CN103563063A - 树脂组合物、使用其的半导体装置和半导体装置的制造方法 - Google Patents
树脂组合物、使用其的半导体装置和半导体装置的制造方法 Download PDFInfo
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- CN103563063A CN103563063A CN201280026092.XA CN201280026092A CN103563063A CN 103563063 A CN103563063 A CN 103563063A CN 201280026092 A CN201280026092 A CN 201280026092A CN 103563063 A CN103563063 A CN 103563063A
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- Prior art keywords
- resin combination
- resin
- methyl
- semiconductor element
- acid
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—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 soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49503—Lead-frames or other flat leads characterised by the die pad
- H01L23/49513—Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract
根据本发明,提供操作性优异的树脂组合物。本发明的膏状的树脂组合物将半导体元件和基材粘接,含有(A)热固性树脂和(B)金属颗粒。(B)金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的d95为10μm以下。换言之,粒径超过10μm的金属颗粒的体积比例小于5%。在此,d95表示累计体积比例为95%的粒径。
Description
技术领域
本发明涉及树脂组合物、使用该树脂组合物的半导体装置和半导体装置的制造方法。
本申请基于2011年5月31日在日本申请的特愿2011-121386号主张优先权,在此援用其内容。
背景技术
在半导体装置中,半导体元件通过粘接层固定在引线框、散热器或基板等基材上。这样的粘接层,除了要求具有粘接性以外,还要求具有导电性和热传导性,已知能够利用含有金属颗粒的膏状的树脂组合物形成这样的粘接层。例如,在专利文献1、2中记载有利用含有银颗粒的膏状的树脂组合物形成上述的粘接层。
现有技术文献
专利文献
专利文献1:日本特开平5-89721号公报
专利文献2:日本特开平7-118616号公报
发明内容
发明要解决的技术问题
这样的树脂组合物,为了得到期望的导电性和热传导性,含有大量金属颗粒。当含有大量金属颗粒时,树脂组合物的粘度增加,涂敷变得困难,因此需要使使用的树脂的粘度降低。
但是,金属颗粒的比重比树脂成分的比重大,因此,当树脂的粘度降低时,在使用过程中和放置过程中,金属颗粒的沉降速度变快。因此,含有大量金属颗粒的树脂组合物,不稳定并且粘度的经时变化大,难以操作。
另一方面,在将发光二极管元件或半导体激光元件等芯片宽度小的半导体元件粘接在基材上时,需要将少量的树脂组合物以高的厚度精度涂敷在基材上,通过压印(stamping)或利用极细针(needle)进行的分配(dispense)等来涂敷树脂组合物。
上述的树脂组合物,当在玻璃板等上较薄地铺展并开放时,粘度变化大,因此,存在不能很好地进行压印的情况。另外,存在上述的树脂组合物在极细针内粘度增加而在针内堵塞,不能很好地排出的情况。因此,含有大量金属颗粒的树脂组合物,特别不适合于将芯片宽度小的半导体元件粘接在基材上。
另一方面,专利文献2中记载有:通过使在热固性树脂中分散有银颗粒的树脂组合物含有平均粒径0.1~1.0μm的球状二氧化硅,能够抑制银颗粒的沉降。但是,球状二氧化硅是绝缘性的,因此,当使粘接层含有球状二氧化硅时,有导电性恶化的情况。另外,在该文献中记载有:当使银颗粒的粒径减小时,有某种程度的抑制金属颗粒沉降的效果,但是,树脂膏变成高粘度,涂敷操作性恶化。
本发明是鉴于上述的技术问题而做出的,其目的在于提供操作性优异的树脂组合物。
本发明人对树脂组合物的粘度经时变化的机理进行了潜心研究,结果发现原因在于粒径超过10μm的金属颗粒,从而完成了本发明。
用于解决技术问题的手段
即,根据本发明,提供一种树脂组合物,其为将半导体元件和基材粘接的膏状的树脂组合物,其特征在于:
包含热固性树脂和金属颗粒,
上述金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的d95为10μm以下。
通过使树脂组合物中包含的金属颗粒的d95为10μm以下,换言之,通过使粒径超过10μm的金属颗粒的体积比例小于5%,难以发生金属颗粒的沉降。因此,本发明的树脂组合物,粘度的经时变化小,且操作性优异。
另外,根据本发明,提供一种半导体装置,其特征在于,具备:
上述基材;
上述半导体元件;和
介于上述基材与上述半导体元件之间,将两者粘接的粘接层,
上述粘接层使用上述的树脂组合物形成。
另外,根据本发明,提供一种半导体装置的制造方法,其为上述的半导体装置的制造方法,其特征在于,包括:
在上述半导体元件和上述基材中的至少一个的粘接面上涂敷上述树脂组合物的工序;和
将上述半导体元件和上述基材压接,进行加热固化形成上述粘接层的工序。
发明效果
根据本发明,能够提供操作性优异的树脂组合物。
附图说明
图1是表示本实施方式的半导体装置的结构的剖面图。
具体实施方式
以下,对本发明的实施方式进行说明。
(树脂组合物)
本实施方式的膏状的树脂组合物将半导体元件和基材粘接,含有(A)热固性树脂和(B)金属颗粒。(B)金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的d95为10μm以下。换言之,粒径超过10μm的金属颗粒的体积比例小于5%。
在此,d95表示累计体积比例为95%的粒径。
当树脂组合物中包含的(B)金属颗粒的d95为10μm以下时,(B)金属颗粒在树脂组合物中的分散性良好,难以发生沉降。因此,本实施方式的树脂组合物,粘度变化小且操作性优异。
另外,在将发光二极管元件或半导体激光元件等芯片宽度小的半导体元件粘接在基材上时,需要通过压印(stamping)或利用极细针(needle)进行的分配(dispense)等,将少量的树脂组合物以高的厚度精度涂敷在基材上。对于压印所使用的树脂组合物,要求在玻璃板等上的粘度变化小,对于利用极细针进行的分配所使用的树脂组合物,要求在针中不发生树脂组合物的堵塞。
本实施方式的树脂组合物,粘度变化小且操作性优异,因此,能够通过压印或利用极细针进行的分配等,将少量的树脂组合物以高的厚度精度涂敷在基材上。因此,虽然没有特别限定,但是适合于将发光二极管元件或半导体激光元件等芯片宽度小的半导体元件粘接在基材上。
(热固性树脂)
(A)热固性树脂为通过加热形成三维网状结构的一般的热固性树脂。该(A)热固性树脂没有特别限定,优选为形成液态树脂组合物的材料,优选在室温为液态。例如,可以列举氰酸酯树脂、环氧树脂、在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂、马来酰亚胺树脂等。
(A)热固性树脂涉及的氰酸酯树脂是分子内具有-NCO基的化合物,是-NCO基通过加热发生反应而形成三维网状结构并固化的树脂,是进行固化的多官能氰酸酯化合物或其低分子聚合物。作为(A)热固性树脂涉及的氰酸酯树脂,没有特别限定,例如可以列举1,3-二氰酰基苯、1,4-二氰酰基苯、1,3,5-三氰酰基苯、1,3-二氰酰基萘、1,4-二氰酰基萘、1,6-二氰酰基萘、1,8-二氰酰基萘、2,6-二氰酰基萘、2,7-二氰酰基萘、1,3,6-三氰酰基萘、4,4’-二氰酰基联苯、双(4-氰酰基苯基)甲烷、双(3,5-二甲基-4-氰酰基苯基)甲烷、2,2-双(4-氰酰基苯基)丙烷、2,2-双(3,5-二溴-4-氰酰基苯基)丙烷、双(4-氰酰基苯基)醚、双(4-氰酰基苯基)硫醚、双(4-氰酰基苯基)砜、三(4-氰酰基苯基)亚磷酸酯、三(4-氰酰基苯基)磷酸酯等反应物、和通过线型酚醛树脂与卤化氰的反应得到的氰酸酯类等,还可以列举将这些多官能氰酸酯树脂的氰酸酯基三聚化而形成的具有三嗪环的预聚物。该预聚物能够通过例如将无机酸、路易斯酸等酸、醇钠、叔胺类等碱、碳酸钠等盐类作为催化剂使上述的多官能氰酸酯树脂单体聚合而得到。
作为(A)热固性树脂涉及的氰酸酯树脂的固化促进剂,可以列举一般公知的固化促进剂。例如,可以列举:辛酸锌、辛酸锡、环烷酸钴、环烷酸锌、乙酰丙酮铁等有机金属配位化合物;氯化铝、氯化锡、氯化锌等金属盐;和三乙胺、二甲基苄胺等胺类,但是并不限定于这些。这些固化促进剂可以单独使用1种或者并用2种以上。
另外,也能够将氰酸酯树脂与环氧树脂、氧杂环丁烷树脂、在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂、马来酰亚胺树脂等其他树脂并用。
(A)热固性树脂涉及的环氧树脂是分子内具有1个以上的缩水甘油基的化合物,是缩水甘油基通过加热发生反应而形成三维网状结构并固化的化合物。在(A)热固性树脂涉及的环氧树脂中,优选在1个分子中含有2个以上的缩水甘油基,这是因为仅是缩水甘油基为1个的化合物的情况下即使反应也不能显示充分的固化物特性。
作为(A)热固性树脂涉及的环氧树脂中的、在1个分子中含有2个以上的缩水甘油基的化合物,可以列举:将双酚A、双酚F、联苯酚等双酚化合物或它们的衍生物,氢化双酚A、氢化双酚F、氢化联苯酚、环己二醇、环己烷二甲醇、环己烷二乙醇等具有脂环结构的二醇或它们的衍生物,丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或它们的衍生物等进行环氧化而得到的2官能的化合物;具有三羟基苯基甲烷骨架或氨基苯酚骨架的3官能的化合物;将苯酚酚醛树脂、甲酚酚醛树脂、苯酚芳烷基树脂、联苯芳烷基树脂、萘酚芳烷基树脂等进行环氧化而得到的多官能的化合物等,但是并不限定于这些。另外,作为树脂组合物,优选在室温为液态,因此,(A)热固性树脂涉及的环氧树脂,优选单独在室温为液态的物质或作为混合物在室温为液态的物质。作为将二醇或其衍生物进行环氧化的方法,可以列举:使二醇或其衍生物的2个羟基与环氧氯丙烷反应,转化为缩水甘油醚,由此进行环氧化的方法等。另外,对于3官能以上的化合物,也是同样。
也能够像通常进行的那样使用反应性的稀释剂。作为反应性的稀释剂,可以列举苯基缩水甘油醚、叔丁基苯基缩水甘油醚、甲苯基缩水甘油醚等1官能的芳香族缩水甘油醚类、脂肪族缩水甘油醚类等。
作为(A)热固性树脂,在使用上述(A)热固性树脂涉及的环氧树脂的情况下,为了使环氧树脂固化,本实施方式的树脂组合物包含固化剂。
作为(A)热固性树脂涉及的环氧树脂的固化剂,例如,可以列举脂肪族胺、芳香族胺、双氰胺、二酰肼化合物、酸酐、酚树脂等。
作为(A)热固性树脂涉及的环氧树脂的固化剂的二酰肼化合物,可以列举己二酸二酰肼、十二烷酸二酰肼、间苯二甲酸二酰肼、对羟基苯甲酸二酰肼等羧酸二酰肼等。
作为环氧树脂的固化剂的酸酐,可以列举邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、4-甲基六氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、十二碳烯基琥珀酸酐、马来酸酐等。
作为(A)热固性树脂涉及的环氧树脂的固化剂的酚树脂,是在1个分子内具有2个以上的酚性羟基的化合物。在1个分子内具有1个酚性羟基的化合物的情况下,不能形成交联结构,因此,固化物特性恶化,不能使用。另外,作为(A)热固性树脂涉及的环氧树脂的固化剂的酚树脂,只要在1个分子内具有2个以上的酚性羟基即可,优选在1个分子内具有2个以上5个以下的酚性羟基,更优选在1个分子内具有2个或3个酚性羟基。在1个分子内的酚性羟基的数量比其多的情况下,分子量变得过大,因此,树脂组合物的粘度变得过高,因此不优选。作为这样的化合物,可以列举:双酚F、双酚A、双酚S、四甲基双酚A、四甲基双酚F、四甲基双酚S、二羟基二苯基醚、二羟基二苯甲酮、四甲基联苯酚、亚乙基双酚、甲基亚乙基双(甲基苯酚)、亚环己基双酚、联苯酚等双酚类及其衍生物;三(羟基苯基)甲烷、三(羟基苯基)乙烷等3官能的酚类及其衍生物;苯酚酚醛树脂、甲酚酚醛树脂等由酚类与甲醛反应得到的、以2核体或3核体为主的化合物及其衍生物等。
作为(A)热固性树脂涉及的环氧树脂的固化促进剂,可以列举咪唑类、三苯基膦或四苯基鏻的盐类、二氮杂双环十一碳烯等胺类化合物及其盐类等,优选2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑、2-苯基-4,5-二羟甲基咪唑、2-C11H23-咪唑、以及2-甲基咪唑与2,4-二氨基-6-乙烯基三嗪的加成物等咪唑化合物。其中,特别优选的是熔点为180℃以上的咪唑化合物。另外,环氧树脂也优选与氰酸酯树脂、在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂、马来酰亚胺树脂并用。
(A)热固性树脂涉及的在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂,是分子内具有碳-碳双键的化合物,是碳-碳双键发生反应而形成三维网状结构并固化的树脂。
在(A)热固性树脂涉及的在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂中,(A)的分子量优选为500以上50000以下。这是因为:在(A)的分子量小于上述范围的情况下,粘接层的弹性模量变得过高,在(A)的分子量大于上述范围的情况下,树脂组合物的粘度变得过高。
以下例示优选的在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂,但是并不限定于这些。
作为在1个分子内具有2个以上的丙烯酰基的化合物,优选的是分子量为500以上50000以下的聚醚、聚酯、聚碳酸酯、聚(甲基)丙烯酸酯、聚丁二烯、丁二烯丙烯腈共聚物且在1个分子内具有2个以上的丙烯酰基的化合物。
作为聚醚,优选碳原子数3~6的有机基团经由醚键重复而得到的聚醚,优选不含芳香族环的聚醚。这是因为:在含有芳香族环的情况下,作为在1个分子内具有2个以上的丙烯酰基的化合物,变成固态或者高粘度,而且在形成为固化物的情况下的弹性模量变得过高。另外,在1个分子内具有2个以上的丙烯酰基的化合物的分子量,如上所述优选为500以上50000以下,更优选为500以上5000以下,特别优选为500以上2000以下。这是因为:当分子量在上述范围时,能得到操作性良好、且弹性模量低的粘接层。这样的在1个分子内具有2个以上的丙烯酰基的聚醚化合物,能够通过聚醚多元醇与(甲基)丙烯酸及其衍生物的反应而得到。
作为聚酯,优选碳原子数3~6的有机基团经由酯键重复而得到的聚酯,优选不含芳香族环的聚酯。这是因为:在含有芳香族环的情况下,作为在1个分子内具有2个以上的丙烯酰基的化合物,变成固态或者高粘度,而且在形成为固化物的情况下的弹性模量变得过高。另外,在1个分子内具有2个以上的丙烯酰基的化合物的分子量,如上所述优选为500以上50000以下,更优选为500以上5000以下,特别优选为500以上2000以下。这是因为:当分子量在上述范围时,能得到操作性良好、且弹性模量低的粘接层。这样的在1个分子内具有2个以上的丙烯酰基的聚酯化合物,能够通过聚酯多元醇与(甲基)丙烯酸及其衍生物的反应而得到。
作为聚碳酸酯,优选碳原子数3~6的有机基团经由碳酸酯键重复而得到的聚碳酸酯,优选不含芳香族环的聚碳酸酯。这是因为:在含有芳香族环的情况下,作为在1个分子内具有2个以上的丙烯酰基的化合物,变成固态或者高粘度,而且在形成为固化物的情况下的弹性模量变得过高。另外,在1个分子内具有2个以上的丙烯酰基的化合物的分子量,如上所述优选为500以上50000以下,更优选为500以上5000以下,特别优选为500以上2000以下。这是因为:当分子量在该范围时,能得到操作性良好、且弹性模量低的粘接层。这样的在1个分子内具有2个以上的丙烯酰基的聚碳酸酯化合物,能够通过聚碳酸酯多元醇与(甲基)丙烯酸及其衍生物的反应而得到。
作为聚(甲基)丙烯酸酯,优选(甲基)丙烯酸与(甲基)丙烯酸酯的共聚物或具有羟基的(甲基)丙烯酸酯与不具有极性基团的(甲基)丙烯酸酯的共聚物、具有缩水甘油基的(甲基)丙烯酸酯与不具有极性基团的(甲基)丙烯酸酯的共聚物等。另外,在1个分子内具有2个以上的丙烯酰基的化合物的分子量,如上所述优选为500以上50000以下,更优选为500以上25000以下。这是因为:当分子量在该范围时,能得到操作性良好、且弹性模量低的粘接层。这样的在1个分子内具有2个以上的丙烯酰基的(甲基)丙烯酸酯化合物,在具有羧基的共聚物的情况下,能够通过与具有羟基的(甲基)丙烯酸酯或者具有缩水甘油基的(甲基)丙烯酸酯反应而得到,在具有羟基的共聚物的情况下,能够通过与(甲基)丙烯酸及其衍生物反应而得到,在具有缩水甘油基的共聚物的情况下,能够通过与(甲基)丙烯酸及其衍生物反应而得到。
作为聚丁二烯,能够通过具有羧基的聚丁二烯与具有羟基的(甲基)丙烯酸酯或具有缩水甘油基的(甲基)丙烯酸酯的反应、具有羟基的聚丁二烯与(甲基)丙烯酸及其衍生物的反应而得到,另外,也能够通过加成有马来酸酐的聚丁二烯与具有羟基的(甲基)丙烯酸酯的反应而得到。
作为丁二烯丙烯腈共聚物,能够通过具有羧基的丁二烯丙烯腈共聚物与具有羟基的(甲基)丙烯酸酯或具有缩水甘油基的(甲基)丙烯酸酯的反应而得到。
作为在1个分子内具有2个以上的烯丙基的化合物,优选的是分子量为500以上50000以下的聚醚、聚酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丁二烯、丁二烯丙烯腈共聚物且具有烯丙基的化合物,例如为乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸以及它们的衍生物等二羧酸及其衍生物和烯丙醇反应而得到的二烯丙酯化合物与乙二醇、丙二醇、1,4-丁二醇等二醇的反应物等。
作为在1个分子内具有2个以上的马来酰亚胺基的化合物,优选的例如可以列举N,N’-(4,4’-二苯基甲烷)双马来酰亚胺、双(3-乙基-5-甲基-4-马来酰亚胺苯基)甲烷、2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷等双马来酰亚胺化合物。更优选的是:通过二聚酸二胺与马来酸酐的反应得到的化合物;通过马来酰亚胺乙酸、马来酰亚胺己酸等马来酰亚胺化氨基酸与多元醇的反应得到的化合物。马来酰亚胺化氨基酸通过使马来酸酐与氨基乙酸或氨基己酸反应而得到,作为多元醇,优选聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚丙烯酸酯多元醇、聚甲基丙烯酸酯多元醇,特别优选不含芳香族环。这是因为:在含有芳香族环的情况下,作为在1个分子内具有2个以上的马来酰亚胺基的化合物,变成固态或者高粘度,而且在形成为固化物的情况下的弹性模量变得过高。
另外,为了调整本实施方式的树脂组合物的各项特性,也能够在不损害(A)热固性树脂的效果的范围内使用以下的化合物。例如,可以列举:(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-3-羟丙酯、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸-3-羟丁酯、(甲基)丙烯酸-4-羟丁酯、丙三醇单(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、三羟甲基丙烷单(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、季戊四醇单(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、新戊二醇单(甲基)丙烯酸酯等具有羟基的(甲基)丙烯酸酯或使这些具有羟基的(甲基)丙烯酸酯与二羧酸或其衍生物反应而得到的具有羧基的(甲基)丙烯酸酯等。在此作为能够使用的二羧酸,例如,可以列举乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸和它们的衍生物。
除上述以外,也能够使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸-2-乙基己酯、其他的(甲基)丙烯酸烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸缩水甘油酯、三羟甲基丙烷三(甲基)丙烯酸酯、单(甲基)丙烯酸锌、二(甲基)丙烯酸锌、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸新戊二醇酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸-2,2,3,3-四氟丙酯、(甲基)丙烯酸-2,2,3,3,4,4-六氟丁酯、(甲基)丙烯酸全氟辛酯、(甲基)丙烯酸全氟辛基乙酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、乙氧基二乙二醇(甲基)丙烯酸酯、N,N’-亚甲基双(甲基)丙烯酰胺、N,N’-亚乙基双(甲基)丙烯酰胺、1,2-二(甲基)丙烯酰胺乙二醇、二(甲基)丙烯酰氧基甲基三环癸烷、N-(甲基)丙烯酰氧基乙基马来酰亚胺、N-(甲基)丙烯酰氧基乙基六氢邻苯二甲酰亚胺、N-(甲基)丙烯酰氧基乙基邻苯二甲酰亚胺、n-乙烯基-2-吡咯烷酮、苯乙烯衍生物、α-甲基苯乙烯衍生物等。
另外,作为(A)热固性树脂涉及的在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂的聚合引发剂,优选使用热自由基聚合引发剂。只要是通常作为热自由基聚合引发剂使用的聚合引发剂就没有特别限定,作为优选的热自由基聚合引发剂,优选在快速加热试验(将1g试样放置在电热板上,以4℃/分钟升温时的分解开始温度)中分解温度为40℃以上140℃以下的热自由基聚合引发剂。当分解温度小于40℃时,树脂组合物在常温的保存性变差,当分解温度超过140℃时,固化时间变得非常长,因此不优选。
作为满足上述条件的热自由基聚合引发剂的具体例子,可以列举过氧化甲乙酮、过氧化甲基环己酮、过氧化乙酰乙酸甲酯、过氧化乙酰丙酮、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、1,1-双(叔己基过氧基)环己烷、1,1-双(叔己基过氧基)-3,3,5-三甲基环己烷、1,1-双(叔丁基过氧基)环己烷、2,2-双(4,4-二叔丁基过氧化环己基)丙烷、1,1-双(叔丁基过氧基)环十二烷、4,4-双(叔丁基过氧基)戊酸正丁酯、2,2-双(叔丁基过氧基)丁烷、1,1-双(叔丁基过氧基)-2-甲基环己烷、叔丁基过氧化氢、萜烷过氧化氢、1,1,3,3-四甲基丁基过氧化氢、叔己基过氧化氢、过氧化二异丙苯、2,5-二甲基-2,5-双(叔丁基过氧基)己烷、α,α’-双(叔丁基过氧基)二异丙苯、叔丁基过氧化异丙苯、过氧化二叔丁基、2,5-二甲基-2,5-双(叔丁基过氧基)-3-己炔、过氧化异丁酰、过氧化3,5,5-三甲基己酰、过氧化辛酰、过氧化月桂酰、过氧化肉桂酸、过氧化间甲苯酰、过氧化苯甲酰、过氧化二碳酸二异丙酯、过氧化二碳酸双(4-叔丁基环己酯)、过氧化二碳酸二-3-甲氧基丁酯、过氧化二碳酸二-2-乙基己酯、过氧化二碳酸二仲丁酯、过氧化二碳酸二(3-甲基-3-甲氧基丁酯)、过氧化二碳酸二(4-叔丁基环己酯)、α,α’-双(新癸酰基过氧基)二异丙苯、过氧化新癸酸异丙苯酯、过氧化新癸酸-1,1,3,3-四甲基丁酯、过氧化新癸酸-1-环己基-1-甲基乙酯、过氧化新癸酸叔己酯、过氧化新癸酸叔丁酯、过氧化新戊酸叔己酯、过氧化新戊酸叔丁酯、2,5-二甲基-2,5-双(2-乙基己酰基过氧基)己烷、过氧化-2-乙基己酸-1,1,3,3-四甲基丁酯、过氧化-2-乙基己酸-1-环己基-1-甲基乙酯、过氧化-2-乙基己酸叔己酯、过氧化-2-乙基己酸叔丁酯、过氧化异丁酸叔丁酯、过氧化马来酸叔丁酯、过氧化月桂酸叔丁酯、过氧化-3,5,5-三甲基己酸叔丁酯、过氧化异丙基单碳酸叔丁酯、过氧化-2-乙基己基单碳酸叔丁酯、2,5-二甲基-2,5-双(苯甲酰基过氧基)己烷、过氧化乙酸叔丁酯、过氧化苯甲酸叔己酯、过氧化间甲苯酰苯甲酸叔丁酯、过氧化苯甲酸叔丁酯、双(叔丁基过氧基)间苯二甲酸酯、过氧化烯丙基单碳酸叔丁酯、3,3’,4,4’-四(叔丁基过氧化羰基)二苯甲酮等,这些能够单独使用,或者也能够为了控制固化性而将2种以上混合使用。另外,上述的在1个分子内具有2个以上的自由基聚合性的碳-碳双键的树脂也优选与氰酸酯树脂、环氧树脂、马来酰亚胺树脂并用。
(A)热固性树脂涉及的马来酰亚胺树脂是在1个分子内含有1个以上的马来酰亚胺基的化合物,是马来酰亚胺基通过加热发生反应而形成三维网状结构并固化的化合物。例如,可以列举N,N’-(4,4’-二苯基甲烷)双马来酰亚胺、双(3-乙基-5-甲基-4-马来酰亚胺苯基)甲烷、2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷的反应物等双马来酰亚胺树脂。更优选的(A)热固性树脂涉及的马来酰亚胺树脂为:通过二聚酸二胺与马来酸酐的反应得到的化合物;通过马来酰亚胺乙酸、马来酰亚胺己酸等马来酰亚胺化氨基酸与多元醇的反应得到的化合物。马来酰亚胺化氨基酸通过使马来酸酐与氨基乙酸或氨基己酸反应而得到,作为多元醇,优选聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚(甲基)丙烯酸酯多元醇,特别优选不含芳香族环。马来酰亚胺基能够与烯丙基发生反应,因此也优选与烯丙酯树脂并用。作为烯丙酯树脂,优选脂肪族的烯丙酯树脂,其中特别优选的是通过环己烷二烯丙酯与脂肪族多元醇的酯交换得到的化合物。另外,也优选与氰酸酯树脂、环氧树脂、丙烯酸树脂并用。
(A)热固性树脂的配合量,在全部树脂组合物中,为2重量%以上40重量%以下,优选为5重量%以上35重量%以下。通过使(A)热固性树脂的配合量在该范围,树脂组合物的操作性和耐热性等更加优异。
(金属颗粒)
作为(B)金属颗粒,只要d95为10μm以下就没有特别限定,因为导电性和热传导性优异,所以优选列举银颗粒。另外,除了银以外,能够使用例如由铜、金、镍、钯、铝、锡、锌等形成的金属颗粒、和这些金属的合金颗粒等中的至少1种以上。
在此,作为银颗粒,包括将由铜、金、镍、钯、铝、锡、锌等形成的金属颗粒的表面用银包覆而得到的金属颗粒。
(B)金属颗粒的形状没有特别限定,优选为鳞片形状或椭球形状。当金属颗粒的形状为鳞片形状或椭球形状时,得到的粘接层的热传导性和导电性特别优异。
另外,(B)金属颗粒的粒径根据需要的树脂组合物的粘度而不同,通常优选金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的中位径d50为0.5μm以上8μm以下,更优选为0.6μm以上6μm以下。在中位径d50小于0.5μm的情况下,粘度变高,当中位径d50超过8μm时,在涂敷或固化时树脂成分容易流出而发生渗出,因此不优选。另外,当中位径d50超过8μm时,在用分配器(dispenser)涂敷树脂组合物时,有将针的出口堵塞而不能长时间连续使用的情况。另外,在金属颗粒的粒径分布中,优选其峰为1个(为单峰性的)。
另外,使用的(B)金属颗粒,优选卤素离子、碱金属离子等离子性杂质的含量为10ppm以下。此外,本实施方式中使用的(B)金属颗粒,也可以使用预先将表面用烷氧基硅烷、酰氧基硅烷、硅氮烷、有机氨基硅烷等硅烷偶联剂等处理后的颗粒。
另外,(B)金属颗粒的配合量,相对于全部树脂组合物100重量份,优选为50重量份以上95重量份以下,更优选为60重量份以上90重量份以下。通过使(B)金属颗粒的配合量在该范围,能够得到良好的热传导性和导电性,操作性也优异。在树脂组合物中的(B)金属颗粒小于50重量份的情况下,(B)金属颗粒由(A)热固性树脂覆盖,有可能不能赋予(B)金属颗粒与重力方向平行的排列,当树脂组合物中的(B)金属颗粒超过95重量份时,树脂组合物的粘度变高,操作性降低,树脂组合物的固化物变脆,因此,有可能耐焊接性降低,不优选。
(绝缘颗粒)
另外,在本实施方式的树脂组合物中,还可以包含(C)绝缘颗粒。作为(C)绝缘颗粒,没有特别限定,例如,可以列举二氧化硅颗粒或氧化铝等无机填料、有机聚合物等有机填料。
(C)绝缘颗粒优选为能够使含有的(B)金属颗粒进行排列的颗粒,另外在用于半导体用途的情况下,进一步优选为粒径一致的颗粒。另外,(C)绝缘颗粒如果是用于对本实施方式的粘接层1赋予低热膨胀性、低吸湿率等,将粘接层1的厚度在固化后保持为一定的绝缘颗粒,则更优选。
另外,(C)绝缘颗粒没有特别限定,优选通过流动式颗粒图像解析装置得到的体积基准粒度分布中的d95为10μm以下。当树脂组合物中包含的(C)绝缘颗粒的d95为10μm以下时,(C)绝缘颗粒或(B)金属颗粒的沉降或凝集更加难以发生,操作性更加优异。
另外,(C)绝缘颗粒的粒径根据需要的树脂组合物的粘度而不同,通常,(C)绝缘颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的中位径d50优选为2μm以上8μm以下,更优选为3μm以上7μm以下。在中位径d50小于2μm的情况下,粘度变高,因此不优选。另外,当中位径d50为2μm以上时,能够更高效率地使(B)金属颗粒以长轴相对于重力方向平行的方式排列。
另外,当中位径d50超过8μm时,在涂敷或固化时树脂成分容易流出而发生渗出,因此不优选。另外,当中位径d50为8μm以下时,能够更高效率地使(B)金属颗粒以长轴相对于重力方向平行的方式排列。
另外,(C)绝缘颗粒的配合量,相对于全部树脂组合物100重量份,优选为5重量份以上30重量份以下,通过使(C)绝缘颗粒的配合量在该范围,能够得到良好的热传导性和导电性,操作性也优异。在树脂组合物中的(C)绝缘颗粒小于5重量份的情况下,有可能不能使(B)金属颗粒与重力方向平行地排列,当树脂组合物中的(C)绝缘颗粒超过30重量份时,树脂组合物的粘度变高,操作性降低,树脂组合物的固化物变脆,有可能耐焊接性降低,因此不优选。
作为无机填料,具体而言,可以列举氮化铝、碳酸钙、二氧化硅、氧化铝等。无机填料优选为能够使(B)金属颗粒进行排列的无机填料,另外在用于半导体用途的情况下,进一步优选为粒径一致的无机填料。另外,无机填料如果是用于对粘接层1赋予低热膨胀性、低吸湿率等,将粘接层1的厚度保持为一定的无机填料,则更优选。其中,特别优选二氧化硅或氧化铝。
作为有机填料,具体而言,可以列举苯乙烯类、苯乙烯/异戊二烯类、苯乙烯/丙烯酸类、甲基丙烯酸甲酯类、丙烯酸乙酯类、丙烯酸类、甲基丙烯酸乙酯类、丙烯腈类、甲基丙烯酸酯类、二乙烯基苯类、丙烯酸正丁酯类、尼龙类、有机硅类、聚氨酯类、三聚氰胺类、纤维素、乙酸纤维素、壳聚糖、丙烯酸橡胶/甲基丙烯酸酯类、乙烯类、乙烯/丙烯酸类、聚丙烯或苯并胍胺类、酚类、氟类、偏氯乙烯等的聚合物等。
有机填料优选为能够使(B)金属颗粒进行排列的有机填料,另外在用于半导体用途的情况下,进一步优选为粒径一致的有机填料。另外,有机填料如果是用于对粘接层1赋予低热膨胀性、低吸湿率等,将粘接层1的厚度保持为一定的有机填料,则更优选。其中,特别优选以聚甲基丙烯酸甲酯为主要成分的交联有机聚合物。
在本实施方式的树脂组合物中,优选进一步含有:环氧硅烷、巯基硅烷、氨基硅烷、烷基硅烷、脲基硅烷、乙烯基硅烷等硅烷偶联剂;钛酸酯偶联剂、铝偶联剂、铝/锆偶联剂等偶联剂。
在本实施方式的树脂组合物中,根据需要可以使用其他添加剂。作为其他添加剂,可以列举:炭黑等着色剂;硅油、硅橡胶等低应力化成分;水滑石等无机离子交换体;消泡剂;表面活性剂;各种阻聚剂;抗氧化剂等,可以适当配合这些各种添加剂。
另外,在本实施方式的树脂组合物中,能够根据需要在不对形成为固化物时的(B)金属颗粒的排列产生影响的范围内添加有机化合物。作为例子,可以列举:己烷、2-甲基戊烷、2,2-二甲基丁烷、2,3-二甲基丁烷、庚烷、辛烷、2,2,3-三甲基戊烷、异辛烷、壬烷、2,2,5-三甲基己烷、癸烷、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、乙苯、异丙苯、均三甲苯、丁苯、对异丙基苯甲烷、二乙苯、甲基环戊烷、环己烷、甲基环己烷、乙基环己烷、萜烷、环己烯、α-蒎烯、双戊烯、十氢化萘、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、异丁醇、叔丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、异戊醇、叔戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、4-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、3,5,5-三甲基-1-己醇、环己醇、1-甲基环己醇、2-甲基环己醇、3-甲基环己醇、4-甲基环己醇、松香醇、1,2-乙二醇、1,2-丙二醇、1,2-丁二醇、2-甲基-2,4-戊二醇、二丙醚、二异丙醚、二丁醚、苯甲醚、苯乙醚、甲氧基甲苯、苄基乙基醚、2-甲基呋喃、四氢呋喃、四氢吡喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、乙缩醛、丙酮、甲基乙基酮、2-戊酮、3-戊酮、2-己酮、甲基异丁基酮、2-庚酮、4-庚酮、二异丁基酮、丙酮基丙酮、异亚丙基丙酮、佛尔酮、环己酮、甲基环己酮、丙酸、丁酸、异丁酸、三甲基乙酸、正戊酸、异戊酸、2-乙基丁酸、丙酸酐、丁酸酐、甲酸乙酯、甲酸丙酯、甲酸丁酯、甲酸异丁酯、甲酸戊酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸异丙酯、乙酸丁酯、乙酸异丁酯、乙酸仲丁酯、乙酸戊酯、乙酸异戊酯、乙酸-3-甲氧基丁酯、乙酸仲己酯、乙酸-2-乙基丁酯、乙酸-2-乙基己酯、乙酸环己酯、丙酸甲酯、丙酸乙酯、丙酸丁酯、丙酸异戊酯、丁酸甲酯、丁酸乙酯、丁酸丁酯、丁酸异戊酯、异丁酸异丁酯、2-羟基-2-甲基丙酸乙酯、异戊酸乙酯、异戊酸异戊酯、苯甲酸甲酯、乙二酸二乙酯、丙二酸二乙酯、乙二醇单乙酸酯、乙二醇二乙酸酯、甘油一乙酸酯、碳酸二乙酯、硝基甲烷、硝基乙烷、1-硝基丙烷、2-硝基丙烷、乙腈、丙腈、丁腈、异丁腈、戊腈、苯甲腈、二乙胺、三乙胺、二丙胺、二异丙胺、二丁胺、二异丁胺、苯胺、N-甲基苯胺、N,N-二甲基苯胺、吡咯、哌啶、吡啶、α-甲基吡啶、β-甲基吡啶、γ-甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、N-甲基甲酰胺、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、2-甲氧基甲醇、2-乙氧基甲醇、2-(甲氧基甲氧基)乙醇、2-异丙氧基乙醇、2-丁氧基乙醇、2-(新戊氧基)乙醇、糠醇、四氢糠醇、二乙二醇单甲醚、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、二丙二醇单甲醚、二丙二醇单乙醚、二丙酮醇、2-(二甲基氨基)乙醇、2-(二乙基氨基)乙醇、吗啉、N-乙基吗啉、乳酸甲酯、乳酸乙酯、乳酸丁酯、乳酸戊酯、乙酸-2-甲氧基乙酯、乙酸-2-乙氧基乙酯、乙酸-2-丁氧基乙酯、乙酰乙酸甲酯、乙酰乙酸乙酯等。这些能够没有特别限定地利用,也可以并用2种以上。
本实施方式的树脂组合物,能够通过例如将各成分预混合后,使用3根辊进行混炼后在真空下进行脱泡来制造。
树脂组合物的粘度优选为1Pa·s以上100Pa·s以下。无论是比其低还是高,在涂敷后都不能得到良好的厚度的粘接剂层,因此不优选。在此,粘度的值是使用E型粘度计(东机产业株式会社制造、3°锥(cone))在25℃、2.5rpm测定的值。更优选的粘度范围为2Pa·s以上90Pa·s以下,进一步优选的粘度范围为2Pa·s以上80Pa·s以下。
另外,优选将树脂组合物在25℃开放24小时的前后的粘度变化率为100%以下。当粘度变化率超过100%时,有将树脂组合物涂敷在基材2或半导体元件3上时的操作性或涂敷后的厚度精度产生问题的情况。此外,在25℃开放24小时,具体而言,是指将5g树脂组合物放置在玻璃板上,用刮刀铺展为100μm厚,在25℃放置24小时。
(半导体装置)
接着,对使用本实施方式的树脂组合物制作的半导体装置进行说明。图1为表示本实施方式的半导体装置10的结构的剖面图。
本实施方式的半导体装置10具备:基材2;半导体元件3;和介于基材2与半导体元件3之间,将两者粘接的粘接层1。
粘接层1通过将本实施方式的树脂组合物涂敷在半导体元件或基材上,并利用半导体元件3和基材2进行压接而形成。
粘接层1的厚度没有特别限定,优选为2μm以上100μm以下,更优选为2μm以上30μm以下。通过使粘接层1的厚度为下限值以上,能够进一步发挥粘接强度。另外,通过使粘接层1的厚度为上限值以下,能够使导电性和热传导性进一步提高。
基材2没有特别限定,可以列举:42合金引线框、铜引线框等引线框;散热器(heat sink)、散热片(heat spreader)等散热部件;玻璃环氧基板(由玻璃纤维强化环氧树脂构成的基板)、BT基板(使用由氰酸酯单体及其低聚物与双马来酰亚胺构成的BT树脂的基板)等有机基板;其他半导体元件;半导体晶片;间隔物等。其中,优选能够更加有效地发挥粘接层1的导电性和热传导性的引线框、散热器或有机基板。进一步优选有机基板为BGA(Ball Grid Array:球栅阵列)基板。
半导体元件3经由焊盘7和接合线6,与引线4电连接。另外,半导体元件3的周围由密封材料层5密封。
以往的树脂组合物,特别在粘接芯片宽度小的半导体元件的情况下,有难以涂敷适量的树脂组合物、树脂组合物从半导体元件溢出的情况。
本实施方式的树脂组合物,粘度变化小且操作性优异,因此适合于粘接芯片宽度小的半导体元件。因此,半导体元件3没有特别限定,优选发光二极管元件或半导体激光元件等芯片宽度为2μm以下的半导体元件。
(使用树脂组合物的半导体装置的制造方法)
使用本实施方式的树脂组合物制作半导体装置10的方法,没有特别限定,能够使用公知的方法。例如,使用市售的芯片接合机(diebonder),在基材2的规定部位分配涂敷或压印涂敷树脂组合物后,将基材2与半导体元件3压接,进行加热固化形成粘接层1。
然后,进行引线接合,使用环氧树脂形成密封材料层5,由此制作半导体装置10。或者,能够采用在倒装式接合后用底层填料密封的倒装BGA(Ball Grid Array:球栅阵列)等半导体芯片背面分配涂敷或压印涂敷树脂组合物,搭载散热片、盖(lid)等散热部件进行加热固化等的方法。
在此,分配是指用树脂组合物将芯片接合机的料筒内充满后,用活塞将该树脂组合物挤出,或者利用空气压力等将该树脂组合物挤出,由此在基材2和半导体元件3中的至少一个的表面的规定位置(粘接面)定量排出树脂组合物进行涂敷的方法。
另外,压印是指将转印针(transfer pin)的前端按压在树脂组合物中,使附着有该树脂组合物的转印针的前端移动至基材2和半导体元件3中的至少一个的表面的规定位置的正上方后,通过按压转印针来在基材2和半导体元件3中的至少一个的粘接面上涂敷树脂组合物的方法。
另外,在粘接芯片宽度为2μm以下的半导体元件的情况下,优选通过利用极细针进行的分配或压印,来涂敷树脂组合物。本实施方式的树脂组合物,粘度变化小且操作性优异,因此,能够通过利用极细针进行的分配或压印,将少量的树脂组合物以高的厚度精度涂敷在基材上。
实施例
以下,对于本实施方式,具体地给出实施例,但是并不限定于这些。在本实施例中,作为树脂组合物的各成分,使用以下的物质。
1.热固性树脂
环氧树脂A:双酚F型环氧树脂(日本化药株式会社制造、RE-303S)
环氧树脂B:间、对-甲苯基缩水甘油醚(阪本药品工业株式会社制、CGE、环氧当量165)
丙烯酸树脂A(丙烯酸酯A):二丙烯酸酯(共荣社化学株式会社制造、LIGHT ESTER4EG)
丙烯酸树脂B(丙烯酸酯B):含有羟基的丙烯酸酯(日本化成株式会社制造、CHDMMA)
丙烯酸树脂C(丙烯酸酯C):含有羧基的丙烯酸酯(共荣社化学株式会社制造、LIGHT ESTER HOMS)
丙烯酸树脂D(丙烯酸酯D):三丙烯酸酯(共荣社化学株式会社制造、LIGHT ESTER TMP)
马来酰亚胺树脂(马来酰亚胺化合物):马来酰亚胺化合物(大日本油墨化学工业株式会社制造、MIA-200)
烯丙酯树脂(烯丙酯化合物):烯丙酯化合物(昭和电工株式会社制造、DA101)
2.添加剂
固化剂A(环氧固化剂A):双酚F(大日本油墨化学工业株式会社制造、BPF、羟基当量100)
固化剂B(环氧固化剂B):双氰胺(株式会社ADEKA制造、DDA)
固化催化剂(环氧催化剂A):2-苯基-4-甲基-5-羟甲基咪唑(四国化成工业株式会社制造、CUREZOL2P4MHZ)
偶联剂A:环氧硅烷(信越化学株式会社制造、KBM-403E)
偶联剂B:双(三甲氧基甲硅烷基丙基)四硫化物(大曹株式会社(DAISO Co.Ltd.)、CABRUS4)
偶联剂C:乙烯基硅烷偶联剂(信越化学株式会社制造、KBM-503P)
聚合引发剂(过氧化物):过氧化物(化药Akzo株式会社(KayakuAkzo Corporation)制造、Perkadox BC)
3.金属颗粒
鳞片形状银颗粒A(片状银粉A):(福田金属箔粉工业株式会社制造、Agc-TC6、d50:14.0μm、d95:23.0μm、10μm<13%)
鳞片形状银颗粒B(片状银粉B):(菲柔公司(Ferro Corporation)制造、SF-78、d50:9.5μm、d95:14.0μm、10μm<54%)
鳞片形状银颗粒C(片状银粉C):(菲柔公司制造、SF-65、d50:4.0μm、d95:13.0μm、10μm<12%)
鳞片形状银颗粒D(片状银粉D):(福田金属箔粉工业株式会社制造、Agc-2611、d50:3.7μm、d95:8.5μm、10μm<5%)
鳞片形状银颗粒E(片状银粉E):(同和电子(DOWA Electronics)株式会社制造、FA-S-6、d50:2.2μm、d95:6.0μm、10μm<0%)
球状银颗粒A(球状银粉A):(同和电子株式会社制造、AG2-1C、d50:1.7μm、d95:3.6μm、10μm<0%)
4.绝缘颗粒
交联PMMA-1:(Art-pearl GR-800、10μm<7%)
交联PMMA-2:(Art-pearl SE-006T、10μm<4%)
交联PMMA-3:(Art-pearl J-7P、10μm<0%)
在此,10μm<X%表示粒径超过10μm的金属颗粒或绝缘颗粒的体积比例为X%。
此外,粒径使用细川密克朗株式会社(Hosokawa MicronCorporation)制造的流动式颗粒图像解析装置FPIA-3000,在以下的条件下测定。
测定模式:HPF
定量计数
物镜:20倍
光学系统:亮视野
温度:室温
压力:0.22MPa
[实施例1~13、比较例1~3]
将上述的成分按照表1的比例配合,使用3根辊进行混炼,在真空腔室以2mmHg进行15分钟脱泡,分别制作树脂组合物。配合比例为重量份。
(评价试验)
对由上述得到的树脂组合物分别进行以下的评价试验。将评价结果示于表1。
(粘度)
在刚制作出上述的树脂组合物之后,使用E型粘度计(3°锥)测定在25℃、2.5rpm时的值。另外,将制作出的树脂组合物在25℃开放24小时后,同样地测定在25℃、2.5rpm时的值,根据下述式(1)算出24小时后的粘度变化率。此外,在25℃开放24小时,具体而言,是指将5g树脂组合物放置在玻璃板上,用刮刀铺展为100μm厚,在25℃放置24小时。
开放24小时后的粘度变化率[%]=100×(开放24小时后的粘度-刚制作后的粘度)/(刚制作后的粘度) (1)
(排出性)
使用喷嘴直径为内径100μm的极细针和分配器,对排出树脂组合物时的操作性进行评价。各符号如以下所述。
OK:树脂组合物的排出速度和扩展都没有问题。
NG:无法排出树脂组合物。
由表1可知,实施例1~13的树脂组合物,粘度变化率小,排出性良好,操作性优异。另外,这些树脂组合物在对芯片宽度为2μm以下的半导体元件进行芯片接合时的操作性也优异。
产业上的可利用性
根据本发明,能够提供操作性优异的树脂组合物,因此本发明在产业上非常有用。
符号说明
1 粘接层
2 基材
3 半导体元件
4 引线
5 密封材料层
6 接合线
7 焊盘
10 半导体装置
Claims (13)
1.一种树脂组合物,其为将半导体元件和基材粘接的膏状的树脂组合物,其特征在于:
包含热固性树脂和金属颗粒,
所述金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的d95为10μm以下。
2.如权利要求1所述的树脂组合物,其特征在于:
所述金属颗粒的通过流动式颗粒图像解析装置得到的体积基准粒度分布中的中位径d50为0.5μm以上8μm以下。
3.如权利要求1或2所述的树脂组合物,其特征在于:
在25℃开放24小时后的粘度变化率为100%以下。
4.如权利要求1~3中任一项所述的树脂组合物,其特征在于:
所述金属颗粒包括银颗粒。
5.如权利要求1~4中任一项所述的树脂组合物,其特征在于:
该树脂组合物还包含选自二氧化硅颗粒、氧化铝和有机聚合物中的一种以上的绝缘颗粒。
6.如权利要求1~5中任一项所述的树脂组合物,其特征在于:
所述热固性树脂包括环氧树脂。
7.如权利要求1~6中任一项所述的树脂组合物,其特征在于:
该树脂组合物用于利用转印针将该树脂组合物转印涂敷在所述半导体元件和所述基材中的至少一个的粘接面上的压印。
8.一种半导体装置,其特征在于,具备:
所述基材;
所述半导体元件;和
介于所述基材与所述半导体元件之间,将两者粘接的粘接层,
所述粘接层使用权利要求1至7中任一项所述的树脂组合物形成。
9.如权利要求8所述的半导体装置,其特征在于:
所述半导体元件的芯片宽度为2μm以下。
10.如权利要求8或9所述的半导体装置,其特征在于:
所述半导体元件为发光二极管元件或半导体激光元件。
11.如权利要求8~10中任一项所述的半导体装置,其特征在于:
所述基材为引线框、散热器或BGA基板。
12.一种半导体装置的制造方法,其为权利要求8~11中任一项所述的半导体装置的制造方法,其特征在于,包括:
在所述半导体元件和所述基材中的至少一个的粘接面上涂敷所述树脂组合物的工序;和
将所述半导体元件和所述基材压接,进行加热固化形成所述粘接层的工序。
13.如权利要求12所述的半导体装置的制造方法,其特征在于:
涂敷所述树脂组合物的工序包括将所述树脂组合物利用转印针进行转印的压印或利用极细针进行的分配。
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CN112341644A (zh) * | 2020-11-02 | 2021-02-09 | 青岛科技大学 | 一种改性壳聚糖补强的自修复天然橡胶及其制备方法 |
CN111801397B (zh) * | 2018-03-01 | 2021-08-20 | 住友电木株式会社 | 糊状粘接剂组合物和半导体装置 |
CN113930167A (zh) * | 2018-03-01 | 2022-01-14 | 住友电木株式会社 | 糊状粘接剂组合物和半导体装置 |
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TW201247816A (en) | 2012-12-01 |
KR101903819B1 (ko) | 2018-10-02 |
KR20140030203A (ko) | 2014-03-11 |
SG194849A1 (en) | 2013-12-30 |
JPWO2012165375A1 (ja) | 2015-02-23 |
SG10201604299YA (en) | 2016-07-28 |
CN103563063B (zh) | 2017-11-14 |
US20140341242A1 (en) | 2014-11-20 |
EP2717304A4 (en) | 2015-05-06 |
WO2012165375A1 (ja) | 2012-12-06 |
TWI608062B (zh) | 2017-12-11 |
EP2717304A1 (en) | 2014-04-09 |
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