TWI480326B - 用於含低k介電質之半導體裝置中作為底填密封劑之可固化樹脂組合物 - Google Patents
用於含低k介電質之半導體裝置中作為底填密封劑之可固化樹脂組合物 Download PDFInfo
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- TWI480326B TWI480326B TW099142644A TW99142644A TWI480326B TW I480326 B TWI480326 B TW I480326B TW 099142644 A TW099142644 A TW 099142644A TW 99142644 A TW99142644 A TW 99142644A TW I480326 B TWI480326 B TW I480326B
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- semiconductor device
- component
- semiconductor wafer
- epoxy resin
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Classifications
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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
- H01L21/56—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- H—ELECTRICITY
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Description
本發明係關於用於覆晶(「FC」)底填密封材料之熱固性樹脂組合物,其中一半導體晶片係透過焊料電互連直接安裝於電路上。類似地,該等組合物適用於安裝在一電路板半導體裝置上,如晶片尺寸或晶片級封裝(「CSP」)、球柵極陣列(「BGA」)、地柵極陣列(「LGA」)及類似物,其等每個在載體基板上皆具有一半導體晶片,如大型積體電路(「LSI」)。
低介電常數(「低k」)介電質材料(或層間介電層「ILD's」)繼續在先進的積體電路製造之未來開發上發揮重要作用,其能在小於0.18微米之製造製程中使用銅互連。低k ILD's係用於積體電路製造中以使銅互連與其周圍環境隔離,以確保互連之間更少的串音。串音係積體電路製造中常見的一個問題,因為其導致該電路故障。隨著該積體電路之尺寸持續變小,串音甚至變得更顯著。用於積體電路製造中之習知層間材料之介電常數一般係在>3.0之範圍。然而,隨著單一晶片上之輸入/輸出密度持續增加,串音問題亦增加。
因此,具有低於2.5之介電常數之低k ILD's係積體電路設計之重要態樣以最大化甚至更緊密之積體電路的效率。一種此材料係稱為黑鑽,且可購自Applied Materials。
已報導工業內指示利用低k ILD's進行0.09微米、及甚至0.065微米之晶片製造製程之趨勢的通告。然而,儘管晶片製造者努力實現可接受的封裝級可靠性,這方面之進展至今受阻。
隨工業持續尋找用於電路板之高級材料(自陶瓷轉向複合材料),在現今所設計之半導體封裝中觀察到比以往固有更脆(由於其不斷減少之厚度),儘管具有更大計算能力、更微細的間距、較高焊料球堆放密度及本身較小直徑焊料球及較高回流溫度(由於含鉛焊料轉變成無鉛焊料)、更大應力(由於翹曲及衝擊)之半導體晶片。
習知市售底填密封材料(如,低熱膨脹係數(「CTE」)、高模量、基於環氧樹脂之底填密封材料)似乎無法提供抗封裝應力之必要保護以防止對易脆低k ILD's之損壞。本質上易脆的低k ILD's一般比習知ILD材料(如矽氧化物、矽氮化物、氟化矽玻璃及類似物)更弱且更脆,且因此在熱偏離期間由於所引起之應力而導致斷裂及破裂。
因此,需要提供適用於高級應用之電子封裝材料,如用於FC底填密封材料之熱固性樹脂組合物,其與低k ILD's之使用相容且降低導致ILD破裂失效之內部封裝應力。此外,亦希望提供與此等熱固性樹脂組合物組裝之電子封裝、提供製造此等提供增強的物理性質之電子封裝之方法、及提供提供具有較低模量及CTE之物理性質概況的熱固性樹脂組合物之方法,其中較低模量及CTE使此等組合物對半導體封裝中之高應力FC底填密封劑應用特別具吸引力。
一般,本發明在電子封裝上提供較低內部封裝應力,如下所述。
經由低模量與低CTE之結合可實現半導體封裝中應力之降低。迄今無法在FC底填密封材料中獲得此等物理性質。直至現在仍無法獲得。
本發明提供藉由顯示室溫下6,000至10,000 MPa(如約7,000 MPa及9,000 MPa)範圍內之模量,及7至20 ppm(如約10及20 ppm)範圍內之CTE α1能顯著降低與低k ILD's組裝之半導體封裝內所發展之內部應力之熱固性樹脂組合物。在能夠固化及承受無鉛焊料回流特性(如,其中溫度在2至5分鐘之時間期間內達到240至260℃之範圍)之FC底填密封材料中之此物理性質組合顯示很可能可克服目前半導體封裝工業所面臨之一重大困難。
此等性能特性在如以下各者之半導體裝置封裝技術中特別重要:使用具有銅電互連及至少一低k ILD層之半導體晶片;大尺寸(通常一邊超過2.5 cm)之半導體晶片;相較於約350微米之目前標稱厚度,使用較薄(如小於100微米)之半導體晶片;及相較於75微米之目前標稱膠合線厚度(「BLT」),使用較薄(如小於20微米)之底填層。
當使用具有銅互連及至少一低k ILD層之半導體晶片時,此性能特性提高組裝半導體裝置之可靠性(即,避免ILD破裂)。更明確而言,在覆晶封裝中,此性能特性提高底填密封劑與由銅互連及至少一低k ILD層所構建之半導體晶片接觸時之可靠性。依此方式,在該半導體裝置上之應力很大程度上係由該底填密封劑吸收,且因此該低k ILD受到保護。
此外,不論該半導體封裝中是否使用低k ILD's,本發明亦賦予具有極薄半導體晶片(如,小於100微米)及半導體晶片與電路板之間小於20微米之底填膠合線之半導體封裝顯著的效益及優勢。
因此,在一態樣中,本發明提供一種熱固性樹脂組合物,其組分包括環氧樹脂組分、經矽烷改質之環氧樹脂、及硬化劑(其可係氰酸酯或芳族胺)以及可選之觸媒。
在另一態樣中,本發明提供一種提高包括至少一低k ILD層之底填半導體裝置的可靠性之方法。該方法之步驟包括:提供一半導體裝置,其包括:一包括銅電互連及其間至少一低k ILD層之半導體晶片;及一表面上具有與該半導體晶片電互連之電接觸墊之載體基板;在該半導體晶片之電互連表面與該載體基板之間提供一熱可固化之底填組合物以形成一半導體裝置組件;及使該半導體裝置組件暴露於足以固化該熱可固化之底填組合物之高溫條件下。如上所述,該熱可固化之底填組合物包括環氧樹脂組分、經矽烷改質之環氧樹脂、及硬化劑(其可係氰酸酯或芳族胺)以及可選之觸媒。
在一實施例中,在組合該半導體晶片與該載體基板之後,藉由分配及充填其間之空間提供該熱可固化之底填組合物以形成該半導體裝置。
在另一實施例中,藉由分配在該半導體晶片或該載體基板中之一或兩者之至少一部份電互連表面上提供該熱可固化之底填組合物,且隨後結合該半導體晶片與該載體基板以形成該半導體裝置。
在此態樣中,亦提供一種作為覆晶組件之半導體裝置且其包括:一包括銅電互連及其間至少一k ILD層之半導體晶片;一表面上具有與該半導體晶片電互連之電接觸墊之電路板;及在該半導體晶片與該電路板之間的底填組合物。在此,該底填組合物亦包括環氧樹脂組分、經矽烷改質之環氧樹脂、及硬化劑(其可係氰酸酯或芳族胺)以及可選之觸媒。
亦提供一種作為晶片級封裝之半導體裝置組件,且其包括:一包括一具有銅電互連及其間至少一k ILD層之半導體晶片之半導體裝置,其與一載體基板電連接;一表面上具有與該半導體裝置電互連之電接觸墊之電路板;及在該半導體裝置與該電路板之間的底填組合物。在此,該底填組合物亦包括環氧樹脂組分、經矽烷改質之環氧樹脂、及硬化劑(其可係氰酸酯或芳族胺)以及可選之觸媒。
亦提供一種用於組裝一積體電路組件之方法,其步驟包括:提供一積體電路晶片;將該積體電路晶片與一載體基板連接以形成一結合組件;及使該如此形成之結合組件暴露於足以使電接觸且固化該熱可固化之底填組合物之高溫條件下,藉此在將該積體電路晶片黏附至該載體基板時建立電互連。
在此等實施例及態樣中,該導電材料可係焊料,如以下焊料合金中之一者:Sn(63):Pb(37)、Pb(95):Sn(5)、Sn:Ag(3.5):Cu(0.5)及Sn:Ag(3.3):Cu(0.7)、或銅柱與焊料互連之組合。
當相較於約350微米之目前標稱厚度,使用較薄(如小於100微米)之半導體晶片時,此性能特性提高該組裝半導體裝置之可靠性(即,避免該低k ILD或該半導體晶片本身破裂)。
更明確而言,在覆晶封裝中,此性能特性提高可靠性,因為無論該封裝中是否使用低k ILD層,預期底填密封劑將減輕晶粒應力。此外,在打線接合晶粒封裝時,此性能特性提高可靠性,因為無論在該封裝中是否使用低k ILD層且無論是否使用堆疊晶粒組件,預期晶粒接合將減輕晶粒應力。
當相較於50微米之目前標稱BLT時,使用較薄(如小於20微米)之晶片接合層時,此性能特性提高該組裝半導體裝置之可靠性(即,降低整體封裝應力,並避免該晶片接合層破裂)。
如上所述,本發明熱固性樹脂組合物除其他成份以外,尤其包括環氧樹脂組分。該環氧樹脂組分之實例如下。
例如,該環氧樹脂組分可包括兩或多種不同基於雙酚之環氧樹脂之組合。此等基於雙酚之環氧樹脂可係選自雙酚A、雙酚F、或雙酚S環氧樹脂、或其組合。此外,亦可使用兩或多種在相同樹脂類型(如A、F或S)內不同的雙酚環氧樹脂。
可令人滿意地用於本文之市售雙酚環氧樹脂之實例包括雙酚-F-型環氧樹脂(如,購自Nippon Kayaku,Japan之RE-404-S、及購自Dai Nippon Ink & Chemicals,Inc.之EPICLON 830(RE1801)、830S(RE1815)、830A(RE1826)及830W、及購自Resolution之RSL 1738及YL-983U)及雙酚-A-型環氧樹脂(如購自Resolution之YL-979及980)。
可購自Dai Nippon且如上所述之雙酚環氧樹脂係經提升為液體未經稀釋之表氯醇-雙酚F環氧樹脂,其具有比基於雙酚A環氧樹脂之習知環氧樹脂低許多之黏度且具有類似於液體雙酚A環氧樹脂之物理性質。雙酚F環氧樹脂具有比雙酚A環氧樹脂更低的黏度,在此兩種類型之環氧樹脂之間所有其他各項皆相同,其提供更低黏度且因此快速流動之底填密封材料。此四種雙酚F環氧樹脂之EEW係在165與180之間。在25℃下之黏度係3,000與4,500 cps之間(除了RE1801以外,其黏度上限為4,000 cps)。據報導,可水解之氯化物含量對RE1815及830W而言係200 ppm,對RE1826而言為100 ppm。
可購自Resolution且如上所述之雙酚環氧樹脂係被宣傳為含低氯化物之液體環氧樹脂。該等雙酚A環氧樹脂之EEW(g/eq)係在180與195之間,且在25℃下之黏度係在100與250 cps之間。據報導,YL-979之總氯化物含量係在500與700 ppm之間,且YL-980之總氯化物含量係在100與300 ppm之間。該等雙酚F環氧樹脂之EEW(g/eq)係在165與180之間,且在25℃下之黏度係在30與60之間。據報導,RSL-1738之總氯化物含量係在500與700 ppm之間,且YL-983U之總氯化物含量係在150與350 ppm之間。
除了該等雙酚環氧樹脂以外,本發明環氧樹脂組分亦包括其他環氧樹脂化合物。例如,可使用環脂族環氧樹脂,如3,4-環氧基環己基甲基-3,4-環氧基環己基碳酸酯。此外,亦可使用單官能基、二官能基或多官能基之反應性稀釋劑以調整黏度及/或降低Tg,如丁基縮水甘油醚、甲苯酚基縮水甘油醚、聚乙二醇縮水甘油醚或聚丙二醇縮水甘油醚。
在適用於本文之環氧樹脂中,亦包括酚系化合物之聚縮水甘油基衍生物,如彼等可以商標名EPON,如EPON 828、EPON 1001、EPON 1009、及EPON 1031購自Resolution者;以DER 331、DER 332、DER 334、及DER 542購自Dow Chemical Co.者;及以BREN-S購自Nippon Kayaku者。其他適宜的環氧樹脂類包括自多元醇及類似物製得之聚環氧化物及酚-甲醛清漆樹脂之聚縮水甘油基衍生物,後者係如購自Dow Chemical之DEN 431、DEN 438、及DEN 439。甲酚類似物亦可以商標名ARALDITE(如ARALDITE ECN 1235、ARALDITE ECN 1273、及ARALDITE ECN 1299)購自Ciba Specialty Chemicals Corporation。SU-8係可購自Resolution之雙酚-A-型環氧酚醛樹脂。胺類、胺基醇類及聚羧酸類之聚縮水甘油基加合物亦適用於本發明,其市售樹脂包括GLYAMINE 135、GLYAMINE 125、及GLYAMINE 115(購自F.I.C. Corporation);ARALDITE MY-720、ARALDITE 0500、及ARALDITE 0510(購自Ciba Specialty Chemicals)及PGA-X及PGA-C(購自Sherwin-Williams Co.)。
用於本文之適當的單官能基環氧樹脂共反應物稀釋劑包括彼等黏度低於該環氧樹脂組分之黏度(通常,低於約250 cps)者。
該等單官能基環氧樹脂共反應物稀釋劑應具有一環氧基及約6至約28個碳原子之烷基,其實例包括C6-28
烷基縮水甘油醚類、C6-28
脂肪酸縮水甘油基酯類及C6-28
烷基酚縮水甘油醚類。
在包括此單官能基環氧樹脂共反應物稀釋劑之情況下,此共反應物稀釋劑應以基於該組合物之總重量至多約5重量%至約15重量%(如約8重量%至約12重量%)之量使用。
該環氧樹脂組分應以約10重量%至約95重量%,理想地約20重量%至約80重量%之範圍(如約60重量%)之量存在於該組合物中。
該經矽烷改質之環氧樹脂係下列物質之組合物,其包括:作為組分(A)之由以下結構所涵蓋之環氧樹脂組分:
其中Y可存在或不存在且當存在之Y係直接鍵、CH2
、CH(CH3
)2
、C=O、或S時,在此R1
係烷基、烯基、羥基、羧基及鹵素,且在此x係1至4;作為組分(B)之由以下結構所涵蓋之環氧官能化之烷氧基矽烷:
R1
─Si(OR2
)3
其中R1
係含環氧乙烷之部分且R2
係經烷基或烷氧基-取代之具有1至10個碳原子之烷基、芳基、或芳烷基;及作為組分(C)之組分(A)與(B)之反應產物。
一種該經矽烷改質之環氧樹脂之實例係以芳族環氧樹脂(如雙酚A、E、F或S環氧樹脂或聯苯基環氧樹脂)與環氧矽烷之反應產物形式而形成,其中該環氧矽烷係由以下結構涵蓋:
R1
─Si(OR2
)3
其中R1
係含環氧乙烷之部分,其實例包括2-(乙氧基甲基)環氧乙烷、2-(丙氧基甲基)環氧乙烷、2-(甲氧基甲基)環氧乙烷、及2-(3-甲氧基丙基)環氧乙烷且R2
係經烷基或烷氧基取代之具有1至10個碳原子之烷基、芳基、或芳烷基。在一實施例中,R1
係2-(乙氧基甲基)環氧乙烷且R2
係甲基。
用於製備該經矽烷改性之環氧樹脂的芳族環氧樹脂之理想結構包括:
其中Y可存在或不存在,且當Y存在時係直接鍵、CH2
、CH(CH3
)2
、C=O、或S時,在此R1
係烷基、烯基、羥基、羧基及鹵素,且在此x係1至4。當然,當x係2至4時,預期鏈伸長型之芳族環氧樹脂亦在由此結構所涵蓋範圍內。
例如,鏈伸長型之芳族環氧樹脂可由以下結構涵蓋:
該經矽烷改質之環氧樹脂亦可係該芳族環氧樹脂、該環氧矽烷、及該芳族環氧樹脂與該環氧矽烷之反應產物之組合。該等反應產物可自該芳族環氧樹脂與環氧矽烷依1:100至100:1之重量比(如1:10至10:1之重量比)製得。
可根據希望發生固化之溫度而使用諸多不同材料作為該觸媒。例如,為了在約150℃至約180℃範圍內之溫度下實現固化,可使用多種其他材料。例如,咪唑可與芳族胺硬化劑一起使用,或金屬鹽(如乙醯丙酮酸銅或鈷)可與氰酸酯硬化劑一起使用。
當存在時,該觸媒應以該總組合物之約0.05重量%至約1重量%(理想地,約0.1重量%至約0.5重量%)之範圍之量存在。
可使用氰酸酯或芳族胺作為硬化劑。該氰酸酯之實例包括各分子上具有至少一個氰酸酯基之芳基化合物,且一般可由式Ar(OCN)m
表示,其中m係2至5之整數,且Ar係芳族基。該芳族基Ar應含有至少6個碳原子,且可衍生自(例如)芳族烴類,如苯、聯苯基、萘、蒽、芘或類似物。該芳族基Ar亦可衍生自至少兩個芳族環係經由橋接基彼此附接的多核芳族烴。亦包括者係衍生自酚醛清漆型酚系樹脂之芳族基,即此等酚系樹脂之氰酸酯類。該芳族基Ar亦可另外含有環附接之非反應性取代基。
此等氰酸酯類之實例包括(例如)1,3-二氰酸基苯;1,4-二氰酸基苯;1,3,5-三氰酸基苯;1,3-、1,4-、1,6-、1,8-、2,6-或2,7-二氰酸基萘;1,3,6-三氰酸基萘;4,4'-二氰酸基-聯苯基;雙(4-氰酸基苯基)甲烷及3,3',5,5'-四甲基雙(4-氰酸基苯基)甲烷;2,2-雙(3,5-二氯-4-氰酸基苯基)丙烷;2,2-雙(3,5-二溴-4-二氰酸基苯基)丙烷;雙(4-氰酸基苯基)醚;雙(4-氰酸基苯基)硫醚;2,2-雙(4-氰酸基苯基)丙烷;參(4-氰酸基苯基)-亞磷酸酯;參(4-氰酸基苯基)磷酸酯;雙(3-氯-4-氰酸基苯基)甲烷;氰化酚醛清漆樹脂;1,3-雙[4-氰酸基苯基-1-(甲基亞乙基)]苯及經氰化雙酚-封端之聚碳酸酯或其他熱塑性寡聚物。
其他氰酸酯類包括揭示於美國專利第4,477,629號及第4,528,366號之氰酸酯類,其揭示內容各以引用的方式明確併入本文中;揭示於英國專利第1,305,702號之氰酸酯類,及揭示於國際專利公開案WO 85/02184之氰酸酯類,其揭示內容各以引用的方式明確併入本文中。當然,本文亦可令人滿意地使用此等氰酸酯與本發明組合物之咪唑組分之組合。
用於本文之特別令人滿意的氰酸酯係可購自Ciba Speciality Chemicals,Tarrytown,New York,商標名為AROCY 366(1,3-雙[4-氰酸基苯基-1-(甲基亞乙基)]苯)。四種其他令人滿意的「AROCY」氰酸酯之結構係:
該芳族胺之實例包括3-胺苯基碸、4-胺苯基碸、及4,4-亞甲基雙(鄰-乙基苯胺),其後者係商業已知的Acetocure MBOEA。
該硬化劑應以該樹脂組合物之10至50%之量存在。
當使用時,諸多材料係可適於作為填充物組分。例如,無機填充物可能適用,特別係在待結合及密封之該半導體晶片與該基板之間的熱膨脹係數(「CTE」)欲更密切匹配之處。該填充物影響CTE,且因此可用於減少該固化材料之熱膨脹,藉此減少翹曲。該填充物組分可經常包括增強矽石,如熔融球形矽石,且可未經處理或經處理以改變其表面之化學性質。然而,該填充物組分應包括平均粒度分佈在0.1至50微米範圍內之顆粒。此等顆粒之可購得實例係由日本的Tatsumori或Denka出售。此外,可添加奈米大小之矽石粉末,如彼等由Nanoresins,Germany以商標名NANOPOX出售者。NANOPOX填充物係以高達約50重量%之濃度含於環氧樹脂中之單分散矽石填充物分散液,其可購自Nanoresins,Germany。通常,咸信NANOPOX填充物之粒度為約5 nm至約80 nm。
Nanoresins亦生產商標名為NANOPOX E之材料。例如,Nanoresins報導NANOPOX E-商標之產品能完全浸透另外不易密封之電子元件,並提供大範圍的機械及熱性質,如減少收縮及熱膨脹、斷裂韌性及模量。在以下表1中,Nanoresins提供四種著名的NANOPOX E產品之資訊:
13,4-環氧基環己基甲基-3,4-環氧基環己基碳酸酯Nanoresins報導藉由使用NANOPOX E-商標的產品可顯著改善環氧樹脂調配物之重要性質。例如:
‧ 黏度比習知增強填充物更低的調配物
‧ 無沉澱
‧ 增加斷裂韌性、耐衝擊性及模量
‧ 改善耐劃傷及磨損性
‧ 減少收縮及熱膨脹
‧ 改善(或至少無負影響)諸多所需性質,如熱安定性、抗化學性、玻璃轉變溫度、耐天候性、及介電性質。
相較於各自基本樹脂,可加工性基本上保持不變。
NANOPOX E係用於希望或必需進行如上性質改善但不因黏度過量增加而損害可加工性(自熔融矽石已知)之應用中。應用實例係封裝材料及塗層。重要地係強調NANOPOX E之極佳浸漬特性係由於小粒度及無聚結物存在。此亦能完全浸漬另外不易密封之電子元件。
根據製造商,NANOPOX E-商標的產品係含於環氧樹脂基質中之膠狀矽石溶膠。根據製造商,分散相係由經表面改質具有小於50 nm之直徑及極窄粒度分佈之球形SiO2
奈米粒子組成。此等球體(大小僅為幾奈米)係無聚結物分配於該樹脂基質中。根據製造商,此產生極低黏度之分散液,其中SiO2
含量高達40重量%。如製造商所報導,該等奈米粒子係自矽酸鈉水溶液化學合成得到。相較於利用溶解器或其他利用高剪切能量之設備分散粉末填充物之製程,此製程無損壞該黏合劑。
其他用作填充物組分之令人滿意的材料包括彼等由氧化鋁、氮化矽、氮化鋁、經矽石塗覆之氮化鋁、氮化硼及其組合構成者或含有如上者。
當使用時,該填充物組分應以該組合物的約10至約80重量%(如,約12至約60重量%,理想地在約15至約35重量%之範圍內)之量使用。
樣品編號1至20係陳述於下表1a至1b及2a至2b中。
該等組合物各藉由利用機械混合器將該等環氧樹脂成分混合一起直至觀測到溶解成均質溶液的方式製得。隨後,在室溫下添加該矽石填充物並連續混合達約30至60分鐘之時間,直至獲得具有實質上均勻一致性之黏稠漿糊。隨後,將因此形成之漿糊移入容器中,直至準備使用。
在烘箱中175℃之溫度下固化該等樣品2小時之時間後,測量機械性質,如模量、玻璃轉變溫度、熱膨脹係數。
此等樣品之物理性質係表示於表3a至3b及4a至4b中。
比較該等對照組合物(樣品編號1至5(表1a及3a)及樣品編號6至10(表1b及3b))與本發明組合物(樣品編號11至15(表2a及4a)及樣品編號16至20(表2b及4b))之物理性質(如模量、熱膨脹係數(「CTE」)α1
及α2
、及玻璃轉變溫度(「Tg」))。所有組合物如上所述般固化時之模量與CTE α1
值之間的函數關係圖示於圖3中。一般,可看到樣品編號11至15及16至20之模量範圍係低於樣品編號1至5及6至10之模量範圍,而CTE α1
值(及Tg,就此而言)仍在相同範圍內。對於用於低k IC微電子裝置中之電子材料(如底填密封劑)而言,低模量與低CTE α1
(及較高Tg)之組合係重要的物理性質組合。
圖1描繪習知0.130 um低k晶粒結構之個別組分及物理尺寸;
圖2描繪可藉以製備本文所述之經矽烷改質之環氧樹脂的合成圖;及
圖3描繪本發明範圍內之熱可固化之組合物(樣品編號16至20)及一系列對照組合物(樣品編號1至15)在室溫下之模量相對於CTE之曲線。
(無元件符號說明)
Claims (17)
- 一種熱固性樹脂組合物,其包括:作為可固化組分之經矽烷改質之環氧樹脂組分,其中該經矽烷改質之環氧樹脂組分係佔該總組合物之10重量%至95重量%之量;硬化劑,其中該硬化劑係氰酸酯或芳族胺;矽石填充物及視情況可選之觸媒,其中該經矽烷改質之環氧樹脂組分為預混物,其包括:作為組分(A)之由以下結構所涵蓋之環氧樹脂:
- 如請求項1之組合物,其中組分(C)係由組分(A)及(B)依1:100至100:1之重量比製得。
- 如請求項1之組合物,其中組分(C)係由組分(A)及(B)依1:10至10:1之重量比製得。
- 如請求項1之組合物,其中固化時,作為底填密封劑之該組合物顯示室溫下7,000至9,000MPa範圍內之模量。
- 如請求項1之組合物,其中固化時,作為底填密封劑之該組合物顯示10至20ppm範圍內之CTE α1。
- 如請求項1之組合物,其中該硬化劑係氰酸酯。
- 如請求項1之組合物,其中該硬化劑係芳族胺。
- 如請求項1之組合物,其中該硬化劑係佔該總組合物之10重量%至50重量%之量。
- 如請求項1之組合物,其中該填充物係佔該總組合物之10重量%至80重量%之量。
- 一種提高一包括至少一低K ILD層之半導體裝置之可靠性之方法,其步驟包括:提供一半導體裝置,其包括:一包括銅電互連及其間至少一低k ILD層且其表面上金屬化之半導體晶片;及一表面上具有電接觸墊之載體基板,該半導體晶片係經由一導電材料電互連至該銅電互連; 在該半導體晶片與該載體基板之電互連表面之間提供如請求項1之熱固性樹脂組合物以形成一半導體裝置組件;及使該半導體裝置組件暴露於足以固化該熱固性樹脂組合物之高溫條件下。
- 如請求項10之方法,其中在該半導體晶片與該載體基板結合之後,該熱固性樹脂組合物係藉由分配及充填其間之空間提供以形成該半導體裝置。
- 如請求項10之方法,其中該熱固性樹脂組合物係藉由分配在該半導體晶片或該載體基板中之一或兩者之至少一部份電互連表面上的方式提供,且隨後使該半導體晶片與該載體基板結合以形成該半導體裝置。
- 如請求項10之方法,其中該載體基板係電路板。
- 如請求項10之方法,其中該導電材料係焊料。
- 如請求項10之方法,其中該焊料係選自由以下各者組成之群:Sn(63):Pb(37)、Pb(95):Sn(5)、Sn:Ag(3.5):Cu(0.5)及Sn:Ag(3.3):Cu(0.7)、或銅柱-焊料互連。
- 一種半導體裝置,其包括:一包括銅電互連及其間之低K ILD層及其表面上之金屬化的半導體晶片;一表面上具有與該半導體晶片電互連之電接觸墊之電路板;及在該半導體晶片與該電路板之間的如請求項1之熱固性樹脂組合物。
- 一種半導體裝置組件,其包括:一半導體裝置,其包括一包括其與其間至少一k ILD層接觸之銅電互連之半導體晶片及其與一載體基板電連接之表面上金屬化;一表面上具有與該半導體裝置電互連之電接觸墊之電路板;及在該半導體裝置與該電路板之間的如請求項1之熱固性樹脂組合物。
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