CN108207115A - 加热接合用片以及带有切割带的加热接合用片 - Google Patents

加热接合用片以及带有切割带的加热接合用片 Download PDF

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Publication number
CN108207115A
CN108207115A CN201680057844.7A CN201680057844A CN108207115A CN 108207115 A CN108207115 A CN 108207115A CN 201680057844 A CN201680057844 A CN 201680057844A CN 108207115 A CN108207115 A CN 108207115A
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Prior art keywords
heating
engagement piece
precursor layer
heating engagement
aforementioned
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CN201680057844.7A
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CN108207115B (zh
Inventor
菅生悠树
镰仓菜穗
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Nitto Denko Corp
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Nitto Denko Corp
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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Abstract

本发明提供一种能通过均匀的厚度防止接合不均、赋予高温接合可靠性的加热接合片以及具有该加热接合用片的带有切割带的加热接合用片。加热接合用片具有通过加热而成为烧结层的前体层，前述前体层的平均厚度为5μm～200μm，并且前述前体层的最大厚度和最小厚度在前述平均厚度的±20％的范围内。加热接合用片具有通过加热而成为烧结层的前体层，前述前体层的平均厚度为5μm～200μm，并且利用共聚焦显微镜以200μm×200μm的视野对前述前体层的表面进行计测时的表面粗糙度Sa为2μm以下。

Description

加热接合用片以及带有切割带的加热接合用片
技术领域
本发明涉及加热接合用片以及带有切割带的加热接合用片。
背景技术
在半导体装置的制造中，将半导体元件粘接于金属引线框等被粘物的方法(所谓的芯片接合法)起源于以往的金-硅共晶，并发展到采用焊料、树脂糊剂的方法。目前，有时会使用导电性的树脂糊剂。
但是，在使用导电性的树脂糊剂的方法中，存在由于空隙的产生而导致导电性的降低以及糊剂厚度的不均匀、由于渗出而发生焊盘的污染等情况。
另一方面，近年来，进行电力的控制、供给的功率半导体装置的普及变得显著。因为功率半导体装置中始终流过电流，所以发热量大。因此，期望在功率半导体装置中使用的导电性的粘接剂具有高散热性和低电阻率。
功率半导体装置被要求低损耗且高速运行。以往，功率半导体装置中使用IGBT(Insulated Gate Bipolar Transistor：绝缘栅双极晶体管)、MOSFET(Metal-Oxide-Semiconductor Field-Effect Transistor：金属氧化物半导体场效应晶体管)等使用Si的半导体。近年，开发出使用SiC、GaN等半导体的装置，预计今后会扩大。
使用SiC、GaN的半导体具有带隙大、介质击穿电场高等特征，能实现低损耗、高速运行、高温运行。高温运行在热环境苛刻的汽车、小型电力转换设备等中成为优点。热环境苛刻的用途的半导体装置会假设250℃前后的高温运行，作为以往的接合/粘接材料的焊料、导电性粘接剂会在热特性、可靠性方面产生问题。因此，提出含有烧结金属颗粒的糊剂材料(例如专利文献1)。含有烧结金属颗粒的糊剂材料包含纳米尺寸至微米尺寸的金属颗粒，这些金属颗粒由于纳米尺寸效应会在低于通常的熔点的温度下熔解，进行颗粒间的烧结。
现有技术文献
专利文献
专利文献1：日本特开2014-111800号公报
发明内容
发明要解决的问题
但是，含有烧结金属颗粒的糊剂材料如字面上显示的那样为糊剂状态，因此，与导电性的树脂糊剂同样厚度会变得不均匀，其结果，有时会产生接合不均，特别是高温下的接合可靠性降低。
本发明是鉴于前述问题而完成的，其目的在于提供能通过均匀的厚度防止接合不均、能赋予高温接合可靠性的加热接合片以及具有该加热接合用片的带有切割带的加热接合用片。
用于解决问题的方案
本申请的发明人等为了解决前述以往的课题而进行了深入研究，结果发现，通过采用下述的构成，可解决前述课题，从而完成了本发明。
即，本发明的一个实施方式的加热接合用片具有通过加热而成为烧结层的前体层，
前述前体层的平均厚度为5μm～200μm，并且
前述前体层的最大厚度和最小厚度在前述平均厚度的±20％的范围内。
该加热接合用片具有通过加热而成为烧结层的前体层，通过实施加热处理而得到烧结层，因此，即使用于工作环境成为高温的功率半导体装置等的接合也能够发挥高接合可靠性。另外，前体层的平均厚度为5μm～200μm，并且前体层的最大厚度和最小厚度在平均厚度的±20％的范围内，因此，以高水平满足厚度的均匀性，由此能够防止接合不均，使高温接合可靠性提高。
本发明的另一个实施方式的加热接合用片具有通过加热而成为烧结层的前体层，
前述前体层的平均厚度为5μm～200μm，并且
利用共聚焦显微镜以200μm×200μm的视野对前述前体层的表面进行计测时的表面粗糙度Sa为2μm以下。
该加热接合用片具有通过加热而成为烧结层的前体层，通过实施加热处理而得到烧结层，因此，即使用于工作环境成为高温的功率半导体装置等的接合也能够发挥高接合可靠性。另外，前体层的平均厚度为5μm～200μm，并且利用共聚焦显微镜以200μm×200μm的视野对前体层的表面进行计测时的表面粗糙度Sa为2μm以下。由此，变得可以抑制厚度方向上的凹凸，以高水平满足厚度的均匀性，其结果，能够防止接合不均，使高温接合可靠性提高。
关于该加热接合用片，优选在大气气氛下、以10℃/分钟的升温速度在23℃至400℃进行差热-热重测定时，通过下述式得到的重量减少率ΔW为-9％～-3％。
ΔW(％)＝{(W400-W23)/W23}×100
(式中，W23为23℃时的加热接合用片的重量，W400为400℃时的加热接合用片的重量。)
若在前体层的烧结时残存有大量的有机成分等，则会阻碍前体层的烧结，有时得到的烧结层的强度、热特性降低。在该加热接合用片中，将加热时的重量减少率设为上述范围，因此，通过使前体层转化为烧结层时的加热，加热接合用片所包含的有机成分、溶剂等被充分去除。由此，前体层的烧结充分地进行，能够使接合可靠性提高。另外，当重量减少率为上述范围时，厚度的均匀性变得良好。
在前述构成中，优选前述前体层含有在23℃下为固态的热分解性粘结剂。
前述前体层含有在23℃下为固态的热分解性粘结剂时，在加热接合工序前容易维持片形状。另外，在加热接合工序时容易被热分解。
在前述构成中，优选前述前体层含有金属微粒，前述金属微粒为选自由银、铜、氧化银和氧化铜组成的组中的至少1种。
在含有金属微粒且前述金属微粒为选自由银、铜、氧化银和氧化铜组成的组中的至少1种时，能够更适宜地进行加热接合。
另外，本发明的带有切割带的加热接合用片具有：
切割带、和
层叠于前述切割带上的前述加热接合用片。
根据前述带有切割带的加热接合用片，由于为与切割带一体的形式，因此能够省略与切割带贴合的工序。另外，由于具备该加热接合用片，因此能够通过厚度均匀性防止接合不均，得到良好的接合可靠性。另外，由于具备具有前述前体层的加热接合用片的，因此，对前述前体层进行加热而得到的烧结层成为牢固的层，能够使高温接合可靠性提高。
附图说明
图1是示出本发明的一个实施方式的带有切割带的加热接合用片的剖视示意图。
图2是示出本发明的另一个实施方式的带有切割带的加热接合用片的剖视示意图。
图3是示出双面带有隔离膜的加热接合用片的剖视示意图。
图4是用于说明本发明的一个实施方式的半导体装置的制造方法的剖视示意图。
图5是用于进行实施例1及比较例1的接合评价的超声波影像装置的观察图像。
具体实施方式
以下，一边参照附图一边对本发明的加热接合用片以及带有切割带的加热接合用片的实施方式进行说明。但是，在图的一部分或全部中，不需要说明的部分省略，另外，还有为了容易进行说明而将其放大或缩小等进行图示的部分。表示上下等位置关系的术语仅仅是为了容易进行说明而使用的，完全没有限定本发明的构成的意思。
《第1实施方式》
(带有切割带的加热接合用片)
本实施方式的加热接合用片可列举出在以下说明的带有切割带的加热接合用片中没有粘贴切割带的状态的加热接合用片。因此，以下对带有切割带的加热接合用片进行说明，关于加热接合用片，将在其中进行说明。图1是示出本发明的一个实施方式的带有切割带的加热接合用片的剖视示意图。
图2是示出本发明的另一个实施方式的另一个带有切割带的加热接合用片的剖视示意图。
如图1所示，带有切割带的加热接合用片10具有在切割带11上层叠有加热接合用片3的结构。切割带11是在基材1上层叠粘合剂层2而构成的，加热接合用片3设置于粘合剂层2上。另外，本发明的带有切割带的加热接合用片也可以是如图2所示的带有切割带的加热接合用片12那样仅在工件贴附部分形成有加热接合用片3’的结构。
(加热接合用片)
加热接合用片3、3’为片状。由于不是糊剂而是片，因此可以得到良好的厚度均匀性和处理性。
本实施方式的加热接合用片3、3’由通过加热而成为烧结层的前体层31形成。在本实施方式中，虽然对加热接合用片包括1层通过加热而成为烧结层的前体层的情况进行说明，但是本发明并不限定于该例。本发明中的通过加热而成为烧结层的前体层也可以是层叠多层该前体层的构成。
另外，在本实施方式中，对加热接合用片由通过加热而成为烧结层的前体层形成的情况进行说明，但是本发明并不限定于该例。本发明的加热接合用片也可以为2层以上。例如，也可以是层叠有通过加热而成为烧结层的前体层和其他层(通过加热不成为烧结层的层)的结构。
即，本发明中的加热接合用片只要至少具有通过加热而成为烧结层的前体层即可，对其他构成没有特别限定。
(通过加热而成为烧结层的前体层)
通过加热而成为烧结层的前体层31(以下也简称为“前体层31”)的平均厚度为5μm～200μm，优选为10μm～150μm，更优选为15μm～100μm。通过将加热前的前体层31的平均厚度设为上述范围，能够确保片形状的维持和厚度均匀性。
前体层31的最大厚度和最小厚度为前述平均厚度的±20％的范围内，优选为±17％的范围内，更优选为±15％的范围内。通过使前体层的最大厚度和最小厚度相对于平均厚度落在规定范围内，可以以高水平满足厚度的均匀性，由此防止接合不均，并使高温接合可靠性提高。需要说明的是，平均厚度、最大厚度以及最小厚度可以用实施例记载的方法测定。
前体层31的通过下述拉伸试验方法得到的拉伸弹性模量优选为10MPa～3000MPa，更优选为12MPa～2900MPa，进一步优选为15MPa～2500MPa。
拉伸试验方法：
(1)作为试验试样，准备厚度为200μm、宽度为10mm、长度为40mm的加热接合用片(拉伸试验用加热接合用片)，
(2)在卡盘间距离为10mm、拉伸速度为50mm/分钟、23℃的条件下进行拉伸试验，
(3)将得到的应力-应变线图的直线部分的斜率作为拉伸弹性模量。
前体层31的前述拉伸弹性模量为10MPa以上时，能够进一步抑制在芯片接合时加热接合用片的构成材料溢出或者爬上芯片表面。另外，前述拉伸弹性模量为3000MPa以下时，例如能够在切割时将半导体晶圆固定。
前体层31的、在大气气氛下以升温速度为10℃/分钟的条件在23℃至400℃进行升温后的利用能量色散型X射线分析所得到的碳浓度优选为15重量％以下，更优选为12重量％以下，进一步优选为10重量％以下。前述碳浓度为15重量％以下时，前体层31在进行直至400℃的升温后几乎不存在有机物。其结果，在加热接合工序后，耐热性优异，即使在高温环境下也可得到高可靠性、热特性。
前体层31的、在大气气氛下以升温速度为10℃/分钟的条件在23℃至500℃进行差热分析时的峰值优选存在于150～350℃，更优选存在于170～320℃，进一步优选存在于180～310℃。前述峰值存在于150～350℃时，可以说有机物(例如构成前体层31的树脂成分)在该温度区域下发生热分解。其结果，加热接合工序后的耐热性更加优异。
关于前体层31，优选相对于整个前体层31在60～98重量％的范围内含有金属微粒。前述金属微粒的含量更加优选在65～97重量％的范围内，进一步优选在70～95重量％的范围内。在60～98重量％的范围内含有前述金属微粒时，能够使金属微粒烧结或熔融，从而使2个物件(例如半导体芯片和引线框)接合。
作为前述金属微粒，可列举出烧结性金属颗粒。
作为前述烧结性金属颗粒，可以适宜地使用金属微粒的凝聚体。作为金属微粒，可列举出由金属构成的微粒等。作为前述金属，可列举金、银、铜、氧化银、氧化铜等。其中，优选为选自由银、铜、氧化银、氧化铜组成的组中的至少1种。前述金属微粒为选自由银、铜、氧化银、氧化铜组成的组中的至少1种时，能够更适宜地进行加热接合。
前述烧结性金属颗粒的平均粒径优选为0.0005μm以上，更优选为0.001μm以上。作为平均粒径的下限，也可以例示出0.01μm、0.05μm、0.1μm。另一方面，烧结性金属颗粒的平均粒径优选为30μm以下，更优选为25μm以下。作为平均粒径的上限，也可以例示出20μm、15μm、10μm、5μm。
前述烧结性金属颗粒的平均粒径通过下述的方法测定。即，用SEM(扫描型电子显微镜)观察前述烧结性金属颗粒，对平均粒径进行计测。需要说明的是，SEM观察优选如下：例如，在烧结性金属颗粒为微米尺寸的情况下，用5000倍进行观察；在为亚微米尺寸的情况下，用50000倍进行观察；在为纳米尺寸的情况下，用300000倍进行观察。
对前述烧结性金属颗粒的形状没有特别限定，例如为球状、棒状、鱗片状、不定形状。
前体层31优选含有低沸点粘结剂。前述低沸点粘结剂是为了容易进行前述金属微粒的处理而使用的。具体而言，可以以使前述金属微粒分散于前述低沸点粘结剂中的含金属微粒糊剂的形式使用。而且，为了将烧结层的前体层调整为任意的机械物性，也优选含有。
前述低沸点粘结剂在23℃为液态。在本说明书中，所谓“液态”包括半液态。具体而言，是指利用动态粘弹性测定装置(流变仪)以下述条件进行粘度测定时的23℃下的粘度为100000Pa·秒以下。
＜粘度测定条件＞
流变仪：Thermo SCIENTFIC公司制、“MER III”
夹具：平行板20mmφ
间隙：100μm
剪切速度：1/秒
作为前述低沸点粘结剂的具体例，可列举出例如：戊醇、己醇、庚醇、辛醇、1-癸醇、乙二醇、二乙二醇、丙二醇、丁二醇、α-萜品醇、1,6-己二醇、异冰片基环己醇(MTPH)等一元醇和多元醇类；乙二醇丁醚、乙二醇苯醚、二乙二醇甲醚、二乙二醇***、二乙二醇丁醚、二乙二醇异丁醚、二乙二醇己醚、三乙二醇甲醚、二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、二乙二醇丁基甲醚、二乙二醇异丙基甲醚、三乙二醇二甲醚、三乙二醇丁基甲醚、丙二醇丙醚、二丙二醇甲醚、二丙二醇***、二丙二醇丙醚、二丙二醇丁醚、二丙二醇二甲醚、三丙二醇甲醚、三丙二醇二甲醚等醚类；乙二醇***乙酸酯、乙二醇丁醚乙酸酯、二乙二醇***乙酸酯、二乙二醇丁醚乙酸酯、二丙二醇甲醚乙酸酯(DPMA)等。这些也可以组合使用2种以上。其中，优选组合使用沸点不同的2种。使用沸点不同的2种时，在维持片形状方面优异。
前体层31优选含有在23℃下为固态的热分解性粘结剂。含有前述热分解性粘结剂时，在加热接合工序前容易维持片形状。另外，在加热接合工序时容易使其热分解。
在本说明书中，所谓“固态”具体而言是指：利用前述流变仪进行粘度测定时的23℃下的粘度大于100000Pa·s。
在本说明书中，所谓“热分解性粘结剂”是指在加热接合工序中能够热分解的粘结剂。前述热分解性粘结剂优选在加热接合工序后几乎不残存于烧结层(加热后的前体层31)。作为前述热分解性粘结剂，可列举例如如下材料：即使在前体层31中含有该材料，在大气气氛下以升温速度为10℃/分钟的条件在23℃至400℃进行升温后的、利用能量色散型X射线分析所得到的碳浓度也成为15重量％以下。例如，作为热分解性粘结剂，若采用更容易热分解的材料，则即使含量比较多，也能够使得加热接合工序后几乎不残存于烧结层(加热后的前体层31)。
作为前述热分解性粘结剂，可列举出聚碳酸酯、丙烯酸类树脂、乙基纤维素、聚乙烯醇等。这些材料可以单独使用或混合使用2种以上。其中，从热分解性高的观点出发，优选聚碳酸酯。
作为前述聚碳酸酯，只要是在加热接合工序中能够热分解的物质就没有特别限定，可列举出在主链的碳酸酯基(-O-CO-O-)间不含芳香族化合物(例如苯环等)的由脂肪族链构成的脂肪族聚碳酸酯、在主链的碳酸酯基(-O-CO-O-)间含有芳香族化合物的芳香族聚碳酸酯。其中，优选脂肪族聚碳酸酯。
作为前述脂肪族聚碳酸酯，可列举出例如聚碳酸亚乙酯、聚碳酸亚丙酯等。其中，从在用于形成片的清漆制作中对有机溶剂的溶解性的观点出发，优选为聚碳酸亚丙酯。
作为前述芳香族聚碳酸酯，可列举出例如主链含有双酚A结构的物质。
前述聚碳酸酯的重均分子量在10,000～1,000,000的范围内是合适的。需要说明的是，重均分子量是利用GPC(凝胶渗透色谱法)测定并利用聚苯乙烯换算而算出的值。
作为前述丙烯酸类树脂，在加热接合工序中能够热分解的范围内，可列举出以具有碳数30以下、特别是碳数4～18的直链或者支链的烷基的丙烯酸或甲基丙烯酸的酯的1种或2种以上作为成分的聚合物(丙烯酸类共聚物)等。作为前述烷基，可列举出例如：甲基、乙基、丙基、异丙基、正丁基、叔丁基、异丁基、戊基、异戊基、己基、庚基、环己基、2-乙基己基、辛基、异辛基、壬基、异壬基、癸基、异癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基或十二烷基等。
另外，作为形成聚合物(丙烯酸类共聚物)的其他单体，没有特别限定，可列举出例如：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、马来酸、富马酸或者巴豆酸等含羧基单体；马来酸酐或者衣康酸酐等酸酐单体；(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-4-羟基丁酯、(甲基)丙烯酸-6-羟基己酯、(甲基)丙烯酸-8-羟基辛酯、(甲基)丙烯酸-10-羟基癸酯、(甲基)丙烯酸-12-羟基月桂酯或者丙烯酸(4-羟基甲基环己基)甲酯等含羟基单体；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯酰氧基萘磺酸等含磺酸基单体；或者2-羟基乙基丙烯酰基磷酸酯等含磷酸基单体。
在丙烯酸类树脂中，更优选重均分子量为1万～100万的物质，进一步优选3万～70万的物质。这是因为：在上述数值范围内时，加热接合工序前的粘接性和加热接合工序时的热分解性优异。需要说明的是，重均分子量是通过GPC(凝胶渗透色谱法)测定并通过聚苯乙烯换算而算出的值。
另外，在丙烯酸类树脂中，优选在200℃～400℃下热分解的丙烯酸类树脂。
关于加热接合用片3、3’，优选的是，在大气气氛下、以10℃/分钟的升温速度在23℃至400℃进行差热-热重测定时，通过下述式得到的重量减少率ΔW为-9％～-3％，更优选为-8％～-3.1％。
ΔW(％)＝{(W400-W23)/W23}×100
(式中，W23为23℃时的加热接合用片的重量，W400为400℃时的加热接合用片的重量。)
若在前体层31的烧结时残存有大量的有机成分等，则会阻碍前体层31的烧结，有时得到的烧结层的强度、热特性降低。由于在加热接合用片3、3’中将加热时的重量减少率设为上述范围，因此，通过使前体层转化为烧结层时的加热，加热接合用片所包含的有机成分(例如上述低沸点粘结剂、热分解性粘结剂等)、溶剂等会被充分去除。由此，前体层的烧结充分地进行，能够使接合可靠性提高。另外，重量减少率为上述范围时，厚度的均匀性会变得良好。
需要说明的是，前体层31除前述成分以外，还可以适当含有例如增塑剂等。
加热接合用片3、3’可以通过通常的方法制造。例如，制作含有用于形成前体层31的前述各成分的清漆，将清漆以成为规定厚度的方式涂布于基材隔离膜上而形成涂布膜后，使该涂布膜干燥，由此可以制造加热接合用片3、3’。
作为用于清漆的溶剂，没有特别限定，优选能够使前述各成分均匀地溶解、混炼或分散的有机溶剂、醇溶剂。作为前述有机溶剂，可列举出例如：二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、丙酮、甲基乙基酮、环己酮等酮系溶剂；甲苯；二甲苯等。另外，作为前述醇溶剂，可列举出：乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2-丁烯-1,4-二醇、1,2,6-己三醇、甘油、辛二醇、2-甲基-2,4-戊二醇、萜品醇。
对涂布方法没有特别限定。作为溶剂涂覆的方法，可列举出例如模涂、凹版涂布、辊涂、反向涂布、逗点涂布、管式刮刀涂布(pipe doctor coater)、丝网印刷等。其中，从涂布厚度的均匀性高的方面出发，优选模涂。另外，对涂布膜的干燥条件没有特别限定，例如，可以以干燥温度70～160℃、干燥时间1～5分钟来进行。需要说明的是，即使在使涂层干燥后，也会根据溶剂的种类的不同而存在溶剂未全部气化而残留于涂层中的情况。
在前体层31含有前述低沸点粘结剂的情况下，根据前述干燥条件，有时前述低沸点粘结剂的一部分会挥发。因此，根据前述干燥条件，构成前体层31的各成分的比率会发生变化。例如，即使是由相同的清漆形成的前体层31，也是干燥温度越高、以及干燥时间越长，在整个前体层31中所占的金属微粒的含量、热分解性粘结剂的含量变得越多。因此，优选设定前述干燥条件使得前体层31中的金属微粒、热分解性粘结剂的含量成为期望的量。
作为基材隔离膜，可以使用通过聚对苯二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯、氟系剥离剂、长链烷基丙烯酸系剥离剂等剥离剂进行表面涂布的塑料薄膜、纸等。
作为加热接合用片3、3’的制造方法，例如，将前述各成分用搅拌机混合，并对得到的混合物进行冲压成型来制造加热接合用片3、3’的方法等也是适合的。作为搅拌机可列举出行星式搅拌机等。
(切割带)
切割带11是在基材1上层叠粘合剂层2而构成的。
基材1成为带有切割带的加热接合用片10、12的强度母体，优选具有紫外线透射性的基材。作为基材1，可列举出例如：低密度聚乙烯、直链状聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、无规共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯、聚丁烯、聚甲基戊烯等聚烯烃；乙烯-乙酸乙烯酯共聚物、离聚物树脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(无规、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯；聚碳酸酯、聚酰亚胺、聚醚醚酮、聚醚酰亚胺、聚酰胺、全芳香族聚酰胺、聚苯硫醚、芳纶(纸)、玻璃、玻璃布、氟树脂、聚氯乙烯、聚偏氯乙烯、纤维素系树脂、有机硅树脂、金属(箔)、纸等。
另外，作为基材1的材料，可列举出前述树脂的交联体等聚合物。前述塑料薄膜可以以未拉伸的方式使用，也可以使用根据需要而实施单向或双向拉伸处理的薄膜。根据利用拉伸处理等而赋予了热收缩性的树脂片，可以通过在切割后使该基材1热收缩来减少粘合剂层2与加热接合用片3、3’的粘接面积，实现使半导体芯片的回收容易。
为了提高与相邻的层的密合性、保持性等，基材1的表面可以实施惯用的表面处理、例如铬酸处理、臭氧暴露、火焰暴露、高压电击暴露、电离辐射线处理等化学或物理处理、基于底涂剂(例如后述的粘合物质)的涂敷处理。
对基材1的厚度没有特别限定，可适当决定，但通常为5～200μm左右。
作为用于粘合剂层2的形成的粘合剂，没有特别限定，例如可以使用丙烯酸系粘合剂、橡胶系粘合剂等通常的压敏性粘接剂。作为前述压敏性粘接剂，从半导体晶圆、玻璃等怕污染的电子部件的利用超纯水、醇等有机溶剂的清洁洗涤性等方面出发，优选将丙烯酸系聚合物作为基础聚合物的丙烯酸系粘合剂。
作为前述丙烯酸系聚合物，可列举出例如：将(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、异丙酯、丁酯、异丁酯、仲丁酯、叔丁酯、戊酯、异戊酯、己酯、庚酯、辛酯、2-乙基己酯、异辛酯、壬酯、癸酯、异癸酯、十一烷酯、十二烷酯、十三烷酯、十四烷酯、十六烷酯、十八烷酯、二十烷酯等烷基的碳数1～30、特别是碳数4～18的直链状或支链状的烷基酯等)和(甲基)丙烯酸环烷基酯(例如，环戊酯、环己酯等)中的1种或2种以上作为单量体成分使用的丙烯酸系聚合物等。需要说明的是，(甲基)丙烯酸酯是指丙烯酸酯和/或甲基丙烯酸酯，本发明的(甲基)全部是同样的含义。
前述丙烯酸系聚合物也可以出于改善内聚力、耐热性等目的而根据需要包含与能够同前述(甲基)丙烯酸烷基酯或环烷基酯共聚的其他单体成分对应的单元。作为这样的单体成分，可列举出例如：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、马来酸、富马酸、巴豆酸等含羧基单体；马来酸酐、衣康酸酐等酸酐单体；(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-4-羟基丁酯、(甲基)丙烯酸-6-羟基己酯、(甲基)丙烯酸-8-羟基辛酯、(甲基)丙烯酸-10-羟基癸酯、(甲基)丙烯酸-12-羟基月桂酯、(甲基)丙烯酸(4-羟基甲基环己基)甲酯等含羟基单体；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯酰氧基萘磺酸等含磺酸基单体；2-羟基乙基丙烯酰基磷酸酯等含磷酸基单体；丙烯酰胺、丙烯腈等。这些能够共聚的单体成分可以使用1种或2种以上。这些能够共聚的单体的使用量优选为全部单体成分的40重量％以下。
进而，前述丙烯酸系聚合物为了进行交联还可以根据需要包含多官能性单体等作为共聚用单体成分。作为这样的多官能性单体，可列举出例如：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等。这些多官能性单体也可以使用1种或2种以上。从粘合特性等方面出发，多官能性单体的使用量优选为全部单体成分的30重量％以下。
前述丙烯酸系聚合物是通过使单一单体或2种以上的单体混合物进行聚合而得到的。聚合也可以通过溶液聚合、乳液聚合、本体聚合、悬浮聚合等中的任一方式进行。从防止对干净的被粘物的污染等方面出发，优选低分子量物质的含量少。从该方面出发，丙烯酸系聚合物的数均分子量优选为10万以上，进一步优选为20万～300万左右，尤其优选为30万～100万左右。
另外，为了提高作为基础聚合物的丙烯酸系聚合物等的数均分子量，在前述粘合剂中也可以适宜地采用外部交联剂。作为外部交联方法的具体方式，可列举出添加多异氰酸酯化合物、环氧化合物、氮丙啶化合物、三聚氰胺系交联剂等所谓的交联剂而使其反应的方法。在使用外部交联剂的情况下，其使用量根据与应交联的基础聚合物的平衡、进而作为粘合剂的使用用途而适当决定。一般而言，相对于前述基础聚合物100重量份优选配混5重量份左右以下，进一步优选配混0.1～5重量份。进而，在粘合剂中，根据需要，除前述成分以外，还可以使用以往公知的各种增粘剂、抗老化剂等添加剂。
粘合剂层2可以通过辐射线固化型粘合剂形成。辐射线固化型粘合剂可以通过紫外线等辐射线的照射使其交联度增大而容易地使其粘合力降低，通过仅对与图2所示的粘合剂层2的工件贴附部分对应的部分2a进行辐射线照射，可以设置与其他部分2b的粘合力的差。
另外，通过与图2所示的加热接合用片3’一起使辐射线固化型的粘合剂层2固化，可以容易地形成粘合力显著降低的前述部分2a。由于在固化而粘合力降低的前述部分2a贴附有加热接合用片3’，因此粘合剂层2的前述部分2a与加热接合用片3’的界面具有在拾取时容易剥离的性质。另一方面，没有照射辐射线的部分具有充分的粘合力，形成前述部分2b。需要说明的是，辐射线对粘合剂层的照射也可以在切割后且拾取前进行。
如前所述，在图1所示的带有切割带的加热接合用片10的粘合剂层2中，通过未固化的辐射线固化型粘合剂形成的前述部分2b与加热接合用片3粘合，能够确保切割时的保持力。这样，辐射线固化型粘合剂能够粘接、剥离的平衡性良好地支撑用于将芯片状工件(半导体芯片等)固定于基板等被粘物的加热接合用片3。在图2所示的带有切割带的加热接合用片11的粘合剂层2中，前述部分2b能够将晶圆环固定。
关于辐射线固化型粘合剂，可以没有特别限制地使用具有碳-碳双键等辐射线固化性的官能团、并且显示粘合性的粘合剂。作为辐射线固化型粘合剂，例如可以例示出在前述丙烯酸系粘合剂、橡胶系粘合剂等通常的压敏性粘合剂中配混有辐射线固化性的单体成分、低聚物成分的添加型的辐射线固化型粘合剂。
作为要配混的辐射线固化性的单体成分，可列举出例如：氨基甲酸酯低聚物、氨基甲酸酯(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。另外，辐射线固化性的低聚物成分可列举出氨基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各种低聚物，其分子量为100～30000左右的范围是适宜的。辐射线固化性的单体成分、低聚物成分的配混量可以根据前述粘合剂层的种类而适当地决定嫩能够降低粘合剂层的粘合力的量。一般而言，相对于构成粘合剂的丙烯酸系聚合物等基础聚合物100重量份，例如为5～500重量份，优选为40～150重量份左右。
另外，作为辐射线固化型粘合剂，除前述说明的添加型的辐射线固化型粘合剂以外，还可列举出使用在聚合物侧链或主链中、或者主链末端具有碳-碳双键的聚合物作为基础聚合物的内在型的辐射线固化型粘合剂。内在型的辐射线固化型粘合剂不必含有或不大量含有作为低分子成分的低聚物成分等，因此低聚物成分等不会经时性地在粘合剂中移动，能够形成稳定的层结构的粘合剂层，故优选。
前述具有碳-碳双键的基础聚合物可以无特别限制地使用具有碳-碳双键并且具有粘合性的基础聚合物。作为这样的基础聚合物，优选以丙烯酸系聚合物为基本骨架的基础聚合物。作为丙烯酸系聚合物的基本骨架，可列举出前述例示的丙烯酸系聚合物。
对于向前述丙烯酸系聚合物中导入碳-碳双键的方法没有特别限定，可以采用各种方法，但碳-碳双键导入至聚合物侧链在分子设计上是容易的。例如，可列举出以下方法：预先使丙烯酸系聚合物与具有官能团的单体共聚后，使具有能够与该官能团反应的官能团及碳-碳双键的化合物在维持碳-碳双键的辐射线固化性的状态下进行缩合或加成反应。
作为这些官能团的组合的例子，可列举出：羧酸基与环氧基、羧酸基与氮丙啶基、羟基与异氰酸酯基等。在这些官能团的组合中，从反应追踪的容易程度出发，羟基与异氰酸酯基的组合是适宜的。另外，只要是利用这些官能团的组合而生成具有前述碳-碳双键的丙烯酸系聚合物的组合，则官能团位于丙烯酸系聚合物和前述化合物中的任一侧均可，但在前述优选的组合中，丙烯酸系聚合物具有羟基、且前述化合物具有异氰酸酯基的情况是适宜的。在该情况下，作为具有碳-碳双键的异氰酸酯化合物，可列举出例如：甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯、间异丙烯基-α,α-二甲基苄基异氰酸酯等。另外，作为丙烯酸系聚合物，可以使用将前述例示的含羟基单体、2-羟基乙基乙烯基醚、4-羟基丁基乙烯基醚、二乙二醇单乙烯基醚的醚系化合物等共聚而得到的丙烯酸系聚合物。
前述内在型的辐射线固化型粘合剂可以单独地使用前述具有碳-碳双键的基础聚合物(特别是丙烯酸系聚合物)，但是，也可以以不使特性变差的程度配混前述辐射线固化性的单体成分、低聚物成分。关于辐射线固化性的低聚物成分等，通常相对于基础聚合物100重量份在30重量份的范围内，优选为0～10重量份的范围。
前述辐射线固化型粘合剂在利用紫外线等使其固化的情况下含有光聚合引发剂。作为光聚合引发剂，可列举处例如：4-(2-羟基乙氧基)苯基(2-羟基-2-丙基)酮、α-羟基-α,α’-二甲基苯乙酮、2-甲基-2-羟基苯丙酮、1-羟基环己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-吗啉代丙烷-1等苯乙酮系化合物；苯偶姻***、苯偶姻异丙醚、茴香偶姻甲醚等苯偶姻醚系化合物；苯偶酰二甲基缩酮等缩酮系化合物；2-萘磺酰氯等芳香族磺酰氯系化合物；1-苯酮-1,1-丙二酮-2-(o-乙氧羰基)肟等光活性肟系化合物；二苯甲酮、苯甲酰基苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、异丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮等噻吨酮系化合物；樟脑醌；卤代酮；酰基氧化膦；酰基膦酸酯等。关于光聚合引发剂的配混量，相对于构成粘合剂的丙烯酸系聚合物等基础聚合物100重量份，例如为0.05～20重量份左右。
另外，作为辐射线固化型粘合剂，可列举出例如日本特开昭60-196956号公报公开的、含有具有2个以上不饱和键的加成聚合性化合物、具有环氧基的烷氧基硅烷等光聚合性化合物和羰基化合物、有机硫化合物、过氧化物、胺、鎓塩系化合物等光聚合引发剂的橡胶系粘合剂、丙烯酸系粘合剂等。
在前述辐射线固化型的粘合剂层2中，根据需要，也可以含有通过辐射线照射而着色的化合物。通过使粘接剂层2含有利用辐射线照射而着色的化合物，能够仅使辐射线照射的部分着色。即，能使与图1所示的工件贴附部分3a对应的部分2a着色。因此，能够通过目视立刻判明辐射线是否照射到粘合剂层2，容易识别工件贴附部分3a，工件的贴合容易。另外，在利用光传感器等检测半导体芯片时，其检测精度提高，不会在进行半导体芯片的拾取时发生误操作。通过辐射线照射而着色的化合物是在进行辐射线照射前为无色或淡色而通过辐射线照射成为有色的化合物，可列举出例如隐色染料等。通过辐射线照射而着色的化合物的使用比例可以适宜设定。
对粘合剂层2的厚度没有特别限定，从防止芯片切断面的缺损、兼顾加热接合用片3、3’的固定保持等方面出发，优选为1～50μm左右。优选为2～30μm，进一步优选为5～25μm。
本实施方式的切割带11例如按照如下方式制作。
首先，基材1可以通过以往公知的制膜方法来制膜。作为该制膜方法，可以例示出例如：压延制膜法、在有机溶剂中的浇铸法、在密闭体系中的吹塑挤出法、T模挤出法、共挤出法、干式层压法等。
接着，在基材1上涂布粘合剂组合物溶液而形成涂布膜后，使该涂布膜在规定条件下干燥(根据需要使其加热交联)，形成粘合剂层2。作为涂布方法没有特别限定，可列举出例如：辊涂覆、丝网涂覆、凹版涂覆等。另外，作为干燥条件，例如在干燥温度为80～150℃、干燥时间为0.5～5分钟的范围内进行。另外，也可以在隔离膜上涂布粘合剂组合物而形成涂布膜后，在前述干燥条件下使涂布膜干燥而形成粘合剂层2。然后，在基材1上将粘合剂层2与隔离膜一起贴合。由此，制作切割带11。
带有切割带的加热接合用片10、12可以通过通常的方法制造。例如，通过使切割带11的粘合剂层2与加热接合用片3贴合，能够制造带有切割带的加热接合用片10。
在带有切割带的加热接合用片10中，优选加热接合用片3被隔离膜覆盖。例如可列举出如下方法：在使切割带11与加热接合用片3贴合后，将层叠于加热接合用片3的前述基材隔离膜剥离，在将前述基材隔离膜剥离后的带有切割带的加热接合用片10的加热接合用片3的露出面贴附隔离膜。即，优选切割带11、加热接合用片3以及前述隔离膜依次层叠的形态。
在上述实施方式中，对层叠有切割带和加热接合用片的带有切割带的加热接合用片进行了说明。但是，本发明的加热接合用片也可以以不与切割带贴合的状态提供。
加热接合用片在设为没有贴合切割带的形态的情况下，优选设为被2片隔离膜夹持的双面带有隔离膜的加热接合用片。即，优选设为第1隔离膜、加热接合用片以及第2隔离膜依次层叠的双面带有隔离膜的加热接合用片。
图3是示出双面带有隔离膜的加热接合用片的一个实施方式的剖视示意图。
图3所示的双面带有隔离膜的加热接合用片30具有第1隔离膜32、加热接合用片3以及第2隔离膜34依次层叠的构成。作为第1隔离膜32和第2隔离膜34，可以使用与前述基材隔离膜相同的隔离膜。
需要说明的是，加热接合用片在设为没有贴合切割带的形态的情况下，也可以是仅在加热接合用片的一个面层叠有隔离膜的形态。
(半导体装置的制造方法)
本实施方式的半导体装置的制造方法包括：准备前述加热接合用片的工序；和
借助前述加热接合用片将半导体芯片加热接合在被粘物上的加热接合工序(以下也称为第1制法)。
另外，本实施方式的半导体装置的制造方法也可以是包括以下工序的制造方法：准备前述记载的带有切割带的加热接合用片的工序；
使前述带有切割带的加热接合用片的加热接合用片与半导体晶圆的背面贴合的贴合工序；
将前述半导体晶圆与前述加热接合用片一起切割而形成芯片状的半导体芯片的切割工序；
从前述带有切割带的加热接合用片将前述半导体芯片与前述加热接合用片一起拾取的拾取工序；以及
借助前述加热接合用片将前述半导体芯片加热接合在被粘物上的加热接合工序(以下也称为第2制法)。
关于第1制法的半导体装置的制造方法，相对于第2制法的半导体装置的制造方法使用带有切割带的加热接合用片，在第1制法的半导体装置的制造方法中，在以单体的形式使用加热接合用片的方面不同，在其他方面相同。在第1制法的半导体装置的制造方法中，如果在准备加热接合用片后进行使其与切割带贴合的工序，则之后可以设为与第2制法的半导体装置的制造方法同样。因此，以下对第2制法的半导体装置的制造方法进行说明。
在本实施方式的半导体装置的制造方法中，首先准备带有切割带的加热接合用片10、12(准备工序)。将任意设置于加热接合用片3、3’上的隔离膜适当地剥离，按如下方式使用带有切割带的加热接合用片10、12。以下，一边参照图3一边以使用带有切割带的加热接合用片10的情况为例进行说明。
首先，在带有切割带的加热接合用片10中的加热接合用片3的半导体晶圆贴附部分3a上压接半导体晶圆4，将其粘接保持而进行固定(贴合工序)。本工序一边通过压接辊等按压单元进行按压一边进行。对安装时的贴附温度没有特别限定，例如优选在23℃～90℃的范围内。
作为半导体晶圆4，优选在一个面形成有电极焊盘并在另一面(以下也称为背面)的最表面形成有银薄膜的半导体晶圆。作为前述银薄膜的厚度，可列举出例如10nm～1000nm。另外，也可以在半导体晶圆4与前述银薄膜之间进一步形成有钛薄膜。作为前述钛薄膜的厚度，可列举出例如10nm～1000nm。当形成有前述银薄膜时，在后述的加热接合工序中能够将半导体芯片5与加热接合用片3牢固地加热接合。另外，当形成有前述钛薄膜时，电极的可靠性提高。前述银薄膜和前述钛薄膜例如可以通过蒸镀来形成。
接着，进行半导体晶圆4的切割(切割工序)。由此，将半导体晶圆4切割为规定尺寸而进行单片化，制造半导体芯片5。对切割的方法没有特别限定，例如从半导体晶圆4的电路面侧按照常规方法进行。另外，在本工序中，可以采用例如切入进行至带有切割带的加热接合用片10的被称为全切的切割方式等。作为本工序中使用的切割装置没有特别限定，可以使用以往公知的切割装置。另外，由于半导体晶圆4被带有切割带的加热接合用片10粘接固定，因此能够抑制芯片缺损、芯片飞散，并且还能够抑制半导体晶圆4的破损。
接着，为了将粘接固定于带有切割带的加热接合用片10的半导体芯片5剥离而进行半导体芯片5的拾取(拾取工序)。作为拾取的方法没有特别限定，可以采用以往公知的各种方法。例如，可列举出利用针将各个半导体芯片5从带有切割带的加热接合用片10侧顶起，并利用拾取装置拾取被顶起的半导体芯片5的方法等。
作为拾取条件，从防止破片的方面出发，优选将针顶起速度设为5～100mm/秒，更优选设为5～10mm/秒。
在此，在粘合剂层2为紫外线固化型的情况下，拾取在向该粘合剂层2照射紫外线后进行。由此，粘合剂层2相对于加热接合用片3的粘合力降低，半导体芯片5的剥离变得容易。其结果，能够不使半导体芯片5损伤地进行拾取。对紫外线照射时的照射强度、照射时间等条件没有特别限定，只要根据需要适当设定即可。另外，作为在紫外线照射中使用的光源，可以使用公知的光源。需要说明的是，在预先向粘合剂层照射紫外线使其固化、并将该固化的粘合剂层与加热接合用片贴合的情况下，这里的紫外线照射是不需要的。
然后，将拾取的半导体芯片5隔着加热接合用片3芯片接合(加热接合)于被粘物6(加热接合工序)。作为被粘物6，可列举出引线框、TAB薄膜、基板或另行制作的半导体芯片等。被粘物6例如可以是容易变形的变形型被粘物，也可以是不易变形的非变形型被粘物(半导体晶圆等)。
作为前述引线框，可列举出Cu引线框、42合金(Alloy)引线框等金属引线框。另外，作为前述基板，可以使用以往公知的基板。例如，可列举出由玻璃环氧、BT(双马来酰亚胺三嗪)、聚酰亚胺等制成的有机基板。其中，使用金属引线框时，可以通过加热接合与金属微粒一体化。另外，作为前述基板，可列举出在陶瓷板等绝缘基板上层叠有铜电路基板的绝缘电路基板。使用绝缘电路基板时，可以制造例如进行电力控制、供给的功率半导体装置。
在前述加热接合工序中，通过加热来烧结金属微粒，并且根据需要使热分解性粘结剂热分解。另外，利用干燥工序使没有挥发完的残留低沸点粘结剂挥发。可以在加热温度优选为180～400℃、更优选为190～370℃、进一步优选为200～350℃下进行。另外，可以在加热时间优选为0.3～300分钟、更优选为0.5～240分钟、进一步优选为1～180分钟下进行。另外，加热接合也可以在加压条件下进行。作为加压条件，优选1～500kg/cm2的范围内，更优选5～400kg/cm2的范围内。加压下的加热接合例如可以使用倒装焊接器那样的同时进行加热和加压的装置来实施。另外，也可以是平行平板压制。
接着，根据需要，如图4所示那样，将被粘物6的端子部(内引线)的顶端和半导体芯片5上的电极焊盘(未图示)用接合引线7电连接(引线接合工序)。作为前述接合引线7，可使用例如金线、铝线或铜线等。在进行引线接合时的温度为23～300℃、优选为23～250℃的范围内进行。另外，其加热时间进行几秒～几分钟。结线在被加热成为前述温度范围内的状态下通过组合使用基于超声波的振动能量和基于施加加压的压接能量来进行。
接着，根据需要，如图4所示那样，利用封装树脂8将半导体芯片5封装(封装工序)。本工序是为了保护搭载于被粘物6的半导体芯片5、接合引线7而进行的。本工序可以通过用模具对封装用的树脂进行成型来进行。作为封装树脂8，例如使用环氧系的树脂。树脂封装时的加热温度通常在175℃下进行60～90秒，但是本发明不限于此，例如可以在165～185℃处理几分钟。由此使封装树脂8固化。需要说明的是，在本封装工序中，也可以采用将半导体芯片5埋入到片状的封装用片的方法(例如参照日本特开2013-7028号公报)。另外，除利用模具进行的封装树脂的成型以外，也可以是使有机硅凝胶流入到壳型容器的凝胶封装型。
然后，根据需要进行加热，使在前述封装工序中固化不足的封装树脂8完全固化(后固化工序)。本工序中的加热温度根据封装树脂的种类而不同，例如在165～185℃的范围内，加热时间为0.5～8小时左右。
需要说明的是，本发明的加热接合用片和带有切割带的加热接合用片也可以适宜地用于将多个半导体芯片层叠而进行三维安装的情况。此时，可以在半导体芯片之间层叠加热接合用片和隔离物，也可以不层叠隔离物而仅将加热接合用片层叠于半导体芯片之间，可以根据制造条件、用途等适当地变更。
另外，本发明的加热接合用片和带有切割带的加热接合用片不限定于上述例示的用途，可以将其利用于对两个物体进行加热接合。
《第2实施方式》
在第1实施方式的加热接合用片中，通过规定利用加热而烧结的前体层的最大厚度和最小厚度相对于平均厚度的比例来确保厚度均匀性，但是也可以取而代之、或者在其基础上从表面粗糙度的观点出发确保厚度均匀性。以下，关于第2实施方式的加热接合用片，仅对与第1实施方式不同的方面进行说明。
本实施方式的加热接合用片具有通过加热而成为烧结层的前体层，
前述前体层的平均厚度为5μm～200μm，并且
利用共聚焦显微镜以200μm×200μm的视野对前述前体层的表面进行计测时的表面粗糙度Sa为2μm以下。
该加热接合用片具有通过加热而成为烧结层的前体层，通过实施加热处理可得到烧结层，因此即使用于工作环境为高温的功率半导体装置等的接合也可以发挥高接合可靠性。另外，前体层的平均厚度为5μm～200μm，并且利用共聚焦显微镜以200μm×200μm的视野对前体层的表面进行计测时的表面粗糙度Sa为2μm以下。由此，可以抑制厚度方向上的凹凸，以高水平满足厚度的均匀性，其结果，能够防止接合不均、使高温接合可靠性提高。
前述表面粗糙度Sa为2μm以下即可，优选为1.5μm以下，更优选为1.0μm以下。
实施例
以下，使用实施例对本发明详细地进行说明，但本发明只要不脱离其宗旨，就并不限定于以下实施例。
＜实施例1＞
在搅拌用容器中放入作为含金属微粒糊剂的对应用纳米颗粒研究所制的ANP-1(分散有纳米尺寸的银微粒的糊剂)中所含的调整粘度用的溶剂量进行适当调整而得到的糊剂100重量份、作为热分解性粘结剂A的丙烯酸类树脂(藤仓化学株式会社制、“MM-2002-1”(在23℃下为固态)1重量份、以及溶剂(甲基乙基酮)35重量份，使用混合搅拌机(KEYENCE制、“HM-500”)以搅拌模式搅拌3分钟进行混合。将得到的清漆涂布于脱模处理薄膜(三菱树脂(株)制、“MRA50”)，使涂布膜在150℃干燥5分钟，得到厚度为40μm的加热接合用片。
＜实施例2＞
将在实施例1中得到的加热接合用片重叠5片，用层压机以80℃贴合，得到厚度为200μm的加热接合用片。
＜实施例3＞
在搅拌用容器中放入作为含金属微粒糊剂的对应用纳米颗粒研究所制的ANP-1(分散有纳米尺寸的银微粒的糊剂)中所含的调整粘度用的溶剂量进行适当调整而得到的糊剂100重量份、作为热分解性粘结剂B的聚碳酸亚丙酯树脂(Empower公司制、“QPAC40”(在23℃下为固态))1重量份、以及溶剂(甲基乙基酮)35重量份，使用混合搅拌机(KEYENCE制、“HM-500”)以搅拌模式搅拌3分钟进行混合。将得到的清漆涂布于脱模处理薄膜(三菱树脂(株)制、“MRA50”)，使涂布膜在150℃干燥5分钟，得到厚度为40μm的加热接合用片。
＜实施例4＞
将在实施例3中得到的加热接合用片重叠5片，用层压机以80℃贴合，得到厚度为200μm的加热接合用片。
＜比较例1＞
直接使用与实施例1相同的含金属微粒糊剂。
《评价》
针对以下项目，评价实施例和比较例的样品。将各自的结果在表1中示出。
(厚度评价(加热接合用片))
关于实施例1～4和比较例2的加热接合用片(以下也简称为“片”。)，在背面金属(Ti/Ag)硅晶圆(10cm×10cm)的背面侧贴附1cm×10cm的片。使用共聚焦显微镜(LaserTec(株)制、“H300”)，对贴附有片的硅晶圆背面(硅晶圆部分和片部分)用下述条件进行非接触计测，求出高度。
＜非接触计测条件＞
物镜：10倍
扫描时间：60秒
分辨率：0.03μm
从片高度h1减去硅晶圆高度h2来作为片厚度Ts(＝h1-h2)。测定部位设定为对1cm×10cm的区域进行十等分所得的1cm×1cm的区域的中心部，共测定10点。将10点的平均值作为平均厚度(μm)，将最大值(最大厚度)和最小值(最小厚度)处于平均厚度的±20％以内的范围内的情况评价为“○”，将超出±20％的范围的情况评价为“×”。将从最大厚度或最小厚度的平均厚度偏离的比例作为偏离率(％)求出。
(厚度评价(含金属微粒糊剂))
关于比较例1的含金属微粒糊剂(以下也简称为“糊剂”。)，在背面金属(Ti/Ag)硅晶圆的背面侧以1cm间隔贴附2根长度为12cm的粘合带(No.31B、宽度20mm、总厚度0.05mm(＝50μm))。将糊剂涂布到从粘合带之间露出的硅晶圆部分，以130℃使其干燥1分钟而将溶剂去除，形成干燥糊剂膜。接着，将粘合带剥离后，使用共聚焦显微镜(LaserTec(株)制、“H300”)，对形成有干燥糊剂膜的硅晶圆背面(硅晶圆部分和干燥糊剂膜部分)以与片的情况相同的条件进行非接触计测，求出高度。
从干燥糊剂膜高度h1′减去硅晶圆高度h2′作为干燥糊剂膜厚度Tp(＝h1′-h2′)。测定部位设定为对1cm×12cm的区域进行12等分并将两端的1cm×1cm的区域去除的1cm×1cm的区域的中心部，共测定10点。将10点的平均值作为平均厚度(μm)，将最大值(最大厚度)和最小值(最小厚度)处于平均厚度±20％以内的范围内的情况评价为“○”，将超出±20％的范围的情况评价为“×”。将从最大厚度或最小厚度的平均厚度偏离的比例作为偏离率(％)求出。
(表面粗糙度Sa评价(片))
用80℃的层压机在背面金属(Ti/Ag)硅晶圆(5cm×5cm)的背面侧以1cm见方以上的尺寸贴附片。使用共聚焦显微镜(LaserTec(株)制、“H300”)对片表面进行非接触计测，测定表面粗糙度Sa。
＜非接触计测条件＞
物镜：10倍
扫描时间：60秒
分辨率：0.03μm
将片的中心部中200μm×200μm的区域作为测定视野，对该区域的表面粗糙度Sa进行计测。将表面粗糙度Sa为2μm以下的情况评价为“○”，将超出2μm的情况评价为“×”。
(表面粗糙度Sa评价(糊剂))
在背面金属(Ti/Ag)硅晶圆(5cm×5cm)的背面侧以1cm见方以上的尺寸涂布糊剂，使得干燥后的厚度成为50μm。通过在130℃干燥1分钟而将多余的溶剂去除，形成干燥糊剂膜。使用共聚焦显微镜(LaserTec(株)制、“H300”)，对干燥糊剂膜表面以与片的情况相同的条件进行非接触计测，测定表面粗糙度Sa。
将片的中心部中200μm×200μm的区域作为测定视野，计测该区域的表面粗糙度Sa。将表面粗糙度Sa为2μm以下的情况评价为“○”，将超出2μm的情况评价为“×”。
(接合不均评价(片))
在5mm×5mm的背面金属(Ti/Ag)硅芯片的整个背面以80℃贴附片，将该带有片的芯片配置于镀银铜板(20mm×20mm，厚度3mm)上。用烧结装置((伯东)制、“HM-3000”)一边维持10MPa的压力载荷一边以300℃将片加热2.5分钟，将其制成烧结层，从而使芯片与镀银铜板隔着烧结层接合。针对接合的5个样品，用SAT(超声波影像装置、日立建机Fine Tech制、“FineSAT II”)的反射模式(换能器型号：PQ-50-13：WD、频率：50MHz)进行观察，确认在芯片与镀银铜板之间有无剥离。对5个样品分别求出剥离的部分相对于整个接合面的面积比例，将其平均值作为平均剥离面积率(％)。将平均剥离面积率为10％以下的情况评价为“○”，将超出10％的情况评价为“×”。
(接合不均评价(糊剂))
在5mm×5mm的背面金属(Ti/Ag)硅芯片的整个背面以厚度成为50μm的方式涂布糊剂。以130℃干燥1分钟而将多余的溶剂去除，形成干燥糊剂膜。将该带有干燥糊剂膜的芯片配置于镀银铜板(20mm×20mm，厚度3mm)上。用烧结装置((伯东)制、“HM-3000”)一边维持10MPa的压力载荷一边以300℃使芯片和镀银铜板隔着干燥糊剂膜接合2.5分钟，制成评价用的样品。针对接合的5个样品，以SAT(超声波影像装置、日立建机Fine Tech制、“FineSATII”)的反射模式(换能器型号：PQ-50-13：WD、频率：50MHz)进行观察，确认在芯片与镀银铜板之间有无剥离。对5个样品分别求出剥离部分相对于整个接合面的面积比例，将其平均值作为平均剥离面积率(％)。将平均剥离面积率为10％以下的情况评价为“○”，将超出10％的情况评价为“×”。
图5中示出使用实施例1的片和比较例1的糊剂分别制作的样品的SAT观察图像。图像中的白色部分是剥离的部位。
(可靠性评价-残存接合面积率)
用与上述接合不均评价同样的方法制作实施例和比较例的评价用样品。
接着，将评价用样品投入到冷热冲击试验机(ESPEC株式会社制的TSE-103ES)，施加-40℃～200℃的冷热冲击100周期(-40℃与200℃之间的升温和降温的时间约为10分钟。)。需要说明的是，此时，分别在-40℃和200℃的温度下保持15分钟。
在100周期后，为了对硅芯片和铜板在烧结层接合的部分进行确认而使用SAT(超声波影像装置、日立建机Fine Tech制、“FineSAT II”)进行撮像。使用的换能器(探针)是PQ-50-13：WD[频率为50MHz]。
在得到的图像中求出残留有接合的部分的面积(残存面积)，算出残存面积相对于整个接合面的面积的比例(残存接合面积率)。另外，将残存接合面积率为50％以上的情况评价为“○”，将低于50％的情况评价为“×”。需要说明的是，与接合不均评价的SAT图像观察同样，图像中的白色部分是剥离的部位(未图示)。
(重量减少率的评价(片))
从制作的加热接合用片按5mm×5mm的尺寸进行切取使其成为约10mg，作为测定样品。在大气气氛下、以10℃/分钟的升温速度在23℃至400℃对该测定样品进行差热-热重测定，读取23℃时的加热接合用片的重量W23和400℃时的加热接合用片的重量W400。将通过下述式得到的重量减少率ΔW在-9％～-3％的范围内的情况评价为“○”，将低于-9％或超过-3％的情况评价为“×”。
ΔW(％)＝{(W400-W23)/W23}×100
(重量减少率的评价(糊剂))
作为测定样品，除使用将含金属微粒糊剂涂布于脱模处理薄膜(三菱树脂(株)制、“MRA50”)上而形成的厚度为40μm的涂布液膜以外，用与前述片的重量减少率的测定同样的步骤求出。
[表1]
在实施例1～4中，厚度评价和表面粗糙度Sa均为良好，随之接合不均评价和可靠性评价均为良好的结果。另外，重量减少率的评价也为良好，可推测通过假定烧结工序的直至400℃的加热，有机成分基本被去除。另一方面，在比较例1中，厚度评价和表面粗糙度Sa均在范围外，由于该原因，接合不均评价和可靠性评价均为差的结果。推测其主要原因在于厚度不均导致的剥离面积变大。另外，重量减少率也大，认为对厚度的均匀性的降低带来影响。
附图标记说明
1 基材
2 粘合剂层
3、3’ 加热接合用片
4 半导体晶圆
5 半导体芯片
6 被粘物
7 接合引线
8 封装树脂
10、12 带有切割带的加热接合用片
11 切割带
30 双面带有隔离膜的加热接合用片
31 通过加热而成为烧结层的前体层
32 第1隔离膜
34 第2隔离膜

Claims (6)

1.一种加热接合用片，其具有通过加热而成为烧结层的前体层，
所述前体层的平均厚度为5μm～200μm，并且
所述前体层的最大厚度和最小厚度在所述平均厚度的±20％的范围内。
2.一种加热接合用片，其具有通过加热而成为烧结层的前体层，
所述前体层的平均厚度为5μm～200μm，并且
利用共聚焦显微镜以200μm×200μm的视野对所述前体层的表面进行计测时的表面粗糙度Sa为2μm以下。
3.根据权利要求1或2所述的加热接合用片，其中，
在大气气氛下、以10℃/分钟的升温速度在23℃至400℃进行差热-热重测定时，通过下述式得到的重量减少率ΔW为-9％～-3％，
ΔW(％)＝{(W400-W23)/W23}×100
式中，W23为23℃时的加热接合用片的重量，W400为400℃时的加热接合用片的重量。
4.根据权利要求1～3中的任一项所述的加热接合用片，其中，
所述前体层含有在23℃下为固态的热分解性粘结剂。
5.根据权利要求1～4中的任一项所述的加热接合用片，其中，
所述前体层含有金属微粒，
所述金属微粒为选自由银、铜、氧化银和氧化铜组成的组中的至少1种。
6.一种带有切割带的加热接合用片，其具有：
切割带、和
层叠于所述切割带上的权利要求1～5中的任一项所述的加热接合用片。
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CN107109146A (zh) * 2014-12-24 2017-08-29 日东电工株式会社 加热接合用片材和带有切割带的加热接合用片材
CN109478519A (zh) * 2016-08-31 2019-03-15 日东电工株式会社 加热接合用片材、及带有切割带的加热接合用片材
US11786966B2 (en) 2016-08-31 2023-10-17 Nitto Denko Corporation Sheet for heat bonding, and sheet for heat bonding having dicing tape

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