CN104170070A - 半导体装置的制造方法及倒装片安装用粘接剂 - Google Patents

半导体装置的制造方法及倒装片安装用粘接剂 Download PDF

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CN104170070A
CN104170070A CN201380013477.7A CN201380013477A CN104170070A CN 104170070 A CN104170070 A CN 104170070A CN 201380013477 A CN201380013477 A CN 201380013477A CN 104170070 A CN104170070 A CN 104170070A
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bonding agent
semiconductor device
mentioned
seconds
manufacture method
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CN104170070B (zh
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胁冈纱香
中川弘章
西村善雄
定永周治郎
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
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Abstract

本发明的目的在于，提供能够通过抑制孔隙来实现高可靠性的半导体装置的制造方法。此外，本发明的目的还在于，提供在该半导体装置的制造方法中使用的倒装片安装用粘接剂。本发明的半导体装置的制造方法具有如下工序：工序1，使形成有突起电极的半导体芯片隔着粘接剂与基板对位，其中，所述突起电极具有由焊料形成的前端部；工序2，将上述半导体芯片加热到焊料熔点以上的温度，使上述半导体芯片的突起电极与上述基板的电极部熔融接合，同时使上述粘接剂临时粘接；以及工序3，在加压气氛下对上述粘接剂进行加热而除去孔隙，上述粘接剂利用差示扫描量热测定及小泽法所求出的活化能ΔE为100kJ/mol以下、于260℃经过2秒后的反应率为20％以下，于260℃经过4秒后的反应率为40％以下。

Description

半导体装置的制造方法及倒装片安装用粘接剂
技术领域
本发明涉及能够通过抑制孔隙来实现高可靠性的半导体装置的制造方法。此外，本发明还涉及在该半导体装置的制造方法中使用的倒装片安装用粘接剂。
背景技术
随着半导体装置的小型化及高密度化，作为将半导体芯片安装于基板的方法，使用了在表面形成有多个突起电极的半导体芯片的倒装片安装受到了关注，并迅速被加以推广。
在倒装片安装中，作为用于确保接合部分的连接可靠性的方法，采用的通常方法是：在将半导体芯片的突起电极与基板的电极部接合后，在半导体芯片与基板的间隙注入液状密封粘接剂(底填材料)，并使其固化。但是，在使用了底填材料的倒装片安装中存在如下问题：制造成本高、底填材料的填充耗时、在缩减电极间的距离以及半导体芯片与基板间的距离上存在限度等。
为此，近年来，提出了在基板上涂布糊状粘接剂后搭载半导体芯片的方法、在向半导体晶片或半导体芯片上供给膜状或糊状粘接剂后将带有粘接剂的半导体芯片搭载于基板上的方法等所谓的先涂布型的倒装片安装。尤其在将带有粘接剂的半导体芯片搭载于基板上的情况下，由于在半导体晶片上一次性地供给粘接剂、并且能够通过切割一并生产大量的带有粘接剂的半导体芯片，因此可以期待大幅地缩短工艺。
但是，在先涂布型的倒装片安装中，在使半导体芯片的突起电极与基板的电极部接触时会在半导体芯片或基板与粘接剂之间卷入空气而产生孔隙，或者在将半导体芯片搭载于基板上时的热压接工序中会因来自粘接剂的挥发成分而产生孔隙。这样的孔隙会导致电极间的短路或成为粘接剂中产生裂纹的主要原因。此外，在先涂布型的倒装片安装中，由于在热压接工序中同时进行突起电极的接合与粘接剂的热固化，因此难以同时进行精度高的突起电极的接合与孔隙的抑制。
为了抑制孔隙，提出了如下方法：在加压气氛下进行粘接剂的热固化，由此使孔隙收缩的方法；将半导体芯片和基板临时接合后，在加压气氛下对临时接合体进行加热，由此减小孔隙的方法等(例如专利文献1～3)。但是，即使采用这些方法，尤其在将带有粘接剂的半导体芯片搭载于基板上的情况下，也会因基板的凹凸而容易卷入空气，因此并不能充分地抑制孔隙。
现有技术文献
专利文献
专利文献1：日本特开2004-311709号公报
专利文献2：日本特开2009-004462号公报
专利文献3：日本专利第4640380号公报
发明内容
发明所要解决的课题
本发明的目的在于，提供能够通过抑制孔隙来实现高可靠性的半导体装置的制造方法。此外，本发明的目的还在于，提供在该半导体装置的制造方法中使用的倒装片安装用粘接剂。
用于解决课题的技术手段
本发明为一种半导体装置的制造方法，其具有如下工序：工序1，使形成有突起电极的半导体芯片隔着粘接剂与基板对位，其中，所述突起电极具有由焊料形成的前端部；工序2，将上述半导体芯片加热到焊料熔点以上的温度，使上述半导体芯片的突起电极与上述基板的电极部熔融接合，同时使上述粘接剂临时粘接；以及工序3，在加压气氛下对上述粘接剂进行加热而除去孔隙，上述粘接剂利用差示扫描量热测定及小泽法所求出的活化能ΔE为100kJ/mol以下，于260℃经过2秒后的反应率为20％以下，于260℃经过4秒后的反应率为40％以下。
以下，对本发明进行详细叙述。
本发明人为了兼顾精度高的突起电极的接合与孔隙的抑制，研究了如下方法：将半导体芯片加热到焊料熔点以上的温度，使半导体芯片的突起电极与基板的电极部可靠地接合，之后，在加压气氛下对粘接剂进行加热，从而除去孔隙。但是，在这样的方法中，即使在加压气氛下进行加热，当在将突起电极接合时粘接剂的固化过度地进行的情况下，也无法充分除去孔隙。
此外，还考虑通过调整将突起电极接合时的条件而来抑制粘接剂的固化，但是为了将突起电极接合而需要将温度保持在焊料熔点以上的温度(240～280℃左右)，因此在仅通过调整条件来抑制粘接剂的固化上存在限度。
因而，作为粘接剂，需要使用即使经过使突起电极接合时的热历程也能极力抑制固化的粘接剂、即、固化速度(反应速度)较慢的粘接剂。但是，以往粘接剂的反应速度的评价方法缺乏客观性或定量性。
另一方面，在热分析、反应速度解析等领域中，已知被称作“小泽法”的解析方法，“小泽法”利用由试样的差示扫描量热测定(DSC测定、Differential scanning calorimetry)所得到的数据来求出活化能ΔE、及在一定温度下到达规定反应率的时间。
本发明人研究了对于用于半导体装置的制造方法的粘接剂应用小泽法的情况。其结果，本发明人发现：利用差示扫描量热测定及小泽法可以对将粘接剂在一定温度下保持一定时间时的反应率进行更客观地且定量性地评价，并且，通过使用由这样的方法求出的活化能ΔE、于260℃经过2秒后的反应率及于260℃经过4秒后的反应率满足规定范围的粘接剂，从而可以兼顾精度高的突起电极的接合和孔隙的抑制，由此完成了本发明。
在本发明的半导体装置的制造方法中，首先，进行使形成有突起电极的半导体芯片隔着粘接剂与基板对位的工序1，其中，所述突起电极具有由焊料形成的前端部。
在上述进行对位的工序1中，通常使用倒装片接合器等安装用装置，并使摄像机识别半导体芯片的突起电极、基板的电极部以及设置于半导体芯片及基板上的对准标记的位置，由此沿着X、Y方向及旋转方向(θ方向)进行自动地对位。
作为上述半导体芯片，例如可列举包含硅、镓、砷等半导体且在表面形成有突起电极的半导体芯片，其中，所述突起电极具有由焊料形成的前端部。另外，对于具有由焊料形成的前端部的突起电极而言，只要使前端部由焊料形成，则可以使突起电极的一部分由焊料形成，也可以使突起电极整体由焊料形成。
供给上述粘接剂的方法并无特别限定，例如可列举：将膜状的粘接剂贴附于基板上或半导体芯片上的方法；将糊状的粘接剂填充于注射器，并在注射器前端安装精密喷嘴，使用分配器装置将该粘接剂喷出至基板上的方法等。
此外，也可采用如下方法：预先利用常压层压、真空层压等将膜状的粘接剂贴附于晶片上，或者利用旋涂法等将糊状的粘接剂涂布或印刷于晶片上而形成涂膜，之后，利用刮刀切割、激光切割等将其单片化成半导体芯片。在常压层压中有时会卷入空气，但可以使用与除去孔隙的工序3同样的加压烘箱(例如PCO-083TA(NTT Advanced Technology公司制))等在加压气氛下对粘接剂进行加热，从而除去孔隙。
上述粘接剂利用差示扫描量热测定及小泽法所求出的活化能ΔE为100kJ/mol以下、于260℃经过2秒后的反应率为20％以下、于260℃经过4秒后的反应率为40％以下。
就利用差示扫描量热测定及小泽法所求出的活化能ΔE、于260℃经过2秒后的反应率及于260℃经过4秒后的反应率满足上述范围的粘接剂而言，其固化速度(反应速度)较慢，反应速度的温度依赖性小，因此对于该粘接剂而言，在使粘接剂临时粘接的工序2中，即使经过使突起电极接合时的热历程，也能极力抑制固化，并且固化不均少。在使用这样的粘接剂而使粘接剂临时粘接的工序2中，使突起电极可靠地接合，之后，进行除去孔隙的工序3，由此可以兼顾精度高的突起电极的接合和孔隙的抑制。
另外，差示扫描量热测定可以使用DSC装置(例如DSC6220(SII NanoTechnology公司制))来进行。此外，小泽法可以使用反应速度解析软件(例如SII Nano Technology公司制)来进行，该小泽法是指下述所示的解析方法。
首先，对试样进行3次以上升温速度不同的差示扫描量热测定，将温度T的倒数和升温速度B的对数(logB)作图。基于下述式(1)，由所得直线的斜率计算出活化能ΔE。接着，基于下述式(2)的定温劣化式，由活化能ΔE计算出于260℃保持2秒或于260℃保持4秒时的反应率。(参照小泽丈夫，热测定1、2(1974)及T.O zawa，Bull.Chem.Soc.Japan38，1881(1965)。)
logB-0.4567ΔE/RT＝const.   (1)
&tau; = &Integral;exp ( - &Delta;E / RT ) dT B exp ( - &Delta;E / RT ) - - - ( 2 )
式(2)中，τ表示定温劣化时间。
在上述活化能ΔE超过100kJ/mol时，粘接剂的反应速度的温度依赖性变大，在使粘接剂临时粘接的工序2中容易受到温度不均、面内的温度分布等的影响。其结果，难以控制孔隙或难以控制粘接剂咬入上下电极间。上述活化能ΔE优选为90kJ/mol以下、更优选为80kJ/mol以下。
上述活化能ΔE的下限并无特别限定，优选的下限为50kJ/mol。在上述活化能ΔE低于50kJ/mol时，即使在较低的温度下也容易进行粘接剂的固化，会使粘接剂的储存稳定性降低。
在上述于260℃经过2秒后的反应率超过20％或上述于260℃经过4秒后的反应率超过40％时，在使粘接剂临时粘接的工序2中，导致粘接剂进行固化，即使进行除去孔隙的工序3，也无法充分除去孔隙，或者在使粘接剂临时粘接的工序2中，导致在突起电极进行熔融接合之前粘接剂就已经进行固化，在上下电极间产生粘接剂的咬入而造成接合不良。上述于260℃经过2秒后的反应率优选为15％以下、更优选为12％以下。上述于260℃经过4秒后的反应率优选为30％以下、更优选为25％以下。
上述于260℃经过2秒后的反应率的下限并无特别限定，优选的下限为3％。上述于260℃经过4秒后的反应率的下限并无特别限定，优选的下限为10％。在上述于260℃经过2秒后的反应率低于3％或上述于260℃经过4秒后的反应率低于10％时，会使粘接剂的固化耗时而无法以短时间来制造半导体装置。
上述粘接剂可以是膜状，也可以是糊状，特别优选为膜状粘接剂。
在上述粘接剂为糊状的情况下，需要对每个半导体芯片供给上述粘接剂。与此相对，在上述粘接剂为膜状的情况下，由于在基板或晶片上一次性地供给上述粘接剂，并且可以利用切割一并生产大量的带有粘接剂的半导体芯片，因此可以期待大幅地缩短工艺。
此外，通常膜状的粘接剂的熔融粘度高，因此使用膜状的粘接剂难以兼顾精度高的突起电极的接合和孔隙的抑制，但在本发明的半导体装置的制造方法中，通过使用由差示扫描量热测定及小泽法所求出的活化能ΔE、于260℃经过2秒后的反应率及于260℃经过4秒后的反应率满足上述范围的粘接剂，从而即使在上述粘接剂为膜状时，也能兼顾精度高的突起电极的接合和孔隙的抑制。
上述粘接剂优选至少含有热固化性树脂和热固化剂，更优选含有固化促进剂。
活化能ΔE是反应体系所固有的特性，因此例如可以通过选择所组合的热固化性树脂、热固化剂、固化促进剂等的种类而将粘接剂的活化能ΔE调整至上述范围。
另一方面，反应速度还依赖于反应体系的浓度，因此例如可以通过调整各成分的含量、尤其是固化促进剂的添加量而将粘接剂的反应率调整至上述范围。具体而言，存在如下倾向：固化促进剂的添加量越多，则反应速度越上升，固化促进剂的添加量越少，则反应速度越下降。但是，适当的固化促进剂的添加量根据各个反应体系而异，因此为了将粘接剂的反应率调整至上述范围，需要适当调整各成分的含量。
上述热固化性树脂并无特别限定，例如可列举通过加成聚合、缩聚、聚加成、加成缩合、开环聚合等反应而进行固化的化合物。作为上述热固化性树脂，具体而言，可列举例如尿素树脂、三聚氰胺树脂、酚醛树脂、间苯二酚树脂、环氧树脂、丙烯酸类树脂、聚酯树脂、聚酰胺树脂、聚苯并咪唑树脂、邻苯二甲酸二烯丙酯树脂、二甲苯树脂、烷基苯树脂、环氧丙烯酸酯树脂、硅树脂、聚氨酯树脂等。其中，从易于将粘接剂的活化能ΔE及反应率调整至上述范围的方面以及固化物的物性等方面出发，优选环氧树脂。
上述环氧树脂优选官能团浓度低、即、环氧当量高的环氧树脂。环氧当量高的环氧树脂与热固化剂的反应概率低、反应性低，因此通过使用这样的环氧树脂，从而容易将粘接剂的反应率调整至上述范围。上述环氧树脂的环氧当量更优选为200以上、进一步优选为250以上。
上述环氧树脂并无特别限定，可列举例如：双酚A型、双酚F型、双酚AD型、双酚S型等双酚型环氧树脂；苯酚酚醛清漆型、甲酚酚醛清漆型等酚醛清漆型环氧树脂；间苯二酚型环氧树脂、三苯酚甲烷三缩水甘油醚等芳香族环氧树脂；萘型环氧树脂；芴型环氧树脂；环戊二烯型或二环戊二烯型环氧树脂；聚醚改性环氧树脂；NBR改性环氧树脂；CTBN改性环氧树脂；以及这些环氧树脂的氢化物等。其中，优选具有体积大的结构的环戊二烯型或二环戊二烯型环氧树脂。环戊二烯型或二环戊二烯型环氧树脂的空间位阻大且反应性低，因此通过使用这样的环氧树脂，从而易于将粘接剂的反应率调整至上述范围。这些环氧树脂可以单独使用，也可以并用2种以上。
上述环氧树脂可以是在常温呈液状的环氧树脂，也可以是在常温呈固体的环氧树脂，还可以将这些环氧树脂适当组合使用。
上述在常温呈液状的环氧树脂中，作为市售品，可列举例如：EPICLON 840、EPICLON 840-S、EPICLON 850、EPICLON 850-S、EXA-850CRP(以上为DIC公司制)等双酚A型环氧树脂；EPICLON 830、EPICLON 830-S、EXA-830CRP(以上为DIC公司制)等双酚F型环氧树脂；EPICLON HP-4032、HP-4032D(以上为DIC公司制)等萘型环氧树脂；EPICLON EXA-7015(DIC公司制)、EX-252(NagaseChemteX公司制)等氢化双酚A型环氧树脂；EX-201(Nagase ChemteX公司制)等间苯二酚型环氧树脂等。
上述在常温呈固体的环氧树脂中，作为市售品，可列举例如：EPICLON 860、EPICLON 10550、EPICLON 1055(以上为DIC公司制)等双酚A型环氧树脂；EPICLON EXA-1514(DIC公司制)等双酚S型环氧树脂；EPICLON HP-4700、HP-4710、HP-4770(以上为DIC公司制)等萘型环氧树脂；EPICLON HP-7200系列(DIC公司制)等二环戊二烯型环氧树脂；EPICLON HP-5000、EXA-9900(以上为DIC公司制)等甲酚酚醛清漆型环氧树脂等。
上述热固化剂并无特别限定，可以根据上述热固化性树脂而适当选择以往公知的热固化剂。在使用环氧树脂作为上述热固化性树脂的情况下，作为上述热固化剂，可列举例如酸酐系固化剂、酚系固化剂、胺系固化剂、双氰胺等潜伏性固化剂、阳离子系催化剂型固化剂等。这些热固化剂可以单独使用，也可以并用2种以上。其中，从使固化物的物性等优异的方面出发，优选酸酐系固化剂。
上述酸酐系固化剂中，作为市售品，可列举例如YH-306、YH-307(以上为三菱化学公司制、在常温(25℃)呈液状)、YH-309(三菱化学公司制、酸酐系固化剂、在常温(25℃)呈固体)等。
上述热固化剂的含量并无特别限定，在使用环氧树脂作为上述热固化性树脂、且使用与环氧基等量反应的热固化剂的情况下，上述热固化剂的含量相对于粘接剂中所含的环氧基的总量的优选下限为60当量，优选上限为110当量。在含量低于60当量时，有时不能使粘接剂充分固化。即使含量超过110当量，也不会特别有助于粘接剂的固化性，有时还会因过剩的热固化剂挥发而成为产生孔隙的原因。含量的更优选下限为70当量，更优选上限为100当量。
上述固化促进剂并无特别限定，可列举例如咪唑系固化促进剂、叔胺系固化促进剂等。其中，从容易将粘接剂的反应率调整至上述范围的方面、以及容易进行用于调整固化物的物性等的反应体系的控制的方面出发，优选咪唑系固化促进剂。
上述咪唑系固化促进剂并无特别限定，可列举例如Fujicure 7000(T&K TOKA公司制、在常温(25℃)呈液状)、咪唑的1位受到氰基乙基保护的1-氰基乙基-2-苯基咪唑、由异氰脲酸保护了碱性的咪唑系固化促进剂(商品名“2MA-OK”、四国化成工业公司制、在常温(25℃)呈固体)、2MZ、2MZ-P、2PZ、2PZ-PW、2P4MZ、C11Z-CNS、2PZ-CNS、2PZCNS-PW、2MZ-A、2MZA-PW、C11Z-A、2E4MZ-A、2MAOK-PW、2PZ-OK、2MZ-OK、2PHZ、2PHZ-PW、2P4MHZ、2P4MHZ-PW、2E4MZ·BIS、VT、VT-OK、MAVT、MAVT-OK(以上为四国化成工业公司制)等。这些咪唑系固化促进剂可以单独使用，也可以并用2种以上。
上述固化促进剂的含量并无特别限定，相对于热固化剂100重量份的优选下限为0.5重量份、优选上限为50重量份。在含量低于0.5重量份时，有时为了使粘接剂热固化而需要在高温下进行长时间的加热。在含量超过50重量份时，有时使粘接剂的储存稳定性变得不充分，或者因过量的固化促进剂挥发而成为产生孔隙的原因。含量的更优选下限为1重量份、更优选上限为30重量份。
在上述粘接剂为膜状的粘接剂的情况下，优选进一步含有高分子量化合物。通过使用上述高分子量化合物，可以对粘接剂赋予制膜性、挠性等，并且可以使粘接剂的固化物具有强韧性，确保较高的接合可靠性。
上述高分子量化合物并无特别限定，可列举例如尿素树脂、三聚氰胺树脂、酚醛树脂、间苯二酚树脂、环氧树脂、丙烯酸类树脂、聚酯树脂、聚酰胺树脂、聚苯并咪唑树脂、邻苯二甲酸二烯丙酯树脂、二甲苯树脂、烷基苯树脂、环氧丙烯酸酯树脂、硅树脂、聚氨酯树脂等公知的高分子量化合物。其中，优选具有环氧基的高分子量化合物。
通过添加上述具有环氧基的高分子量化合物，从而使粘接剂的固化物体现出优异的挠性。即，上述粘接剂的固化物兼具源自作为上述热固化性树脂的环氧树脂的优异机械强度、耐热性及耐湿性以及源自上述具有环氧基的高分子量化合物的优异挠性，因此使得耐冷热循环性、耐焊料回流性、尺寸稳定性等优异，并且体现出较高的接合可靠性及较高的导通可靠性。
上述具有环氧基的高分子量化合物只要是在末端和/或侧链(侧位)具有环氧基的高分子量化合物，则并无特别限定，可列举例如含环氧基的丙烯酸类橡胶、含环氧基的丁二烯橡胶、双酚型高分子量环氧树脂、含环氧基的苯氧基树脂、含环氧基的丙烯酸类树脂、含环氧基的聚氨酯树脂、含环氧基的聚酯树脂等。其中，从可以得到含有大量环氧基的高分子化合物、使固化物的机械强度及耐热性更优异的方面出发，优选含环氧基的丙烯酸类树脂。这些具有环氧基的高分子量化合物可以单独使用，也可以并用2种以上。
在使用上述具有环氧基的高分子量化合物、尤其是含环氧基的丙烯酸类树脂作为上述高分子量化合物的情况下，上述具有环氧基的高分子量化合物的重均分子量的优选下限为1万、优选上限为100万。在重均分子量低于1万时，有时会使粘接剂的制膜性变得不充分、或者无法充分提高粘接剂的固化物的挠性。在重均分子量超过100万时，在进行对位的工序1中会难以以一定的厚度供给粘接剂，或者在除去孔隙的工序3中会因粘接剂的熔融粘度变得过高而使流动性降低，无法充分除去孔隙。
在使用上述具有环氧基的高分子量化合物、尤其是含环氧基的丙烯酸类树脂作为上述高分子量化合物的情况下，上述具有环氧基的高分子量化合物优选官能团浓度低、即、环氧当量高的高分子量化合物。环氧当量高的高分子量化合物的反应性低，因此通过使用这样的高分子量化合物，从而容易将粘接剂的反应率调整至上述范围。上述具有环氧基的高分子量化合物的环氧当量更优选为200以上、进一步优选为250以上。
上述粘接剂中的上述高分子量化合物的含量并无特别限定，优选下限为3重量％、优选上限为30重量％。在含量低于3重量％时，有时无法得到对于热应变的充分的可靠性。在含量超过30重量％时，有时使粘接剂的耐热性降低。
上述粘接剂优选进一步含有无机填料。上述无机填料的含量优选为60重量％以下。在含量超过60重量％时，有时在除去孔隙的工序3中会使粘接剂的流动性降低，无法充分除去孔隙。
上述粘接剂中的上述无机填料的含量的下限并无特别限定，从确保粘接剂的固化物的强度及接合可靠性的观点出发，优选下限为10重量％。
上述无机填料并无特别限定，可列举例如二氧化硅、氧化铝、氮化铝、氮化硼、氮化硅、碳化硅、氧化镁、氧化锌等。其中，从使流动性优异的方面出发，优选球状二氧化硅，更优选用甲基硅烷偶联剂、苯基硅烷偶联剂等进行过表面处理的球状二氧化硅。通过使用经过表面处理的球状二氧化硅，可以抑制粘接剂的增稠，并且可以在除去孔隙的工序3中极有效地除去孔隙。
上述无机填料的平均粒径并无特别限定，从粘接剂的透明性、流动性、接合可靠性等观点出发，优选0.01～1μm左右。
上述粘接剂可以根据需要进一步含有稀释剂、触变性赋予剂、溶剂、无机离子交换体、防渗剂、咪唑硅烷偶联剂等粘接性赋予剂、密合性赋予剂、橡胶粒子等应力松弛剂等其他添加剂。
制造上述粘接剂的方法并无特别限定，可列举例如在热固化性树脂及热固化剂中根据需要配合规定量的固化促进剂、高分子量化合物、无机填料及其他添加剂并进行混合的方法。上述混合的方法并无特别限定，可列举例如使用均质机(homodisper)、万能混合机、班伯里密炼机(Banburymixer)、捏合机、珠磨机、匀浆机(homogenizer)等的方法。
上述粘接剂在从常温至焊料熔点的温度区域中的最低熔融粘度的优选下限为10Pa·s、优选上限为104Pa·s。在最低熔融粘度低于10Pa·s时，有时使焊角(fillet)的露出过多而导致污染其他器件。在最低熔融粘度超过104Pa·s时，有时无法充分除去孔隙。
另外，在从常温至焊料熔点的温度区域中的最低熔融粘度可以使用流变仪进行测定。
在本发明的半导体装置的制造方法中，接下来，进行工序2，即，将上述半导体芯片加热至焊料熔点以上的温度，使上述半导体芯片的突起电极与上述基板的电极部熔融接合，同时使上述粘接剂临时粘接。
使上述粘接剂临时粘接的工序2通常还使用倒装片接合器等安装用装置来进行。
焊料熔点通常为215～235℃左右。上述焊料熔点以上的温度的优选下限为240℃、优选上限为300℃。在温度低于240℃时，有时突起电极未充分熔融而无法形成电极接合。在温度超过300℃时，有时由粘接剂产生挥发成分而使孔隙增加。此外，还会导致粘接剂的固化加剧，在除去孔隙的工序3中会使粘接剂的流动性降低而无法充分除去孔隙。
将上述带有粘接剂的半导体芯片加热到焊料熔点以上的温度的时间(保持时间)的优选下限为0.1秒、优选上限为5秒。在保持时间低于0.1秒时，有时突起电极未充分熔融而无法形成电极接合。在保持时间超过5秒时，有时由粘接剂产生挥发成分而使孔隙增加。此外，还导致粘接剂的固化加剧，在除去孔隙的工序3中会使粘接剂的流动性降低而无法充分除去孔隙。
在上述使粘接剂临时粘接的工序2中，优选对上述半导体芯片施加压力。压力只要是形成电极接合的压力，则并无特别限定，但优选0.3～3MPa。
在本发明的半导体装置的制造方法中，接下来，进行工序3，即，在加压气氛下对上述粘接剂进行加热而除去孔隙。
加压气氛下是指比常压(大气压)高的压力气氛下。在上述除去孔隙的工序3中，可认为不仅不会使孔隙生长，而且还能将其主动除去，因此，在本发明的半导体装置的制造方法中，即使在暂时使粘接剂中卷入空气的情况下，也能除去孔隙。
作为在加压气氛下对上述粘接剂进行加热的方法，可列举例如使用加压烘箱(例如PCO-083TA(NTT Advanced Technology公司制))的方法等。
上述加压烘箱的压力的优选下限为0.2MPa、优选上限为10MPa。在压力低于0.2MPa时，有时无法充分除去孔隙。在压力超过10MPa时，有时产生粘接剂本身的变形而对半导体装置的可靠性造成不良影响。压力的更优选下限为0.3MPa、更优选上限为1MPa。
在加压气氛下对上述粘接剂进行加热时的加热温度的优选下限为60℃、优选上限为150℃。其中，当在加压气氛下对上述粘接剂进行加热时，可以将其保持在一定温度及一定压力下，也可以边升温和/或升压，边阶段性地改变温度和/或压力。
此外，为了更可靠地除去孔隙，而使在加压气氛下对上述粘接剂进行加热时的加热时间优选为10分钟以上。
在本发明的半导体装置的制造方法中，进行除去孔隙的工序3之后，进行使粘接剂完全固化的工序4。
作为使上述粘接剂完全固化的方法，可列举例如：在进行除去孔隙的工序3之后，在加压气氛下直接进行升温而使粘接剂完全固化的方法；在常压下对粘接剂进行加热而使其完全固化的方法等。使上述粘接剂完全固时的加热温度并无特别限定，优选为150～200℃左右。
在本发明的半导体装置的制造方法中，通过在使用下述的粘接剂且使粘接剂临时粘接的工序2中使突起电极可靠地接合，之后进行除去孔隙的工序3，从而可以兼顾精度高的突起电极的接合与孔隙的抑制，所述粘接剂是由差示扫描量热测定及小泽法所求出的活化能ΔE、于260℃经过2秒后的反应率及于260℃经过4秒后的反应率满足上述范围的粘接剂。本发明的半导体装置的制造方法中使用的、利用差示扫描量热测定及小泽法所求出的活化能ΔE、于260℃经过2秒后的反应率及于260℃经过4秒后的反应率满足上述范围的倒装片安装用粘接剂也是本发明之一。
发明效果
根据本发明，可以提供能够通过抑制孔隙来实现高可靠性的半导体装置的制造方法。此外，根据本发明，可以提供在该半导体装置的制造方法中使用的倒装片安装用粘接剂。
具体实施方式
以下列举实施例对本发明的实施方式进行更详细的说明，但本发明并不仅限于这些实施例。
(实施例1～5及比较例1～5)
(1)粘接剂的制造
按照表2记载的配合组成，将表1中记载的各材料添加到作为溶剂的MEK中，使用均质机进行搅拌混合，由此制造了粘接剂溶液。使用敷贴器在脱模PET膜上以使干燥后的厚度达到30μm的方式涂敷所得的粘接剂溶液，对其进行干燥，由此制造出膜状的粘接剂。直到使用时，所得的粘接剂层的表面被脱模PET膜(保护膜)保护。
(2)差示扫描量热测定及小泽法
对所得的粘接剂，在升温速度为1、2、5、10℃/min的4个条件下进行差示扫描量热测定，将温度T的倒数和升温速度B的对数(logB)作图。基于上述式(1)，由所得的直线的斜率计算出活化能ΔE。接着，基于上述式(2)的定温劣化式，由活化能ΔE计算出于260℃保持2秒或于260℃保持4秒时的反应率。
另外，使用了DSC6220(SII Nano Technology公司制)及反应速度解析软件(SII Nano Technology公司制)。
(3)半导体装置的制造
(3-1)进行对位的工序1、及使粘接剂临时粘接的工序2
准备形成有具有由焊料形成的前端部的突起电极的半导体芯片(WALTS MB50-0101JY、焊料熔点235℃、厚度100μm、WALTS公司制)、和具有Ni/Au电极的基板(WALTS-KIT MB50-0101JY、WALTS公司制)。将粘接剂的单面的保护膜剥离，使用真空层压机(ATM-812M、Takatori公司制)，在平台温度80℃、真空度80Pa下将其贴附于半导体芯片上。
使用倒装片接合器(FC-3000S、Toray Engineering公司制)，将半导体芯片隔着粘接剂与基板对位(工序1)，在接合台温度120℃的条件下，以160℃接触并升温至260℃，以0.8MPa施加载荷2秒钟，使半导体芯片的突起电极与基板的电极部熔融接合，同时使粘接剂临时粘接(工序2)。
(3-2)除去孔隙的工序3
将所得的临时粘接体投入加压烘箱(PCO-083TA、NTT AdvancedTechnology公司制)，利用以下的加压、加热条件在加压气氛下对粘接剂进行加热而除去孔隙(工序3)，且使粘接剂完全固化，从而得到半导体装置。
<加压、加热条件>
STEP1：用10分钟从25℃恒定升温至80℃、0.5MPa
STEP2：在80℃下保持60分钟、0.5MPa
STEP3：从80℃恒定升温至170℃、0.5MPa
STEP4：在170℃下保持10分钟、0.5MPa
STEP5：用30分钟从170℃降温至25℃、0.5MPa
STEP6：用60分钟恒定降温至室温、0.5MPa
<评价>
对实施例及比较例中所得的半导体装置进行了以下的评价。将结果示于表2中。
(1)孔隙的有无
使用超声波探测映像装置(C-SAM D9500、Japan Barns公司制)，对除去孔隙的工序3的前后的半导体装置的孔隙进行观察，评价了孔隙的有无。将相对于半导体芯片面积而言的孔隙产生部分的面积小于1％的情况评价为“○”，将相对于半导体芯片面积而言的孔隙产生部分的面积为1％以上且小于5％的情况评价为“△”，将相对于半导体芯片面积而言的孔隙产生部分的面积为5％以上的情况评价为“×”。
(2)电极接合状态
使用研磨机对半导体装置进行剖面研磨，使用显微镜观察电极接合部的电极接合状态。将在上下电极间无粘接剂的咬入且电极接合状态良好的情况评价为“○”，将虽然在上下电极间存在少许粘接剂的咬入但是上下电极相接合的情况评价为“△”，将在上下电极间存在粘接剂的咬入且上下电极完全不接合的情况评价为“×”。
(3)可靠性评价(TCT试验)
对半导体装置进行-55℃～125℃(30分钟/循环)的冷热循环试验，并测定每100个循环时的导通电阻值。将导通电阻值与冷热循环试验前的初期导通电阻值相比变化5％以上的时刻判定为NG，并对保持有小于5％的导通电阻值的循环数进行了评价。将循环数为1000次循环以上的情况评价为“○”，将循环数为300次循环以上且小于1000次循环的情况评价为“△”，将循环数小于300次循环的情况评价为“×”。
[表1]
[表2]
产业上的可利用性
根据本发明，可以提供能够通过抑制孔隙来实现高可靠性的半导体装置的制造方法。此外，根据本发明，可以提供在该半导体装置的制造方法中使用的倒装片安装用粘接剂。

Claims (6)

1.一种半导体装置的制造方法，其特征在于，具有如下工序：
工序1，使形成有突起电极的半导体芯片隔着粘接剂与基板对位，其中，所述突起电极具有由焊料形成的前端部，
工序2，将所述半导体芯片加热到焊料熔点以上的温度，使所述半导体芯片的突起电极与所述基板的电极部熔融接合，同时使所述粘接剂临时粘接，以及
工序3，在加压气氛下对所述粘接剂进行加热而除去孔隙；
所述粘接剂利用差示扫描量热测定及小泽法所求出的活化能ΔE为100kJ/mol以下，于260℃经过2秒后的反应率为20％以下，于260℃经过4秒后的反应率为40％以下。
2.根据权利要求1所述的半导体装置的制造方法，其特征在于，粘接剂至少含有热固化性树脂和热固化剂，所述热固化性树脂为环氧树脂。
3.根据权利要求1或2所述的半导体装置的制造方法，其特征在于，粘接剂还含有固化促进剂。
4.根据权利要求1、2或3所述的半导体装置的制造方法，其特征在于，粘接剂还含有无机填料，所述无机填料的含量为60重量％以下。
5.根据权利要求1、2、3或4所述的半导体装置的制造方法，其特征在于，粘接剂为膜状粘接剂。
6.一种倒装片安装用粘接剂，其特征在于，用于权利要求1、2、3、4或5所述的半导体装置的制造方法中，并且，所述粘接剂利用差示扫描量热测定及小泽法所求出的活化能ΔE为100kJ/mol以下，于260℃经过2秒后的反应率为20％以下，于260℃经过4秒后的反应率为40％以下。
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