TWI445729B - 系統級封裝型半導體裝置用樹脂組成物套組 - Google Patents
系統級封裝型半導體裝置用樹脂組成物套組 Download PDFInfo
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- TWI445729B TWI445729B TW96134199A TW96134199A TWI445729B TW I445729 B TWI445729 B TW I445729B TW 96134199 A TW96134199 A TW 96134199A TW 96134199 A TW96134199 A TW 96134199A TW I445729 B TWI445729 B TW I445729B
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- resin
- epoxy resin
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- underfill
- semiconductor device
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- 239000004065 semiconductor Substances 0.000 title claims description 60
- 239000011342 resin composition Substances 0.000 title description 13
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- 239000003822 epoxy resin Substances 0.000 claims description 91
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- 238000000034 method Methods 0.000 claims description 25
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- 239000000758 substrate Substances 0.000 claims description 22
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 13
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
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Classifications
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- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
- H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
- H01L23/3128—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation the substrate having spherical bumps for external connection
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- 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
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
- H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
- H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
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Description
本發明涉及一種適合用於製作系統級封裝(system-in-package,以下簡稱為SIP)型半導體裝置的樹脂組成物。詳細而言,本發明是涉及一種樹脂組成物套組,此樹脂組成物套組由根據特定特性的觀點而選擇的底部填充劑及樹脂密封劑的組合構成,並且可提供與基板表面的密著性以及耐高溫熱衝擊性優良的半導體裝置。
隨著電氣機器的小型化、輕量化、高功能化,半導體的封裝方法的主流也由插針型(pin-insertion type)向表面封裝(surface mounting)轉變。近年來,廣泛使用SIP,此SIP是通過將多個半導體元件(矽晶片,silicon die)形成一個封裝(package),來減少表面封裝面積。特別是也使用堆疊積層(stack lamination)型SIP,此SIP是在以倒裝晶片(flip chip)方式封裝的半導體元件上積層至少一個其他半導體裝置,且以打線接合(wire bonding)連接。
如圖1所示,倒裝晶片是在基板1的佈線圖案(wiring pattern)面上介隔多個凸點(bump)2來搭載半導體晶片3的方式,所述基板1與半導體晶片3的間隙(焊料凸點(solder bump)2之間的間隙)中填充了底部填充劑4。圖2以及圖3是如下SIP,即,在利用所述倒裝晶片進行連接的半導體晶片上,介隔晶片黏接劑層(die attach adhesive layer)5來積層其他半導體晶片。
必須使此SIP在進行回流焊(soldering reflow)時不在底部填充劑與晶片(die)或者基板的界面產生剝離,在基板封裝時不在封裝中產生龜裂(crack)。特別是隨著焊料(solder)的無鉛化,有必要以底部填充劑來彌補已降低的焊料接著性。
作為不會產生所述剝離以及龜裂的樹脂,提出有液狀環氧樹脂/烷基取代芳香族二胺系樹脂材料(日本專利特開平9-176287號公報、日本專利特開平9-176294號公報)。一般認為,此材料與基板、金屬、阻焊劑(solder resist)等的接著性優良,可提供耐回流焊性(reflow resistance)、耐溫度循環龜裂性優良的高可靠性封裝。
但是,發現在以樹脂密封導體裝置整體後,這些樹脂有時也會產生剝離等。因此,本發明的目的在於提供一種底部填充劑及樹脂密封劑,所述底部填充劑即使在裝置被樹脂密封以後,也不會在基板的界面產生剝離,所述樹脂密封劑與所述底部填充劑組合後,可提供高可靠性封裝。即,本發明如下所述。
〔1〕一種套組,其是用來形成系統級封裝型半導體裝置的底部填充部的底部填充劑、用來形成系統級封裝型半導體裝置的樹脂密封部的樹脂密封劑的套組,系統級封裝型半導體裝置包括:基板;以倒裝晶片方式連接在基板上的第一半導體元件;第一半導體元件與基板之間的底部填充部;配置在第一半導體元件上側的至少1個第二半導體元件;以及覆蓋第一半導體元件、底部填充部以及第二半導體元件的樹脂密封部。
套組之特徵在於滿足下述條件:1)底部填充劑硬化物的Tg大於等於100℃,並且與樹脂密封劑硬化物的Tg之差小於等於20℃;2)底部填充劑硬化物在小於等於(Tg-30℃)的溫度下的線膨脹係數(coefficient of linear expansion)與樹脂密封劑硬化物在小於等於(Tg-30℃)的溫度下的線膨脹係數之和小於等於42 ppm/℃;以及3)樹脂密封劑硬化物在小於等於(Tg-30℃)下的線膨脹係數相對於底部填充劑硬化物在小於等於(Tg-30℃)下的線膨脹係數之比為0.3~1.0。
〔2〕一種半導體裝置,其是系統級封裝型半導體裝置,系統級封裝型半導體裝置包括:基板;以倒裝晶片方式連接在基板上的第一半導體元件;第一半導體元件與基板之間的底部填充部;配置在第一半導體元件上側的至少1個第二半導體元件;以及覆蓋第一半導體元件、底部填充部以及第二半導體元件的樹脂密封部。
半導體裝置的特徵在於:底部填充部以及樹脂密封部分別由〔1〕的套組的底部填充劑硬化物以及樹脂密封劑硬化物所構成。
因為底部填充劑硬化物與樹脂密封劑硬化物的Tg以及線膨脹係數為特定組合,所以套組在回流焊時等即使處於高溫中,也不會在硬化物間等產生剝離。
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說明如下。
對所述1)~3)的各條件加以說明。條件1)是底部填充劑硬化物的Tg與樹脂密封劑硬化物的Tg的關係。Tg的測定可利用熱機械分析(thermomechanical analysis,TMA)分析、黏彈性測定(viscoelasticity test)等眾所周知的方法進行。底部填充劑硬化物的Tg大於等於100℃,優選大於等於120℃。如果此Tg小於100℃,則有回流焊時所述底部填充劑硬化物與元件的密著性下降而產生剝離的情況。Tg的上限實際上為200℃左右。並且,此Tg與樹脂密封劑硬化物的Tg之差小於等於20℃,差也可以為0℃,即兩者的Tg相同。2個Tg中無論哪一個較高均可。如果所述差大於等於20℃,則處於高熱時,會存在如下情況:在底部填充部與樹脂密封部之間施加應力,而產生底部填充部及樹脂密封部的剝離、底部填充部與鈍化膜(passivation film)的剝離。
所述2)以及3)是線膨脹係數的關係。線膨脹係數例如可利用TMA分析進行測定。在小於等於(Tg-30℃)的溫度下的線膨脹係數如果小於等於(Tg-30℃),則在任意溫度範圍內均無有意義的差,在本發明中使用50℃~80℃。在小於等於(Tg-30℃)的溫度下,底部填充劑硬化物的線膨脹係數與樹脂密封劑硬化物的線膨脹係數之和小於等於42 ppm/℃,優選小於等於40 ppm/℃。如果此和大於42 ppm/℃,則存在如下情況:在高熱下會施加應力,而產生底部填充部與樹脂密封部的剝離、底部填充部與鈍化膜的剝離。
並且,所述兩者之比,即在小於等於(Tg-30℃)的溫度下的樹脂密封劑硬化物的線膨脹係數/在小於等於(Tg-30℃)的溫度下的底部填充劑硬化物的線膨脹係數,為0.3~1.0,優選0.3~0.9。在此比小於所述下限值的情況下,有在與底部填充部之間產生龜裂或者剝離的顧慮。另一方面,在此比大於所述上限值,即樹脂密封劑硬化物的線膨脹係數大於底部填充劑硬化物的線膨脹係數的情況下,也有產生龜裂的顧慮。
優選的底部填充劑含有:(A)環氧樹脂;(B)硬化劑,其量滿足[(A)環氧樹脂中環氧基的當量/(B)硬化劑中的環氧基及反應性基團的當量]為0.7~1.2;以及(C)無機填充劑,相對於100重量份(A),此(C)無機填充劑為50重量份~500重量份。以下,對各成分加以說明。
本發明中所使用的(A)環氧樹脂優選為:雙酚A型環氧樹脂、雙酚F型環氧樹脂等雙酚(bisphenol)型環氧樹脂,苯酚酚醛清漆(phenol novolac)型環氧樹脂、甲酚酚醛清漆(cresol novolac)型環氧樹脂等酚醛清漆(novolac)型環氧樹脂,萘(naphthalene)型環氧樹脂,聯苯(biphenyl)型環氧樹脂,環戊二烯(dicyclopentadiene)型環氧樹脂等,以及這些環氧樹脂的混合物。這些環氧樹脂中,優選雙酚A型環氧樹脂、雙酚F型環氧樹脂。
也優選使用以下述式表示的環氧樹脂。
此處,R是碳數為1~20、優選為1~10、更優選為1~3的一價烴基,例如可列舉甲基、乙基、丙基等烷基,乙烯基、烯丙基等烯基等。另外,n是1~4的整數,特別是1或者2。
此外,在使用所述式(5)的環氧樹脂時,推薦此環氧樹脂的含量在總環氧樹脂中為25 wt%(重量百分比)~100 wt%,更優選為50 wt%~100 wt%,最優選為75 wt%~100 wt%。如果所述環氧樹脂的含量小於25 wt%,則有組成物的黏度上升、或者硬化物的耐熱性下降的顧慮。所述通式(5)的環氧樹脂之例,可列舉日本化藥公司製造的MRGE等。
環氧樹脂的硬化劑,可列舉胺(amine)系、聚硫醇(polymercaptan)系、咪唑(imidazole)系、酸酐(anhydride)系以及雙氰胺(dicyandiamide)等。優選使用胺硬化劑以及酸酐硬化劑。胺硬化劑優選以下述通式(1)~(4)表示的至少1種芳香族胺化合物。
(式中,R1
~R4
獨立為選自碳數為1~6的一價烴基、CH3
S-以及C2
H5
S-的基團。)
上式中,R1
~R4
的一價烴基優選碳數為1~6的基團,特別優選碳數為1~3的基團,可列舉:甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基、己基等烷基,乙烯基、烯丙基、丙烯基、丁烯基、己烯基等烯基,苯基等,或者這些烴基的氫原子的一部分或者全部被氯、氟、溴等鹵原子取代的氯甲基、溴乙基、三氟丙基等被鹵素取代的一價烴基。
所述芳香族胺系硬化劑通常在常溫下為固體,如果直接調配,則樹脂黏度會上升,操作性明顯變差,因此優選在不與環氧樹脂反應的溫度下進行熔融混合。即,希望以後述調配量,在70℃~150℃的溫度範圍,與環氧樹脂熔融混合1小時~2小時。如果混合溫度低於70℃,則有芳香族胺系硬化劑變得難以充分相容的顧慮,如果混合溫度高於150℃,則有與環氧樹脂反應而黏度上升的顧慮。並且,如果混合時間小於1小時,則有芳香族胺系硬化劑並不充分相容而導致黏度上升的顧慮,如果混合時間大於2小時,則有與環氧樹脂反應而黏度上升的顧慮。
酸酐硬化劑,可列舉:甲基四氫鄰苯二甲酸酐(methyl tetrahydrophthalic anhydride)、甲基六氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基雙環庚烯二甲酸酐(methyl himic anhydride)、均苯四甲酸二酐(Pyromellitic dianhydride)、順丁烯二醯化別羅勒烯(Allo-ocimene Maleate)、二苯甲酮四甲酸二酐(benzophenone tetracarboxylic dianhydride)、3,3',4,4'-聯苯四雙二苯甲酮四甲酸二酐、(3,4-二羧基苯基)醚二酐((3,4-dicarboxy phenyl)ether dianhydride、雙(3,4-二羧基苯基)甲烷二酐(bis(3,4-dicarboxy phenyl)methane dianhydride、2,2-雙(3,4-二羧基苯基)丙烷二酐、3,4-二甲基-6-(2-甲基-1-丙烯基)-1,2,3,6-四氫鄰苯二甲酸酐、1-異丙基-4-甲基-二環[2.2.2]辛-5-烯-2,3-二甲酸酐的混合物。特別優選甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、3,4-二甲基-6-(2-甲基-1-丙烯基)-1,2,3,6-四氫鄰苯二甲酸酐、1-異丙基-4-甲基-二環[2.2.2]辛-5-烯-2,3-二甲酸酐以及這些酸酐的混合物。所述硬化劑,例如市售有Rikacid MH700(新日本理化股份有限公司製造)、YH306、YH307(日本環氧樹脂公司製造)。
以相對於(A)環氧樹脂的當量比[(A)環氧樹脂/(B)硬化劑]計,將(B)硬化劑的調配量設為大於等於0.7且小於等於1.2、優選0.8~1.0的範圍。調配莫耳比小於所述下限值時,有如下顧慮:殘存未反應的環氧基,玻璃化轉變溫度(glass transition temperature)降低,且密著性降低。調配莫耳比大於所述上限值時,有如下顧慮:硬化物變硬變脆,在回流焊時或者溫度循環時會產生龜裂。
無機填充劑(C)可使用眾所周知的各種無機填充劑。例如可列舉:熔融二氧化矽、結晶二氧化矽、氧化鋁(alumina)、氮化硼(boron nitride)、氮化鋁(aluminium nitride)、氮化矽、氧化鎂(magnesia)、矽酸鎂(magnesium silicate)、鋁等。所述無機填充劑中,從使組成物的黏度降低的方面考慮,優選細球狀(fine spherical)的熔融二氧化矽,更優選利用溶膠凝膠法(sol-gel method)或者爆燃法(deflagration method)製造的球狀二氧化矽。
為了增強與樹脂的結合強度,無機填充劑優選調配預先以矽烷偶聯劑、鈦酸酯偶聯劑等偶聯劑進行表面處理的無機填充劑。所述偶聯劑,優選使用:γ-縮水甘油氧基丙基三甲氧基矽烷(γ-glycidoxy propyl triethoxy silane)、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷等環氧基矽烷,N-β(胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷,γ-巰基矽烷(γ-mercaptosilane)等巰基矽烷等矽烷偶聯劑。此處對表面處理所使用的偶聯劑的調配量以及表面處理方法並無特別限制。
無機填充劑的粒徑優選根據半導體裝置的間隙尺寸(gap size)、即基板與半導體晶片的間隙寬度來進行適當調整。間隙尺寸典型的是10 μm~200 μm左右,此時,從底部填充劑的黏度以及硬化物的線膨脹係數方面考慮,平均粒徑為0.1 μm~5 μm,優選0.5 μm~2 μm。如果平均粒徑小於所述下限值,則組成物的黏度上升,變得難以浸入到間隙內;如果平均粒徑大於所述上限值,則有填充劑阻礙浸入而產生未填充部分的顧慮。
並且,無機填充劑優選具有如下粒度分佈:具有大於等於所述間隙尺寸1/2的粒徑的無機填充劑少於等於無機填充劑全體的0.1 wt%,特別優選0 wt%~0.08 wt%。優選使用如下無機填充劑:相對於間隙尺寸,平均粒徑(d50
:中值粒徑(median size))小於等於約1/10,最大粒徑(d98
:98%累積徑)小於等於1/2。此外,填充劑的粒徑及粒度分佈可利用激光衍射法的粒度分佈測定來獲得。另外,相對於間隙尺寸粒徑大於等於1/2的填充劑的測定方法,例如可使用粒徑檢查方法,此粒徑檢查方法是將無機填充劑與純水以1:9(重量)的比例混合,然後進行超聲波處理使凝集物充分粉碎,接著以孔徑尺寸為間隙尺寸的1/2的過濾器篩濾所述凝集物,秤量篩上的剩餘量。
為了控制所述粒徑及其分佈,發現最適合的是溶膠凝膠法或者爆燃法。與熔融二氧化矽相比,以這些方法製造出的球狀二氧化矽具有為細球狀且粒度分佈也易於設計的優點。此外,溶膠凝膠法以及爆燃法可以是先前眾所周知的方法。
大於等於無機填充劑全體的80 wt%、特別優選90 wt%~100 wt%、尤其優選95 wt%~100 wt%,優選以溶膠凝膠法或者爆燃法製造的球狀二氧化矽。如果小於無機填充劑的80 wt%,則有組成物的流動性較差的情況。
相對於100重量份(A)環氧樹脂,無機填充劑(C)的調配量優選設為50重量份~500重量份,更優選為100重量份~400重量份的範圍。如果所述調配量小於所述下限值,則有硬化物的膨脹係數變大的顧慮。如果所述調配量大於所述上限值,則有組成物的黏度變高,對間隙的浸入性不良的顧慮。
為了降低硬化物的應力,可在本發明的底部填充劑中,以不阻礙本發明目的之量調配:矽酮改性環氧樹脂(silicone modified epoxy resin)、矽橡膠(silicone gum)、矽油(silicone oil)、液態的聚丁二烯橡膠(polybutadiene gum)、甲基丙烯酸甲酯-丁二烯-苯乙烯等柔性樹脂(flexibility resin)、用於提高接著性的碳官能性矽烷、碳黑(carbon black)等顏料、染料、抗氧化劑。
矽酮改性環氧樹脂優選矽酮環氧改性樹脂,其是由通過使含有烯基的環氧樹脂或者含有烯基的酚樹脂的烯基、與有機聚矽氧烷(organopolysiloxane)的SiH基進行加成反應(addition reaction)而獲得的共聚物所構成,所述有機聚矽氧烷是以下述平均組成式(6)表示,1分子中的矽原子數為20~400,且與矽原子直接鍵結的氫原子(SiH基)個數為1~5,優選2~4,特別優選2個。
Ha
R5 b
SiO(4-a-b)
(6)
(其中,式中R5
是被取代或者未被取代的一價烴基,a為0.01~0.1,b為1.8~2.2,且1.81≦a+b≦2.3)
所述式中的R5
的一價烴基,優選碳數為1~10、特別優選1~8的烴基,可列舉:甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基、己基、辛基、癸基等烷基,乙烯基、烯丙基、丙烯基、丁烯基、己烯基等烯基,苯基、二甲苯基、甲苯基等芳基,苄基、苯乙基、苯丙基等芳烷基等,或者這些烴基的氫原子的一部分或者全部被氯、氟、溴等鹵原子取代的氯甲基、溴乙基、三氟丙基等被鹵素取代的一價烴基。
所述共聚物優選以下述式(7)表示的結構。
所述式(7)中,R5
如上所述,R6
為-CH2
CH2
CH2
-、-OCH2
-CH(OH)-CH2
-O-CH2
CH2
CH2
-或-O-CH2
CH2
CH2
-,R7
是氫原子或者碳數為1~4的烷基。n為4~199、優選19~109的整數,p為1~10的整數,q為1~10的整數。
調配所述矽酮改性環氧樹脂時,相對於100重量份(A)環氧樹脂,優選以有機矽氧烷部分的量含有1重量份~20重量份、特別是2重量份~15重量份之方式進行調配,借此,可降低硬化物的應力,並提高對基板的密著性。此處,有機矽氧烷部分的量以下述式表示。
有機矽氧烷部分的量=(有機矽氧烷部分的分子量/矽酮改性環氧樹脂的分子量)×添加量
本發明的底部填充劑,例如是將所述(A)~(C)無機填充劑以及所需的任意成分,同時或者分別,根據需要一邊進行加熱處理,一邊進行攪拌、溶解、混合、分散。這些操作中所使用的裝置並無特別限定,可使用具備攪拌、加熱裝置的擂潰機、三輥混合機(three roll)、球磨機(ball mill)、行星式混合機(planetary mixer)等。另外,也可將這些裝置加以適當組合。
以所述製備法獲得的底部填充劑,優選在25℃下具有1 Pa.s~500 Pa.s的黏度,特別優選具有1 Pa.s~150 Pa.s的黏度。此底部填充劑的成形方法、成形條件可為眾所周知,優選最初在100℃~120℃下進行大於等於0.5小時的熱烘箱固化(hot oven cure),接著在150℃~175℃下進行大於等於0.5小時的熱烘箱處理。如果100℃~120℃下的加熱小於0.5小時,則有在硬化後產生空隙(void)的情況。另外,如果150℃~175℃下的加熱小於0.5小時,則有無法獲得充分的硬化物特性的情況。
其次,對本發明中的樹脂密封劑加以說明。樹脂密封劑含有:(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂;(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂,其量滿足[(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂中環氧基的當量/(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂中酚性羥基的當量]為0.8~1.2;以及(c)無機填充劑,相對於(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂與(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂的總量100重量份,所述無機填充劑為500重量份~1,100重量份。以下對各成分加以說明。
密封劑的環氧樹脂,例如使用以下述式表示的環氧樹脂。
式中,R1
是碳數為1~4的烷基,例如可列舉:甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基等,其中優選甲基。a為0~4,b為0~3的整數,Q為0~10的數。此樹脂的硬化物的柔性優良,彈性率低且耐衝擊性優良。
以上式表示的樹脂,可例示以下樹脂。
(式中,p為0.5~1.5。)
三苯基環氧樹脂,例如有以下述式表示的樹脂。
此處,Gr是縮水甘油基。此樹脂從高耐熱性方面來看較為有用。
可於密封劑組成物中並用其他環氧樹脂。所並用的環氧樹脂可列舉:酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、三酚烷烴型環氧樹脂、雜環型環氧樹脂、含萘環的環氧樹脂、雙酚A型環氧化合物、雙酚F型環氧化合物、芪(stilbene)型環氧化合物等,這些環氧樹脂中,可單獨使用1種,或者混合2種或2種以上使用。另外,這些環氧樹脂中,優選熔融時黏度低的雙酚A型環氧化合物、雙酚F型環氧化合物、芪型環氧化合物等。此外,並用其他環氧樹脂時,所述雙苯基樹脂、三官能性環氧樹脂量優選為(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂的50 wt%~100 wt%,更優選為70 wt%~100 wt%。
使用以下述式表示的聯苯基芳烷基型酚樹脂可提供耐熱性及耐龜裂性優良的硬化物,因此優選使用。
式中,R2
是碳數為1~4的烷基,例如為甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基或者苯基,其中優選甲基、苯基。a為0~4,b為0~3的整數,Q為0~10的數。
以上式表示的酚樹脂,可例示以下樹脂。
(式中,m平均為0.5~1.5。)
三酚樹脂以下述式表示。
式中,R是氫原子或者碳數為1~4的烷基,例如為甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基。
三酚型樹脂的耐熱性優良,且黏度低,因此可提高玻璃化轉變溫度,實現填料(filler)的高填充化,例如可使用R為氫原子的下述樹脂。
此外,(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂也可含有其他酚樹脂硬化劑。例如可與如下樹脂並用:苯酚酚醛清漆樹脂、含萘環的酚樹脂、苯酚芳烷基型酚樹脂、聯苯型酚樹脂、脂環式酚樹脂、雜環型酚樹脂、雙酚A型酚樹脂、雙酚F型酚樹脂等。並用時,優選設為小於等於(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂的50 wt%,更優選為30 wt%。
所述(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂及(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂的調配比例如果是相對於(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂的環氧基1當量,(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂中所含的苯酚當量小於0.8,則有成型時的硬化性變差的情況,如果大於1.2,則有硬化物的吸水量增大的情況。
(c)無機填充劑,可使用通常調配於樹脂組成物中的填充劑,例如可列舉:球狀的熔融二氧化矽、破碎狀熔融二氧化矽、結晶性二氧化矽等二氧化矽類,氧化鋁、莫來石(mullite)、氮化矽、氮化鋁、氮化硼、氧化鈦、玻璃纖維等。這些無機填充劑中,優選二氧化矽,特別優選球狀的熔融二氧化矽,從成形性、流動性方面考慮,更優選其平均粒徑為5 μm~30 μm、且以濕篩法測定的大於75 μm的粒徑少於等於0.2 wt%的二氧化矽。
(c)無機填充劑的調配量優選相對於(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂與(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂的總量100重量份設為500重量份~1,100重量份。如果所述調配率小於500重量份,則樹脂的比例較高,線膨脹係數變大,有時半導體裝置會產生翹曲。另外,如果所述調配量大於1,100重量份,則有因黏度變高而難以成形的顧慮。
此外,為了增強樹脂與無機填充劑表面的結合強度,無機填充劑優選調配預先以胺基矽烷、環氧基矽烷等矽烷偶聯劑等進行表面處理的填充劑。此處,對表面處理中所使用的偶聯劑量以及表面處理方法並無特別限制。
另外,密封劑組成物可進一步調配各種添加劑。例如可在不損害本發明目的之範圍內添加調配:熱塑性樹脂、熱塑性彈性體、有機合成橡膠、矽酮系等低應力劑、巴西棕櫚蠟(carnauba wax)等蠟類等脫模劑(mold release agent)、碳黑等著色劑、鹵化樹脂、銻氧化物、鉬酸鹽等阻燃劑、鹵素捕集劑(haolgen trapping agent)等添加劑。
製備密封劑組成物的方法,可按照規定的組成比來調配環氧樹脂、酚樹脂硬化劑、無機填充劑以及所需的其他添加物,以亨舍爾混合機(Henschel mixer)等將其充分均勻地混合,然後利用熱輥(hot roll)、捏合機(kneader)、擠壓機(extruder)等進行熔融混合處理,接著使其冷卻固化,粉碎成適當大小,來製作成形材料。另外,為了在進行攪拌、混合以及分散時使組成物充分融合,可添加先前眾所周知的各種矽烷偶聯劑。矽烷偶聯劑可使用與所述底部填充劑相關說明的偶聯劑相同的偶聯劑。
以下,列舉實施例以及比較例,來進一步詳細說明本發明。
底部填充劑的製備
通過將表1所示的各重量份的各成分以三輥混合機均勻地混練,來獲得12種液狀環氧樹脂組成物(UF-1~UF-12)。
在表1中,各成分如下所述。
(A)環氧樹脂
環氧樹脂A1:以下述式表示的三官能型環氧樹脂(Epikote 630H:日本環氧樹脂股份有限公司製造)
環氧樹脂A2:以下述式表示的雙酚F型環氧樹脂(RE303S-L:日本化藥股份有限公司製造)
(B)硬化劑
硬化劑B1:3,3'-二乙基-4,4'-二胺基二苯基甲烷(Kayahard AA:日本化藥公司製造)硬化劑B2:3,3',5,5'-四乙基-4,4'-二胺基二苯基甲烷(C-300S:日本化藥公司製造)硬化劑B3:以下述式表示的順丁烯二醯化別羅勒烯(Allo-ocimene Maleate)(YH307:日本環氧樹脂股份有限公司製造)
硬化劑B4:以下述式表示的六氫鄰苯二甲酸酐混合物(Rikacid MH700:新日本理化股份有限公司製造)
(C)無機填充劑
球狀二氧化矽:在下述粒徑檢查方法中,過濾器1剩餘量(粒徑大於等於25 μm)為0.01 wt%、平均粒徑為2.5 μm的以爆燃法製造的球狀二氧化矽。
二氧化矽粒徑檢查方法
將二氧化矽與純水以1:9(重量)的比例混合,然後進行超聲波處理,將凝集物充分粉碎,以過濾器1(孔徑為25 μm)或者過濾器2(孔徑為10 μm)篩濾,秤量篩上所殘留的二氧化矽來測定剩餘量。進行5次測定,將其平均值作為測定值,以wt%表示。
其他添加劑
矽烷偶聯劑:γ-縮水甘油氧基丙基三甲氧基矽烷(KBM403:信越化學工業股份有限公司製造)溶劑:聚乙二醇甲基乙基乙酸酯(PGMEA:沸點為146℃)硬化催化劑:2-乙基-4-甲基咪唑(2E4MZ:四國化成股份有限公司製造)對所得的各組成物進行以下所示的試驗。將結果表示於表1中。
(1)黏度對各組成物,依據JIS Z-8803,於測定溫度25℃下,使用E型黏度計,測定將樣品制成套組2分鐘後的值。
(2)Tg(玻璃化轉變溫度)、CTE1(小於等於(Tg-30℃)的溫度下的線膨脹係數)、CTE2(大於Tg的溫度下的膨脹係數)
以10℃/min從常溫升溫,在200℃~260℃的溫度下保持大於等於30秒且小於等於5分鐘,獲得硬化物。將此硬化物冷卻至常溫,然後切割成5 mm×5 mm×15 mm的試驗片,利用TMA(熱機械分析裝置),以毎分鐘5℃進行升溫,來測定Tg。
硬化物的(Tg-30℃)小於100℃時,在-30℃~0℃下測定CTE1,在150℃~180℃下測定CTE2。
硬化物的(Tg-30℃)大於等於100℃時,在50℃~80℃下測定CTE1,在200℃~230℃下測定CTE2。
(3)空隙試驗在倒裝晶片型半導體裝置的間隙中,滴下各樹脂組成物使其浸入,在165℃下使其硬化30分鐘,然後以C-SAM(SONIX公司製造)確認有無空隙,所述倒裝晶片型半導體裝置是在30 mm×30 mm的FR-4基板上,以間隙尺寸達到50 μm的方式設置塗布有聚醯亞胺(polyimide,PI)膜的10 mm×10 mm矽晶片的倒裝晶片型半導體裝置。
(4)接著力試驗在上表面直徑為2 mm、下表面直徑為5 mm、高度為3 mm的圓錐台(truncated cone)狀聚四氟乙烯制模具中注入各樹脂組成物,然後在其上載置塗布有PI膜的矽晶片,在150℃下使其硬化3小時。硬化後,以固定速度(1 mm/sec)擠壓除去聚四氟乙烯制模具後獲得的試驗片,借此來測定剪斷接著力,作為初始值。進一步,將硬化的試驗片在壓力鍋試驗機(pressure cooker tester)(121℃/2.1 atm)中保存336小時後,以相同的方法測定接著力。在任一情況下均以5個試驗片進行測定,將其平均值記作接著力。
(5)韌性值K1c
將各樹脂組成物在150℃下硬化3小時,然後根據ASTM # D5045,對所得的硬化物測定常溫下的韌性值K1c
。
樹脂密封劑的製備
通過將表2所示的各成分以三輥混合機進行均勻混練,來獲得6種密封樹脂組成物(EMC-1~EMC-6)。在表2中,各成分如下所述。
(a)環氧樹脂
環氧樹脂a1:以下述式表示的聯苯基芳烷基型環氧樹脂(NC-3000:日本化藥股份有限公司製造)
環氧樹脂a2:以下述式表示的三官能型環氧樹脂(EPPN-501H:日本化藥股份有限公司製造)
(b)酚樹脂
酚樹脂b1:以下述式表示的三官能型酚樹脂(MEH-7500:明和化成股份有限公司製造)
酚樹脂b2:以下述式表示的聯苯基芳烷基型酚樹脂(MEH-7851:明和化成股份有限公司製造)
(c)無機填充劑
球狀二氧化矽:在下述粒徑檢查方法中,過濾器1剩餘量(粒徑大於等於25 μm)為0.01 wt%、平均粒徑為2.5 μm的以爆燃法製造的球狀二氧化矽。
二氧化矽粒徑檢查方法
將二氧化矽與純水以1:9(重量)的比例混合,然後進行超聲波處理,將凝集物充分粉碎,以過濾器1(孔徑為25 μm)或者過濾器2(孔徑為10 μm)進行篩濾,秤量篩上所殘留的二氧化矽,來測定剩餘量。進行5次測定,將其平均值作為測定值,以wt%表示。
其他添加劑
硬化促進劑:三苯基膦(北興化學股份有限公司製造)矽烷偶聯劑:γ-縮水甘油氧基丙基三甲氧基矽烷(KBM403:信越化學工業股份有限公司製造)碳黑:(Denka Black:電氣化學工業股份有限公司製造)脫模劑:巴西棕櫚蠟(Nikko Fine Products股份有限公司製造)使用所得的各樹脂組成物,進行以下所示的試驗。將其結果表示於表2中。
(1)旋流(spiral flow)值使用符合EMMI規格的金屬模具,在175℃、6.9 N/mm2
、成形時間為120秒的條件下進行測定。
(2)熔融黏度使用高化式流變儀(Koka Flow Tester),在10 kgf的加壓條件下,使用直徑為1 mm的噴嘴,在溫度175℃下測定黏度。
(3)Tg(玻璃化轉變溫度)、CTE1(低於等於(Tg-30℃)的溫度下的線膨脹係數)、CTE2(高於Tg的溫度下的膨脹係數)以10℃/min從常溫升溫,在180℃的溫度下保存24小時,獲得硬化物。將此硬化物冷卻至常溫,然後切割成5 mm×5 mm×15 mm的試驗片,利用TMA(熱機械分析裝置),以毎分鐘5℃進行升溫,來測定Tg。
硬化物的(Tg-30℃)低於100℃時,在-30℃~0℃下測定CTE1,在150℃~180℃下測定CTE2。
硬化物的(Tg-30℃)高於等於100℃時,在50℃~80℃下測定CTE1,在200℃~230℃下測定CTE2。
(4)凝膠化時間在加熱至175℃的熱板上薄薄地攤開組成物,以刮刀(spatula)刮取樹脂,將樹脂從熱板面剝落的時刻作為凝膠化時間。
(5)韌性值K1c
在溫度為175℃、壓力為6.9 N/mm2
、成形時間為90秒的條件下使樹脂組成物成形,在180℃下硬化4小時後獲得硬化物,根據ASTM # D5045,測定此硬化物在常溫下的韌性值K1c
。
(6)彎曲強度以及彈性率在溫度為175℃、壓力為6.9 N/mm2
、成形時間為90秒的條件下使樹脂組成物成形,在180℃下硬化4小時後獲得硬化物,根據JIS # K6911,測定此硬化物在常溫下的彎曲彈性率、強度。
(7)比重在溫度為175℃、壓力為6.9 N/mm2
、成形時間為90秒的條件下使樹脂組成物成形,在180℃下硬化4小時後獲得硬化物,根據JIS # K6911,測定此硬化物在常溫下的比重。
實施例1~22、參考例1~19
使用表3所示的底部填充劑與樹脂密封劑的組合,製成SIP型半導體裝置,進行以下所示的剝離試驗以及熱衝擊試驗。將結果表示於表3~表6中。
半導體裝置的製作
製作具有圖1所示結構的試驗用半導體裝置。在用於製作32 mm×32 mm且厚度為1.2 mm的封裝的厚度為0.4 mm的雙順丁烯二醯亞胺三嗪樹脂(bismaleimide-triazine resin,BT樹脂)基板上,使用約100 μm的間隔片(spacer)設置9個10 mm×10 mm×0.3 mm矽晶片,使樹脂進入到矽晶片與基板之間的間隙中,以120℃/0.5小時+165℃/3小時的條件使其硬化。
在175℃、6.9 N/mm2
、固化時間為2分鐘的轉變(transfer)條件下使樹脂密封劑成型,來密封所得的裝置,然後在175℃下進行5小時的後固化(post cure),利用切片機(dicer)切割(dicing)成12 mm×12 mm,獲得12 mm×12 mm×約3 mm的半導體晶片。
(1)壓力鍋試驗將18個以所述方法獲得的半導體晶片在30℃/65%RH的條件下放置192小時(JEDEC Level 3的條件)後,使其通過設定為最高溫度265℃的IR回流焊爐5次,然後使用SONIX公司製造的超聲波影像診斷儀C-SAM來檢查有無剝離。接著,與上述同樣來檢查在壓力鍋中、121℃/2.1 atm的環境下放置336小時後有無剝離。在表3~表6中,將未觀察到剝離的晶片以G表示,將觀察到剝離的晶片以NG表示。
(2)熱衝擊試驗將18個以所述方法獲得的半導體晶片在30℃/65%RH的條件下放置192小時後,使其通過設定為最高溫度265℃的IR回流焊爐5次,然後以-65℃下30分鐘、150℃下30分鐘作為一個週期,與上述同樣檢查250、500、750、以及1000個週期後的剝離。在表3~表6中表示觀察到剝離的晶片數(%)。
參考例10~22中,底部填充劑與樹脂密封劑的Tg均具有大於20℃的差,在壓力鍋試驗中觀察到剝離。參考例1、2、4、5中,在小於等於Tg-30℃的溫度下的膨脹係數之和大於45 ppm/℃,在回流焊後觀察到剝離。參考例3中,樹脂密封劑的線膨脹係數相對於底部填充劑的線膨脹係數之比小於0.3,在回流焊後觀察到剝離。
相對於這些情況,實施例1~22的裝置沒有剝離,耐熱衝擊性也優良。
本發明的樹脂組成物套組適於製作耐熱衝擊性優良的系統級封裝型半導體裝置。
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
1...有機基板
2...凸點
3...半導體晶片
4...底部填充劑
5...晶片黏接劑層
6...樹脂密封部
圖1是倒裝晶片型半導體裝置的一例的剖面圖。
圖2是系統級封裝型半導體裝置的一例的剖面圖。
圖3是系統級封裝型半導體裝置的一例的剖面圖。
Claims (5)
- 一種系統級封裝型半導體裝置包括:基板;以倒裝晶片方式連接在所述基板上的第一半導體元件;所述第一半導體元件與所述基板之間的底部填充部;配置在所述第一半導體元件上側的至少1個第二半導體元件;以及覆蓋所述第一半導體元件、所述底部填充部以及所述第二半導體元件的全體的樹脂密封部,所述系統級封裝型半導體裝置的特徵在於,所述底部填充部是由含有下述(A)成分至(C)成分的底部填充劑的硬化物所組成:(A)環氧樹脂;(B)硬化劑,其量滿足[(A)環氧樹脂中的環氧基的當量/(B)硬化劑中的與環氧基反應的反應性基團的當量]為0.7~1.2;以及(C)無機填充劑,相對於100重量份(A),此(C)無機填充劑為50重量份~500重量份;以及所述樹脂密封部是由含有下述(a)成分至(c)成分的樹脂密封劑的硬化物所組成:(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂;(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂,其量滿足[(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂 中的環氧基的當量/(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂中的酚性羥基的當量]為0.8~1.2;以及(c)無機填充劑,相對於(a)聯苯基芳烷基型環氧樹脂或者三苯基環氧樹脂與(b)聯苯基芳烷基型酚樹脂或者三苯基酚樹脂的總量100重量份,(c)無機填充劑為500重量份~1,100重量份,所述系統級封裝型半導體裝置滿足下述條件:1)所述底部填充劑的硬化物的Tg大於等於100℃,並且與樹脂密封劑的硬化物的Tg之差小於等於20℃;2)所述底部填充劑的硬化物在小於等於(Tg-30℃)的溫度下的線膨脹係數與所述樹脂密封劑的硬化物在小於等於(Tg-30℃)的溫度下的線膨脹係數之和小於等於42ppm/℃;以及3)所述樹脂密封劑的硬化物在小於等於(Tg-30℃)下的線膨脹係數相對於所述底部填充劑的硬化物在小於等於(Tg-30℃)下的線膨脹係數之比為0.3~1.0。
- 如申請專利範圍第1項所述的系統級封裝型半導體裝置,其中(B)硬化劑是胺硬化劑或者酸酐硬化劑。
- 如申請專利範圍第2項所述的系統級封裝型半導體裝置,其中(B)硬化劑是以下述式(1)、式(2)、式(3)或者式(4)表示的芳香族胺化合物中的至少1種,式中,R1 ~R4 互相獨立為選自碳數為1~6的一價烴基、CH3 S-以及C2 H5 S-中的基團,
- 如申請專利範圍第1項所述的系統級封裝型半導體裝置,其中(C)無機填充劑是以溶膠凝膠法或者爆燃法製造的平均粒徑為0.1μm~5μm的球狀二氧化矽。
- 如申請專利範圍第1項至第4項中任一項所述的系統級封裝型半導體裝置,其中(A)環氧樹脂是選自雙酚A型環氧樹脂、雙酚F型環氧樹脂以及下述3種環氧樹脂,式中,R是碳數為1~20的一價烴基,n是1~4的整數;以及
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