CN105358647B - 粘接剂组合物、粘接片及半导体装置的制造方法 - Google Patents
粘接剂组合物、粘接片及半导体装置的制造方法 Download PDFInfo
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- CN105358647B CN105358647B CN201480037865.3A CN201480037865A CN105358647B CN 105358647 B CN105358647 B CN 105358647B CN 201480037865 A CN201480037865 A CN 201480037865A CN 105358647 B CN105358647 B CN 105358647B
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- methyl
- acrylate copolymer
- adhesive composite
- adhesive
- bond layer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明提供可以充分的粘接强度接合、特别是在半导体装置中可实现高密封可靠性的粘接剂组合物;具有由该粘接剂组合物组成的粘接剂层的粘接片;以及使用了该粘接片的半导体装置的制造方法。本发明的粘接剂组合物的特征在于包含:通过使用含有有机碲的化合物作为聚合引发剂的活性自由基聚合法使丙烯酸类单体聚合而得到的重均分子量(Mw)为35万以上的丙烯酸聚合物(A)、环氧类热固化性树脂(B)及热固化剂(C)。
Description
技术领域
本发明涉及一种粘接剂组合物、具有该粘接剂组合物所构成的粘接剂层的粘接片以及使用该粘接片的半导体装置的制造方法,所述粘接剂组合物特别适合用于将半导体元件(半导体芯片)管芯键合(die bonding))于有机基板或引线框架(Lead frame)的工序,以及将硅晶圆等切割、且将半导体芯片管芯键合于有机基板或引线框架的工序。
背景技术
硅、砷化镓等的半导体晶圆以大直径的状态制造,此晶圆被切割分离(dicing)为元件小片(半导体芯片)后,移至作为下一工序的安装工序。此时,在半导体晶圆预先贴附于粘接片的状态下施加切割、清洗、干燥、扩展、拾取的各工序后,移送至下个工序的键合(bonding)工序。
在这些工序中,为了简化拾取工序以及键合工序的工艺,提出了各种同时兼具有晶圆固定功能与管芯粘接功能的切割·管芯键合用粘接片(专利文献1等)。专利文献1所公开的粘接片,能够进行所谓的管芯直接键合,并能够省略管芯粘接用粘接剂的涂布工序。
然而,对于近年的半导体装置,所要求的物性变得非常严苛。例如,在电子部件的连接中,进行了将封装整体都暴露于焊料熔点以上的高温中的表面封装法(回焊(reflow))。进一步,近年来由于过渡到不含铅的焊料,封装温度上升至260℃左右。因此,封装时的半导体封装内部所产生的应力变得比以往大,产生粘接界面的剥离或封装破裂等不良状况的可能性高。
因此,在所述专利文献1中,以防止切割后的粘接剂层相互之间的粘着为主,提出了一种粘接剂组合物,其特征在于,包含重均分子量(Mw)为90万以上、分子量分布(Mw/Mn)为7以下的丙烯酸聚合物、环氧类树脂以及热固化剂。
现有技术文献
专利文献
专利文献1:日本专利特开2009-292888号公报
发明内容
本发明要解决的技术问题
作为解决实现高的密封可靠性这一课题的手段,本发明的发明人由聚合法方面着眼于控制丙烯酸聚合物的分子量分布。上述专利文献1的粘接剂组合物通过使重均分子量Mw变大,相对减少低分子量成分的含量,由此防止因为低分子量成分的粘接剂的塑化,防止粘接剂层相互的粘着。但是,在专利文献1的实施例中公开的用于粘接剂的丙烯酸聚合物的分子量分布为4左右而相对较高,因此为了将低分子量成分的含量充分地减低,不得不使重均分子量大至100万以上。
如此,丙烯酸聚合物的重均分子量高时,无法追随近年更加微细化的芯片表面的凹凸,而有成为粘接强度降低的主因的可能。此外,由于需要使用重均分子量高的丙烯酸类聚合物,因此限制了粘接剂的设计自由度。
本发明的目的在于提供可以充分的粘接强度接合、特别是在半导体装置中可实现高密封可靠性的粘接剂组合物;具有由该粘接剂组合物组成的粘接剂层的粘接片;以及使用该粘接片的半导体装置的制造方法。
解决技术问题的技术手段
解决上述问题的本发明包含以下的要旨。
(1)一种粘接剂组合物,包含:通过使用含有有机碲的化合物作为聚合引发剂的活性自由基聚合法使丙烯酸类单体聚合而得到的重均分子量(Mw)为35万以上的丙烯酸聚合物(A)、环氧类热固化性树脂(B)及热固化剂(C)。
(2)根据(1)所述的粘接剂组合物,其中,进一步含有交联剂(D),丙烯酸聚合物(A)具有可与该交联剂反应的官能基。
(3)根据(2)所述的粘接剂组合物,其中,交联剂(D)含有异氰酸酯基,丙烯酸聚合物(A)含有羟基。
(4)根据(1)~(3)中任一项所述的粘接剂组合物,其中,丙烯酸聚合物(A)的重均分子量(Mw)为90万以下。
(5)根据(1)~(4)中任一项所述的粘接剂组合物,其中,丙烯酸聚合物(A)的分子量分布(Mw/Mn)为3以下。
(6)一种单层粘接膜,由上述(1)~(5)中任一项所述的粘接剂组合物构成。
(7)一种粘接片,将上述(1)~(5)中任一项所述的粘接剂组合物所构成的粘接剂层形成于支撑体上而成。
(8)一种半导体装置的制造方法,包括如下工序:将半导体晶圆粘贴于上述(7)所述的粘接片的粘接剂层,将所述半导体晶圆切割成半导体芯片,使粘接剂层固着残留于所述半导体芯片上,再由支撑体剥离,将所述半导体芯片经由所述粘接剂层粘接于管芯焊盘(die pad)上或其他的半导体芯片上。
发明效果
将半导体芯片固定时,通过使用本发明的粘接片,可以充分的粘接强度接合,即使在严苛的环境下,也可得到体现高密封可靠性的半导体装置。
具体实施方式
以下,对本发明的粘接剂组合物、粘接片以及使用该片的半导体装置的制造方法进行更具体的说明。
(粘接剂组合物)
关于本发明的粘接剂组合物,作为必要成分包含丙烯酸聚合物(A)(以下也称为“(A)成分”。关于其他的成分也相同)、环氧类树脂(B)(以下也称为“化合物(B)”或“(B)成分”)、热固化剂(C),为改良各种物性,也可根据需要包含其他的成分。以下,具体说明上述各成分。
(A)丙烯酸聚合物
丙烯酸聚合物(A)的重均分子量(Mw)为35万以上,优选为不足200万,更加优选为40万~180万,进一步优选为60万~150万,特别优选为60万~90万。若丙烯酸聚合物的重均分子量过低,则可能会因为粘接剂层的低分子量成分的流动性而有损密封可靠性。此外,若丙烯酸聚合物的重均分子量过高,则成为粘接剂层无法追随基板或芯片表面的凹凸而产生气孔的主要原因。通过使丙烯酸聚合物的重均分子量在上述范围内,可使丙烯酸聚合物具有适度的柔软性,提升粘接剂层对于表面平滑性高的被粘物表面的粘贴性,可将芯片与基板,或者芯片与芯片牢固地粘接。此外,可防止因为低分子量成分导致的密封可靠性下降。再者,本发明的丙烯酸聚合物(A)通过如下所述使分子量分布变小,无需将重均分子量设定为过大的范围,即可充分地降低低分子量成分的含量。
丙烯酸聚合物(A)的分子量分布(Mw/Mn)优选为3以下,更加优选为2以下,进一步优选为1.7以下,特别优选为1.5以下。分子量分布在3以下的丙烯酸聚合物即使重均分子量高,由于分子量分布窄,因此流动性高的低分子量成分的含量少,有避免该低分子量成分降低密封可靠性的趋势。由与各成分的相溶性的角度考虑分子量分布的下限值为1.2左右。
再者,丙烯酸聚合物(A)的重均分子量(Mw)、数均分子量(Mn)及分子量分布(Mw/Mn)的值为通过凝胶渗透色谱法(GPC)的方法(聚苯乙烯标准)、以下述的实施例的测定条件下测定时的值。此外,使用下述的交联剂(D)时,丙烯酸聚合物(A)的重均分子量(Mw)、数均分子量(Mn)及分子量分布(Mw/Mn)为与交联剂(D)反应前的值。
丙烯酸聚合物的玻璃化转变温度(Tg)优选为-10℃以上50℃以下,进一步优选为0℃以上40℃以下,特别优选为0℃以上30℃以下的范围。若玻璃化转变温度过低,则粘接剂层与支撑体的剥离力变大,有时会引起芯片的拾取不良,若过高则有用于固定晶圆的粘接剂层的粘接力变得不充分的可能。
作为构成该丙烯酸聚合物(A)的单体,至少包含(甲基)丙烯酸酯单体或其衍生物。作为(甲基)丙烯酸酯单体或其衍生物,可列举烷基的碳原子数为1~18的(甲基)丙烯酸烷基酯,例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等;具有环状骨架的(甲基)丙烯酸酯,例如(甲基)丙烯酸环烷基酯、(甲基)丙烯酸苄酯、异佛尔酮丙烯酸酯、丙烯酸二环戊酯、丙烯酸二环戊烯酯、丙烯酸二环戊烯氧乙酯、丙烯酸酰亚胺酯等;具有羟基的丙烯酸酯,例如(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2-羟基丁酯等;具有缩水甘油基的(甲基)丙烯酸酯,例如(甲基)丙烯酸缩水甘油酯;具有胺基的(甲基)丙烯酸酯,例如(甲基)丙烯酸单乙基胺基酯、(甲基)丙烯酸二乙基胺基酯等。对于丙烯酸聚合物(A),此外,也可使(甲基)丙烯酸、依康酸等具有羧基的单体、乙烯基醇、N-羟甲基(甲基)丙烯酰胺等具有(甲基)丙烯酸酯以外的羟基的单体、(甲基)丙烯酰胺、醋酸乙烯酯、丙烯腈、苯乙烯等共聚。
粘接剂组合物包含下述的交联剂(D)时,优选丙烯酸聚合物具有羟基、胺基、羧基等与交联剂(D)反应的官能基,可通过选择上述具有羟基的丙烯酸酯、(甲基)丙烯酸单乙基胺基酯、(甲基)丙烯酸等作为构成丙烯酸聚合物(A)的单体,向丙烯酸聚合物导入可与交联剂(D)反应的官能基。特别是具有羟基的丙烯酸聚合物(A),由于容易将羟基导入丙烯酸聚合物(A)、与环氧类树脂(B)的相溶性佳、此外变得容易使用交联剂导入交联结构,因而优选。此外,也可组合使用多种丙烯酸聚合物。
通过使用具有可与交联剂(D)反应的官能基的单体作为构成丙烯酸聚合物(A)的单体,向丙烯酸聚合物(A)导入与交联剂(D)反应的官能基时,具有与交联剂(D)反应的官能基的单体的质量在构成丙烯酸聚合物(A)的单体总质量中的比例优选为1~20质量%左右,更加优选为3~15质量%。
如上所述的丙烯酸聚合物(A)为通过使用有机碲化合物作为聚合引发剂将上述丙烯酸类单体进行活性自由基聚合的方法(以下有时记为“TERP聚合法”)而得到的。通过采用活性自由基聚合法,容易调整丙烯酸聚合物(A)的分子量分布(Mw/Mn),可提升使用本发明的粘接剂组合物的半导体装置的可靠性。此外,通过采用TERP聚合法,可提升分子量的控制性。特别是适用于获得高分子量的聚合物。
这种作为活性自由基聚合引发剂的含有碲的化合物优选使用下述物质。
[化学式1]
式中,R1表示碳原子数1~8的烷基、芳基、取代芳基或芳香族杂环基。R2及R3表示氢原子或碳原子数1~8的烷基。R4表示芳基、取代芳基、芳香族杂环基、酰基、氧羰基(oxycarbonyl)或氰基。
以R1表示的基团具体如下。作为碳原子数1~8的烷基,可列举甲基、乙基、正丙基、异丙基、环丙基、正丁基、仲丁基、叔丁基、环丁基、正戊基、正己基、正庚基、正辛基等碳原子数1~8的直链状、支链状或环状的烷基。作为优选的烷基,可以是碳原子数1~4的直链状或支链状烷基,更加优选为甲基或乙基。
作为芳基,可列举苯基、萘基等;作为取代芳基,可列举具有取代基的苯基、具有取代基的萘基等;作为芳香族杂环基,可列举吡啶基、呋喃基、噻吩基等。作为具有上述取代基的芳基的取代基,例如可列举卤素原子、羟基、烷氧基、胺基、硝基、氰基、-COR5表示的含有羰基的基团(R5=碳原子数1~8的烷基、芳基、碳原子数1~8的烷氧基、芳氧基)、磺酰基、三氟甲基等。作为优选的芳基,可以是苯基、三氟甲基取代苯基。此外,上述取代基,可以取代1个或2个,优选为对位或者邻位。
R2及R3所示的各基团具体如下。碳原子数1~8的烷基可列举与上述R1所示的烷基相同的烷基。
R4所示的各基团具体如下。作为芳基、取代芳基、芳香族杂环基,可列举与上述R1所示的基团相同的基团。作为酰基,可列举甲酰基、乙酰基、苯甲酰基等。作为氧羰基,优选为-COOR6(R6=H、碳原子数1~8的烷基、芳基)表示的基团,例如可列举羧基、甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基、仲丁氧基羰基、叔丁氧基羰基、正戊氧基羰基、苯氧基羰基等。作为优选的氧羰基,可以是甲氧基羰基、乙氧基羰基。
作为R4所示的各基团,可以是芳基、取代芳基、氧羰基。作为优选的芳基,可以是苯基。作为优选的取代芳基,可以是卤素原子取代苯基、三氟甲基取代苯基。此外,上述取代基为卤素原子时,可以取代1~5个。为烷氧基或三氟甲基时,可以取代1个或2个,取代1个时,优选为对位或者邻位,取代2个时,优选为间位。作为优选的氧羰基,可以是甲氧基羰基、乙氧基羰基。
作为优选的通式(1)所示的含有碲的化合物,可以是R1表示碳原子数1~4的烷基、R2及R3表示氢原子或碳原子数1~4的烷基、R4由芳基、取代芳基、氧羰基表示的化合物。特别优选为,R1表示碳原子数1~4的烷基,R2及R3表示氢原子或碳原子数1~4的烷基,R4可以是苯基、取代苯基、甲氧基羰基、乙氧基羰基。
通式(1)所示的含有碲的化合物具体如下。作为含有碲的化合物,可列举(甲基碲基(tellanyl)-甲基)苯、(1-甲基碲基-乙基)苯、(2-甲基碲基-丙基)苯、1-氯-4-(甲基碲基-甲基)苯、1-羟基-4-(甲基碲基-甲基)苯、1-甲氧基-4-(甲基碲基-甲基)苯、1-胺基-4-(甲基碲基-甲基)苯、1-硝基-4-(甲基碲基-甲基)苯、1-氰基-4-(甲基碲基-甲基)苯、1-甲基羰基-4-(甲基碲基-甲基)苯、1-苯基羰基-4-(甲基碲基-甲基)苯、1-甲氧基羰基-4-(甲基碲基-甲基)苯、1-苯氧基羰基-4-(甲基碲基-甲基)苯、1-磺酰-4-(甲基碲基-甲基)苯、1-三氟甲基-4-(甲基碲基-甲基)苯、1-氯-4-(1-甲基碲基-乙基)苯、1-羟基-4-(1-甲基碲基-乙基)苯、1-甲氧基-4-(1-甲基碲基-乙基)苯、1-胺基-4-(1-甲基碲基-乙基)苯、1-硝-4-(1-甲基碲基-乙基)苯、1-氰基-4-(1-甲基碲基-乙基)苯、1-甲基羰基-4-(1-甲基碲基-乙基)苯、1-苯基羰基-4-(1-甲基碲基-乙基)苯、1-甲氧基羰基-4-(1-甲基碲基-乙基)苯、1-苯氧基羰基-4-(1-甲基碲基-乙基)苯、1-磺酰-4-(1-甲基碲基-乙基)苯、1-三氟甲基-4-(1-甲基碲基-乙基)苯[1-(1-甲基碲基-乙基)-4-三氟甲基苯]、1-(1-甲基碲基-乙基)-3,5-双-三氟甲基苯、1,2,3,4,5-五氟-6-(1-甲基碲基-乙基)苯、1-氯-4-(2-甲基碲基-丙基)苯、1-羟基-4-(2-甲基碲基-丙基)苯、1-甲氧基-4-(2-甲基碲基-丙基)苯、1-胺基-4-(2-甲基碲基-丙基)苯、1-硝基-4-(2-甲基碲基-丙基)苯、1-氰基-4-(2-甲基碲基-丙基)苯、1-甲基羰基-4-(2-甲基碲基-丙基)苯、1-苯基羰基-4-(2-甲基碲基-丙基)苯、1-甲氧基羰基-4-(2-甲基碲基-丙基)苯、1-苯氧基羰基-4-(2-甲基碲基-丙基)苯、1-磺酰-4-(2-甲基碲基-丙基)苯、1-三氟甲基-4-(2-甲基碲基-丙基)苯、2-(甲基碲基-甲基)吡啶、2-(1-甲基碲基-乙基)吡啶、2-(2-甲基碲基-丙基)吡啶、2-甲基-2-甲基碲基-丙醇、3-甲基-3-甲基碲基-2-丁酮、2-甲基碲基-乙酸甲酯、2-甲基碲基-丙酸甲酯、2-甲基碲基-2-甲基丙酸甲酯、2-甲基碲基-乙酸乙酯、2-甲基碲基-丙酸乙酯、2-甲基碲基-2-甲基丙酸乙酯[乙基-2-甲基-2-甲基碲基-丙酸酯]、2-(正丁基碲基)-2-甲基丙酸乙酯[乙基-2-甲基-2-正丁基碲基-丙酸酯]、2-甲基碲基丙烯腈、2-甲基碲基丙腈、2-甲基-2-甲基碲基丙腈、(苯基碲基-甲基)苯、(1-苯基碲基-乙基)苯、(2-苯基碲基-丙基)苯等。
此外,在上述化合物中,包含全部将甲基碲基、1-甲基碲基、2-甲基碲基的部分分别变更为乙基碲基、1-乙基碲基、2-乙基碲基、丁基碲基、1-丁基碲基、2-丁基碲基的化合物。优选可以为(甲基碲基-甲基)苯、(1-甲基碲基-乙基)苯、(2-甲基碲基-丙基)苯、1-氯-4-(1-甲基碲基-乙基)苯、1-三氟甲基-4-(1-甲基碲基-乙基)苯[1-(1-甲基碲基-乙基)-4-三氟甲基苯]、2-甲基碲基-2-甲基丙酸甲酯、2-甲基碲基-2-甲基丙酸乙酯[乙基-2-甲基-2-甲基碲基-丙酸酯]、2-(正丁基碲基)-2-甲基丙酸乙酯[乙基-2-甲基-2-正丁基碲基-丙酸酯]、1-(1-甲基碲基-乙基)-3,5-双-三氟甲基苯、1,2,3,4,5-五氟-6-(1-甲基碲基-乙基)苯、2-甲基碲基丙腈、2-甲基-2-甲基碲基丙腈、(乙基碲基-甲基)苯、(1-乙基碲基-乙基)苯、(2-乙基碲基-丙基)苯、2-乙基碲基-2-甲基丙酸甲酯、2-乙基碲基-2-甲基丙酸乙酯、2-乙基碲基丙腈、2-甲基-2-乙基碲基丙腈、(正丁基碲基-甲基)苯、(1-正丁基碲基-乙基)苯、(2-正丁基碲基-丙基)苯、2-正丁基碲基-2-甲基丙酸甲酯、2-正丁基碲基-2-甲基丙酸乙酯、2-正丁基碲基丙腈、2-甲基-2-正丁基碲基丙腈。
以上述通式(1)表示的含有碲的化合物可以单独或组合2种以上使用。作为通式(1)所示的含有碲的化合物,例如采用乙基-2-甲基-2-甲基碲基-丙酸酯时,作为其合成方法,可以通过日本特开2011-74380号公报所公开的方法获得。
在聚合工序中,除了上述含有碲的化合物之外,还可添加偶氮类聚合引发剂作为聚合促进剂。偶氮类聚合引发剂只要是用于通常的自由基聚合的引发剂即可,并无特别限定,作为例示,可列举2,2'-偶氮双(异丁腈)(AIBN)、2,2'-偶氮双(2-甲基丁腈)(AMBN)、2,2'-偶氮双(2,4-二甲基戊腈)(ADVN)、1,1'-偶氮双(1-环六甲腈)(ACHN)、二甲基-2,2'-偶氮双异丁酯(MAIB)、4,4'-偶氮双(4-氰基吉草酸)(ACVA)、1,1'-偶氮双(1-乙酰氧基-1-苯基乙烷)、2,2'-偶氮双(2-甲基丁基酰胺)、2,2'-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮双(2-甲基脒基丙烷)二盐酸盐、2,2'-偶氮双[2-(2-咪唑啉-2-基)丙烷]、2,2'-偶氮双[2-甲基-N-(2-羟基乙)丙酸酰胺]、2,2'-偶氮双(2,4,4-三甲基戊烷)、2-氰基-2-丙基偶氮甲酰胺、2,2'-偶氮双(N-丁基-2-甲基丙酸酰胺)、2,2'-偶氮双(N-环己-2-甲基丙酸酰胺)等。使用上述偶氮类聚合引发剂时,相对于1mol用作聚合引发剂的式(1)的含有碲的化合物,最好优选以0.01~100mol、更加优选以0.1~100mol、进一步优选以0.1~5mol的比例使用。
丙烯酸聚合物(A)通过活性自由基聚合而形成的方法举例如下。在非活性气体置换的容器中,将上述单体的混合物与通式(1)所示的活性自由基聚合引发剂及根据需要的偶氮类聚合引发剂混合。此时,作为非活性气体,可列举氮、氩、氦等。优选可以是氩、氮。特别可以是氮。单体与通式(1)所示的活性自由基聚合引发剂的使用量只要根据目标的丙烯酸聚合物(A)的分子量或者分子量分布适当调节即可。作为优选的使用量,大约为以各单体的分子量乘以添加比例所得的值的总和除以目标丙烯酸聚合物(A)的重均分子量(Mw)的值(使用量的单位为摩尔数),根据情况使用该值的0.3~3倍左右的量。
聚合通常为在无溶剂的条件下进行,使用通常用于自由基聚合的有机溶剂也无妨。作为可使用的溶剂,可列举例如苯、甲苯、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、丙酮、氯仿、四氯化碳、四氢呋喃(THF)、醋酸乙酯、三氟甲基苯等。此外,也可使用水性溶剂,例如水、甲醇、乙醇、异丙醇、正丁醇、乙基溶纤剂、丁基溶纤剂、1-甲氧基-2-丙醇等。作为溶剂的使用量,只要适当调节即可,例如相对于1g单体,溶剂可以为0.01~100ml,优选为0.05~10ml,特别优选为0.05~0.5ml。
其次,对上述混合物进行搅拌。反应温度、反应时间只要根据所得的丙烯酸聚合物(A)的分子量或者分子量分布适当调节即可,但通常为在60~150℃下搅拌5~100小时。优选可以在80~120℃下搅拌10~30小时。聚合通常以常压进行,但加压或者减压也无妨。反应结束后,根据常法在减压下去除所使用的溶剂或残留的单体,或沉淀过滤然后再沉淀,或者进行管柱分离等根据需要将目标丙烯酸聚合物(A)纯化。关于反应处理,只要不阻碍目标物可进行任何处理方法。
例如,在丙烯酸聚合物(A)中,使包含于其中的重均分子量Mw为5万以下的低分子量成分的比例为0.1质量%以下,可采用下述分离法。首先,在100质量份甲醇、乙醇、正丙醇、异丙醇等低级醇、或戊烷、己烷、庚烷等碳原子数5~10的脂肪族烃、优选为甲醇或己烷中,以固含量为1~30质量份左右的比例添加丙烯酸聚合物(A),在室温下搅拌以形成沉淀。接着,将此沉淀物以倾析等方法进行固液分离后,用所述低级醇或碳原子数5~10的脂肪烃清洗后使用。通过此分离法,可使丙烯酸聚合物(A)中的分子量Mw为5万以下的低分子量成分的比例为0.1质量%以下。
在此活性自由基聚合法中,通过使用构成丙烯酸聚合物(A)的各单体的混合物,可以获得无规共聚物丙烯酸聚合物(A)。该无规共聚物无关于单体的种类,可按照反应的单体的比例(摩尔比)得到共聚物。通过以含有碲的化合物作为聚合引发剂,可在非常温和的条件下进行分子量控制及分子量分布控制。丙烯酸聚合物(A)的分子量可根据反应时间、含有碲的化合物的量进行调整。具体而言,为增加分子量,只要减少含有碲的化合物占单体的调合比例、增加聚合时间即可。但是,由此得到分子量大的丙烯酸聚合物(A)需要长时间。因此,在图谋减少聚合时间时,可通过提高聚合温度、或添加所述偶氮类聚合引发剂来达成。但是,若聚合温度过高、或偶氮为聚合引发剂的添加量过多,则会增大丙烯酸聚合物(A)的分子量分布,因此需要与其进行调整。
丙烯酸聚合物(A)占粘接剂组合物全体的质量的添加比例优选为35~90质量%,更加优选为40~85质量%,进一步优选为45~80质量%。通过将丙烯酸聚合物(A)的添加量以上述方式进行限制,可提高粘接剂组合物在固化前的弹性,在未使粘接剂层固化而进行打线接合的半导体装置的制造方法中,不容易因接合时的冲击使粘接剂层发生变形,而有抑制发生不适的趋势。此外,这种丙烯酸聚合物(A)占粘接剂组合物的比例多的情况下,通过使用重均分子量(Mw)为35万以上、分子量分布(Mw/Mn)为3以下的丙烯酸聚合物(A)的本发明的密封可靠性的提升効果变得更加显着。
(B)环氧类热固性树脂
作为环氧类热固性树脂(B),可使用以往公知的环氧树脂。作为环氧类热固性树脂(B),具体可列举多官能环氧树脂,或联苯化合物、双酚A二缩水甘油醚或其氢化物、邻甲酚酚醛环氧树脂、二环戊二烯型环氧树脂、联苯基型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、亚苯基骨架型环氧树脂等在分子中具有2官能以上的环氧化合物。他们可以1种单独或组合2种以上使用。
在粘接剂组合物中,相对于100质量份丙烯酸聚合物(A),环氧类热固性树脂(B)优选含有1~100质量份,更加优选含有3~70质量份,特别优选含有5~50质量份。通过使环氧类热固性树脂(B)的含量在如此的范围内,可在保持充分的粘接性的同时,保持粘接剂层的弹性,即使在固化前的状态下,使粘接剂层变得不容易因在打线接合工序的接合时的冲击而发生变形,有抑制发生不适的趋势。
(C)热固化剂
热固化剂(C)作为针对环氧类热固化性树脂(B)的固化剂而起作用。作为优选的热固化剂(C),可列举在1分子中具有2个以上可与环氧基反应的官能基的化合物。作为此官能基,可列举酚性羟基、醇性羟基、胺基、羧基及酸酐等。他们之中,优选可列举酚性羟基、胺基、酸酐等,进一步优选可列举酚性羟基、胺基。
作为酚类固化剂的具体例子,可列举多官能酚树脂、双酚、酚醛型酚树脂、二环戊二烯类酚树脂、新酚型酚树脂、芳烷基酚树脂。作为胺类固化剂的具体例子,可列举DICY(二氰基二酰胺)。他们可以1种单独或混合2种以上使用。
粘接剂组合物中的热固化剂(C)的含量相对于100质量份环氧类热固性树脂(B),优选为0.1~500质量份,更加优选为1~200质量份。若热固化剂(C)的含量少,则有时会因为固化不足而无法得到粘接性,若过剩,则粘接剂层的吸湿率有时会变高而降低密封可靠性。
(D)交联剂
在粘接剂组合物中,优选添加交联剂(D)。作为交联剂(D),可列举有机多元异氰酸酯化合物、有机多元亚胺化合物等。通过导入交联结构,可提升使用了本发明的粘接剂组合物的半导体装置的可靠性。活性自由基聚合与自由基聚合(free radicalpolymerization)相比,具有在活性部位的反应非常缓和的特征。即,在自由基聚合中,可认为由于在活性部位的反应非常的快,而由反应性高的单体开始聚合,然后,反应性低的单体聚合。另一方面,在活性自由基聚合中,可认为是由于在活性部位的反应缓和,因此不会受到单体的反应性的影响而均等地进行聚合,可获得均等的组成。作为所述活性自由基聚合的特征的结果,使用具有与交联剂(D)反应的官能基的单体时,在所得丙烯酸聚合物(A)中,具有与交联剂(D)反应的官能基的单体未进入聚合物中,降低了产生实质上不具有与交联剂(D)反应的官能基的丙烯酸聚合物(A)分子的机率。由此认为,即使存在低分子量的丙烯酸聚合物(A)分子,通过与交联剂的反应进入三维网状结构的可能性高,也降低了未进入三维网状结构而残留的低分子量聚合物损及密封可靠性的可能性。
作为上述有机多元异氰酸酯化合物,可列举芳香族多元异氰酸酯化合物、脂肪族多元异氰酸酯化合物、脂环族多元异氰酸酯化合物及这些有机多元异氰酸酯化合物的三聚物、以及这些有机多元异氰酸酯化合物与多元醇化合物反应而得到的末端异氰酸酯尿烷预聚物等。
作为有机多元异氰酸酯化合物,例如可列举2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-二甲苯二异氰酸酯、1,4-二甲苯二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、二苯基甲烷-2,4’-二异氰酸酯、3-甲基二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己甲烷-4,4’-二异氰酸酯、二环己甲烷-2,4’-二异氰酸酯、赖胺酸异氰酸酯、及对这些多元醇的加成物。
使用异氰酸酯类交联剂时,丙烯酸聚合物(A)优选具有羟基而作为与交联剂反应的官能基。若交联剂具有异氰酸酯基、丙烯酸聚合物(A)具有羟基,则通过异氰酸酯基与羟基的反应,容易形成交联剂与丙烯酸聚合物(A)的键结,可简便地向粘接剂导入交联结构。
作为上述有机多元亚胺化合物,可列举N,N’-二苯基甲烷-4,4’-双(1-吖丙啶羧酰胺)、三羟甲基丙烷-三-β-吖丙啶基丙酸酯、四羟甲基甲烷-三-β-吖丙啶基丙酸酯及N,N’-甲苯-2,4-双(1-吖丙啶羧酰胺)三亚乙基三聚氰胺等。
使用有机多元亚胺化合物作为交联剂时,丙烯酸聚合物(A)优选具有羧基作为与交联剂反应的官能基,由此可在丙烯酸聚合物与交联剂之间产生键结,向粘接剂导入交联结构。
使用交联剂(D)时,相对于100质量份丙烯酸聚合物(A),交联剂(D)通常以0.01~20质量份、优选以0.1~10质量份、更加优选以0.5~5质量份的比例使用。
其他成分
粘接剂组合物除了上述成分以外,还可包含下述成分。
(E)固化促进剂
固化促进剂(E)用于调整粘接剂组合物的固化速度。固化促进剂(E)特别优选用于并用环氧类热固性树脂(B)与热固化剂(C)的情况。
作为优选的固化促进剂,可列举三乙二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)酚等3级胺类;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑等咪唑类;三丁基膦、二苯基膦、三苯基膦等有机膦类;四苯基鏻四苯基硼酸酯、三苯基鏻四苯基硼酸酯等四苯基硼盐等。他们可以1种单独或混合2种以上使用。
使用固化促进剂(E)时,相对于环氧类热固性树脂(B)及热固化剂(C)的总量100质量份,固化促进剂(E)优选以0.01~10质量份、进一步优选以0.1~1质量份的量含有。通过以上述范围的量含有固化促进剂(E),即使暴露于高温度高湿度下也可具有优异的粘接特性,即使暴露于严酷的回焊条件下,也可实现高密封可靠性。若固化促进剂(E)的含量少,则存在因固化不足而无法得到充分的粘接特性的可能,若过剩,则存在具有高极性的固化促进剂在高温度高湿度下通过从粘接剂层移向粘接界面侧、进行偏析而降低密封可靠性的可能。
(F)能量线聚合性化合物
在粘接剂组合物中,也可加入能量线聚合性化合物。能量线聚合性化合物(F)包含能量线聚合性基团,受到紫外线、电子束等能量线的照射会发生聚合固化。作为这样的能量线聚合性化合物(F),具体可列举三羟甲基丙烷三丙烯酸酯、季戊四醇基三丙烯酸酯、季戊四醇基四丙烯酸酯、二季戊四醇基单羟基五丙烯酸酯、二季戊四醇基六丙烯酸酯或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、寡聚酯丙烯酸酯、尿烷丙烯酸酯类寡聚物、环氧改性丙烯酸酯、聚醚丙烯酸酯及依康酸寡聚物等丙烯酸酯类化合物。这样的化合物在分子内至少具有1个聚合性双键,通常,重均分子量为100~30000,优选为300~10000左右。使用能量线聚合性化合物(F)时,其添加量并无特别限定,在粘接剂组合物的固含量总量的100质量%中,优选以1~50质量%左右的比例使用。
(G)光聚合引发剂
粘接剂组合物含有上述能量线聚合性化合物(F)的情况下,在其使用时,照射紫外线等能量线,使能量线聚合性化合物固化。此时,通过在粘接剂层中含有光聚合引发剂(G),可减少聚合固化时间及光线照射量。
作为这样的光聚合引发剂(G),具体可列举二苯甲酮、苯乙酮、安息香、安息香甲基醚、安息香乙基醚、安息香异丙基醚、安息香异丁基醚、安息香安息香酸、安息香安息香酸甲酯、安息香二甲基缩酮、2,4-二乙基噻吨酮、α-羟基环己苯基酮、苄基二苯基硫醚、四甲基秋兰姆单硫醚、偶氮双异丁腈、苄基、二苄基、二乙酰、1,2-二苯基甲烷、2-羟基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮、2,4,6-三甲基苯甲酰二苯基氧化膦及β-氯蒽醌等。光聚合引发剂(G)可1种单独或组合2种以上使用。
使用光聚合引发剂(G)时,相对于100质量份能量线聚合性化合物(F),其添加比例优选包含0.1~10质量份,更加优选包含1~5质量份。若不足0.1质量份,则光聚合有可能不足而无法得到充分的拾取性,若超过10质量份,则有可能产生不参与光聚合的残留物,使粘接剂层的固化性不充分。
(H)偶联剂
偶联剂(H)为具有可与有机化合物键结的基团及可与无机化合物反应的基团的化合物,也可将所述偶联剂用于提升粘接剂层对被粘物的粘接性、贴附性。此外,通过使用偶联剂(H),可在不损及使粘接剂层固化而得到的固化物的耐热性的情况下提升其耐水性。
作为偶联剂(H)的可与有机化合物键结的基团,优选为可与上述丙烯酸聚合物(A)、环氧类热固性树脂(B)等所具有的官能基反应的基团。作为偶联剂(H),最好是硅烷偶联剂。作为这种偶联剂,可列举γ-缩水甘油基丙基三甲氧基硅烷、γ-缩水甘油基丙基甲基二乙氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-(甲基丙烯酰氧丙基)三甲氧基硅烷、γ-胺基丙基三甲氧基硅烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基硅烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基硅烷、N-苯基-γ-胺基丙基三甲氧基硅烷、γ-脲基丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、γ-巯丙基甲基二甲氧基硅烷、双(3-三乙氧基硅基丙基)四硫化物、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙酰氧基硅烷、咪唑硅烷、3-异氰酸酯丙基三乙氧基硅烷、异氰酸酯甲基甲基二丁氧基硅烷、异氰酸酯甲基三乙氧基硅烷等。他们可以1种单独或混合2种以上使用。
使用偶联剂(H)时,相对于丙烯酸聚合物(A)、环氧类热固性树脂(B)、及热固化剂(C)共计100质量份,偶联剂通常以0.1~20质量份、优选以0.2~10质量份、更加优选以0.3~5质量份的比例含有。若偶联剂(H)的含量不足0.1质量份,则有无法得到上述効果的可能性,若超过20质量份,则有成为脱气的原因的可能性。
(I)无机填料
通过将无机填料(I)加入粘接剂组合物,可调整粘接剂层的热膨张系数,通过使固化后的粘接剂层的热膨张系数对半导体芯片、金属或有机基板最适化,可提升密封可靠性。此外,也可减低粘接剂层在固化后的吸湿率。
作为优选的无机填料,可列举二氧化硅、滑石、碳酸钙、钛白、氧化铁、碳化硅、氮化硼等的粉末、将他们球形化的小珠、单晶纤维及玻璃纤维等。在他们之中,优选二氧化硅填充剂。上述无机填料(I)可以单独或混合2种以上使用。使用无机填料(I)时,其含量相对于粘接剂组合物的全部固含量100质量份,通常可在0~80质量%的范围内调整。
(J)通用添加剂
在粘接剂组合物中,除了上述成分之外,也可根据需要添加各种添加剂。作为各种添加剂,可列举塑化剂、抗静电剂、抗氧化剂、颜料、染料、除气(gettering)剂等。
由如上所述各成分组成的粘接剂组合物所构成的粘接剂层具有感压粘接性与加热固化性,在未固化状态下具有将各种被粘物暂时保持的功能。然后,经由热固化最终可获得耐冲击性高的固化物,剪切强度也优异,即使在严酷的高温度高湿度条件下,也可保持充分的粘接特性。
粘接剂层也可为将上述粘接剂组合物制膜而成的单层的粘接片,优选为由上述粘接剂组合物所构成的粘接剂层可剥离地形成于支撑体上而成的粘接片。
(粘接片)
以下,以由粘接剂层可剥离地形成于支撑体上而成的粘接片为例,对粘接剂组合物的适宜方案及使用方案进行说明。使用由粘接剂层可剥离地形成于支撑体上而成的粘接片时,使粘接剂层粘接于晶圆、芯片等被粘物上,将支撑体剥离,将粘接剂层转印于被粘物。关于本发明的粘接片的形状,可采取带状、标签状等任何形状。
作为粘结片的支撑体,可使用例如聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚对苯二甲酸乙二醇酯膜、聚萘二甲酸乙二醇酯膜、聚对苯二甲酸丁二醇酯膜、聚尿烷膜、乙烯醋酸乙烯酯共聚物膜、离聚物树脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚酰亚胺膜、氟树脂膜等膜。此外,也可使用他们的交联膜。再者,也可为他们的层叠膜。此外,也可使用将他们着色的膜。支撑体的具有紫外线、可见光等放射线的穿透性可按照其用途选择适当水平的。
在本发明的粘接片粘贴于各种被粘物上,对被粘物施以所需加工之后,使粘接剂层固着残留于被粘物上,再由支撑体剥离。即,用于包括将粘接剂层由支撑体转印于被粘物的工序的工序。因此,支撑体没有作粘着处理时,支撑体的连接于粘接剂层的面的表面张力优选为40mN/m以下,进一步优选为37mN/m以下,特别优选为35mN/m以下。下限值通常为25mN/m左右。这种表面张力低的支撑体可通过适当选择材质而得到,此外,也可通过在支撑体的表面涂布剥离剂施以剥离处理而得到。
作为用于支撑体的剥离处理的剥离剂,可使用醇酸类、硅类、氟类、不饱和聚酯类、聚烯烃类、蜡类等,特别是醇酸类、硅类、氟类的剥离剂由于具有耐热性而优选。
为了使用上述剥离剂对支撑体的表面进行剥离处理,剥离剂可直接以无溶剂、或以溶剂稀释或乳化,通过凹版涂布机、刮棒涂布机、气刀涂布机、辊涂机等涂布,通过常温、加热或电子束固化,湿式层压或干式层压、热熔融层压、溶融挤出层压、共挤出加工等形成层叠体即可。
支撑体也可为具备粘着剂层的粘着片。粘着片在如上所述的树脂膜上具有粘着剂层,在粘着剂层上,可剥离地层叠有所述粘接剂层。因此,粘着片的粘着剂层可由具有再剥离性的公知粘着剂构成,通过选择紫外线固化型、加热发泡型、水溶胀型、弱粘型等的粘着剂,可容易地剥离粘接剂层。
此外,粘接片也可将支撑体及粘接剂层,预先冲模成与被粘物(半导体晶圆等)同形状或较晶圆形状大的同心圆状而成的形状。特别是,支撑体及粘接剂层所组成的层叠体,优选为保持于长条的支撑体上的形态。
支撑体的厚度通常为10~500μm,优选为15~300μm,特别优选为20~250μm左右。支撑体为粘着片时,通常,在支撑体的厚度中,粘着剂所组成的层占1~50μm左右的厚度。此外,粘接剂层的厚度通常为2~500μm,优选为6~300μm,特别优选为10~150μm左右。
在粘接片中,为了在使用前保护粘接剂层、粘着片的粘着剂、以下所述的夹具的固定用粘着剂层等,也可在粘接剂层的上面层叠剥离膜。该剥离膜使用在聚对苯二甲酸乙二醇酯膜或聚丙烯膜等塑料材料上涂布了硅树脂等剥离剂的剥离膜。此外,在粘接片的表面外周部也可设置用于固定环框等其他夹具的其他粘着剂层或粘着胶带。
粘接片的制造方法并无特别限定,可在支撑体上涂布干燥粘接剂组合物、形成粘接剂层来进行制造,此外,也可将粘接剂层设在用于保护上述粘接剂层的剥离膜上、通过将其转印于上述支撑体上来进行制造。
其次,关于本发明的粘接片的利用方法,以将该粘接片用于半导体装置的制造的情况为例进行说明。
(半导体装置的制造方法)
本发明的半导体装置的制造方法包括如下工序:在上述粘接片的粘接剂层上粘着半导体晶圆,将该半导体晶圆及粘接剂层切割作成半导体芯片,使该半导体芯片的背面固着残留粘接剂层而由支撑体剥离,将该半导体芯片设置于有机基板或引线框架的管芯焊盘上、或在层叠芯片时经由粘接剂层设置于其他半导体芯片上。
以下、详细说明关于本发明的半导体装置的制造方法。
在本发明的半导体装置的制造方法中,首先,制备在表面形成电路、背面经过研削的半导体晶圆。
半导体晶圆可为硅晶圆,此外,也可为砷化镓等的化合物半导体晶圆。晶圆表面的电路形成可以通过包括蚀刻法、举离法(lift-off)等传统通用方法的各种方法进行。其次,对半导体晶圆的电路面的相反面(背面)进行研削。研削法并无特别限定,可以使用研磨机等公知手段进行研削。背面研削时,为了保护表面电路,在电路面上粘贴称为表面保护片的粘着片。背面研削为将晶圆的电路面侧(即,表面保护片侧)以吸盘等固定,将没有形成电路的背面侧用研磨机进行研削。晶圆研削后的厚度并无特别限定,通常为20~500μm左右。
接着,将环框及半导体晶圆的背面侧设置于本发明的粘接片的粘接剂层上,轻轻按压,根据情况加热使粘接剂层软化,同时将半导体晶圆固定。接着,在粘接剂层中加入有能量线聚合性化合物(F)时,也可以对粘接剂层由支撑体侧照射能量线,使能量线聚合性化合物(F)固化,提高粘接剂层的凝聚力,降低粘接剂层与支撑体之间的粘接力。作为照射的能量线,可列举紫外线(UV)或电子束(EB)等,优选使用紫外线。接着,使用切割锯等的切割手段,对上述半导体晶圆及粘接剂层进行切割,得到半导体芯片。将此时的切割深度设为半导体晶圆的厚度与粘接剂层的厚度的合计再加上切割锯的磨损部分的深度,将粘接剂层也切割成与芯片相同尺寸。再者,能量线照射也可于粘贴半导体晶圆后,或在剥离(拾取)半导体芯片之前的任一阶段进行,例如,可于切割后进行,此外,也可于进行下述扩展工序之后进行。再者,也可将能量线照射分成多次进行。
接着,若根据需要进行粘接片的扩展,则半导体芯片的间隔被扩张,可使半导体芯片的拾取更容易进行。此时,在粘接剂层与支撑体之间会发生偏离,减少粘接剂层与支撑体之间的粘接力,提升半导体芯片的拾取性。若是如此进行半导体芯片的拾取,则可将切割成的粘接剂层固着残留于半导体芯片的背面再由支撑体剥离。
经由粘接剂层,将半导体芯片设置于作为芯片安装部的引线框架的管芯焊盘上或其他半导体芯片(下段芯片)表面上。为提升粘接剂层的贴附性,可在芯片安装部上设置半导体芯片之前对其进行加热,或在设置后立刻进行加热。加热温度通常为80~200℃,优选为100~180℃,加热时间通常为0.1秒~5分钟,优选为0.5秒~3分钟。此外,设置时的加压压力通常为1kPA~200MPa。
将半导体芯片设置于芯片安装部之后,也可不等如下所述的利用了树脂密封的加热的粘接剂层的主固化(日语:本硬化),通过在树脂密封前进行加热使粘接剂层主固化。此时的加热条件在上述加热温度的范围内,加热时间通常为1~180分钟,优选为10~120分钟。
此外,也可在设置后不进行加热处理,作成假粘接状态,利用在密封制造中通常进行的树脂密封的加热使粘接剂层固化。通过经过这样的工序,可使粘接剂层固化,牢固地将半导体芯片与芯片安装部粘接。粘接剂层由于在管芯接合条件下为流动性的,因此对芯片安装部的凹凸也可进行充分填埋,可防止气孔的发生,提高密封可靠性。此时,经由粘接剂层安装于芯片安装部的半导体芯片以粘接剂层为固化前的状态经过打线接合工序。采用这样的工序时,通过打线接合(wire bonding)时的加热,有助于粘接剂层的热固化的成分的一部分进行反应,有降低半导体装置中的密封可靠性的可能。但是,通过使用本发明的粘接剂组合物,提升粘接剂层对芯片的粘接性,有保持密封可靠性的趋势。
本发明的粘接剂组合物及粘接片除了如上所述的使用方法之外,也可用于半导体化合物、玻璃、陶瓷、金属等的粘接。
[实施例]
以下,通过实施例对本发明进行说明,但本发明并不局限于这些实施例。再者,在以下的实施例及比较例中,<GPC测定>及<耐IR回焊性评价>以如下方式进行。
<GPC测定>
关于各例所使用的丙烯酸聚合物,通过凝胶渗透色谱(GPC)法测定以标准聚苯乙烯换算的重均分子量Mw、数均分子量Mn,此外,由测定值求得分子量分布(Mw/Mn)。
测定装置:在TOSO公司制的高速GPC装置“HLC-8120GPC”中,依序连接高速柱“TSKgurd column HXL-H”、“TSK Gel GMHXL”、“TSK Gel G2000 HXL”(以上,均为TOSO公司制)进行测定。
柱温度:40℃;进样速度:1.0mL/分钟;检测器:差示折射计
<耐IR回焊性评价>
(半导体芯片的制造)
在干式抛光硅晶圆(150mm径,厚度75μm)的研磨面上,将实施例及比较例的粘接片以上胶机(Lintec公司制,Adwill RAD2500)进行粘贴,固定于晶圆切割用环框中。接着,使用切割装置(株式会社DISCO制,DFD651)切割成8mm×8mm的芯片尺寸。切割时的切入量为将支撑体切入20μm。
(半导体封装的制造)
在作为基板的贴铜箔层叠板(三菱气体化学株式会社制CCL-HL830)的铜箔(18μm厚)上形成电路图案,在图案上使用具有防焊油墨(太阳油墨制PSR-4000 AUS303)的基板(株式会社CHINO技研制LN001E-001 PCB(Au)AUS303)。将上述所得粘接片上的芯片与粘接剂层一起从支撑体取下,经由粘接剂层以120℃、250gf、0.5秒的条件压接于基板上,进一步经由粘接剂在芯片上以同条件进行压接。用模具树脂(Kyocera chemical株式会社制KE-1100AS3)以密封厚度400μm密封(密封装置Apicyamada株式会社制MPC-06M TriAl Press),以175℃、5小时使树脂固化。接着,将密封的基板粘贴于切割带(Lintec株式会社制AdwillD-510T)上,使用切割装置(株式会社DISCO制,DFD651)切割成8mm×8mm尺寸的,得到可靠性评价用半导体封装。
(半导体封装表面封装性的评价)
将所得半导体封装在85℃、60%RH的条件下放置168小时,使其吸湿后,进行以最高温度260℃、加热时间1分钟的IR回焊(回焊炉:相模理工制WL-15-20DNX型)3次后,接合部的浮起和有无剥离、有无发生封装龟裂通过扫描式超声波探伤装置(日立建机finetec株式会社制Hye-Focus)及剖面观察进行评价。在基板/半导体芯片的接合部观察到0.5mm以上的剥离时判断为“不良”,将27个封装投入试验,计算没有发生剥离的优品个数。
<由TERP法得到的丙烯酸聚合物的合成例>
将甲基丙烯酸酯(MA,东京化成(株)制)及2-羟乙基丙烯酸酯(HEA,东京化成(株)制)作为单体以质量比95:5的比例使用,按如下方式进行聚合,制造由MA/HEA的无规共聚物组成的丙烯酸聚合物(A-1)。首先,在氩置换过的手套箱内,使乙基-2-甲基-2-正丁基碲基-丙酸酯37.7μL、甲基丙烯酸酯(同上)133g、2-羟乙基丙烯酸酯(同上)7.0g及2,2’-偶氮双(异丁腈)(AIBN,大冢化学(株)制)8.1mg在60℃下反应20小时。
反应结束后,将反应器由手套箱取出,溶解于醋酸乙酯500ml之后,将该聚合物溶液通过以活性氧化铝[和光纯薬工业株式会社制]制作的柱。添加醋酸乙酯使聚合物溶液的粘度为10,000mPa·s(25℃)。所得聚合物的固含量为17.3质量%。此外,调整乙基-2-甲基-2-正丁基碲基-丙酸酯及AIBN的添加量以及聚合时间,除此以外,与丙烯酸聚合物(A-1)同样地通过活性自由基聚合,制造丙烯酸聚合物(A-2)、(A-3)、及(A-5)。
<粘接剂组合物>
构成粘接剂组合物的各成分如下所示。
(A)丙烯酸聚合物:
(A-1)~(A-3)以上述的合成例制造的、体现出表2所示重均分子量及分子量分布的丙烯酸聚合物
(A-4)单体的种类及质量比例与(A-1)相同的、以自由基聚合法制作的体现出表2所示重均分子量及分子量分布的丙烯酸聚合物
(A-5)以上述TERP法的合成例所制造的、体现出表2所示重均分子量及分子量分布的丙烯酸聚合物
(A-6)、(A-7)单体的种类及质量比例与(A-1)相同的、以游离自由基聚合法制作的体现出表2所示重均分子量及分子量分布的丙烯酸聚合物
(B)环氧类热固性化合物;双酚A型环氧树脂(日本环氧树脂株式会社制EPICOAT828,环氧当量189g/eq)
(C)热固化剂:酚醛型酚树脂(昭和高分子株式会社制Shonol BRG-556,酚性羟基当量104g/eq)
(D)交联剂:芳香族性聚异氰酸酯(日本聚氨酯工业株式会社制Coronate L)
(E)固化促进剂:咪唑(四国化成工业株式会社制Curesol 2PHZ)
(H)偶联剂:硅烷偶联剂(三菱化学株式会社制MKC Silicate MSEP2)
(I-1)无机填充剂:日产化学公司制Silicasol MEK-ST
(I-2)无机填充剂:日产化学公司制MEK-AC-4101
(实施例及比较例)
(粘接剂层)
将上述各成分以表1所述的量混合,得到粘接剂组合物。将所得组合物的甲基乙基酮溶液(固形物浓度61质量%)涂布于经过硅酮的剥离处理的剥离膜(Lintec株式会社制,SP-PET381031)的剥离处理面上,使干燥后的厚度为10μm,干燥(干燥条件:烘箱中100℃,1分钟)后,与支撑体(聚乙烯膜,厚度100μm,表面张力33mN/m)粘贴,通过将粘接剂层转印于支撑体上得到粘接片。将所得粘接片的耐IR回焊评价结果示于表2。
[表1]
单位:重量部(固含量换算值)
[表2]
丙烯酸聚合物 | 交联剂 | Mw | Mw/Mn | 耐IR回焊性评价 | |
实施例1 | A-1 | 有 | 68万 | 2 | 27/27 |
实施例2 | A-2 | 有 | 52万 | 1.8 | 27/27 |
实施例3 | A-3 | 有 | 45万 | 1.3 | 27/27 |
实施例4 | A-3 | 无 | 45万 | 1.3 | 27/27 |
实施例5 | A-1 | 有 | 68万 | 2 | 27/27 |
实施例6 | A-1 | 有 | 68万 | 2 | 27/27 |
比较例1 | A-4 | 有 | 42万 | 4.2 | 13/27 |
比较例2 | A-5 | 有 | 13万 | 1.3 | 0/27 |
比较例3 | A-4 | 无 | 42万 | 4.2 | 0/27 |
比较例4 | A-6 | 有 | 27万 | 2.4 | 15/27 |
比较例5 | A-7 | 有 | 33万 | 3.3 | 15/27 |
Claims (8)
1.一种粘接剂组合物的制备方法,所述粘接剂组合物包含:通过使用含有有机碲的化合物作为聚合引发剂的活性自由基聚合法使丙烯酸类单体聚合而得到的重均分子量(Mw)为35万以上的丙烯酸聚合物(A)、环氧类热固化性树脂(B)及热固化剂(C)。
2.根据权利要求1所述的粘接剂组合物的制备方法,其中,所述粘接剂组合物进一步含有交联剂(D),丙烯酸聚合物(A)具有可与该交联剂反应的官能基。
3.根据权利要求2所述的粘接剂组合物的制备方法,其中,交联剂(D)含有异氰酸酯基,丙烯酸聚合物(A)含有羟基。
4.根据权利要求1~3中任一项所述的粘接剂组合物的制备方法,其中,丙烯酸聚合物(A)的重均分子量(Mw)为90万以下。
5.根据权利要求1所述的粘接剂组合物的制备方法,其中,丙烯酸聚合物(A)的分子量分布(Mw/Mn)为3以下。
6.一种单层粘接膜的制造方法,所述单层粘接膜由根据权利要求1~5中任一项所述的粘接剂组合物的制备方法制得的粘接剂组合物构成。
7.一种粘接片的制造方法,包括如下工序:将由根据权利要求1~5中任一项所述的粘接剂组合物的制备方法制得的粘接剂组合物所构成的粘接剂层形成于支撑体上。
8.一种半导体装置的制造方法,包括如下工序:将半导体晶圆粘贴于根据权利要求7所述的粘接片的制造方法制得的粘接片的粘接剂层上,将所述半导体晶圆切割成半导体芯片,使粘接剂层固着残留于所述半导体芯片上,再由支撑体剥离,将所述半导体芯片经由所述粘接剂层粘接于管芯焊盘上或其他的半导体芯片上。
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