CN110603624A - 半导体密封成形用临时保护膜 - Google Patents

半导体密封成形用临时保护膜 Download PDF

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Publication number
CN110603624A
CN110603624A CN201880030197.XA CN201880030197A CN110603624A CN 110603624 A CN110603624 A CN 110603624A CN 201880030197 A CN201880030197 A CN 201880030197A CN 110603624 A CN110603624 A CN 110603624A
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CN
China
Prior art keywords
protective film
temporary protective
semiconductor
lead frame
adhesive layer
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Pending
Application number
CN201880030197.XA
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English (en)
Inventor
友利直己
名儿耶友宏
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Resonac Corp
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Hitachi Chemical Co Ltd
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Publication of CN110603624A publication Critical patent/CN110603624A/zh
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    • H01L23/293—Organic, e.g. plastic
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    • H01L21/568—Temporary substrate used as encapsulation process aid
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    • B32—LAYERED PRODUCTS
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    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Abstract

本发明公开一种半导体密封成形用临时保护膜(10)，其具备支撑膜(1)和设置在支撑膜(1)上且含有丙烯酸系橡胶的粘接层(2)。半导体密封成形用临时保护膜(10)的200℃下的固体剪切弹性模量可以为5.0MPa以上。

Description

半导体密封成形用临时保护膜
技术领域
本发明涉及半导体密封成形用临时保护膜。本发明还涉及带有临时保护膜的引线框、带有临时保护膜的密封成形体及半导体装置的制造方法。
背景技术
一直以来使用如下结构的半导体封装：利用银糊料等粘接剂将半导体元件粘接在芯片焊盘上，利用导线将其与引线框接合之后，残留外部连接用的外部引线而将整体密封。但是，随着近年的半导体封装的高密度化、小面积化、薄型化等要求的提高，提出了各种结构的半导体封装。作为这种半导体封装，开发了将仅对封装的单面(半导体元件一侧)进行密封而背面裸露出的引线框用于外部连接用的结构的半导体封装(例如QFN(QuadFlatNon-leaded，方形扁平无引脚)封装)。根据该结构的半导体封装，由于引线框不从密封树脂突出，因此可谋求小面积化及薄型化。但是，有时在密封成形时会发生密封树脂绕到引线框背面等不良情况。
作为防止这种不良情况的方法，已知有下述方法：将半导体用粘接膜作为临时保护膜粘贴在引线框背面，对引线框背面进行保护，在对搭载于引线框表面侧的半导体元件进行密封成形之后，将临时保护膜剥去(例如专利文献1)。
现有技术文献
专利文献
专利文献1：国际公开第2001/035460号
发明内容
发明要解决的技术问题
半导体密封成形中使用的临时保护膜期待能够在常温条件这样的低温下粘贴在引线框上、且在密封后简易地剥离。但是，例如专利文献1的半导体用粘接膜为了粘贴在引线框的背面而需要高温-高压条件(例如200～250℃、3～8MPa)，常温条件(未刻意控制温度的条件、例如24℃)下的粘贴是困难的。
另外，专利文献1的半导体用粘接膜为了密封后的剥离而优选进行加热处理。另一方面，在为常温下的粘贴性较为良好的膜时，在从密封后的引线框及密封材料上剥离时，有时在引线框一侧发生残胶等，在密封成形后的剥离性的方面仍有改善的余地。
因此，本发明的目的在于提供能够在常温下粘贴在引线框上、并且在密封成形后能够在抑制残胶的情况下容易地从引线框及密封层上剥离的半导体密封成形用临时保护膜。
用于解决技术问题的手段
本发明人们为了解决上述技术问题进行了深入研究，结果发现，通过使用特定的粘接层可以解决上述技术问题，从而完成了本发明。
本发明的一个方面涉及一种半导体密封成形用临时保护膜，其具备支撑膜和设置在上述支撑膜上且含有丙烯酸系橡胶的粘接层，上述临时保护膜的200℃下的固体剪切弹性模量为5.0MPa以上。
上述粘接层可以进一步含有剥离性赋予剂。上述剥离性赋予剂的含量可以相对于上述丙烯酸系橡胶100质量份为10质量份以上且小于60质量份。
上述粘接层的厚度可以为1μm以上且5μm以下。
上述支撑膜可以是聚酰亚胺膜。
上述丙烯酸系橡胶可以是含有选自(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸、丙烯腈、(甲基)丙烯酸2-羟基乙酯及(甲基)丙烯酸缩水甘油酯中的至少1种单体单元的共聚物。上述丙烯酸系橡胶的重均分子量可以是450000以上且900000以下。
上述粘接层可以在24℃下具有压敏粘接性。上述临时保护膜的5％重量减少温度可以是350℃以上。
上述半导体密封成形用临时保护膜可以进一步具备设置在上述粘接层的与设置有上述支撑膜的面相反一侧的面上的覆盖膜。
另外，本发明的一个方面涉及一种带有临时保护膜的引线框，其具备：具有芯片焊盘及内引线的引线框；和上述半导体密封成形用临时保护膜，临时保护膜按照其粘接层与引线框的单面接触的方式粘贴在引线框上。
另外，本发明的一个方面涉及一种带有临时保护膜的密封成形体，其具备：具有芯片焊盘及内引线的引线框；搭载于芯片焊盘的半导体元件；将半导体元件与内引线连接的导线；将半导体元件及导线密封的密封层；以及上述半导体密封成形用临时保护膜，临时保护膜的粘接层粘贴在引线框的与搭载有引线框的半导体元件的面相反一侧的面上。
另外，本发明的一个方面涉及一种制造半导体装置的方法，其依次具备下述工序：将上述半导体密封成形用临时保护膜以其粘接层与引线框接触的朝向来粘贴在具有芯片焊盘及内引线的所述引线框的单面上的工序；在芯片焊盘的与临时保护膜相反一侧的面上搭载半导体元件的工序；设置将半导体元件与内引线连接的导线的工序；形成将半导体元件及导线密封的密封层，从而获得具有引线框、半导体元件及密封层的密封成形体的工序；以及将临时保护膜从密封成形体上剥离的工序。
引线框具有多个芯片焊盘、在多个芯片焊盘的各个芯片焊盘上搭载半导体元件时，上述制造半导体装置的方法可以进一步具备下述工序：在将临时保护膜从密封成形体上剥离之前或之后，将密封成形体进行分割，获得具有1个芯片焊盘及半导体元件的半导体装置。
发明效果
根据本发明，可以提供能够在常温下粘贴于引线框上、并且在从密封成形后的引线框及密封材料上剥离时能够在抑制残胶的情况下容易地剥离的半导体密封成形用临时保护膜。
附图说明
图1为表示临时保护膜的一个实施方式的截面图。
图2为表示临时保护膜的一个实施方式的截面图。
图3为说明半导体装置的制造方法的一个实施方式的截面图。
图4为表示半导体装置的一个实施方式的截面图。
具体实施方式
以下对本发明的优选实施方式详细地进行说明。但本发明并不受以下实施方式所限定。本说明书中记载的数值范围的上限值及下限值可以任意地组合。实施例中记载的数值也可作为数值范围的上限值或下限值进行使用。
本说明书中，“(甲基)丙烯酸”是指“丙烯酸”及“甲基丙烯酸”。
＜临时保护膜＞
图1为表示一个实施方式的临时保护膜的截面图。图1所示的临时保护膜10由支撑膜1和设置在支撑膜1的单面上的粘接层2构成。也可在支撑膜1的两面上形成有粘接层。图2也是表示一个实施方式的临时保护膜的截面图。图2的临时保护膜10’具有支撑膜1、设置在支撑膜1的一个主面上的粘接层2、和设置在支撑膜1的另一个主面上且实质上没有粘接性的树脂层(非粘接层3)。这些临时保护膜在形成对搭载于引线框的半导体元件进行密封的密封层的密封成形的工序中，通过粘贴在引线框的背面(与搭载半导体元件的面相反一侧的面)上，可以在对引线框进行密封成形的期间作为用于临时保护的半导体密封成形用临时保护膜进行使用。
＜粘接层＞
粘接层含有丙烯酸系橡胶。丙烯酸系橡胶一般来说是含有(甲基)丙烯酸酯作为单体单元的共聚物。丙烯酸系橡胶例如是通过含有(甲基)丙烯酸酯与(甲基)丙烯酸、芳香族乙烯基化合物、氰化乙烯基化合物等其它单体的单体混合物的聚合反应所获得的共聚物。
作为构成丙烯酸系橡胶的(甲基)丙烯酸酯，例如可举出(甲基)丙烯酸丁酯(例如(甲基)丙烯酸正丁酯)、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲酯。(甲基)丙烯酸酯例如还可以是(甲基)丙烯酸2-羟基乙酯及(甲基)丙烯酸缩水甘油酯等具有反应性官能团的化合物。但是，丙烯酸系橡胶还可以是含有选自(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲酯中的至少1种(甲基)丙烯酸酯作为单体单元的主成分的共聚物。此时，由于在丙烯酸系橡胶的侧链上少有官能团，因此可抑制因热处理导致的与被粘接体表面的反应，粘接层从被粘接体上的剥离性变得更为良好。另外，当使用含有具有直链烃基的单体作为单体单元的丙烯酸系橡胶时，有粘接层在被粘接体上的润展性变得良好的倾向。这里，“主成分”是指相对于共聚物的总质量占50质量％以上的单体单元。
作为构成丙烯酸系橡胶的其它单体，例如可举出(甲基)丙烯酸及丙烯腈。
丙烯酸系橡胶含有选自(甲基)丙烯酸及(甲基)丙烯酸2-羟基乙酯中的至少1种作为单体单元时，丙烯酸系橡胶还可以具有羧基及/或羟基。可以将该羧基及/或羟基利用于与后述的剥离性赋予剂的反应。
丙烯酸系橡胶的玻璃化转变温度(Tg)从维持粘接层的常温下的粘贴性的观点出发，可以是-50～40℃、-40℃～30℃、或-30℃～20℃。当丙烯酸系橡胶的玻璃化转变温度为-50℃以上时，由于因热处理而润湿性减小，因而有剥离性的降低相对地被抑制的倾向。当丙烯酸系橡胶的玻璃化转变温度为20℃以下时，有常温下的粘贴性降低相对地被抑制的倾向。这里，丙烯酸系橡胶的玻璃化转变温度并无特别限定，一般来说是指利用差示扫描热量测定、差示热测定、动态粘弹性测定或热机械分析进行测定的值。
丙烯酸系橡胶可以是以选自(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯及(甲基)丙烯酸甲酯中的至少1种单体单元为主成分的共聚物、且丙烯酸系橡胶的玻璃化转变温度为-30℃～20℃。此时，在被粘接体上的润展性变得良好的同时，能够以特别高的水平兼顾粘接性及剥离性。
丙烯酸系橡胶的重均分子量从低排气性及凝聚力保持的观点出发，可以是400000以上、450000以上、或700000以上。丙烯酸系橡胶的重均分子量并无特别限定，可以是900000以下。这里的丙烯酸系橡胶的重均分子量是指利用凝胶渗透色谱法测定的值(利用标准聚苯乙烯的换算值)。
丙烯酸系橡胶还可以使用作为市售品获得者。作为丙烯酸系橡胶的市售品，例如可举出HTR-280DR(Nagasechemtex株式会社制、重均分子量为80万～90万)、WS-023EK30(Nagasechemtex株式会社制、重均分子量为45万～50万)。这些丙烯酸系橡胶可以单独使用1种，还可以组合使用2种以上。
粘接层中的丙烯酸系橡胶的含量以粘接层的质量为基准计，可以为50质量％以上、60质量％以上、70质量％以上、或80质量％以上，可以为100质量％以下。
含有丙烯酸系橡胶的粘接层可以具有常温下的良好的粘贴性。换而言之，粘接层可以在不刻意控制温度的例如24℃下具有压敏粘接性。“24℃下具有压敏粘接性”是指在不刻意控制温度的例如24℃的条件下、以20N的负荷将粘接层(40mm×160mm尺寸)与引线框(50mm×157mm尺寸)压接时、粘接层对引线框的粘接力为5N/m以上。此外，该粘接力可以按照后述实施例所记载的方法进行测定。
临时保护膜的200℃下的固体剪切弹性模量(以下也仅称作“固体剪切弹性模量”)为5.0MPa以上。临时保护膜的200℃下的固体剪切弹性模量可以是6MPa以上、8MPa以上、或10MPa以上，可以是25MPa以下、或20MPa以下。通过临时保护膜的固体剪切弹性模量在这些范围内，可进一步抑制密封成形后的引线框及密封层上的残胶。
这里的固体剪切弹性模量是指下述的值：将具有5mm×8mm尺寸的临时保护膜的试验片安装在固体剪切测定夹具上，使用动态粘弾性测定装置(例如株式会社UBM制、Rheogel-E4000)，在正弦波、30～250℃、升温速度为5℃/miN、频率为400Hz的条件下测定的值。作为试验片，使用由支撑膜及粘接层形成的层叠体。
这里，在半导体装置的制造中，引线接合工序例如是在一边于200～270℃下加热3～60分钟、一边利用超声波和按压压力的条件下进行。这种条件的引线接合工序中，由于粘接层变软，因此有时会发生无法准确地配置导线的不良情况。另外，还会发生因粘接层的热分解产生的排气会污染半导体元件及内引线面的不良情况。临时保护膜的固体剪切弹性模量为上述范围内时，还可进一步地抑制引线接合工序中的这些不良情况。
具有粘接层的厚度(膜厚)越薄、则固体剪切弹性模量越高的倾向。例如，就含有丙烯酸系橡胶的粘接层而言，通过将厚度在1～5μm的范围内进行调节，可以容易地使临时保护膜的200℃下的固体剪切弹性模量为5.0MPa以上。
粘接层的厚度从抑制或防止引线接合时的不良情况(例如导线的未粘接、断线、导线的粘接强度不足)的观点出发，可以是5μm以下或3μm以下。从相同的观点出发，粘接层的厚度(膜厚)可以是1μm以上、还可以是2μm以上。
粘接层还可以进一步含有剥离性赋予剂。剥离性赋予剂是指与粘接层不含该剥离性赋予剂的情况相比、使得密封成形后的粘接层对于引线框及/或密封层的粘接力得以降低的成分。
作为剥离性赋予剂，可以使用脂肪族化合物。脂肪族化合物是指具有直链状、支链状或脂环式烃基的化合物。脂肪族化合物可以具有选自环氧基及羟基中的至少1种官能团，还可以具有环氧基。换而言之，剥离性赋予剂可以是脂肪族环氧树脂。另外，脂肪族化合物还可以是水溶性的。从以上的观点出发，剥离性赋予剂可以含有具有含可具有侧链(分支)的碳数为2以上的主链的烃基及键合在主链末端的环氧基的脂肪族环氧树脂。具体地说，剥离性赋予剂可以含有选自(聚)乙二醇二缩水甘油基醚、山梨糖醇聚缩水甘油基醚及甘油聚缩水甘油基醚中的至少1种脂肪族化合物(或脂肪族环氧树脂)。这些脂肪族化合物可以单独使用1种，也可并用2种以上，从进一步抑制残胶的观点出发，可以并用2种以上。
丙烯酸系橡胶含有选自(甲基)丙烯酸及丙烯酸2-羟基乙酯中的至少1种作为单体单元、且使用具有环氧基的脂肪族化合物作为剥离性赋予剂时，从引线框及密封层上的剥离性变得更为良好、并且粘接层残留在引线框及密封层上时的洗涤处理变得更有效率。推测其原因在于，通过剥离性赋予剂的环氧基与丙烯酸系橡胶的侧链的羟基及/或羧基的反应，以相比较于丙烯酸系橡胶为低分子量体且具有溶解性的剥离性赋予剂为契机，洗涤性增加。
剥离性赋予剂的含量相对于丙烯酸系橡胶100质量份可以为6质量份以上、或10质量份以上，可以小于60质量份、50质量份以下、或30质量份以下。剥离性赋予剂的含量小于60质量份时，有抑制粘接层与支撑膜的密合性的降低、粘接层变得难以剥离的倾向。剥离性赋予剂的含量为6质量份以上时，有变得更容易确保充分的剥离性及洗涤性的倾向。
粘接层还可根据需要进一步含有其它的成分。作为其它的成分，例如可举出氨基醇酸树脂、脂肪酸。
粘接层对引线框及密封层的粘接力在密封成形后可以为450N/m以下、还可以为300N/m以下。密封成形后的对引线框及密封层的粘接力可以按照后述实施例记载的方法进行测定。
临时保护膜的5％重量减少温度可以为350℃以上。由此，排气量减少、引线接合性变得更为良好。临时保护膜的5％重量减少温度可以为500℃以下、还可以为450℃以下。5％重量减少温度可以使用差示热天平(例如Seiko Instruments株式会社制、SSC5200型)、在升温速度为10℃/分钟、空气环境气体下的条件下进行测定。
＜支撑膜＞
支撑膜并无特别限定，可以是耐热性树脂膜。使用耐热性树脂膜作为支撑膜时，即便是高温条件(例如200℃以上)，支撑膜也不会软化、操作性变得更为优异。具体地说，从耐热性提高的观点出发，支撑膜的玻璃化转变温度(Tg)可以为200℃以上、或250℃以上。
作为构成支撑膜的耐热性树脂，可举出芳香族聚酰亚胺、芳香族聚酰胺、芳香族聚酰胺酰亚胺、芳香族聚砜、芳香族聚醚砜、聚苯硫醚、芳香族聚醚酮、聚芳酯、芳香族聚醚醚酮、聚萘二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯等。
支撑膜从具有耐热性且可以进一步提高对粘接层的密合性的方面出发，可以是聚酰亚胺膜。使用聚酰亚胺膜作为支撑膜时，聚酰亚胺膜还可以经过等离子体处理、电晕处理、底涂处理等高密合处理。支撑膜对粘接层的密合性较低时，当将临时保护膜从引线框及密封层上剥下时，在粘接层与支撑膜的界面处会发剥离，粘接层易于残留在引线框及密封层一侧。由此，支撑膜优选对粘接层的密合性充分地高。
支撑膜的厚度(膜厚)并无特别限定，从使得与在将临时保护膜粘贴在引线框之后的引线框的翘曲等有关的残存应力降低的观点出发，可以是100μm以下、50μm以下、或25μm以下。支撑膜的厚度可以是5μm以上或10μm以上。
一个实施方式的临时保护膜中，支撑膜的厚度可以为5μm以上且50μm以下、粘接层的厚度可以为1μm以上且5μm以下。
＜覆盖膜＞
上述半导体密封成形用临时保护膜还可以具备设置于上述粘接层的与设置有上述支撑膜的面相反一侧的面上的覆盖膜。即，上述半导体密封成形用临时保护膜还可以是带有覆盖膜的半导体密封成形用临时保护膜的方式。上述覆盖膜并无特别限定，可以是聚对苯二甲酸乙二醇酯膜，还可以是设置有剥离层的聚对苯二甲酸乙二醇酯膜。
上述覆盖膜的厚度可以是10μm以上且100μm以下、或者20μm以上且100μm以下。
图2的实施方式的临时保护膜10’所具有的非粘接层3是在0～270℃下实质上没有对引线框的粘接性(或压敏粘接性)的树脂层。例如，具有高玻璃化转变温度的树脂层可以作为非粘接层发挥功能。具体地说，非粘接层例如可以是含有聚酰胺酰亚胺的树脂层。非粘接层的厚度并无特别限定，例如可以是1～10μm。
＜临时保护膜的制造方法＞
一个实施方式的临时保护膜例如可利用以下的方法进行制造。首先，将丙烯酸系橡胶与环己酮、甲乙酮等溶剂以及根据需要使用的剥离性赋予剂等其它成分进行混合，制作清漆。将所制作的清漆涂布在支撑膜的单面上之后，通过加热处理将溶剂从涂膜中除去，在支撑膜上形成粘接层。由此，可以获得二层结构的临时保护膜。
作为将清漆涂布在支撑膜的单面上的方法并无特别限定，例如可以使用辊涂法、反向辊涂法、凹版涂布法、棒涂法、逗号涂布法、模涂法、减压模涂法。
＜半导体装置的制造方法＞
通过含有使用了一个实施方式的临时保护膜的半导体元件的密封成形工序的方法，可以制造半导体装置。所制造的半导体装置例如可以具有引线框及担载于其上的半导体元件、和在引线框的半导体元件一侧将半导体元件密封的密封层、且引线框的背面为了外部连接用而露出的Non Lead Type Package(无引线型封装)。作为其具体例子，可举出QFN(Quad Flat Non-leaded Package，方形扁平无引脚封装)、SON(Small Outline Non-leaded Package，小外型无引脚封装)。
图3是表示一个实施方式的半导体装置的制造方法的截面图。图4是表示通过图3的制造方法获得的半导体装置的一个实施方式的截面图。以下根据需要参照各附图说明各工序。
图3实施方式的半导体装置的制造方法依次具备以下工序：将临时保护膜10以其粘接层与引线框接触的朝向来粘贴在具有芯片焊盘11a及内引线11b的所述引线框11的单面(背面)上的工序；在芯片焊盘11a的与临时保护膜10相反一侧的面上搭载(粘接)半导体元件14的工序；设置将半导体元件14与内引线11b连接的导线12的工序；形成将半导体元件14及导线12密封的密封层13、获得具有引线框11、半导体元件14及密封层13的密封成形体20的工序；以及将临时保护膜10从密封成形体20上剥离的工序。
临时保护膜10在引线框11上的粘贴可以在常温(例如5～35℃)下进行。粘贴的方法并无特别限定，例如可以是辊式层压法。
一个实施方式的带有临时保护膜的引线框具备具有芯片焊盘11a及内引线11b的引线框11、和临时保护膜10，临时保护膜10按照其粘接层2与引线框11的单面接触的方式粘贴在引线框11上。
引线框11的材质并无特别限定，例如可以是42合金等的铁系合金、铜、或铜系合金。使用铜及铜系合金的引线框时，还可以对引线框的表面实施钯、金、银等的被覆处理。为了提高与密封材料的密合力，还可以对引线框表面物理性地进行粗糙化处理。还可以对引线框表面实施防止银糊料渗出的树脂渗出(EBO，Epoxy bleed out)防止处理等化学性处理。
半导体元件14通常通过粘接剂(例如银糊料)搭载(粘接)在芯片焊盘11a上。还可以通过加热处理(例如140～200℃、30分钟～2小时)使粘接剂固化。
导线12并无特别限定，例如可以是金线、铜线或钯被覆铜线。例如，还可以在200～270℃下加热3～60分钟，利用超声波和按压压力使半导体元件及内引线与导线12接合。
在利用导线12进行引线接合之后、获得密封成形体20(形成密封层13)的密封成形的工序之前，也可对引线框11实施等离子体处理。通过等离子体处理，可以进一步提高密封层与引线框的密合性、进一步提高半导体装置的可靠性。作为等离子体处理，例如可举出在减压条件(例如9.33Pa以下)下以规定的气体流量注入氩气、氮气、氧气等气体并进行等离子体照射的方法。等离子体处理中的等离子体的照射输出功率例如可以为10～500W。另外，等离子体处理的时间例如可以为5～50秒钟。等离子体处理中的气体流量可以为5～50sccm。
密封成形的工序中，使用密封材料形成密封层13。通过密封成形，获得具有多个半导体元件14及将它们一并密封的密封层13的密封成形体20。在密封成形的期间，由于设置有临时保护膜10，可抑制密封材料绕到引线框11的背面侧。
一个实施方式的带有临时保护膜的密封成形体具备具有芯片焊盘11a及内引线11b的引线框11、搭载于芯片焊盘11a的半导体元件14、将半导体元件14与内引线11b连接的导线12、将半导体元件14及导线12密封的密封层13、以及临时保护膜10，临时保护膜10的粘接层2粘贴在引线框11的与搭载有半导体元件14的面相反一侧的面上。
形成密封层期间的温度(密封温度)可以是140～200℃、还可以是160～180℃。形成密封层期间的压力(密封压力)可以是6～15MPa、还可以是7～10MPa。密封成形的加热时间(密封时间)可以是1～5分钟、还可以是2～3分钟。
还可以根据需要将所形成的密封层13加热固化。用于密封层的固化的加热温度(密封固化温度)可以为150～200℃、还可以为160～180℃。用于密封层的固化的加热时间(密封固化时间)可以为4～7小时、还可以为5～6小时。
密封材料的材质并无特别限定，例如可举出甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、联苯二环氧树脂、萘酚酚醛清漆环氧树脂等环氧树脂。密封材料中例如可添加有填充物、溴化合物等阻燃性物质、蜡成分等添加材料
在形成密封层13(密封成形)之后，将临时保护膜10从所得的密封成形体20的引线框11及密封层13上剥离。将密封层固化时，可以在密封层的固化前或固化后的任一个时间点将临时保护膜10剥离。
剥离临时保护膜时的温度并无特别限定，可以是常温(例如5～35℃)。该温度还可以是粘接层的玻璃化转变温度以上。此时，临时保护膜对引线框及密封材料的剥离性变得更为良好。粘接层中的丙烯酸系橡胶的Tg例如为5℃以下或0℃以下时，粘接层的Tg变为与常温为同等以下，易于获得常温下的良好剥离性。
半导体装置的制造方法也可根据需要进一步包含在剥离工序后将残留在引线框11及密封层13上的粘接层(残胶)除去的工序。此时，例如可以使用溶剂将残留的粘接层除去。作为溶剂，例如可以使用二甲基亚砜、乙二醇、水。溶剂可以单独使用1种，也可混合使用2种以上。溶剂中也可添加有表面活性剂。溶剂含有水时，溶剂可以是调整为碱性的溶液(碱性溶液)。碱性溶液的pH可以是10以上或12以上。在利用溶剂进行除去的同时，还可根据需要进行机械刷洗。另外，还可以将密封层的毛边及氧化膜除去。
当引线框含有具有芯片焊盘及内引线的多个图案时，可以根据需要将密封成形体20分割，从而获得多个分别具有1个半导体元件的图4的半导体装置100。
即，当引线框11具有多个芯片焊盘11a、在多个芯片焊盘11a的各个芯片焊盘上分别搭载半导体元件14时，一个实施方式的制造方法可以进一步具备在将临时保护膜10从密封成形体20上剥离之前或之后将密封成形体20分割、从而获得具有1个芯片焊盘11a及半导体元件14的半导体装置100的工序。
使用一个实施方式的临时保护膜所制造的半导体装置在高密度化、小面积化、薄型化等方面是优异的，例如可以优选地利用于手机、智能手机、个人笔记本电脑、平板电脑等电子设备。
实施例
以下通过实施例对本发明进一步具体地进行说明，但本发明不受以下实施例所限定。
＜实施例1～15及比较例1～4的临时保护膜的制造＞
(涂饰用清漆的制作)
在具有表1或表2所示组成(单位：质量份)的树脂组合物中添加作为溶剂的环己酮并进行搅拌混合，获得不挥发成分为12质量％的清漆A～O。表中所示的丙烯酸系橡胶及剥离性赋予剂的详细情况如下。
丙烯酸系橡胶
·丙烯酸系橡胶Ai(Nagasechemtex株式会社制、商品名：WS-023EK30、重均分子量：50万)
·丙烯酸系橡胶Aii(Nagasechemtex株式会社制、商品名：HTR-280DR、重均分子量：90万)
·剥离性赋予剂Bi(Nagasechemtex株式会社制、商品名：EX-614B、山梨糖醇聚缩水甘油基醚、环氧当量：174)
·剥离性赋予剂Bii(Nagasechemtex株式会社制、商品名：EX-810、乙二醇二缩水甘油基醚、环氧当量：113)
[表1]
[表2]
(临时保护膜的制作)
实施例1～13
将所得清漆A～M分别涂布在支撑膜(聚酰亚胺膜、宇部兴产株式会社制、商品名：UPILEX25SGA、膜厚：25μm)上。将涂膜在90℃下加热2分钟、并在150℃下加热2分钟，从而进行干燥，在支撑膜上形成厚度为2μm的粘接层，获得实施例1～13的临时保护膜。对于实施例1～13的各临时保护膜，利用下述方法测定200℃下的固体剪切弹性模量。将结果示于表3。
固体剪切弹性模量的测定方法
把将临时保护膜剪切成5mm×8mm尺寸所获得的试验片安装在固体剪切测定夹具中，使用动态粘弹性测定装置(株式会社UBM制、Rheogel-E4000)，在正弦波、30～250℃、升温速度为5℃/miN、频率为400Hz的条件下测定固体剪切弹性模量。此外，输入厚度固定在0.1mm，使变形控制为1.95μm、1.95％。由测定结果读取200℃下的固体剪切弹性模量。
实施例14
除了使粘接层的厚度为1μm以外，与实施例1同样地获得实施例14的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为8.2MPa。
实施例15
除了使粘接层的厚度为5μm以外，与实施例1同样地获得实施例15的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为5.7MPa。
比较例1
除了使粘接层的厚度为6μm以外，与实施例1同样地获得比较例1的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为4.0MPa。
比较例2
除了使粘接层的厚度为8μm以外，与实施例1同样地获得比较例2的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为3.1MPa。
比较例3
除了使粘接层的厚度为10μm以外，与实施例1同样地获得比较例3的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为1.8MPa。
比较例4
将清漆O涂布在支撑膜(DU PONT-TORAY株式会社制、商品名：Kapton 100EN、膜厚：25μm)上。将涂膜在90℃下加热2分钟、并在150℃下加热2分钟，从而进行干燥，在支撑膜上形成厚度为5μm的粘接层，获得比较例4的临时保护膜。临时保护膜的200℃下的固体剪切弹性模量为3.2MPa。
＜比较例5的临时保护膜的制造＞
(涂饰用清漆的制作)
在安装有温度计、搅拌器、氮气导入管及分馏塔的5升四口烧瓶中，在氮气环境气体下加入2,2-双[4-(4-氨基苯氧基)苯基]丙烷270.9g(0.66摩尔)、1,3-双(3-氨基丙基)-四甲基二硅氧烷8.7g(0.035摩尔)，将它们溶解在N-甲基-2-吡咯烷酮1950g中。然后将该溶液冷却至0℃，在该温度下添加偏苯三酸酐酰氯149.5g(0.71摩尔)。偏苯三酸酐酰氯溶解之后，添加三乙基胺100g。在室温下持续搅拌2小时之后，升温至180℃，通过5小时的反应完成酰亚胺化。将反应液投入到甲醇中，将聚合物分离出。对其进行干燥之后，溶解在N-甲基-2-吡咯烷酮中，投入到甲醇中，再次将聚合物分离出。对分离出的聚合物进行减压干燥，获得经纯化的粉末状的聚醚酰胺酰亚胺。将该聚醚酰胺酰亚胺120g和硅烷偶联剂(Dow CorningToray株式会社制、商品名：SH6040)3.6g溶解在N-甲基-2-吡咯烷酮360g中，获得粘接层形成用的清漆P。
在安装有温度计、搅拌器、氮气导入管及分馏塔的5升四口烧瓶中，在氮气环境气体下添加2,2-双[4-(4-氨基苯氧基)苯基]丙烷172.4g(0.42摩尔)、4,4’-亚甲基双(2,6-二异丙基苯胺)153.7g(0.42摩尔)，将它们溶解在N-甲基-2-吡咯烷酮1550g中。然后将该溶液冷却至0℃，在该温度下添加偏苯三酸酐酰氯174.7g(0.83摩尔)。偏苯三酸酐酰氯溶解之后，添加三乙基胺130g。在室温下持续搅拌2小时之后，升温至180℃，通过5小时的反应完成酰亚胺化。将反应液投入到甲醇中，将聚合物分离出。对其进行干燥之后，溶解在N-甲基-2-吡咯烷酮中，投入到甲醇中，再次将聚合物分离出。对分离出的聚合物进行减压干燥，获得经纯化的粉末状的聚醚酰胺酰亚胺。将该聚醚酰胺酰亚胺120g和硅烷偶联剂(Dow CorningToray株式会社制、商品名：SH6040)6g溶解在N-甲基-2-吡咯烷酮360g中，获得非粘接层形成用的清漆Q。
(临时保护膜的制作)
将清漆P涂布在支撑膜(聚酰亚胺膜、宇部兴产株式会社制、商品名：UPILEX25SGA、膜厚：25μm)上，通过100℃下10分钟及300℃下10分钟的加热进行干燥，形成膜厚为8μm的粘接层。接着，在涂布粘接剂清漆后的支撑膜的背面涂布清漆Q，通过100℃下10分钟及300℃下10分钟的加热进行干燥，获得膜厚为6μm的非粘接层。由此，获得具有粘接层及非粘接层的比较例5的临时保护膜。临时保护膜的固体剪切弹性模量为21.0MPa。
＜评价＞
(粘接层的粘接力)
(1)常温粘贴后(常温下的粘贴性)
作为引线框，准备CDA194框(Cu、新光电气工业株式会社制)、及CDA194镀钯框(PPF、新光电气工业株式会社制)。使用手压辊，将实施例及比较例的各临时保护膜以粘接层(40mm×160mm尺寸)与引线框接触的朝向、在常温(24℃)、负荷为20N的条件下粘贴在这些引线框(50mm×157mm尺寸)上。之后，使用测力计在180°方向上以50mm/分钟的速度将各临时保护膜剥下，将此时的负荷最大值记录为粘接力。由此，评价各临时保护膜的常温下的粘贴性(压敏粘接性)。
但是，在为比较例5的临时保护膜时，由于粘接层的常温下的粘贴性弱，因此通过使用加热至230℃的压制机，使施加于带的压力为6MPa，并加压10秒钟，从而将粘接层粘贴在引线框上(以下的粘接力测定中也同样)。
(2)加热处理后(加热处理后的剥离性评价)
作为引线框，准备CDA194框(Cu、新光电气工业株式会社制)、及CDA194镀钯框(PPF、新光电气工业株式会社制)。使用手压辊，将实施例及比较例的各临时保护膜以粘接层(40mm×160mm尺寸)与引线框接触的朝向、在常温(24℃)、负荷为20N的条件下粘贴在这些引线框(50mm×157mm尺寸)上。之后，在空气环境气体下、在烘箱内以180℃下60分钟、200℃下60分钟、175℃下2分钟的顺序改变条件的同时对引线框及临时保护膜进行加热。之后，使用测力计在180°方向上以50mm/分钟的速度将各临时保护膜剥下，将此时的负荷最大值记录为粘接力。由此，评价各临时保护膜在相当于密封成形的条件下的加热处理后的自引线框上的剥离性。
(3)密封成形后(密封成形后的剥离性评价)
作为引线框，准备CDA194框(Cu、新光电气工业株式会社制)。使用手压辊，将实施例及比较例的各临时保护膜以粘接层(40mm×160mm尺寸)与引线框接触的朝向、在常温(24℃)、负荷为20N的条件下粘贴在上述引线框(50mm×157mm尺寸)上。之后，在空气环境气体下、在烘箱内以180℃下60分钟、200℃下60分钟的顺序改变条件的同时对引线框及临时保护膜进行加热。
接着，在氩气环境气体下(流量：20sccm)、150W、15秒的条件下、在引线框的与临时保护膜相反一侧的面上进行等离子体处理。之后，使用模塑成型机(Apicyamada株式会社制)在175℃、6.8MPa、2分钟的条件下进行密封成形，利用密封材料(商品名：GE-7470L-A、日立化成株式会社制)在引线框的与临时保护膜相反一侧的面上形成密封层。
之后，使用测力计在180°方向上以50mm/分钟的速度将各临时保护膜剥下，将把粘接层从密封层上剥下时的负荷最大值记录为对密封成形后的密封层的粘接力。由此，评价各临时保护膜的密封成形后的自密封层上的剥离性。
(4)密封层固化后(密封层固化后的剥离性评价)
作为引线框，准备CDA194框(Cu、新光电气工业株式会社制)、及CDA194镀钯框(PPF、新光电气工业株式会社制)。使用手压辊，将实施例及比较例的各临时保护膜以粘接层(40mm×160mm尺寸)与引线框接触的朝向、在常温(24℃)、负荷为20N的条件下粘贴在这些引线框(50mm×157mm尺寸)上。之后，在空气环境气体下、在烘箱内以180℃下60分钟、200℃下60分钟的顺序改变条件的同时对引线框及临时保护膜进行加热。在氩气环境气体下(流量：20sccm)、150W、15秒的条件下、在引线框的与临时保护膜相反一侧的面上进行等离子体处理。接着，使用模塑成型机(Apicyamada株式会社制)在175℃、6.8MPa、2分钟的条件下进行密封成形，利用密封材料(商品名：GE-7470L-A、日立化成株式会社制)在引线框的与临时保护膜相反一侧的面上形成密封层。进而，利用在烘箱中、空气环境气体下、180℃、5小时的加热，使密封层固化。在加热后，使用测力计在180°方向上以50mm/分钟的速度将各临时保护膜剥下，将把粘接层从引线框或密封层上剥下时的负荷最大值分别记录为对密封成形后的引线框或密封层的粘接力。由此，评价各临时保护膜的密封层固化后的剥离性。
(5)残胶
将实施例及比较例的临时保护膜以粘接层与引线框接触的朝向、在常温(24℃)、负荷为20N的条件下粘贴在CDA194框(Cu、新光电气工业株式会社制)上。在空气环境气体下、在烘箱内以180℃下60分钟、200℃下60分钟的顺序改变条件的同时对引线框及临时保护膜进行加热。在氩气环境气体下(流量：20sccm)、150W、15秒的条件下、在引线框的与临时保护膜相反一侧的面上进行等离子体处理。
使用模塑成型机(Apicyamada株式会社制)在175℃、6.8MPa、2分钟的条件下进行密封成形，利用密封材料(商品名：GE-7470L-A、日立化成株式会社制)在引线框的与临时保护膜相反一侧的面上形成密封层。
之后，在180°方向上以50mm/分钟的速度将各临时保护膜剥下，确认剥下后的密封层及引线框上的残胶的状态。根据有残胶部分的面积相对于密封层及引线框的表面合计起来的总面积的比例，按以下标准、以6个阶段来评价残胶。
5：60～100％(残留的粘接层整体都比较厚)
4：60～100％(残留的粘接层整体都比较薄)
3：30％以上且小于60％
2：10％以上且小于30％
1：超过0％且小于10％
0：0％
(6)5％重量减少温度
使用差示热天平(Seiko Instruments株式会社制、SSC5200型)，在空气环境气体下、以升温速度为10℃/分钟的条件测定实施例及比较例的各临时保护膜的5％重量减少温度。
将以上的评价结果示于表3及表4中。各实施例的临时保护膜在常温下可以粘贴在引线框上，且在密封成形后、在抑制残胶的情况下容易地从引线框及密封层上剥离了下来。
[表3]
[表4]
符号说明
1支撑膜、2粘接层、3非粘接层、10、10’临时保护膜、11引线框、11a芯片焊盘、11b内引线、12导线、13密封层、14半导体元件、20密封成形体、100半导体装置。

Claims (14)

1.一种半导体密封成形用临时保护膜，其具备支撑膜和设置在所述支撑膜上且含有丙烯酸系橡胶的粘接层，
所述临时保护膜的200℃下的固体剪切弹性模量为5.0MPa以上。
2.根据权利要求1所述的半导体密封成形用临时保护膜，其中，所述粘接层进一步含有剥离性赋予剂。
3.根据权利要求2所述的半导体密封成形用临时保护膜，其中，所述剥离性赋予剂的含量相对于所述丙烯酸系橡胶100质量份为6质量份以上且小于60质量份。
4.根据权利要求1～3中任一项所述的半导体密封成形用临时保护膜，其中，所述粘接层的厚度为1μm以上且5μm以下。
5.根据权利要求1～4中任一项所述的半导体密封成形用临时保护膜，其中，所述支撑膜为聚酰亚胺膜。
6.根据权利要求1～5中任一项所述的半导体密封成形用临时保护膜，其中，所述丙烯酸系橡胶是含有选自(甲基)丙烯酸丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸、丙烯腈、(甲基)丙烯酸2-羟基乙酯及(甲基)丙烯酸缩水甘油酯中的至少1种单体单元的共聚物。
7.根据权利要求1～6中任一项所述的半导体密封成形用临时保护膜，其中，所述丙烯酸系橡胶的重均分子量为450000以上且900000以下。
8.根据权利要求1～7中任一项所述的半导体密封成形用临时保护膜，其中，所述粘接层在24℃下具有压敏粘接性。
9.根据权利要求1～8中任一项所述的半导体密封成形用临时保护膜，其中，所述临时保护膜的5％重量减少温度为350℃以上。
10.根据权利要求1～9中任一项所述的半导体密封成形用临时保护膜，其进一步具备设置在所述粘接层的与设置有所述支撑膜的面相反一侧的面上的覆盖膜。
11.一种带有临时保护膜的引线框，其具备：
具有芯片焊盘及内引线的引线框；和
权利要求1～10中任一项所述的半导体密封成形用临时保护膜，
所述临时保护膜按照其粘接层与所述引线框的单面接触的方式粘贴在所述引线框上。
12.一种带有临时保护膜的密封成形体，其具备：
具有芯片焊盘及内引线的引线框；
搭载于所述芯片焊盘的半导体元件；
将所述半导体元件与所述内引线连接的导线；
将所述半导体元件及所述导线密封的密封层；以及
权利要求1～10中任一项所述的半导体密封成形用临时保护膜，
所述临时保护膜的粘接层粘贴在所述引线框的与搭载有所述半导体元件的面相反一侧的面上。
13.一种制造半导体装置的方法，其依次具备下述工序：
将权利要求1～10中任一项所述的半导体密封成形用临时保护膜以其粘接层与引线框接触的朝向来粘贴在具有芯片焊盘及内引线的所述引线框的单面上的工序；
在所述芯片焊盘的与所述临时保护膜相反一侧的面上搭载半导体元件的工序；
设置将所述半导体元件与所述内引线连接的导线的工序；
形成将所述半导体元件及所述导线密封的密封层，从而获得具有所述引线框、所述半导体元件及所述密封层的密封成形体的工序；以及
将所述临时保护膜从所述密封成形体上剥离的工序。
14.根据权利要求13所述的方法，其中，
所述引线框具有多个所述芯片焊盘，在所述多个芯片焊盘的各个芯片焊盘上搭载所述半导体元件，
所述方法进一步具备下述工序：在将所述临时保护膜从所述密封成形体上剥离之前或之后，将所述密封成形体进行分割，获得具有1个所述芯片焊盘及所述半导体元件的半导体装置。
CN201880030197.XA 2017-05-10 2018-01-25 半导体密封成形用临时保护膜 Pending CN110603624A (zh)

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