TWI381036B - Then the film - Google Patents

Then the film Download PDF

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Publication number
TWI381036B
TWI381036B TW098111452A TW98111452A TWI381036B TW I381036 B TWI381036 B TW I381036B TW 098111452 A TW098111452 A TW 098111452A TW 98111452 A TW98111452 A TW 98111452A TW I381036 B TWI381036 B TW I381036B
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TW
Taiwan
Prior art keywords
particles
conductive
particle diameter
average particle
filler
Prior art date
Application number
TW098111452A
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English (en)
Other versions
TW200948923A (en
Inventor
Yasuhiro Suga
Original Assignee
Sony Chem & Inf Device Corp
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Publication date
Application filed by Sony Chem & Inf Device Corp filed Critical Sony Chem & Inf Device Corp
Publication of TW200948923A publication Critical patent/TW200948923A/zh
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Publication of TWI381036B publication Critical patent/TWI381036B/zh

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • 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
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    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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Description

接著膜
本發明係關於一種接著膜，係用以將具有凸塊之半導體晶片覆晶(Flip Chip)封裝於配線基板。
將具有凸塊之半導體晶片覆晶封裝於配線基板時，係廣泛使用在絕緣性黏合劑組成物中分散有導電性粒子而成的異向性導電膜。此種導電性粒子，為了使其在配線基板之連接焊墊與半導體晶片之凸塊間得到壓合，而使用在樹脂芯之表面形成無電解鍍敷層者。
然而，凸塊之小面積化亦隨著封裝基板中配線之窄間距化而發展，因此亦必須減小用於異向性導電接著膜之導電性粒子之粒徑，但其問題在於製造均勻且較小粒徑之樹脂粒子係相當困難。因此，係在配線基板與半導體晶片間夾持非導電性接著膜(NCF)，並使半導體晶片之凸塊與配線基板之連接焊墊或凸塊相抵接使得其相壓合，再使非導電性接著膜硬化，藉此而將兩者連接固定(NCF接合)。
在NCF接合的情況，為了提高非導電性接著膜之連接可靠性，有人提出在非導電性接著膜中調配相對於樹脂固形物100體積份為1~50體積份之粒徑為0.005~0.1μm的二氧化矽微粒子等非導電性填料，以調整其儲存彈性模數、線膨脹係數、熔融黏度等(參照專利文獻1、段落0043-0044)。
專利文獻1：日本專利特開2002-275444號公報
然而，藉由使用調配有二氧化矽微粒子等填料之非導電性接著膜將具有凸塊之半導體晶片覆晶封裝於配線基板時，有時會無法充分地將二氧化矽微粒子以及黏合劑組成物從配線基板之連接焊墊或凸塊與半導體晶片之凸塊間排除，在此種情況下，會產生在配線基板與半導體晶片間無法取得導通之問題。
本發明之目的在於：藉由使用調配有二氧化矽微粒子等填料之絕緣性接著膜的NCF接合來將具有凸塊之半導體晶片覆晶封裝於配線基板時，即便無法充分地將非導電性填料以及絕緣性黏合劑組成物從配線基板之連接焊墊或凸塊與半導體晶片之凸塊間排除，亦可確保可靠的導通。
本發明者等人為了改良NCF接合用非導電性接著膜，發現：不僅特別規定應調配至黏合劑組成物中之填料量，而且使用粒徑與先前所用之填料的粒徑(即，0.005~0.1μm)相比非常大者，且對該填料之一部分進行無電解鍍敷處理，製成粒徑(1.5μm以下)大幅小於先前使用樹脂芯之異向性導電連接用導電性粒子的粒徑(約5μm)之導電性粒子，並以特定比例加以使用，而可達成上述目的，從而完成本發明。
即，本發明提供一種接著膜，其係由含有環氧化合物、硬化劑及填料之黏合劑組成物所構成，並用以將具有凸塊之半導體晶片覆晶封裝於對配線基板者，
其特徵在於：填料含量相對於環氧化合物、硬化劑及填料之總量為10~70質量%，該填料含有平均粒徑為0.5~1.0μm之第1非導電性無機粒子、以及將平均粒徑為0.5~1.0μm之第2非導電性無機粒子以平均粒徑不超過1.5μm的方式經無電解鍍敷處理而成之導電性粒子，填料之10~60質量%為該導電性粒子。
又，本發明提供一種具有凸塊之半導體晶片透過上述接著膜連接固定於配線基板上而成的連接構造體。
本發明之接著膜由於特別規定調配至黏合劑組成物中之填料量，且以特定比例來使用作為填料之特定粒徑之非導電性無機粒子以及導電性粒子，因此即便在無法充分地將填料以及黏合劑樹脂從配線基板之連接焊墊或凸塊與半導體晶片之凸塊間排除之情況下，亦可藉由其導電性粒子而確保可靠的導通。
本發明係一種接著膜，其係用以將具有凸塊之半導體晶片覆晶封裝於配線基板者，且係使填料分散於黏合劑組成物中並經膜化而成者。此處，配線基板可應用玻璃環氧化物配線基板、玻璃配線基板、可撓性配線基板等廣泛用於半導體裝置之配線基板，半導體晶片可應用積體電路晶片、發光二極體晶片等廣泛用於半導體裝置之半導體晶片。又，黏合劑組成物除了含有為成膜成分之環氧化合物及硬化劑之外還含有填料，並表現出熱硬化性。
填料主要係用以降低接著膜之線膨脹係數以及吸水性，並含有第1非導電性無機粒子、以及將第2非導電性無機粒子加以無電解鍍敷處理而得之導電性粒子第1非導電性無機粒子以及第2非導電性無機粒子可使用NCF接合時所使用之習知的用於非導電性接著膜之填料，較佳為例如二氧化矽微粒子、氧化鋁粒子、二氧化鈦粒子等。其中，就可較廉價地獲得硬質之硬化物方面而言係使用二氧化矽微粒子。再者，所謂第1非導電性無機粒子以及第2非導電性無機粒子可相同亦可不同。再者，本發明之填料中不含有以無電解鍍敷處理將金屬層設置於有機樹脂芯表面而得之導電性粒子。
第1及第2非導電性無機粒子之平均粒徑分別為0.5~1.0μm，較佳為0.5~0.8μm。其原因在於：若未滿0.5μm，則在進行半導體之封裝時，所含之較大粒徑的填料會突破保護半導體電路面之保護膜而產生不良情況，尤其當為導電性粒子時會導致絕緣性變差，另一方面，若超過1.0μm，則絕緣特性會變差。此處，所謂「平均粒徑」係藉由雷射繞射法所測得之值。
又，第2非導電性無機粒子可藉由習知之無電解鍍敷處理於表面上形成無電解鍍敷層來賦予導電性而製成導電性粒子來使用。其原因在於：即便在無法充分地將填料以及黏合劑組成物從配線基板之連接焊墊或凸塊與半導體晶片之凸塊間排除之情況下，亦可確保該等之間的導通。無電解鍍敷層可使用先前異向性導電性粒子之無電解鍍敷層，例如可較佳地使用由金、鎳、鎳/金、或焊錫等所構成之無電解鍍敷層。其中，係使導電性粒子之平均粒徑不超過1.5μm，較佳為1.1μm以下。其原因在於：若超過1.5μm，則難以確保鄰接之端子間的絕緣性。
進而，若導電性粒子之平均粒徑相對於第1該非導電性無機粒子之平均粒徑過小，則使半導體之凸塊與基板之電極導通的效力會變少，若過大，則鄰接之端子間的絕緣性會變差，因此較佳為前者為後者之1.0~2.0倍，更佳為1.0~1.5倍。
填料中上述導電性粒子之含有比例為10~60質量%，較佳為30~50質量%。其原因在於：若未滿10質量%，則初始導通特性會明顯降低，若超過60質量%，則絕緣性會明顯降低。
於本發明之接著膜中，由第1及第2非導電性無機粒子所構成之填料含量，相對於環氧化合物、硬化劑以及填料之總量(相當於黏合劑組成物之固形物總體)為10~70質量%，較佳為40~60質量%，更佳為50~60質量%。其原因在於：若未滿10質量%，則連接構造體之壽命特性會降低，若超過70質量%，則難以進行膜成形。
構成本發明之接著膜的黏合劑組成物如前所述，係含有為成膜成分之環氧化合物以及其硬化劑。
環氧化合物，較佳例如分子內具有2個以上環氧基之化合物或樹脂。該等可為液態、亦可為固態。此種環氧化合物例如：雙酚A型環氧樹脂或雙酚F型環氧樹脂等二官能環氧樹脂、苯酚酚醛清漆型環氧樹脂或甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂等。又，亦可使用3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯等脂環式環氧化合物。
在黏合劑組成物中可併用與環氧化合物相溶之苯氧樹脂或丙烯酸系樹脂。
構成本發明之接著膜的硬化劑，可使用先前異向性導電膜中所使用之環氧化合物用硬化劑，例如：胺系硬化劑、咪唑系硬化劑、酸酐系硬化劑等。硬化劑可為潛伏性。
在黏合劑組成物中，視需要可調配習知之硬化促進劑、偶合劑、金屬捕獲劑等。
本發明之接著膜可藉由常法來製造。可藉由在環氧化合物中共同均勻混合填料與甲苯、乙酸乙酯等溶劑，再將所得的混合物塗佈於剝離膜上使其達到特定之乾燥膜厚並進行乾燥來製造。
本發明之接著膜可較佳地用作為將具有凸塊之半導體晶片覆晶封裝於對配線基板時所使用之接著膜。因此，具有凸塊之半導體晶片透過本發明之接著膜而連接固定於配線基板上而成之連接構造體，即便在無法充分地將黏合劑樹脂從配線基板之連接焊墊或凸塊與半導體晶片之凸塊間排除之情況下，亦可藉由其導電性粒子來確保可靠的導通。該連接構造體可藉由以下方式製造，即，將接著膜暫時貼合於配線基板之連接焊墊或凸塊上，於其上載置具有凸塊之半導體晶片使該凸塊面為配線基板側，再進行加熱加壓來連接固定。
實施例
以下，藉由實施例具體說明本發明。
又，於以下實施例或比較例中所使用之評價用配線基板係0.6mm厚×35mm長×35mm寬尺寸的玻璃環氧化物基板，其表面係形成有施有鍍鎳/金而成之厚度為12μm之銅配線。又，評價用半導體晶片係設有柱螺金凸塊(544pin、間距為50μm)之0.4mm厚×7.3mm長×7.3mm寬之尺寸的矽晶片。
參考例1(非導電性無機粒子芯之導電性粒子之製造)
使用無電解鍍鎳液對平均粒徑為0.5μm之二氧化矽粒子(球狀二氧化矽、Tokuyama公司)進行無電解鍍鎳處理。進而使用無電解鍍金液對由無電解鍍鎳處理所得之粒子施以無電解鍍金處理，藉此獲得平均粒徑為0.6μm之導電性粒子。
參考例2(非導電性無機粒子芯之導電性粒子之製造)
使用平均粒徑為1.0μm之二氧化矽微粒子(環狀二氧化矽、Tokuyama公司)代替平均粒徑為0.5μm之二氧化矽微粒子，除此以外，以與參考例1相同之方式，獲得平均粒徑為1.1μm之導電性粒子。
參考例3(非導電性無機粒子芯之導電性粒子之製造)
使用平均粒徑為3.5μm之二氧化矽微粒子(HIPRESICA、宇部日東化成公司)代替平均粒徑為0.5μm之二氧化矽微粒子，除此以外，以與參考例1相同之方式，獲得平均粒徑為3.6μm之導電性粒子。
比較例1(接著膜之製造)
將環氧樹脂(EPIKOTE 828、日本環氧樹脂(Japan Epoxy Resins)公司)50質量份、潛伏性硬化劑(HX3941HP、旭化成化學(Asahi Kasei Chemicals)公司)100質量份、平均粒徑為0.5μm之二氧化矽微粒子(球狀二氧化矽、Tokuyama公司)50質量份之混合物，溶解、分散於甲苯中使固形物為50質量%，將所得之熱硬化型接著組成物以乾燥厚度為40μm之方式塗佈於經剝離處理後之50μm厚的聚對苯二甲酸乙二酯(PET，polyethylene terephthalate)膜(Separator、TOHCELLO公司)上，並於80℃下進行乾燥，藉此製作熱硬化型比較例1之接著膜。
實施例1
將環氧樹脂(EPIKOTE 828、日本環氧樹脂公司)50質量份、潛伏性硬化劑(HX3941HP、旭化成化學公司)100質量份、平均粒徑為0.5μm之二氧化矽微粒子(球狀二氧化矽、Tokuyama公司)45質量份、參考例1之導電性粒子5質量份之混合物，溶解、分散於甲苯中使固形物為50質量%，將所得之熱硬化型接著組成物以乾燥厚度為40μm之方式塗佈於經剝離處理後之50μm厚的PET膜(Separator、TOHCELLO公司)上，並於80℃下進行乾燥，藉此製作熱硬化型實施例1之接著膜。填料含量相對於總固形物(環氧樹脂、硬化劑以及填料之總計)為25質量%。
實施例2
將平均粒徑為0.5μm之二氧化矽微粒子45質量份變更為25質量份，將導電性粒子變更為25質量份，除此以外，以與實施例1相同之方式，製作熱硬化型實施例2之接著膜。
比較例2
將平均粒徑為0.5μm之二氧化矽微粒子45質量份變更為5質量份，將參考例1之導電性粒子5質量份變更為45質量份，除此以外，以與實施例1相同之方式，製作熱硬化型比較例2之接著膜。
實施例3
將平均粒徑為0.5μm之二氧化矽微粒子45質量份變更為25質量份，使用參考例2之導電性粒子25質量份代替參考例1之導電性粒子5質量份，除此以外，以與實施例1相同之方式，製作熱硬化型實施例3之接著膜。
比較例3
使用平均粒徑為3.5μm之二氧化矽粒子(HIPRESICA、宇部日東化成公司)代替平均粒徑為0.5μm之二氧化矽微粒子，使用參考例3之導電性粒子代替參考例2之導電性粒子，除此以外，以與實施例3相同之方式，製作熱硬化型比較例3之接著膜。
比較例4
不使用平均粒徑為0.5μm之二氧化矽微粒子，且使用在有機粒子芯之表面施有無電解鍍鎳/金的平均粒徑為4.0μm之導電性粒子(Bright、日本化學公司)10質量份代替參考例1之導電性粒子5質量份，除此以外，以與實施例1相同之方式，製作熱硬化型比較例4之異向性導電膜。
比較例5
使用在有機粒子芯之表面施有無電解鍍鎳/金的平均粒徑為4.0μm之導電性粒子(Bright、日本化學公司)代替參考例1之導電性粒子，除此以外，以與實施例1相同之方式，製作熱硬化型比較例5之異向性導電膜。
實施例4
將二氧化矽微粒子45質量份變更為75質量份，將導電性粒子5質量份變更為75質量份，除此以外，以與實施例1相同之方式，製作熱硬化型實施例4之異向性導電膜。於本實施例中，填料含量相對於環氧化合物、硬化劑、填料之總量(相當於黏合劑組成物之固形物總體)為50質量%。
實施例5
將二氧化矽微粒子45質量份變更為175質量份，將導電性粒子5質量份變更為175質量份，除此以外，以與實施例1相同之方式，製作熱硬化型實施例5之異向性導電膜。於本實施例中，填料含量相對於環氧化合物、硬化劑、填料之總量(相當於黏合劑組成物之固形物總體)為70質量%。
(評價1)
將各實施例及比較例之各接著膜及各異向性導電膜暫時貼合於評價用配線基板之電極焊墊上，去除剝離膜後，於其上自該凸塊面載置評價用半導體晶片，再於溫度180℃、壓力2.5MPa下將半導體晶片加熱加壓20秒鐘，藉此製作導通電阻測定用連接構造體樣品。
對所得之連接構造體樣品測定初始之導通電阻值(Ω)(菊鍊(daisy chain)電阻值(136電極連接電阻十配線電阻))、以及絕緣電阻值(Ω)(菊鍊配線間絕緣電阻值(Ω)(136電極間之最小值、未滿108 Ω判定為短路))。繼而，對上述樣品進行作為導通可靠性試驗的PCT試驗(條件：121℃、於飽和水蒸氣壓之腔室中放置24小時)，再測定導通電阻值。又，綜合評價係將斷路、短路均未產生之情形評價為「良好」，至少任意一種產生之情形評價為「不良」。所得之結果示於表1。
由表1可知，使用二氧化矽微粒子以及對其進行無電解鍍敷處理之導電性粒子的實施例1~5之接著膜，在評價項目中表現出良好的結果。
另一方面，在比較例1之接著膜時，由於完全不含有導電性粒子，因此在初始之導通電阻測定中為斷路。在比較例2之接著膜時，由於導電性粒子之調配量過多，因此在鄰接電極間產生短路。在比較例3之接著膜時，由於導電性粒徑過大，因此每單位體積之導電性粒子個數變少，而產生在電極間無法捕獲之情況，在菊鍊之電阻測定中產生斷路，在另一電極間空間較小之時，亦產生短路。
再者，在不使用二氧化矽微粒子、而使用先前之有機樹脂芯型導電性粒子的比較例4之接著膜時，初始特性良好，但PCT試驗後之導通電阻為斷路，而為導通可靠性欠缺之結果。又，在除了有機樹脂芯型導電性粒子外還使用二氧化矽微粒子的比較例5之接著膜時，初始之導通電阻為斷路。
(評價2)
如以下所說明，對實施例1之接著膜及比較例4之異向性導電膜的相對介電係數以及絕緣特性進行評價。
相對介電係數係使用相對介電係數測定裝置{LF INPEDANCE ANALYZER 4192A、Hewlet Pachard公司；使用介電係數測定用電極16451B(電極A、直徑為38mm)；頻率為1、2、5、10、20、50、100、200、500、1000、2000、5000(kHz)；電壓為1V}進行測定。相對介電係數越低，則絕緣性表現地越高。所得之結果示於圖1。由圖1可知，實施例1之接著膜的絕緣性高於比較例4之異向性導電膜的絕緣性。
絕緣特性方面，係將半導體晶片(凸塊尺寸：50×150μm、間距：80μm)覆晶封裝於ITO焊墊上，研究短路(絕緣電阻值為108 Ω以下)之產生與鄰接端子間距離之關係。所得之結果示於圖2以及圖3。由該等圖可知，實施例1之接著膜完全未產生短路，但在比較例4之異向性導電膜時，短路之產生明顯。
(產業利用性)
本發明之半導體裝置之製造方法，由於係使用具有特定厚度的熱硬化型密封樹脂層之密封樹脂膜，藉由一次熱壓接處理同時將半導體晶片封裝於電路基板、將半導體晶片加以密封，故在電路基板與半導體晶片間所形成之連接部不會在連接後再次受到加熱加壓。因此，可實現步驟之縮減以及良率之提高。因此本發明係有用於作為半導體裝置之製造方法。
圖1係表示實施例1之接著膜及比較例4之異向性導電膜的相對介電係數之測定結果。
圖2係表示使用實施例1之接著膜時的短路之產生與鄰接端子間距離之關係。
圖3係表示使用比較例4之異向性導電膜時的短路之產生與鄰接端子間距離之關係。

Claims (8)

  1. 一種接著膜，其係由含有環氧化合物、硬化劑及填料之黏合劑組成物所構成，並用以將具有凸塊之半導體晶片覆晶封裝於配線基板者，其特徵在於：填料含量相對於環氧化合物、硬化劑及填料之總量為10~70質量%；該填料含有平均粒徑為0.5~1.0μm之第1非導電性無機粒子、以及平均粒徑為0.5~1.0μm之第2非導電性無機粒子以平均粒徑不超過1.5μm的方式經無電解鍍敷處理而成之導電性粒子；填料之10~60質量%為該導電性粒子。
  2. 如申請專利範圍第1項之接著膜，其中，第1及第2非導電性無機粒子為二氧化矽微粒子、氧化鋁粒子或二氧化鈦粒子。
  3. 如申請專利範圍第1或2項之接著膜，其中，第1及第2該非導電性無機粒子具有0.5~0.8μm之平均粒徑。
  4. 如申請專利範圍第1或2項之接著膜，其中，該導電性粒子之粒徑為1.1μm以下。
  5. 如申請專利範圍第1或2項之接著膜，其中，該導電性粒子之平均粒徑為第1非導電性無機粒子之平均粒徑的1.0~2.0倍。
  6. 如申請專利範圍第1或2項之接著膜，其中，該無電解鍍敷處理之金屬種類為金、鎳、鎳/金、或焊錫。
  7. 一種連接構造體，係具有凸塊之半導體晶片透過申請專利範圍第1至6項中任一項之接著膜連接固定於配線基板而成者。
  8. 如申請專利範圍第7項之連接構造體，其中，半導體晶片之凸塊與配線基板之凸塊係相連接。
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