中直到测定程序中的样品量从Low变为OK。之后,进行测定程序中的测量(Measure),得到粒度分布。作为激光散射法粒度分布测定装置的设定,使用泵速(Pump Speed):70%、包括PIDS的数据(Include PIDS data):ON、运行长度(Run Length):90秒、分散介质折射率:1.332、分散质折射率:0.23。
通过该测定,通常得到具有除一次粒子以外还包含凝聚体的峰的多个峰的粒度分布,以最低粒径的一个峰为处理范围,得到一次粒子的平均粒径。
另外,后述的锌粒子的一次粒子的平均粒径也可以通过同样的方法进行测定。
(锌粒子)
锌粒子为含有金属锌的粒子,优选为含有金属锌作为主要成分的粒子。例如可以使用金属锌粒子、粒子核为金属锌且表面具有氧化锌层的锌粒子、粒子核为金属锌且具有有机保护被膜的锌粒子、粒子核为金属锌且表面具有金属银层的锌粒子。
从得到与导体层、基板等无机材料的接触面积的观点考虑,锌粒子优选一次粒子的平均粒径小于或等于150000nm,更优选小于或等于50000nm,进一步优选小于或等于15000nm。
另一方面,锌容易被氧化,而氧化锌得不到上述的效果。因此,从防止氧化的观点考虑,锌粒子的一次粒子的平均粒径优选大于或等于50nm。
作为锌粒子的形状,例如可列举球状、块状、针状、片状。在这些形状中,从烧结时熔入银中的观点考虑,优选比表面积大的形状。另外,从降低上述氧化造成的影响的观点考虑,更优选片状的粒子。
(分散介质)
分散介质可以为有机、无机中的任一种,从防止涂布工序中的干燥的观点考虑,优选具有大于或等于200℃的沸点,更优选具有大于或等于300℃的沸点。另外,为了烧结后分散介质不残留,优选具有小于或等于400℃的沸点。
另外,作为分散介质,优选使用从具有大于或等于300℃沸点的醇、羧酸和酯中选择的至少1种以上,更优选并用从具有大于或等于300℃且小于或等于400℃沸点的醇、羧酸和酯中选择的至少1种以上与沸点大于或等于100℃且小于300℃的挥发性成分。
作为具有大于或等于300℃沸点的醇、羧酸或者酯,例如可列举:棕榈酸、硬脂酸、花生酸、对苯二甲酸、油酸等脂肪族羧酸,均苯四酸、邻苯氧基苯甲酸等芳香族羧酸,鲸蜡醇、异冰片基环己醇、四乙二醇等脂肪族醇,对苯基苯酚等芳香族醇、辛酸辛酯、肉豆蔻酸乙酯、亚油酸甲酯、柠檬酸三丁酯、苯甲酸苄酯等酯。在这些物质中,优选碳原子数为6~20的脂肪族醇或者羧酸。
作为沸点大于或等于100℃且小于300℃的挥发性成分,例如可列举:戊醇、己醇、庚醇、辛醇、癸醇、乙二醇、二乙二醇、丙二醇、丁二醇、α-萜品醇等一元和多元醇类,乙二醇丁基醚、乙二醇苯基醚、二乙二醇甲基醚、二乙二醇乙基醚、二乙二醇丁基醚、二乙二醇异丁基醚、二乙二醇己基醚、三乙二醇甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、二乙二醇丁基甲基醚、二乙二醇异丙基甲基醚、三乙二醇二甲基醚、三乙二醇丁基甲基醚、丙二醇丙基醚、二丙二醇甲基醚、二丙二醇乙基醚、二丙二醇丙基醚、二丙二醇丁基醚、二丙二醇二甲基醚、三丙二醇甲基醚、三丙二醇二甲基醚等醚类,乙二醇乙基醚乙酸酯、乙二醇丁基醚乙酸酯、二乙二醇乙基醚乙酸酯、二乙二醇丁基醚乙酸酯、二丙二醇甲基醚乙酸酯、乳酸乙酯、乳酸丁酯、γ-丁内酯等酯类,N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺等酸酰胺,环己酮、辛烷、壬烷、癸烷、十一烷等脂肪族烃,甲苯、二甲苯等芳香族烃,适当的硫醇(包含1至18的碳原子的例如乙基硫醇、正丙基硫醇、异丙基硫醇、正丁基硫醇、异丁基硫醇、叔丁基硫醇、戊基硫醇、己基硫醇和十二烷基硫醇之类的硫醇)、或者环烷基硫醇(包含5至7的碳原子的环戊基硫醇、环己基硫醇、环庚基硫醇之类的硫醇类)。其中,优选沸点大于或等于150℃的挥发性成分,更优选碳原子数为4~12的醇、酯、醚类。
上述分散介质可以单独使用1种或者混合使用2种以上。将粘接剂组合物总量设为100质量份时,分散介质的含量优选为0.1质量份~20质量份。
将粘接剂组合物总量设为100质量份时,上述的银粒子、锌粒子和分散介质的合计含量优选大于或等于90质量份,更优选大于或等于95质量份,进一步优选大于或等于98质量份。
在本实施方式的粘接剂组合物中也可以包含烧结助剂、润湿性提高剂和消泡剂中的一种以上。另外,本实施方式的粘接剂组合物还可以包含这里列举以外的成分。
在本实施方式的粘接剂组合物中,可以根据需要进一步适当添加氧化钙、氧化镁等吸湿剂,非离子系表面活性剂、氟系表面活性剂等润湿提高剂,有机硅油等消泡剂,无机离子交换体等离子捕捉剂,阻聚剂等。
关于上述的粘接剂组合物,可以适当组合搅拌器、混砂机、3辊研磨机、行星式混合器等分散、溶解装置,将上述成分统一或者分批地根据需要进行加热,并进行混合、溶解、解粒混炼或者分散,制成均匀的糊状来使用。
在粘接剂组合物进行成型的情况下,优选适合于各种印刷、涂布方法的粘度,优选25℃下的卡森粘度为0.05Pa·s~2.0Pa·s,更优选为0.06Pa·s~1.0Pa·s。
粘接剂组合物的卡森粘度的测定可以通过粘弹性测定装置(PhysicaMCR-501、Anton Paar制)进行。安装角度1°直径50mm的锥型测定夹具(CP50-1),将粘接剂组合物在测定位置从测定夹具溢出程度的粘接剂组合物导入测定装置,记录在将测定夹具下降到测定位置时溢出的粘接剂组合物后进行测定。测定是在25℃连续地进行以下的2个步骤,在第2步骤记录剪切速度和剪切应力。(1)剪切速度0s-1、600秒钟,(2)剪切速度0~100s-1、剪切速度增加率100/60s-1/step、测定间隔1秒钟、测定点数60点。
由所得的剪切速度和剪切应力,通过公知的文献(技术信息协会:流变学的测定和控制(レオロジーの測定とコントロール)一问一答集-レオロジーを測って、物性を丸裸にする-,东京,技术信息协会,2010,p39-46)所记载的方法,算出卡森粘度。具体而言,计算所得的各剪切速度和剪切应力的平方根,算出由(剪切应力)^(1/2)相对(剪切速度)^(1/2)通过最小二乘法近似的直线的斜率。将该斜率平方所得的值作为卡森粘度。
上述的粘接剂组合物例如可以通过在100~300℃加热5秒钟~10小时进行固化。如上所述银原子和锌原子的含量在加热前后实质上不变化。
固化后的粘接剂组合物中的全部过渡金属原子中占据的银原子和锌原子的含量可以通过固化后的粘接剂组合物的SEM-EDX、TEM-EDX、俄歇电子分光法进行定量。
显示通过SEM-EDX的定量方法的例子。
对于具有厚度大于或等于3μm的粘接剂组合物固化物层的样品,用环氧铸型树脂固定周围。使用研磨装置,削出与粘接剂组合物固化物层垂直的截面,平滑地加工该截面。在截面上,使用溅射装置或者蒸镀装置,由厚度10nm左右的贵金属形成防静电层,从而制作SEM用的样品。
将该SEM用样品置于SEM-EDX(例如,ESEM XL、Philips制)装置,以5,000~10,000倍程度的倍率进行观察。在粘接剂组合物固化物的中央附近,在试样倾斜角度:0°、加速电压25kV、Ev/Chan:10、Amp.Time:50μS、ChoosePreset:Live Time 300secs的条件下累积EDX点分析,在分析条件Matrix:ZAF、SEC(Standardless Element Coefficient):EDAX、定量法:None的条件下进行定量分析,从而得到固化后的粘接剂组合物中各过渡金属原子的比例。
固化后的粘接剂组合物的体积电阻率优选小于或等于1×10-4Ω·cm,热导率优选大于或等于30W/m·K。
<半导体装置的制造方法>
(半导体元件和半导体元件搭载用支撑构件)
作为本发明的半导体元件和半导体元件搭载用支撑构件,被粘物表面为金属。作为能够适用于本发明的被粘物表面的金属,可列举金、银、铜、镍等。另外,也可以在基材上将上述中的多个材料图案化。
通过本发明的粘接剂组合物制作的半导体装置的制造方法至少具有以下工序。
(A)将粘接剂组合物赋予在半导体元件或者半导体元件搭载用支撑构件上,使半导体元件与半导体元件搭载用支撑构件贴合的工序(以下,称为“工序(A)”。);
(B)将粘接剂组合物固化,将半导体元件与半导体元件搭载用支撑构件接合的工序(以下,称为“工序(B)”。)。
进一步在工序(A)中,在赋予粘接剂组合物后,可以具有干燥工序。
(工序(A))-粘接剂组合物的赋予工序-
〔粘接剂组合物的调制〕
粘接剂组合物可以通过将上述的银粒子、锌粒子和任意的成分混合在分散介质中来调制。混合后,可以进行搅拌处理。另外,可以通过过滤来调整分散液的最大粒径。
搅拌处理可以使用搅拌机进行。作为这样的搅拌机,例如可列举自转公转型搅拌装置、混砂机、双轴混炼机、三辊研磨机、行星式混合器、薄层剪切分散机。
过滤可以使用过滤装置进行。作为过滤用的过滤器,例如可列举金属筛网、金属过滤器、尼龙筛网。
〔粘接剂组合物的赋予〕
通过将粘接剂组合物赋予在基板或者半导体元件上,从而形成粘接剂组合物层。作为赋予方法,可列举涂布或者印刷。
作为粘接剂组合物的涂布方法,例如可以使用浸渍、喷涂、棒涂、模涂、逗号涂布、狭缝涂布(slit coating)、敷料器。
作为印刷粘接剂组合物的印刷方法,例如可以使用分配器、孔版印刷(Stencil Printing)、凹版印刷、丝网印刷、针式分配器(Needle Dispenser)、喷射分配器法。
通过粘接剂组合物的赋予形成的粘接剂组合物层,从抑制固化时的流动和空隙产生的观点考虑,可以适当干燥。
干燥方法可以使用通过常温放置进行的干燥、加热干燥或者减压干燥。加热干燥或者减压干燥,可以使用加热板、热风干燥机、热风加热炉、氮干燥机、红外线干燥机、红外线加热炉、远红外线加热炉、微波加热装置、激光加热装置、电磁加热装置、电热器加热装置、蒸气加热炉、热板加压装置等。
用于干燥的温度和时间优选根据所使用的分散介质的种类和量进行适当调整,例如优选在50~180℃干燥1~120分钟。
在粘接剂组合物层形成后,通过粘接剂组合物将半导体元件与半导体元件搭载用支撑构件贴合。在具有干燥工序的情况下,可以在贴合工序之前或者之后的任一阶段进行。
(工序(B))-固化处理-
接着,对粘接剂组合物层进行固化处理。固化处理可以通过加热处理进行,也可以通过加热加压处理进行。就加热处理而言,可以使用加热板、热风干燥机、热风加热炉、氮干燥机、红外线干燥机、红外线加热炉、远红外线加热炉、微波加热装置、激光加热装置、电磁加热装置、电热器加热装置、蒸气加热炉等。另外,就加热加压处理而言,可以使用热板加压装置等,也可以一边施加重压进行加压一边进行上述的加热处理。
通过以上的本发明的粘接剂组合物的制造方法,能够制造将半导体元件与半导体元件搭载用支撑构件通过粘接性、高热导性和高耐热性优异的粘接剂组合物固化物接合而成的半导体装置。
<半导体装置>
半导体装置可以用于包含二极管、整流器、晶闸管(Thyristor)、MOS栅极驱动器、功率开关、功率MOSFET、IGBT、肖特基二极管、快恢复二极管等的功率模块、发报机、放大器、LED模块等。所得的功率模块、发报机、放大器、LED模块在半导体元件和半导体元件搭载用支撑构件之间具有高粘接性、高热导性、高导电性且高耐热性。
图9是表示使用本实施方式的粘接剂组合物制造的半导体装置的一例的示意截面图。图9所示的半导体装置包括3个引线框(散热体)12a、12b、12c、在引线框12a上通过本实施方式的粘接剂组合物13连接的芯片(发热体)11、和对它们进行铸模的铸模树脂(mold resin)15。芯片11通过2根电线14与引线框12b、12c分别连接。
图10是表示使用本实施方式的粘接剂组合物制造的半导体装置的另一例的示意截面图。图10所示的半导体装置包括基板16、以包围基板16的方式形成的2个引线框17、在引线框17上通过本实施方式的粘接剂组合物13连接的LED芯片18、以及将它们密封的透光性树脂19。LED芯片18通过电线14与引线框17连接。
实施例
下面,通过实施例进一步具体说明本发明,但本发明不限于以下的实施例。
各实施例中各特性的测定如下操作实施。
(1)粒子的平均粒径
将锌粒子0.1g和十二烷基苯磺酸钠(和光纯药工业制)0.01g以及蒸馏水(和光纯药工业制)9.99g混合,使用超声波清洗机处理5分钟而得到水分散液。使用安装了具有超声波分散单元的通用液体模块的激光散射法粒度分布测定装置LS13320(贝克曼库尔特制),为了稳定光源,接通主体电源并放置30分钟后,通过测定程序中的Rinse指令向液体模块导入蒸馏水,进行测定程序中的De-bubble、Measure Offset、Align、Measure Background。接下来,进行测定程序中的Measure Loading,将该水分散液振动混合变得均匀时,使用玻璃吸管添加至液体模块中直到测定程序中的样品量从Low变为OK。之后,进行测定程序中的测定,得到粒度分布。作为激光散射法粒度分布测定装置的设定,使用Pump Speed:70%、Include PIDS data:ON、Run Length:90seconds、分散介质折射率:1.332、分散质折射率:0.23。
(2)芯片剪切强度
使用顶端尖的小镊子,按照使用精密天平为0.1mg的方式将粘接剂组合物涂布在镀银的PPF-Cu引线框(接地(land)部:10×5mm)上。在涂布的粘接剂组合物上,依次镀钛、镍和金,放置1×1mm2的被粘面为镀金的硅芯片(镀金的厚度0.1μm、芯片厚:400μm),使用小镊子轻轻按压。将其摆在不锈钢托盘中,在设定为200℃的洁净烘箱(PVHC-210、TABAIESPEC CORP.制)中处理1小时,从而使用粘接剂组合物将引线框与硅芯片粘接。
粘接剂组合物固化物的粘接强度通过芯片剪切强度进行评价。使用安装了50N的负载元件的万能型接合试验机(4000系列、DAGE公司制),以测定速度500μm/s、测定高度100μm在水平方向按压被粘面为镀金的硅芯片,测定粘接剂组合物固化物的芯片剪切强度。将12次测定的平均作为芯片剪切强度。
(3)热导率
使用洁净烘箱(PVHC-210、TABAIESPEC CORP.制)以200℃将粘接剂组合物加热处理1小时,得到10mm×10mm×1mm的粘接剂组合物固化物。用激光闪光法(NETZSCH公司制LFA 447、25℃)对该粘接剂组合物固化物的热扩散率进行测定。进一步由该热扩散率、用差示扫描热量测定装置(Pyris1、Perkin Elmer公司制)得到的比热容量和用阿基米德法得到的比重的积,算出25℃下的粘接剂组合物固化物的热导率(W/m·K)。
(4)体积电阻率
在玻璃板上隔着约1mm的间隔粘贴2根长度50mm的Mylar胶带(日东电工制),在Mylar胶带间的间隙使用刮刀涂布粘接剂组合物。
使用洁净烘箱(PVHC-210、TABAIESPEC CORP.制)以200℃将粘接剂组合物加热处理1小时,在玻璃板上得到1×50×0.03mm的粘接剂组合物固化物。使用恒定电流电源(Model 5964、METRONIX制)在该粘接剂组合物固化物的两端施加1mA的电流,将与万用表(R687E DIGTAL MULTIMETER、ADVANTEST制)连接的针形探头(needle probe)以10mm的间隔放在粘接剂组合物固化物上,测定电压。使用数字线性测量器(digital linear gauge)(DG-525H、小野测器制),以玻璃基板厚度与玻璃基板和粘接剂组合物固化物的合计厚度的差的形式,测定粘接剂组合物固化物的膜厚,将4点的平均作为粘接剂组合物固化物的厚度。粘接剂组合物固化物的宽度使用光学显微镜测长装置(Measure scope UM-2、日本光学制)测定,将4点的平均作为粘接剂组合物固化物的宽度。将上述粘接剂组合物固化物的电压、电流(1mA)、电压测定间隔(10mm)、膜厚和宽度代入四端子法的下述式(1)中,从而求出体积电阻率。对粘接剂组合物固化物的4个不同位置进行该测定,将平均值作为粘接剂组合物固化物的体积电阻率。
[数1]
体积电阻率=(电压/电流)×(宽度×厚度/电压测定间隔)…(1)
(5)截面形态观察
用样品夹(SamplklipI、Buehler制)将使用粘接剂组合物将芯片与基板粘接而成的样品固定在杯内,向周围注入环氧铸型树脂(Epomount,Refinetec制)直到样品整体被埋没,在真空干燥器内静置,减压1分钟进行脱泡。之后,使用60℃的恒温机将环氧铸型树脂固化2小时。
使用带有耐水研磨纸(カーボマックペーパー、Refinetec制)的研磨装置(Refine Polisher HV、Refinetec制)进行切削直到粘接部,露出截面。之后,使用安装有渗入了抛光剂的抛光布的研磨装置平滑地加工截面。使用溅射装置(ION SPUTTER、日立高新技术制)在截面上以10nm的厚度溅射Pt而制成SEM用的样品。对于该SEM用样品,通过SEM装置(ESEM XL30、Philips制),以施加电压10kV、1000倍观察粘接剂组合物固化物的截面。
[实施例1~4、比较例1~3]
(粘接剂组合物的调制)
将作为分散介质的异冰片基环己醇(Terusolve MTPH、日本Terpene制)、二丙二醇甲基醚乙酸酯(DPMA、大赛璐化学制)和作为粒子表面处理剂的硬脂酸(新日本理化)在聚乙烯瓶中混合,盖严,在50℃的水浴中加热,一边时常振动混合一边制成透明均匀的溶液。向该溶液中添加作为锌粒子的鳞片状锌粒子(产品号13789、Alfa Aesar,A Johnson Matthey Company制)、作为银粒子的鳞片状银粒子(AGC239、福田金属箔粉工业制)和球状银粒子(K-0082P、METALOR制),使用调漆刀(spatula)搅合直到干燥粉消失。进一步将其盖严,使用自转公转型搅拌装置(Planetary Vacuum Mixer ARV-310、THINKY制),以2000rpm搅拌1分钟,得到粘接剂组合物。这时,各成分的添加量如表1所示。
另外,鳞片状锌粒子的平均粒径为23μm,鳞片状银粒子的平均粒径为5.42μm,球状银粒子的平均粒径为1.64μm。
对于实施例2和比较例3的粘接剂组合物,通过“(2)芯片剪切强度”所记载的方法,使用粘接剂组合物将引线框与硅芯片粘接而得到样品。对于该样品,通过“(5)截面形态观察”所记载的方法进行截面形态观察。图1是实施例2的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片,图2、图3分别是比较例2的粘接剂组合物固化物的截面形态观察结果的倍率1000倍、5000倍的SEM照片。
图1~3中的符号分别表示:1:硅芯片、2:镀敷层、3:在镀金层与粘接剂组合物固化物的界面附近产生的空隙、4:粘接剂组合物固化物、5:镀银的PPF-Cu引线框的镀银层、6:镀银的PPF-Cu引线框的铜层、7:锌粒子。另外,这些符号对于图4~7也同样。
从图1清楚地看出:在使用了实施例2的粘接剂组合物的情况下,在粘接剂组合物固化物4中均匀地存在烧结引起的空隙,未看到空隙的偏集等。另一方面,从图2和3清楚地看出:在使用了比较例3的粘接剂组合物的情况下,大量的空隙在与镀金层的连接界面附近偏集,认为这是粘接力降低的原因。
对于实施例2和比较例1的粘接剂组合物,以1000倍的倍率对芯片剪切强度试验后的基板侧断裂面进行SEM观察。图4是实施例2的芯片剪切强度试验后的基板侧断裂面的倍率1000倍的SEM照片,图5是比较例1的芯片剪切强度试验后的基板侧断裂面的倍率1000倍的SEM照片。
从图4清楚地看出:在使用了实施例2的粘接剂组合物的情况下,仅观察到烧结成网眼状的金属,未观察到添加的鳞片状的锌粒子。推测这是因为锌粒子已熔入粘接剂组合物固化物4中。
另一方面,从图5清楚地看出:在使用了比较例的粘接剂组合物的情况下,在烧结的金属中观察到鳞片状的锌粒子7。
该鳞片状的锌粒子7为添加的锌粒子的一部分未熔入粘接剂组合物固化物4中而残留的粒子,看似与周围的金属未结合。推测:由于混入这样的粒子,因此粘接力降低。
[表1]
[实施例5、6]
(粘接剂组合物的调制)
将异冰片基环己醇1.112g和二丙二醇甲基醚乙酸酯1.112g以及硬脂酸0.132g在聚乙烯瓶中混合,盖严,在50℃的水浴中加热,一边时常振动混合一边制成透明均匀的溶液。向该溶液添加锌粒子0.0176g(相对于固体成分中的全部过渡金属元素为0.1质量%)、鳞片状银粒子8.791g和球状银粒子8.791g,使用调漆刀搅合直到干燥粉消失,将其盖严,使用自转公转型搅拌装置,以2000rpm搅拌1分钟,从而得到粘接剂组合物。另外,使用表2所记载的粒子作为锌粒子,关于除此以外的原料,使用与实施例1等相同的物质。
[比较例4~9]
除了使用表3所记载的添加粒子代替锌粒子以外,与实施例5、6同样地操作,得到粘接剂组合物。
[表2]
[表3]
[实施例7]
(粘接剂组合物的调制)
与实施例2同样地操作,调制粘接剂组合物。
(芯片与基板的热压接)
在对氧化铝基板的铜电极表面实施了镀银的带铜板的氧化铝基板上,使用具有10mm×10mm的正方形开口的不锈钢板将粘接剂组合物进行孔版印刷。在印刷的粘接剂组合物上依次镀钛、镍和金,放置1×1mm2的被粘面为镀金的硅芯片(镀金的厚度0.1μm、芯片厚:400μm),在设定为90℃的洁净烘箱中处理30分钟后,使用热压接试验装置(Tester产业制)在300℃、10MPa下热压接10分钟,从而用粘接剂组合物将基板与芯片粘接。
对于所得的样品,通过“(5)截面形态观察”所记载的方法进行截面形态观察。图6是实施例7的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。从图6清楚地看出:关于实施例7的粘接剂组合物固化物,在粘接剂组合物固化物4中均匀地存在烧结导致的空隙,未看到空隙的偏集等。
[比较例10]
(粘接剂组合物的调制)
将异冰片基环己醇1.370g和二丙二醇甲基醚乙酸酯1.370g以及硬脂酸0.270g在聚乙烯瓶中混合,盖严,在50℃的水浴中加热,一边时常振动混合一边制成透明均匀的溶液。向该溶液中添加鳞片状银粒子27g,使用调漆刀搅合直到干燥粉消失,将其盖严,使用自转公转型搅拌装置,以2000rpm搅拌1分钟而得到粘接剂组合物。
(芯片与基板的热压接)
对于所得的粘接剂组合物,与实施例7同样地操作,进行芯片与基板的热压接,对于所得的样品,通过“(5)截面形态观察”所记载的方法进行截面形态观察。图7是比较例10的粘接剂组合物固化物的截面形态观察结果的倍率1000倍的SEM照片。从图7清楚地看出:关于比较例10的粘接剂组合物固化物,在与镀金层的连接界面附近,偏集了与其它部分相比更多的空隙3。
[实施例8]
与实施例1同样地操作,调制粘接剂组合物,以每1组12个样品制作3组芯片剪切强度用样品。在加热至200℃的加热板上,将这3组芯片剪切强度用样品分别保持2、5、10小时进行热处理。测定恢复至室温的经热处理的芯片剪切强度用样品的芯片剪切强度。将结果示于图8中。
[比较例11]
除了使用与比较例1同样地操作而调制的粘接剂组合物以外,通过与实施例8同样的方法,制作芯片剪切强度用的样品,测定芯片剪切强度。将结果示于图8中。
从图8清楚地看出:实施例8与比较例11相比,以200℃保持的情况下的芯片剪切强度的降低率小,能够保持高温下的粘接性。
符号说明
1:硅芯片、2:镀敷层、3:在镀金层与粘接剂组合物固化物的界面附近产生的空隙、4:粘接剂组合物固化物、5:镀银的PPF-Cu引线框的镀银层、6:镀银的PPF-Cu引线框的铜层、7:锌粒子。

Claims (9)

1.一种粘接剂组合物,其为包含含有银原子的银粒子和含有金属锌的锌粒子的粘接剂组合物,
相对于该粘接剂组合物的固体成分中的全部过渡金属原子,银原子的含量大于或等于90质量%,锌原子的含量大于或等于0.01质量%且小于或等于0.6质量%。
2.根据权利要求1所述的粘接剂组合物,进一步包含分散介质。
3.根据权利要求1或者2所述的粘接剂组合物,卡森粘度大于或等于0.05Pa·s且小于或等于2.0Pa·s。
4.根据权利要求1~3中任一项所述的粘接剂组合物,所述锌粒子的一次粒子的平均粒径大于或等于50nm且小于或等于150000nm。
5.根据权利要求1~4中任一项所述的粘接剂组合物,所述锌粒子为片状。
6.根据权利要求1~5中任一项所述的粘接剂组合物,所述银粒子的一次粒子的平均粒径大于或等于0.1μm且小于或等于50μm。
7.根据权利要求2~6中任一项所述的粘接剂组合物,所述分散介质包含从具有大于或等于300℃沸点的醇、羧酸和酯中选择的至少1种以上。
8.根据权利要求1~7中任一项所述的粘接剂组合物,将所述粘接剂组合物热固化而成的固化物的体积电阻率和热导率分别为小于或等于1×10-4Ω·cm、大于或等于30W/m·K。
9.一种半导体装置,具有通过权利要求1~8中任一项所述的粘接剂组合物将半导体元件与半导体元件搭载用支撑构件粘接而成的结构。
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