TW201211187A - Adhesive composition, adhesive sheet used to connect electric circuit components and preparation method of semiconductor device - Google Patents

Adhesive composition, adhesive sheet used to connect electric circuit components and preparation method of semiconductor device Download PDF

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Publication number
TW201211187A
TW201211187A TW99130500A TW99130500A TW201211187A TW 201211187 A TW201211187 A TW 201211187A TW 99130500 A TW99130500 A TW 99130500A TW 99130500 A TW99130500 A TW 99130500A TW 201211187 A TW201211187 A TW 201211187A
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Taiwan
Prior art keywords
adhesive
film
adhesive layer
mass
parts
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TW99130500A
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Chinese (zh)
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TWI509043B (en
Inventor
Akira Nagai
Keisuke Ookubo
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/731—Location prior to the connecting process
    • H01L2224/73101—Location prior to the connecting process on the same surface
    • H01L2224/73103—Bump and layer connectors
    • H01L2224/73104—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides an adhesive composition characterized by containing: a thermoplastic resin (A), a heat-curable resin (B), a latent curing agent (C), an inorganic filler (D), and organic microparticles (E). Based on 100 parts by mass of total content of the thermoplastic resin (A), the heat-curable resin (B) and the latent curing agent (C), the content of the inorganic filler (D) is 50 to 150 parts by mass, the content of the organic microparticles (E) is 5 to 30 parts by mass. Moreover, the total content of the inorganic filler (D) and the organic microparticle (E) is 65 to 165 parts by mass.

Description

201211187 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種接著劑組成物、接著劑薄片及半導 體裝置之製造方法。 【先前技術】 近年，隨電子機器之小型化、薄型化，於電路構件所 形成之電路的高密度化進展，與鄰接之電極的間隔或電極 之寬度有變成非常狹窄的傾向。伴隨此，對於半導體封裝 體之薄型化或小型化的要求亦高漲。因此，就半導體晶片 封裝方式而言，取代使用金屬導線而連接之習知導線黏結 方式，而於晶片電極上形成所謂凸塊之突起電極，使基板 電極與晶片電極介由凸塊而直接連接之覆晶連接方式被受 注目。 覆晶連接方式係已知有使用焊錫凸塊的方式、使用金 凸塊與導電性接著劑之方式、熱壓接方式、超音波方式等 。在此等的方式中，源自晶片與基板之熱膨脹係數差的熱 應力會集中於連接部分而連接信賴性降低之問題仍存在。 爲防止如此之連接信賴性的降低，一般，可藉樹脂形成塡 充晶片與基板之間隙的底部塡充劑。藉由於底部塡充劑之 分散緩和熱應力，故可提昇連接信賴性。 形成底部塡充劑之方法一般係使晶片與基板連接之後 ，使液狀樹脂注入於晶片與基板之間隙的方法已爲人知（ 參照專利文獻1 )。又，在使用異方導電性接著薄膜（以 -5- 201211187 下稱爲ACF )或非導電性接著薄膜（以下稱爲nCF )等的 薄膜狀樹脂而連接晶片與基板之步驟中，底部塡充劑形成 亦完了的方法亦已爲人知（參照專利文獻2)。 另外’在近年’就可使更高功能化、高速動作者而言 ，使晶片間以最短距離連接之3次元封裝技術的矽貫通電 極（TSV : Through Silicon Via )被受注目（參照非專利 文獻1 )。此結果，半導體晶圓之厚度係儘可能地薄化， 且機械強度不降低已被要求起來。 繼而，伴隨半導體裝置之更薄型化的要求，爲使半導 體晶圓更薄化，硏削晶圓的背面即進行所謂背硏磨，半導 體裝置之製造步驟變煩雜。因此，適於步驟之簡略化的方 法，兼備背硏磨時保持半導體晶圓之功能與底部塡充功能 的樹脂已被提出（參照專利文獻3、4 )。 先前技術文獻 專利文獻 專利文獻1 :特開2000-100862號公報 專利文獻2:特開2003- 1 42529號公報 專利文獻3 :特開2001-332520號公報 專利文獻4:特開2005-028734號公報 非專利文獻 非專利文獻 1: OKI Technical Review 2007 年 1〇 月 /第 21 1 號 VOL. 74 Νο·3 【發明內容】 -6- 201211187 [發明欲解決之課題] 因此，伴隨半導體裝置之薄膜化，連接部之空隙或端 子間的晶片變成更狹窄，連接時之薄膜狀樹脂的流動不足 造成之界面潤濕不足、或薄膜狀樹脂之發泡產生氣泡等， 薄膜狀樹脂於節距間的塡充變成不充分，有時使連接信賴 性降低。因此，於電路構件之連接所使用的薄膜狀接著劑 係從確保連接信賴性之點，要求壓接時很難產生氣泡且具 有優異之埋入性，或硬化後之接著力非常高。 本發明係有鑑於上述事情而成者，目的在於提供一種 形成薄膜狀時之埋入性非常優異，同時可製作連接信賴性 優異之半導體裝置的接著劑組成物、使用其之接著劑薄片 、及半導體裝置的製造方法。 [用以解決課題之手段] 爲解決上述課題，本發明係提供一種接著劑組成物， 其特徵爲含有（A )熱可塑性樹脂、（B )熱硬化性樹脂、 (C)潛在性硬化劑、（D)無機塡充物、與（E)有機微 粒子。201211187 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an adhesive composition, an adhesive sheet, and a semiconductor device. [Prior Art] In recent years, with the miniaturization and thinning of electronic equipment, the density of circuits formed in circuit components has progressed, and the distance between adjacent electrodes and the width of electrodes tend to be extremely narrow. Along with this, the demand for thinning or miniaturization of the semiconductor package is also increasing. Therefore, in the semiconductor chip packaging method, instead of the conventional wire bonding method in which the metal wires are connected, a so-called bump protruding electrode is formed on the wafer electrode, and the substrate electrode and the wafer electrode are directly connected via the bump. The flip chip connection method has been attracting attention. The flip chip connection method is known in which a solder bump is used, a gold bump and a conductive adhesive are used, a thermocompression bonding method, an ultrasonic method, or the like. In such a mode, the problem that the thermal stress derived from the difference in thermal expansion coefficient between the wafer and the substrate concentrates on the connection portion and the connection reliability is lowered still exists. In order to prevent such a decrease in connection reliability, a bottom smear which is a gap between the wafer and the substrate can be formed by a resin. The reliability of the connection can be improved by dispersing the thermal stress at the bottom of the dopant. The method of forming the underlying sizing agent is generally known in which a liquid resin is injected into the gap between the wafer and the substrate after the wafer is bonded to the substrate (refer to Patent Document 1). Further, in the step of connecting the wafer and the substrate using a film-like resin such as a film of a different conductivity (hereinafter referred to as ACF under -5 to 201211187) or a non-conductive film (hereinafter referred to as nCF), the bottom portion is filled. A method in which the formation of the agent is completed is also known (refer to Patent Document 2). In addition, in recent years, it has become more highly functional and high-speed actor, and the TSV (through silicon Via) of the three-dimensional packaging technology that connects the wafers at the shortest distance has been attracting attention (refer to the non-patent literature). 1 ). As a result, the thickness of the semiconductor wafer is as thin as possible, and mechanical strength is not lowered. Further, with the demand for thinner semiconductor devices, in order to make the semiconductor wafer thinner, the back surface of the wafer is boring, that is, the so-called back honing, and the manufacturing steps of the semiconductor device become complicated. Therefore, a method suitable for simplification of the steps and a resin which maintains the function of the semiconductor wafer and the bottom rinsing function during back honing have been proposed (see Patent Documents 3 and 4). CITATION LIST Patent Literature Patent Literature 1: JP-A-2001-332520 (Patent Document No. JP-A-2001-332520) Patent Document 4: JP-A-2005-028734 Non-Patent Document Non-Patent Document 1: OKI Technical Review 2007 〇月/第21 1 VOL. 74 Νο·3 [Summary of the Invention] -6- 201211187 [Problems to be Solved by the Invention] Therefore, thin film formation with semiconductor devices The gap between the connecting portions or the wafer between the terminals becomes narrower, and the insufficient wettability of the interface due to insufficient flow of the film-like resin at the time of connection or the foaming of the film-like resin or the like, and the film-like resin between the pitches The charging becomes insufficient, and the connection reliability is sometimes lowered. Therefore, the film-like adhesive used for the connection of the circuit members is required to ensure the reliability of the connection, and it is difficult to generate bubbles at the time of pressure bonding, and it has excellent embedding property, or the adhesion force after hardening is very high. In view of the above, it is an object of the present invention to provide an adhesive composition which is excellent in embedding property in the case of forming a film, and which can be used as a semiconductor device having excellent connection reliability, and an adhesive sheet using the same, and A method of manufacturing a semiconductor device. [Means for Solving the Problems] In order to solve the above problems, the present invention provides an adhesive composition comprising (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) inorganic inclusions and (E) organic fine particles.

若依本發明之接著劑組成物，藉含有上述（A) 、( B )、(C ) 、 （ D )及（E )成份，連接時之埋入性降低， 可充分降低氣泡之產生，可形成連接信賴性優異的薄膜狀 接著劑。 本發明之接著劑組成物中，使上述（A )熱可塑性樹 月旨、上述（B )熱硬化性樹脂及上述（C )潛在性硬化劑之 201211187 總含有量爲100質量份時，宜上述（D)無機塡充物的含有 量爲5 0~ 150質量份，上述（E)有機微粒子的含有量爲 5~3 0質量份，且上述（D)無機塡充物及上述（E)有機微 粒子的含有量之合計爲65〜165質量份。如此之接著劑組成 物係可於埋入性與連接信賴性形成更優異之薄膜狀接著劑 〇 本發明之接著劑組成物，其爲介在相對向的電路構件 間，用於將上述電路構件彼此接著。此時，藉由熱壓接電 路構件間，可抑制氣泡發生同時並以充分的接著力接著。 藉此，可得到連接信賴性優異之連接體。電路構件係可使 用具有已高密度化之電路的電路構件，例如，本發明之接 著劑組成物係用以連接具備矽貫通電極之電路構件而使用 0 本發明之接著劑片，其特徵爲具備支持基材、及設置 於該支持基材上且由本發明之接著劑組成物所成的接著劑 層。 上述支持基材宜爲具備塑質薄膜與設置於該塑質薄膜 上的黏著劑層，上述接著劑層設置於黏著劑層上。藉此， 本發明之接著劑片係半導體晶圓的背硏磨時可使半導體晶 圓安定而保持。 本發明之接著劑片，其爲介在相對向的電路構件間， 用於將上述電路構件彼此接著。此時，藉由熱壓接電路構 件間，可抑制氣泡發生同時並以充分的接著力接著。藉此 ’可得到連接信賴性優異之連接體。 -8- 201211187 本發明係又提供一種半導體裝置之製造方法，其特徵 爲具備： 準備於一者之主面具有複數電路電極的半導體晶圓’ 於該半導體晶圓之設有前述電路電極的面側上，設置由本 發明之接著劑組成物所成的接著劑層之步驟；將上述半導 體晶圓之設有前述電路電極的面側之相反側進行硏削，使 上述半導體晶圓薄化的步驟；切割上述經薄化的半導體晶 圓及上述接著劑層，使附有薄膜狀接著劑的半導體元件個 片化的步驟；與，將上述附有薄膜狀接著劑之半導體元件 的上述電路電極焊接接合於半導體元件載持用支持構件之 電路電極的步驟。 [發明之效果] 若依本發明，可提供一種形成薄膜狀時之埋入性非常 優異，同時可製作連接信賴性優異之半導體裝置的接著劑 組成物及使用其之接著劑薄片。又，若依本發明之半導體 裝置的製造方法，可提供連接信賴性優異之半導體裝置。 [用以實施發明之形態] 於以下說明有關本發明之接著劑組成物、接著劑片及 半導體裝置的製造方法較佳之實施形態。 本發明之接著劑片係可使用來作爲電路構件連接用。 圖1係表示本發明之電路構件連接用接著劑片的適宜之一 實施形態的模式剖面圖。圖1所示之電路構件連接用接著 -9- 201211187 劑片10係具備支持基材3、及設置於該支持基材3上之本發 明的接著劑組成物所成的接著劑層2、被覆接著劑層2之保 護膜1。 首先，說明有關構成本實施形態的接著劑層2之接著 劑組成物。 本實施形態之接著劑組成物係含有（A )熱可塑性樹 脂、（B )熱硬化性樹脂、（C )潛在性硬化劑、（D )無 機塡充物、與（E)有機微粒子。 (A)熱可塑性樹脂（以下，稱爲「（A)成分」） 可舉例如聚酯樹脂、聚醚樹脂、聚醯胺樹脂、聚醯胺醯亞 胺樹脂、聚醯亞胺樹脂、聚乙烯丁縮醛樹脂、聚乙烯甲醛 樹脂、苯氧基樹脂、聚羥基聚醚樹脂、丙烯酸樹脂、聚苯 乙烯樹脂、丁二烯樹脂、丙烯腈•丁二烯共聚物、丙烯腈 •丁二烯•苯乙烯樹脂、苯乙烯•丁二烯共聚物、丙烯酸 共聚物。此等係可單獨或混合2種以上而使用。 (A )成分係可使接著劑組成物之薄膜形成性良好。 所謂薄膜形成性係表示使液狀之接著劑組成物固形化，形 成薄膜狀時，容易破裂，或龜裂，或未沾黏之機械特性者 。若以一般之狀態（例如，常溫）作爲薄膜的處理性很容 易，可謂薄膜形成性良好。即使上述之熱可塑性樹脂中， 因耐熱性及機械強度優異’宜使用聚醯亞胺樹脂或苯氧樹 脂。 (A)成分之重量平均分子量宜爲2萬〜80萬，更宜爲3 萬〜50萬，最宜爲4萬〜10萬，尤宜爲4萬〜8萬。若重量平均 -10- 201211187 分子量在此範圍，形成片狀或薄膜狀之接著劑層2的強 、使可撓性良好地平衡變成很容易，同時接著劑層2之 動性變良好，故可充分確保配線之電路塡充性（埋入性 。又，在本說明書中，重量平均分子量係表示以凝膠滲 色層分析進行測定，使用標準聚苯乙烯檢量線而換算之 〇 又，從維持薄膜形成性，同時並對硬化前之接著劑 2賦予黏接著性之觀點，（A )成分之玻璃轉移溫度宜 20〜170 °C，更宜爲25〜120 °C。 （A)成分之玻璃轉移溫 未達20°C時在室溫之薄膜形成形降低，在背硏磨步驟之 導體晶圓的加工中接著劑層2有易變形之傾向，若超過1 °C，必須使接著劑層2貼黏於半導體晶圓時之貼黏溫度 1701：更高溫，故進行（B)成分之熱硬化反應，接著劑 2之流動性降低而易產生連接不良之傾向。 (A)成分之含量相對於（A) 、（B)及（C)成 之合計100質量份，宜爲10〜50質量份，更宜爲15〜50質 份，最宜爲20〜40質量份，尤宜爲25 ~35質量份。使（A 成分之含量爲上述範圍內，接著劑組成物之薄膜形成性 成更良好，熱壓接時顯示適度的流動性，凸塊與電路電 之間的樹脂排除性變成更良好。具體上係（A )成分之 量爲1 0質量份以上，薄膜形成性變成更良好，從支持基 與保護薄膜之腋下，接著劑組成物滲出之不良發生可被 確實地防止。又，若（A)成分之含量爲50質量份以下 熱壓接時具有適度的流動性，凸塊與電路電極之間的排 度 流 ) 透 値 層 爲 度 半 70 較 層 分 量 ) 變 極 含 板 更 除 -11 - 201211187 性變良好，可更確實地防止連接不良的發生。 (B)熱硬化性樹脂（以下，稱爲「（B)成分」）可 舉例如環氧樹脂、不飽和聚酯樹脂、三聚氰胺樹脂、尿素 樹脂、二烯丙基酞酸酯樹脂、雙馬來醯亞胺樹脂、三嗪樹 脂、聚胺基甲酸酯樹脂、酚樹脂、氰基丙烯酸酯樹脂、聚 異氰酸酯樹脂、呋喃樹脂、間苯二酚樹脂、二甲苯樹脂、 苯並胍胺樹脂、聚矽氧樹脂、矽氧烷改性環氧樹脂及矽氧 烷改性聚醯胺醯亞胺樹脂。此等係可單獨或混合2種以上 而使用。從提昇耐熱性及接著性之觀點，就（B)成分而 言，宜爲含有環氧樹脂。 上述環氧樹脂係只要爲進行硬化而具有接著作用者即 可，無特別限定，可廣泛地使用例如於環氧樹脂手冊（新 保正樹編，日刊工業新聞社）等記載之環氧樹脂。具體上 可使用例如雙酚A型環氧等之二官能環氧樹脂、酚酚醛清 漆型環氧樹脂或甲酚酚醛清漆型環氧樹脂等之酚醛清漆型 環氧樹脂、三酚甲烷型環氧樹脂。又，可適用多官能環氧 樹脂、縮水甘油基胺型環氧樹脂、含有雜環之環氧樹脂或 脂環式環氧樹脂等一般所知者。 (B)成分之含量相對於（A) 、（B)及（C)成分 之合計100質量份，宜爲5~88質量份，更宜爲20〜50質量份 ’最宜爲20〜40質量份。使（B)成分之含量爲上述範圍內 ’硬化後之接著劑的耐熱性、接著性優異，可顯現高信賴 性。具體上，若（B)成分之含量爲5質量份以上，硬化物 之凝集力提高，於連接信賴性變成更優異。又，若（B) -12- 201211187 成分之含量爲88質量份以下，在 膜狀形體易被保持，處理性優異 (C )潛在性硬化劑可舉例 、硫醇系、苯並噁嗪、三氟化胡 醯亞胺、聚胺之鹽、二氰二醯胺 劑。從延長可視時間之觀點，宜 核，以高分子物質、無機物或金 者作爲（C )成分。 微膠囊型之潛在性硬化劑可 苯乙烯、明膠及聚異氰酸酯等之 石等之無機物、或以鎳或銅等之 覆由上述硬化劑所構成之核者。 接著劑組成物爲具備於半導 保護、切割及於電路基板之連接 裝置製造步驟時，認爲會長期間 到熱、濕度、光等之外在因素的 物係宜對於上述之半導體裝置製 響的耐性優異，經過一連串之步 性。 本實施形態之接著劑組成物 影響的耐性優異，故經過半導體 可保持充分使用的特性。繼而， 微膠囊型潛在性硬化劑作爲（C 在因素影響的耐性更優異。 硬化前之薄膜狀態中，薄 〇 如酚系、咪唑系、聯胺系 J -胺錯合物、硫鑰鹽、胺 及有機過氧化物系之硬化 使用以此等之硬化劑作爲 屬薄膜等被覆而微膠囊化 舉例如聚胺基甲酸酯、聚 高分子物質、矽酸鈣或沸 金屬薄膜的被膜實質上被 體晶圓之貼黏、硏削時之 ，適用於一連串之半導體 曝露於常溫環境下、或受 影響。因此，接著劑組成 造步驟中的外在因素之影 驟而可保持充分使用的特 係對於如上述之外在因素 裝置製造之一連串步驟而 上述接著劑組成物係使用 )成分，對於如上述之外 -13- 201211187 微膠囊型潛在性硬化劑之平均粒徑宜爲1 〇μπι以下，更 宜爲5fxm以下，如此之微膠囊型潛在性硬化劑係反應起始 溫度更均一，且含有該微膠囊型潛在性硬化劑之接著劑組 成物的硬化開始溫度亦均一。又，若平均粒徑變成大於 1 Ομιη，有時使接著劑組成物硬化而成形爲薄膜狀時之表面 平坦性無法充分得到。又，若表面平坦性不充分，使用來 作爲電路構件連接用時，恐無法充分密封塡充節距間。又 ，平均粒徑之下限値係宜爲1 μιη以上。如此之微膠囊型潛 在性硬化劑係耐溶劑性對於薄膜形成時之清漆（Varnish)的 溶劑高，可長期間維持加熱加壓前之接著劑組成物的流動 性。此等之微膠囊型潛在性硬化劑係可一種單獨使用或組 合兩種以上而使用。 本實施形態中之接著劑組成物中的（C )成分之含量 相對於（A) 、（B)及（C)成分之合計100質量份，宜 爲2〜45質量份，更宜爲10-40質量份，最宜爲20〜40質量份 。（C)成分之含量未達2質量份時，硬化反應有很難進行 之傾向，若超過45質量份，占有接著劑組成物全量之硬化 劑的比率太多，故相對地熱硬化性樹脂之比率變少，有使 耐熱性或接著性等之特性惡化之傾向。 本實施形態中之接著劑組成物係含有（D)無機塡充 物，可降低硬化後之接著劑層2的吸濕率及線膨脹係數， 可提高彈性率，故可提昇所製作之半導體裝置的連接信賴 性。又，（D)成分係爲防止接著劑層2中之可見光的散射 而提昇可見光透過率，可選擇未降低可見光透過率之無機 -14- 201211187 塡充物。可抑制可見光透過率的降低之（D)成分，選擇 具有較可見光之波長更細的粒徑之無機塡充物，或，選擇 具有折射率近似於樹脂成分之（A ) 、 （ B )及（C )成分 所構成的樹脂組成物（以下，依情況稱爲「樹脂組成物」 )之折射率的無機塡充物。 具有較可見光之波長更細的粒徑之無機塡充物係只要 爲具有透明性之塡充物即可，未特別限制於塡充物之組成 ，宜爲平均粒徑未達〇.3μπι，更宜爲0.1 μιη以下。又，如此 之無機塡充物的折射率宜爲1.46~1 .7。 具有折射率近似於樹脂組成物之折射率的無機塡充物 係製作由（A ) 、（ B )及（C )成分所構成之樹脂組成物 ，測定折射率後’可選定具有折射率近似於該折射率的無 機塡充物。就該無機塡充物而言，從接著劑層2之半導體 晶片與電路基板之空隙的塡充性之觀點及抑制在連接步驟 之氣泡的發生之觀點，宜使用微細的塡充物。如此之無機 塡充物的平均粒徑宜爲0.01~5μηι，更宜爲〇.1〜2μιη，最宜 爲0.3〜Ιμπι。平均粒徑未達〇·〇1μηι時，粒子之被表面積變 大’接著劑組成物之黏度增加，無機塡充物有很難塡充之 傾向。 具有折射率近似於樹脂組成物之折射率的無機塡充物 之折射率係宜爲樹脂組成物之折射率± 〇 . 〇 6的範圍。例如 ’樹脂組成物之折射率爲1.60時，可適宜使用於折射率爲 1 . 5 4〜1 · 6 6的無機塡充物。折射率係使用a b b e折射計，可 以鈉D線（5 8 9nm )作爲光源而進行測定。如此之無機塡 -15- 201211187 充物係可舉例如複合氧化物塡充物、複合氫氧化物塡充物 、硫酸鋇及黏度礦物，具體上，可使用堇青石（Cordierite) 、鎂橄欖石、莫來石（Mullite)、硫酸鋇、氫氧化鎂、硼酸 鋁、鋇或氧化矽氧化鈦。又亦可使用二氧化矽、矽酸鈣、 氧化鋁、碳酸鈣等》 又，上述之2型的無機塡充物係可組合而使用，亦可 組合同一型內之無機塡充物的2種以上而使用。但，爲不 妨礙接著劑組成物之黏度增加，具有較可見光之波長更細 的粒徑之無機塡充物之添加量就由（A)成分、（B)成分 及（C)成分所構成之樹脂組成物的全量基準宜爲未達10 質量％。 又，（D)成分從提昇接著劑層2之彈性率的觀點，宜 線膨脹係數在〇〜700°C之溫度範圍爲7xl(T6/°C以下，更宜 爲 3xl(T6/°C 以下。According to the adhesive composition of the present invention, by containing the above components (A), (B), (C), (D) and (E), the embedding property at the time of connection is lowered, and the generation of bubbles can be sufficiently reduced. A film-like adhesive excellent in connection reliability is formed. In the adhesive composition of the present invention, when the total amount of the 201211187 of the (A) thermoplastic resin, the (B) thermosetting resin, and the (C) latent curing agent is 100 parts by mass, (D) The content of the inorganic filler is 50 to 150 parts by mass, and the content of the (E) organic fine particles is 5 to 30 parts by mass, and the above (D) inorganic inclusions and the above (E) organic The total content of the fine particles is 65 to 165 parts by mass. Such an adhesive composition can form a film-like adhesive which is more excellent in embedding property and connection reliability, and an adhesive composition of the present invention, which is interposed between opposing circuit members for connecting the above-mentioned circuit members to each other then. At this time, by thermocompression bonding between the circuit members, it is possible to suppress the occurrence of bubbles while adhering with a sufficient adhesion force. Thereby, a connector having excellent connection reliability can be obtained. For the circuit member, a circuit member having a circuit having a high density can be used. For example, the adhesive composition of the present invention is used to connect a circuit member having a through-electrode electrode, and the adhesive sheet of the present invention is used. A support substrate and an adhesive layer formed on the support substrate and composed of the adhesive composition of the present invention. Preferably, the support substrate is provided with a plastic film and an adhesive layer provided on the plastic film, and the adhesive layer is provided on the adhesive layer. Thereby, the backside honing of the adhesive chip semiconductor wafer of the present invention allows the semiconductor crystal to be stabilized and held. The adhesive sheet of the present invention is interposed between opposing circuit members for connecting the above-mentioned circuit members to each other. At this time, by thermocompression bonding between the circuit members, it is possible to suppress the occurrence of bubbles while continuing with a sufficient adhesion force. Thereby, a connector having excellent connection reliability can be obtained. -8- 201211187 The present invention further provides a method of fabricating a semiconductor device, comprising: preparing a semiconductor wafer having a plurality of circuit electrodes on a main surface of one of the surfaces of the semiconductor wafer on which the circuit electrode is provided a step of providing an adhesive layer formed of the adhesive composition of the present invention on the side; and stepping the opposite side of the surface side of the semiconductor wafer on which the circuit electrode is provided to thin the semiconductor wafer Cutting the thinned semiconductor wafer and the adhesive layer to form a semiconductor element with a film-like adhesive; and soldering the circuit electrode of the semiconductor element with the film-like adhesive The step of bonding to the circuit electrode of the semiconductor element supporting member. [Effect of the Invention] According to the present invention, it is possible to provide an adhesive composition which is excellent in embedding property in the case of forming a film, and which can be used as a semiconductor device having excellent connection reliability, and an adhesive sheet using the same. Moreover, according to the method of manufacturing a semiconductor device of the present invention, it is possible to provide a semiconductor device having excellent connection reliability. [Formation for Carrying Out the Invention] A preferred embodiment of the adhesive composition, the adhesive sheet, and the method for producing the semiconductor device of the present invention will be described below. The adhesive sheet of the present invention can be used for connection as a circuit member. Fig. 1 is a schematic cross-sectional view showing an embodiment of a suitable adhesive sheet for connecting circuit members of the present invention. The circuit member for connection shown in FIG. 1 is followed by a -9-201211187 granule 10 comprising a support substrate 3 and an adhesive layer 2 of the adhesive composition of the present invention provided on the support substrate 3 Next, the protective film 1 of the agent layer 2. First, the adhesive composition constituting the adhesive layer 2 of the present embodiment will be described. The adhesive composition of the present embodiment contains (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic filling, and (E) organic fine particles. (A) thermoplastic resin (hereinafter referred to as "(A) component") may, for example, be a polyester resin, a polyether resin, a polyamide resin, a polyamidimide resin, a polyimide resin, or a polyethylene. Butyral resin, polyethylene formaldehyde resin, phenoxy resin, polyhydroxy polyether resin, acrylic resin, polystyrene resin, butadiene resin, acrylonitrile butadiene copolymer, acrylonitrile butadiene • Styrene resin, styrene-butadiene copolymer, acrylic copolymer. These may be used alone or in combination of two or more. The component (A) is such that the film formation property of the adhesive composition is good. The film-forming property means that the liquid-based adhesive composition is solidified, and when it is formed into a film, it is easily broken, cracked, or mechanically viscous. It is easy to treat the film in a normal state (for example, normal temperature), and the film formability is good. Even in the above thermoplastic resin, it is preferable to use a polyimide resin or a phenoxy resin because it is excellent in heat resistance and mechanical strength. The weight average molecular weight of the component (A) is preferably from 20,000 to 800,000, more preferably from 30,000 to 500,000, most preferably from 40,000 to 100,000, and particularly preferably from 40,000 to 80,000. When the weight average -10-201211187 molecular weight is in this range, it is easy to form a sheet-like or film-like adhesive layer 2, and it is easy to balance the flexibility, and the adhesiveness of the adhesive layer 2 becomes good. It is sufficient to ensure the circuit's electrical compatibility (buriability). In this specification, the weight average molecular weight is measured by gel bleed layer analysis, and converted using standard polystyrene calibration lines. The glass transition temperature of the component (A) is preferably from 20 to 170 ° C, more preferably from 25 to 120 ° C, in view of maintaining the film formability and imparting adhesion to the adhesive 2 before curing. When the glass transfer temperature is less than 20 ° C, the film formation shape at room temperature is lowered, and the adhesive layer 2 tends to be easily deformed during the processing of the conductor wafer in the back honing step. If it exceeds 1 ° C, the adhesive must be made. When the layer 2 is adhered to the semiconductor wafer, the adhesion temperature is 1701: higher temperature, so the thermal hardening reaction of the component (B) is performed, and the fluidity of the adhesive 2 is lowered to cause a connection failure. (A) Content of the component Compared to (A), (B) and (C) It is preferably 10 to 50 parts by mass, more preferably 15 to 50 parts by mass, most preferably 20 to 40 parts by mass, particularly preferably 25 to 35 parts by mass, so that the content of the component A is within the above range. The film composition of the adhesive composition is more excellent, and moderate fluidity is exhibited during thermocompression bonding, and the resin exclusion property between the bump and the circuit is further improved. Specifically, the amount of the component (A) is 10 When the amount of the component (A) is 50 parts by mass or less, the amount of the component (A) is less than 50 parts by mass, and the film formation property is more excellent, and the occurrence of the bleeding of the adhesive composition can be reliably prevented from the support base and the protective film. Appropriate fluidity during crimping, flow rate between bump and circuit electrode) Transverse layer is half of 70 layer component) Pore-containing plate is more than -11 - 201211187 Sexually good, more reliably Prevent the occurrence of poor connection. (B) The thermosetting resin (hereinafter referred to as "(B) component") may, for example, be an epoxy resin, an unsaturated polyester resin, a melamine resin, a urea resin, a diallyl phthalate resin, or a double horse.醯imine resin, triazine resin, polyurethane resin, phenol resin, cyanoacrylate resin, polyisocyanate resin, furan resin, resorcinol resin, xylene resin, benzoguanamine resin, poly An epoxy resin, a siloxane-modified epoxy resin, and a decane-modified polyamidoximine resin. These may be used alone or in combination of two or more. From the viewpoint of improving heat resistance and adhesion, the component (B) preferably contains an epoxy resin. The above-mentioned epoxy resin is not particularly limited as long as it is used for curing, and an epoxy resin described in, for example, an epoxy resin handbook (New Baozheng Shu, Nikkan Kogyo Shimbun) can be widely used. Specifically, for example, a difunctional epoxy resin such as bisphenol A epoxy, a novolak epoxy resin such as a phenol novolak epoxy resin or a cresol novolak epoxy resin, or a trisphenol methane epoxy resin can be used. Resin. Further, a general-purpose ones such as a polyfunctional epoxy resin, a glycidylamine type epoxy resin, a heterocyclic epoxy resin or an alicyclic epoxy resin can be used. The content of the component (B) is preferably from 5 to 88 parts by mass, more preferably from 20 to 50 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C). Share. When the content of the component (B) is within the above range, the adhesive after curing is excellent in heat resistance and adhesion, and high reliability can be exhibited. Specifically, when the content of the component (B) is 5 parts by mass or more, the cohesive force of the cured product is improved, and the connection reliability is further improved. In addition, when the content of the component (B) -12-201211187 is 88 parts by mass or less, the film-shaped body is easily retained, and the handleability is excellent (C) The latent hardener can be exemplified by a thiol type, a benzoxazine, or a third. Fluorinated sulphate, polyamine salt, dicyandiamide. From the viewpoint of extending the visual time, it is preferable to use a high molecular substance, an inorganic substance or a gold as the component (C). The microcapsule-type latent curing agent may be an inorganic substance such as styrene, gelatin or polyisocyanate or a core composed of the above-mentioned curing agent such as nickel or copper. When the composition of the second component is provided in the manufacturing process of the semiconductor device for semi-conductive protection, dicing, and circuit board, it is considered that the factor of the external temperature to the temperature, the humidity, the light, and the like is suitable for the semiconductor device described above. Excellent resistance, after a series of steps. Since the adhesive composition of the present embodiment is excellent in resistance to the influence of the composition, the semiconductor can be sufficiently used. Then, the microcapsule-type latent hardener is more excellent as (C is affected by factors. In the film state before hardening, thinner such as phenol type, imidazole type, hydrazine type J-amine complex, sulfur key salt, The curing of an amine or an organic peroxide is carried out by coating a curing agent such as a thin film or the like, and microcapsules, for example, a film of a polyurethane, a polypolymer, a calcium citrate or a boiling metal film. When the wafer is adhered or diced, it is suitable for a series of semiconductors to be exposed to or exposed to a normal temperature environment. Therefore, the external factors in the composition of the adhesive can be fully utilized. The above-mentioned adhesive composition is used in a series of steps of the factor device manufacturing as described above, and the average particle diameter of the microcapsule latent curing agent is preferably 1 〇μπι or less as described above. More preferably, it is 5fxm or less, such that the microcapsule-type latent curing agent is more uniform in reaction initiation temperature, and the hardening start temperature of the adhesive composition containing the microcapsule-type latent curing agent The degree is also uniform. When the average particle diameter is more than 1 Ομηη, the surface flatness of the adhesive composition may not be sufficiently obtained when the adhesive composition is cured to form a film. Further, when the surface flatness is insufficient and it is used for connection as a circuit member, it may not be possible to sufficiently seal the inter-pitch pitch. Further, the lower limit of the average particle diameter is preferably 1 μmη or more. Such a microcapsule-type latent curing agent is solvent-resistant, and has a high solvent for the varnish at the time of film formation, and can maintain the fluidity of the adhesive composition before heating and pressurization for a long period of time. These microcapsule-type latent hardeners can be used singly or in combination of two or more. The content of the component (C) in the adhesive composition of the present embodiment is preferably 2 to 45 parts by mass, more preferably 10 parts by mass based on 100 parts by mass of the total of the components (A), (B) and (C). 40 parts by mass, most preferably 20 to 40 parts by mass. When the content of the component (C) is less than 2 parts by mass, the hardening reaction tends to be difficult, and if it exceeds 45 parts by mass, the ratio of the total amount of the hardener to the binder composition is too large, so the ratio of the thermosetting resin is relatively large. There is a tendency that the properties such as heat resistance and adhesion are deteriorated. The adhesive composition of the present embodiment contains (D) an inorganic ruthenium, which can reduce the moisture absorption rate and the coefficient of linear expansion of the adhesive layer 2 after curing, and can improve the modulus of elasticity, thereby improving the fabricated semiconductor device. Connection reliability. Further, the component (D) is for preventing the scattering of visible light in the adhesive layer 2 and improving the visible light transmittance, and the inorganic-14-201211187 enthalpy which does not lower the visible light transmittance can be selected. (D) component capable of suppressing a decrease in visible light transmittance, selecting an inorganic filler having a particle diameter smaller than a wavelength of visible light, or selecting (A), (B) and (having a refractive index close to a resin component) C) An inorganic entanglement of the refractive index of the resin composition (hereinafter referred to as "resin composition"). The inorganic ruthenium having a finer particle diameter than the wavelength of visible light may be a condensate having transparency, and is not particularly limited to the composition of the ruthenium, and the average particle diameter is preferably less than 33 μm. It should be 0.1 μmη or less. Further, the refractive index of such an inorganic ruthenium is preferably from 1.46 to 1.7. An inorganic inclusion having a refractive index close to the refractive index of the resin composition is a resin composition composed of the components (A), (B), and (C). After the refractive index is measured, the refractive index is selected to have a refractive index similar to that. The inorganic inclusion of the refractive index. In the inorganic filler, it is preferable to use a fine ruthenium from the viewpoint of the adhesion of the gap between the semiconductor wafer of the adhesive layer 2 and the circuit board and the suppression of the generation of bubbles in the connection step. The average particle diameter of such an inorganic filler is preferably from 0.01 to 5 μm, more preferably from 1 to 2 μm, most preferably from 0.3 to Ιμπι. When the average particle diameter is less than 〇·〇1μηι, the surface area of the particles becomes large. The viscosity of the adhesive composition increases, and the inorganic ruthenium tends to be difficult to replenish. The refractive index of the inorganic cerium having a refractive index close to the refractive index of the resin composition is preferably in the range of the refractive index ± 〇 〇 6 of the resin composition. For example, when the refractive index of the resin composition is 1.60, it can be suitably used for an inorganic ruthenium having a refractive index of 1.54 to 1.66. The refractive index was measured using an a b b e refractometer using a sodium D line (589 μm) as a light source. Such an inorganic 塡-15-201211187 filling system may, for example, be a composite oxide ruthenium, a composite hydroxide ruthenium, a barium sulfate, and a viscous mineral. Specifically, cordierite or forsterite may be used. Mullite, barium sulfate, magnesium hydroxide, aluminum borate, barium or barium oxide. Further, it is also possible to use cerium oxide, calcium citrate, aluminum oxide, calcium carbonate, etc. Further, the above-mentioned two types of inorganic chelating substances may be used in combination, or two types of inorganic chelates in the same type may be combined. Use above. However, in order not to hinder the increase in the viscosity of the adhesive composition, the amount of the inorganic filler having a particle diameter smaller than the wavelength of visible light is composed of the components (A), (B) and (C). The total amount of the resin composition is preferably less than 10% by mass. Further, the component (D) preferably has a linear expansion coefficient of 7 x 1 (T6/° C. or less, more preferably 3 x 1 (T6/° C. or less) from the viewpoint of improving the elastic modulus of the adhesive layer 2 at a temperature of 〇 to 700 ° C. .

(D)成分之調配量係相對於樹脂成分之（A) 、( B )及（C )成分之合計100質量份，宜爲25〜200質量份，更 宜爲50〜150質量份，最宜爲75〜125質量份。（D)成分之 調配量未達25質量份時，引起從接著劑組成物所形成之接 著劑層的線膨脹係數之增大與彈性率之降低，故壓接後之 半導體晶片與基板之連接信賴性易降低，進一步，亦很難 得到連接時之氣泡抑制效果。另外，若（D)成分之調配 量超過200質量份，接著劑組成物之熔融黏度增加，半導 體晶片與接著劑層之界面或電路基板與接著劑層之界面的 潤濕性降低，致剝離或埋入不足易引起氣泡的殘留。 -16- 201211187 (E )有機微粒子係可舉例如含有丙烯酸樹脂、聚矽 氧樹脂、丁二烯橡膠、聚酯、聚胺基甲酸酯、聚乙烯丁縮 醛、聚丙烯酸酯、聚甲基丙烯酸甲酯、丙烯酸橡膠、聚苯 乙烯、NBR、SBR、聚矽氧改性樹脂等作爲成分之共聚物 。有機微粒子宜分子量爲100萬以上之有機微粒子或具有 三次元交聯構造之有機微粒子。如此之有機微粒子係於接 著劑組成物之分散性高。又，含有如此之有機微粒子的接 著劑組成物係於接著性與硬化後之應力緩和性更優異。又 ，此處所謂「具有三次元交聯構造」係顯示聚合物鏈具有 三次元網目構造，具有如此之構造的有機微粒子係例如以 具有可使具複數反應點之聚合物與該反應點結合之官能基 二個以上之交聯劑進行處理來得到。分子量爲1 00萬以上 之有機微粒子、具有三次元交聯構造之有機微粒子係宜任 一者均於溶劑的溶解性低。於溶劑的溶解性低之此等的有 機微粒子係可更顯著地得到上述之效果。又，從可更顯著 地得到上述之效果之觀點，分子量爲100萬以上之有機微 粒子及具有三次元交聯構造之有機微粒子係宜爲（甲基） 丙烯酸烷酯-聚矽氧共聚物、聚矽氧-(甲基）丙烯酸共聚 物或此等之複合體所構成的有機微粒子。又，亦可使用如 特開200 8- 1 50 5 7 3公報所記載之聚醯胺酸粒子、聚醯亞胺 粒子等之有機微粒子。 就（E)成分而言，亦可使用具有核殼型之構造，於 核層與殼層組成相異之有機微粒子。核殼型之有機微粒子 具體上可舉例如以聚矽氧-丙烯酸橡膠作爲核而使丙烯酸 -17- 201211187 樹脂接枝之粒子、以丙烯酸共聚物作爲核而使丙烯酸樹脂 接枝之粒子等。又，如wo 2009/051067公報所記載之核殻 型聚矽氧微粒子、或如WO 2009/020005公報所記載之（甲 基）丙烯酸烷酯-丁二烯-苯乙烯共聚物或複合體、（甲基） 丙烯酸烷酯-聚矽氧共聚物或複合體、聚矽氧·（甲基）丙烯 酸共聚物或複合體等之有機微粒子、或如特開2002_ 25603 7公報所記載之核殼構造聚合物粒子或如特開2004-1 8 803記載之核殼構造的橡膠粒子等。此等之核殼型的有 機微粒子係可一種單獨使用或組合兩種以上而使用。 (E)成分爲分子量爲1〇〇萬以上之有機微粒子及具有 三次元交聯構造之有機微粒子時’對有機溶劑之溶解性低 ，故可維持粒子形狀而直接調配於接著劑組成物中。因此 ，於硬化後之接著劑層2中有機微粒子呈島狀分散，連接 體之強度提高。又，（E)成分係具有作爲含應力緩和性 之耐衝擊緩和劑之功能者。 (E)成分宜平均粒徑爲〇.1~2μιη。更宜爲0.1〜0·9μηι 。（Ε )成分之平均粒徑未達0.1 μιη時接著劑組成物之熔融 黏度增加，電路構件連接時使用焊錫時，有防止其焊錫潤 濕性之傾向，若超過2μιη，熔融黏度之降低效果會變少， 連接時有很難得到氣泡抑制效果的傾向。 (Ε )成分係爲對接著劑層2賦予連接時之氣泡抑制、 與連接後之應力緩和效果，相對於（A ) 、（ B )及（C ) 成分之合計100質量份，宜爲5~3 0質量份。（E)成分之調 配量未達5質量份時係很難發揮抑制連接時之氣泡的效果 -18· 201211187 ’同時並亦很難顯現應力緩和效果的傾向，若超過3 〇質量 份，流動性變低’焊錫潤濕性降低，成爲殘留氣泡的原因 ，同時硬化物之彈性率太低而有連接信賴性降低之傾向。 充分抑制氣泡’連接後之應力緩和效果優異，且從降 低吸濕率及線膨脹係數，提高彈性率的觀點，相對於（A )成分、（B)成分及（C)成分之總含量100質量份，宜 (D) 成分之含量爲5〇〜150質量份’ （E)成分之含量爲 5〜3 0質量份’且（D)成分及（E)成分之含量的合計爲 65〜165質量份。更宜（D)成分之含量爲$0430質量份， (E) 成分之a里爲7〜20質量份’且（D)成分及（E)成 分之含量的合計爲65〜132質量份，最宜（D)成分之含量 爲50〜110質量份，（E)成分之含量爲1〇〜20質量份，且（ D)成分及（E)成分之含量的合計爲65〜110質量份。 (D)成分之調配量未達50質量份時，從接著劑組成 物所形成之接著劑層的塊體強度低，有在耐熱試驗之連接 信賴性降低的傾向’（D )成分之調配量多於1 50質量份時 ’接著劑組成物之觸變性太高，有剝離不良增加之傾向。 又’若（D)成分與（E)成分之含量的合計爲65質量份以 上’氣泡的抑制效果更提高，故佳，若爲1 65質量份以下 ’接著劑組成物爲維持適宜作爲電路構件連接用的流動性 ’界面的潤濕性提高，剝離不良抑制效果更優異，故佳。 又’若（D)成分與（E)成分之含量的合計多於165質量 份’有連接阻抗惡化之傾向。 又’ （E)成分之含量係相對於（D)成分1〇〇質量份 -19- 201211187 ，宜爲5〜100質量份，更宜爲5〜60質量份，最宜爲ι〇~30質 量份。若（E)成分之含量相對於（D)成分1〇〇質量份爲5 質量份以上，接著劑組成物之變形性變良好，被黏體界面 之剝離不良抑制效果優異。又，若多於100質量份，無法 得到無機塡充物所產生的熱膨脹抑制效果，故連接信賴性 惡化。另外，（D )成分過剩地存在時，觸變性太高，故 於被黏體界面之潤濕不充分，連接性降低。 於本實施形態之接著劑組成物中係改質無機塡充物的 表面，提昇異種材料間之界面結合，增大接著強度，亦可 添加各種偶合劑。偶合劑可舉例如矽烷系、鈦系及鋁系之 偶合劑，其中，就效果高而言，宜爲矽烷系偶合劑。 矽烷系偶合劑可舉例如γ-甲基丙烯醯氧丙基三甲氧基 矽烷、γ-甲基丙烯醯氧丙基甲基二甲氧基矽烷、γ-氫硫基 丙基三甲氧基矽烷、γ-氫硫基丙基三乙氧基矽烷、3-胺基 丙基甲基二乙氧基矽烷、3-脲基丙基三乙氧基矽烷、3-脲 基丙基三甲氧基矽烷。此等係可單獨使用或組合兩種以上 而使用。 在本實施形態之接著劑組成物中係爲吸附離子性雜質 ，提高吸濕時之絕緣信賴性，亦可添加離子捕捉劑。如此 之離子捕捉劑無特別限制，爲防止例如三嗪硫醇化合物、 雙酚系還原劑等之銅進行離子化而溶出者，可舉例如已知 作爲防止銅害劑的化合物、锆系、銻系鉍系鎂鋁化合物等 之無機離子吸附劑。 接著劑組成物係連接半導體晶片與電路基板後之溫度 -20- 201211187 變化、或抑制因加熱吸濕所產生之膨脹等，爲達成高連接 信賴性，宜硬化後之接著劑層2在40〜100 °C中的線膨脹係 數爲60xl0_6/°C以下，更宜爲55xlO_6/°C以下，最宜爲50χ 1CT6/°C以下。若硬化後之接著劑層2的線膨脹係數超過60χ 1 (T6/°c，有時因封裝後之溫度變化或加熱吸濕造成之膨脹 而於半導體晶片之連接端子與電路基板之配線之間的電性 連接無法保持。又，於本發明之接著劑組成物中含有導電 粒子而形成異方導電性接著薄膜（ACF )，但宜不含有導 電粒子而形成非導電性接著薄膜（NCF )。 由本實施形態之接著劑組成物所形成的接著劑層2係 以2 5 0 °C加熱1 〇秒後，以微分掃描熱量測定（以下，稱爲 「DSC」）所測定的反應率爲60%以上，更宜爲70%以上。 又，在室溫下保管電路構件連接用組成物薄片1 4日後，宜 以DSC所測定之接著劑層2的反應率未達10%。藉此，使用 本實施形態之接著劑組成物’可得到連接時之反應性非常 優異，且保存安定性亦優異之薄膜狀接著劑。 接著劑層2係宜未硬化時之可見光透過率爲5 %以上， 更宜爲可見光透過率爲8%以上，最宜爲可見光透過率爲 1 0%以上。可見光透過率未達5%時，覆晶黏晶機之辨識標 記識別很難進行，有無法進行定位作業之傾向。另外，有 關可見光透過率的上限無特別限定。 可見光透過率係可使用日立製U-3 3 10形分光光度計而 進行測定。例如以膜厚5〇μιη之帝人杜邦製PET薄膜（ Pyrex，5 5 5nm透過率86.03% )作爲基準物質而進行基線補 -21 - 201211187 正測定後，於PET薄膜以25μηι之厚度形成接著劑層2後’ 測定400〜8 0Onm之可見光透過率的透過率。於覆晶黏晶機 所使用之鹵素光源與光導的波長相對強度中5 5 0〜6 0 0nm最 強，故在本說明書中係使用5 5 5nm中之透過率而進行接著 劑層2之透過率的比較。 接著劑層2係可使上述之本發明的接著劑組成物溶解 或分散於溶劑中而形成清漆，將此清漆塗佈於保護薄膜（ 以下，依情況稱爲「第一薄膜」）1上，藉加熱除去溶劑 而形成。其後，於接著劑層2在常溫〜60 °C進行層合支持基 材3 ’可得到本發明之電路構件連接用接著劑片。又，接 著劑層2係亦可使上述清漆塗佈於支持基材3上，藉加熱除 去溶劑而形成。 所使用之溶劑並無特別限定，宜從沸點考量接著劑層 形成時之揮發性等而決定。具體上例如甲醇、乙醇、2 -甲 氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇、甲乙酮、丙酮 、甲基異丁基酮、甲苯、二甲苯等之比較低沸點之溶劑就 接著劑層形成時接著劑層之硬化很難進行之點，佳。此等 之溶劑係可一種單獨使用或組合兩種以上而使用。 保護膜1係可使用例如聚對苯二甲酸乙二酯、聚四氟 乙烯薄膜 '聚乙烯薄膜、聚丙烯薄膜、聚甲基戊烯薄膜等 之塑質薄膜。從離型性之觀點，就保護膜丨而言，亦宜使 用由如聚四氟乙烯薄膜之氟樹脂所構成的表面能量低的薄 膜。 爲提昇保護膜1之離型性，宜以聚矽氧系離型劑、氟 -22- 201211187 系離型劑、長鏈烷基丙烯酸酯系離型劑等之離型劑處理形 成保護膜1之接著劑層2的面。就市售者而言可取自例如帝 人Dupont Film公司製的「A-63」（離型處理劑：改性聚 矽氧系）、或「A - 3 1」（離型處理劑：P t系聚矽氧系）。 保護膜1係宜厚度爲10〜ΙΟΟμηι，更宜爲1〇〜75μηι ,尤 宜爲25〜5〇μηι。此厚度未達ΙΟμηι，塗佈時，有保護膜破損 之傾向，若超過ΙΟΟμπι，有廉價性差之傾向。 使上述清漆塗佈於保護膜1 (或支持基材3 )上之方法 ，可舉例如刮刀塗佈法、輥塗法、噴塗法、凹版塗佈法、 桿塗法、簾塗法等一般周知的方法。 接著劑層2之厚度並無特別限定，但宜爲5〜2 ΟΟμηι，更 且爲7〜150μηα’最宜爲10〜ΙΟΟμπι。若厚度小於5μηι，很難 確保充分的接著力，有無法掩埋電路基板之凸電極之傾向 ’若厚度大於200μηι，變成不經濟，很難符合半導體裝置 之小型化的要求。 支持基材3可舉例如聚對苯二甲酸乙二酯薄膜、聚四 氟乙烯薄膜、聚乙烯薄膜、聚丙烯薄膜、聚甲基戊烯薄膜 、聚乙烯乙酸酯薄膜、聚氯化乙烯薄膜、聚醯亞胺薄膜等 之塑質薄膜。又，支持基材3係混合選自上述材料之2種以 上者，或，亦可爲上述薄膜被複層化者。 支持基材3之厚度並無特別限定，但宜爲5〜25 0μηι。若 厚度薄於5 μπι，半導體晶圓之硏削（背硏磨）時有可能切 割支持基材，若厚於2 5 0 μ m，不經濟，故不佳。 支持基材3係宜光透過性商，具體上宜在500〜8〇〇nm之 -23- 201211187 波長域中的最小光透過率爲1 0%以上。 又’就支持基材3而言，可使用於上述塑質薄膜（以 下，依情形’稱爲「第二薄膜」）上層合黏著劑層者。 圖2係表示本發明之電路構件連接用接著劑片的適宜 之一實施形態的模式剖面圖。圖2所示之電路構件連接用 接著劑片11係具備：具有塑質薄膜3b與設置於該塑質薄膜 3b上的黏著劑層3a之支持基材3、設於該接著劑層3a上且 由本發明之接著劑組成物所構成之接著劑層2、與被覆接 著劑層2之保護膜1。 爲提昇第二薄膜3b與黏著劑層3a之密著性，故於第二 薄膜之表面係亦可實施鉻酸處理、曝露於臭氧、曝露於火 焰、曝露於高壓電擊、離子化輻射線處理等之化學性或物 理性處理。 黏著劑層3a係宜於室溫具有黏著力，具有對被黏體之 必要密著力，且宜具備藉輻射線等高能量線或熱而硬化（ 亦即，降低黏著力）特性者。黏著劑層3 a係可使用例如丙 烯酸系樹脂、各種合成橡膠、天然橡膠、聚醯亞胺樹脂而 形成。黏著劑層3a之厚度一般爲5〜25μιη左右。 上述之電路構件連接用接著劑片10及11係介於具有相 對向且被接合之電路電極之電路構件與半導體元件之間或 半導體元件彼此之間，用以接著電路構件與半導體元件或 半導體元件間而使用。此時，藉由熱壓接電路構件與半導 體元件或半導體元件間，可抑制氣泡發生同時並以充分的 接著力接著，且可良好地接合電路電極間。藉此，可得到 -24 - 201211187 連接信賴性優異之連接體。又，電路構件連接用接著劑片 1 0及1 1係亦可使用來作爲使用矽貫通電極之層合技術中的 接著劑片。 其次，說明有關使用電路構件連接用接著劑片1 0而製 造半導體裝置的方法。 圖3~7係用以說明本發明之半導體裝置的製造方法之 適宜的一實施形態之模式剖面圖。本實施形態之半導體裝 置的製造方法係具備： (a) 準備於一者之主面具有複數電路電極的半導體晶圓 ，於該半導體晶圓之設有電路電極的面側上，設置由本實 施形態之接著劑組成物所成的接著劑層之步驟； (b) 將半導體晶圓之設有電路電極的面側之相反側進行 硏削，使半導體晶圓薄化的步驟； (c) 切割經薄化的半導體晶圓及接著劑層，使附有薄膜 狀接著劑的半導體元件個片化的步驟；與 (d) 將附有薄膜狀接著劑之半導體元件的電路電極接合 於半導體元件載持用支持構件之電路電極的步驟。 在本實施形態中之（a )步驟中係藉由使上述之接著 劑片1 〇的接著劑層2貼黏於半導體晶圓設有電路電極之側 ，俾設有接著劑層。又，在本實施形態中之（d )步驟中 係藉加熱進行焊錫接合，同時並亦進行介於半導體元件與 半導體元件載持用支持基材之間的薄膜狀接著劑之硬化。 以下，一邊參照圖面，一邊說明有關各步驟。 -25- 201211187 (a)步驟 首先，使接著劑片10配置於特定之裝置，剝離保護膜 1。繼而，準備於主面之一者具有複數之電路電極20之半 導體晶圓A，於半導體晶圓A設有電路電極之側貼黏接著 劑層2 ’得到支持基材3/接著劑層2/半導體晶圓A層合之層 合體（參照圖3)。於電路電極20係亦可設有已塗佈焊錫 接合用的焊錫之凸塊。又，亦可於半導體元件載持用支持 構件的電路電極設有焊錫》 電路電極20係可舉例如使用電鏟或蒸鏟或金屬導線而 形成之金凸塊 '銅凸塊、鎳凸塊等。又，亦可爲以樹脂所 形成之導電樹脂凸塊或以樹脂作爲核且於表面蒸鍍金屬之 樹脂核凸塊》突出之電路電極係不須以單_之金屬所構成 ’亦可含有金、銀、銅、鎳、銦、鈀、錫、鉍等複數的金 屬成分，亦可形成層合此等之金屬層的形式。 在上述（a )步驟中，得到支持基材3 /接著劑層2/半導 體晶圓A層合之層合體的方法係可使用市售之薄膜貼黏裝 置或積層機。爲於半導體晶圓A不捲入氣泡且貼黏接著劑 層2’宜於貼黏裝置具備加熱機構及加壓機構，更宜具備 真空吸引機構。又，接著劑片1 0之形狀係只要爲可以貼黏 裝置作業的形狀即可，可爲輥狀或薄片狀，亦可爲符合半 導體晶圓A之外形而被加工者。 半導體晶圓A與接著劑層2之積層係宜以接著劑層2軟 化之溫度進行，積層溫度宜爲40〜80°C，更宜爲50〜8(TC， 最宜爲60〜80°C。以未達接著劑層2軟化之溫度進行積層時 -26- 201211187 ，於半導體晶圓A突出之電路電極20周邊產生埋入不足， 成爲捲入氣泡的狀態，易造成切割時之接著劑層的剝離、 拾取時之接著劑層的變形、定位時之辨識標記識別不良、 進一步因氣泡產生連接信賴性的降低。 (b )步驟 其次，如圖4所示般，藉硏磨機4而硏削半導體晶圓a 設有電路電極20之面側的相反側，薄化半導體晶圓。半導 體晶圓之厚度可形成例如10〜3 ΟΟμπι。從半導體裝置之小型 化、薄型化之觀點，宜使半導體晶圓之厚度爲20〜1 〇〇 μΐΏ。 在（b )步驟中，半導體晶圓Α的硏削係可使用一般之 背硏磨（B/G )裝置而進行。在B/G步驟中爲無厚度不均且 均一地硏削半導體晶圓A，係在（a )步驟中無氣泡捲入且 均一地貼黏接著劑層2。 (c )步驟 其次，如圖5 (a)所示般，於層合體之半導體晶圓A 貼黏切割膠帶5，再配置於特定的裝置而剝離支持基材3。 此時，支持基材3具備黏著劑層3 a，黏著劑層3 a爲_射線 硬化性時，藉由從支持基材3側照射輻射線，可使黏著劑 層3a硬化，降低接著劑層2與支持基材3之間的接著力。此 處，所使用之輻射線可舉例如紫外線、電子束、紅外，線等 。藉此可容易地剝離支持基材3。支持基材3剝離後，如圖 5 ( b )所示般，藉切割鋸6切割半導體晶圓a及接著劑層2 -27- 201211187 。如此一來，半導體晶圓A係被分割成複數之半導體元件 A’，接著劑層2被分割成複數之薄膜狀接著劑2a。 其次，如圖6所示般，藉由使切割膠帶5擴張，使以上 述切割所得到之各半導體元件A ’互相離開，同時並從切割 膠帶5側以頂針突起之半導體元件A’及薄膜狀接著劑2a所 構成的附薄膜狀接著劑之半導體元件1 2以吸引收集器7進 行吸引而拾取。附薄膜狀接著劑之半導體元件12係可放置 托盤而回收，亦可直接以覆晶黏晶機封裝於電路基板。 在（c )步驟中，於被硏削之半導體晶圓A貼合切割膠 帶5之作業，係可使用一般之晶圓固定機，以與在切割架 之固定相同步驟實施。切割膠帶5係可適用市售之切割膠 帶，可爲UV硬化型，亦可爲感壓型。 (d )步驟 其次，如圖7所示般，使附著有薄膜狀接著劑2a之半 導體元件A’的電路電極20、與半導體元件載持用支持構件 8的電路電極22定位，熱壓接附薄膜狀接著劑之半導體元 件12與半導體元件載持用支持構件8。藉此熱壓接，電路 電極20與電路電極22接合，被電性且機械性連接，同時並 於半導體元件A ’與半導體元件載持用支持構件8之間形成 薄膜狀接著劑2a之硬化物。 熱壓接時之溫度從焊錫接合之觀點，宜爲200 °C以上 ，更宜爲220~260 °C。熱壓接時間可爲1~20秒。熱壓接之 壓力可爲0. 1 ~5MPa。 -28- 201211187 於使用覆晶黏晶機之電路基板的封裝上，係使形成於 半導體晶片的電路面之對位標記透過形成於半導體晶片的 電路面之接著劑層2a而確認，確認於電路基板之載持位置 而實施。 經過以上之步驟，可得到半導體裝置3 〇。由本實施形 態之接著劑組成物所構成之薄膜狀接著劑係埋入性及硬化 後之接著力優異。因此，半導體裝置30係可充分抑制氣泡 的發生’並良好地接合電路電極間，半導體元件A，與半導 體兀件載持用支持構件以充分的接著力接著，可成爲耐回 焊龜裂性或連接信賴性優異者。 以上，說明有關本發明之適當的實施形態，但本發明 係不限定於上述實施形態者。例如，在上述實施形態係形 成電路構件連接用接著劑片而進行說明，但本發明之接著 劑片係可爲底部塡充劑形成用接著劑片。 如於上述實施形態形成電路構件連接用接著劑片而進 行說明般’本發明之接著劑片係壓接時很難產生氣泡且具 有優異之埋入性。因此，例如在基板與晶片之連接中使用 本發明之接著劑片時，於晶片與基板之間隙形成充分塡充 之底部塡充劑。若依如此之底部塡充劑，源自於晶片與基 板之熱膨脹係數差之熱應力會被分散，故可防止起因於熱 應力之連接信賴性的降低。本發明之底部塡充劑形成用接 著劑片係可採用與上述之電路構件連接用接著劑片的適當 實施形態同樣的形態。 -29- 201211187 【實施方式】 實施例 以下，舉出實施例及比較例而更具體地說明本發明。 但，本發明係不限定於此等之實施例。 (支持基材之準備） 首先，藉由使用2 -乙基己基丙烯酸酯與甲基丙烯酸甲 酯作爲主要單體且使用羥乙基丙烯酸酯與丙烯酸作爲官能 基單體之溶液聚合法，合成丙烯酸共聚物。所得到之丙烯 酸共聚物的重量平均分子量爲4〇萬，玻璃轉移點爲-38 r 。相對於此丙烯酸共聚物100質量份，調配多官能異氰酸 酯交聯劑（日本Polyurethane工業股份公司製，商品名「 Coronate HL」）10質量份而調整黏著劑組成物溶液。 使所得到之黏著劑組成物溶液以乾燥時之黏著劑層的 厚度成爲ΙΟμηι的方式塗佈於聚烯烴薄膜（厚：ΙΟΟμιη)之 上而乾燥。進一步，使經聚矽氧系離型劑表面處理之雙軸 延伸聚酯薄膜（帝人Dupont公司製、商品名Α3170、厚： 2 5μη〇積層於黏著劑層面。將此附黏著劑層之層合體在室 溫下放置1週，進行充分熟化後，以已剝離聚烯烴薄膜者 作爲支持基材。 (實施例1 ) <接著劑組成物之調製> 使「ΖΧ 1 356-2」（東都化成股份公司製商品名、苯 -30- 201211187 氧樹脂）25質量份、「1032H60」 （Japan Epoxy Resin 股 份公司製商品名、環氧樹脂）25質量份、「Epikote 82 8」 (Japan Epoxy Resin股份公司製商品名、液狀環氧樹脂） 15質量份及「HX 3941 HP」（旭化成Electronics股份公司 製商品名、微膠囊型潛在性硬化劑）3 5質量份溶解於甲苯 與醋酸乙酯之混合溶劑中。於此溶液中，使「K W - 4 4 2 6」 (三菱Rayon股份公司製商品名、核殼型之有機微粒子） 質量份、已進行5μιη之分級處理的平均粒徑Ιμηι堇青石 (Cordierite)粒子（2Mg〇 · 2Α12〇3 · 5Si02、比重 2.4、線膨 脹係數：1 . 5 X 1 (Γ6 / °C、折射率：1 · 5 7 ) 1 0 0質量份分散，得 到接著劑清漆。 <電路構件連接用接著劑片之製作> 使所得到之接著劑清漆使用輥塗器而塗佈於聚對苯二 甲酸乙二酯（PET)薄膜（帝人Dupont Film公司製、商品 名「AH-3」、厚：50μηι)上，以70°c之烘箱乾燥1〇分鐘 ，形成厚2 5 μ m之接著劑層。其次，使接著劑層與上述支持 基材中之黏著劑層面在常溫下貼合，得到電路構件連接用 接著劑片。 (實施例2 ) 除使接著劑清漆調整中之「KW-4426」的調配量爲20 質量份、堇青石粒子之調配量爲50質量份以外，其餘係與 實施例1同樣地做法’而得到電路構件連接用接著劑片。 -31 · 201211187 (實施例3 ) 除使接著劑清漆調整中之「KW-4426」的調配量爲7 質量份、堇青石粒子之調配量爲125質量份以外，其餘係 與實施例1同樣地做法，而得到電路構件連接用接著劑片 (實施例4 ) 除調配「EXL-2655」 （Rohm & Hass Japan股份公司 製商品名、核殼型之有機微粒子）3 〇質量份取代接著劑清 漆調整中之「KW-4426」、並調配「SE2050」 （Admatech 股份公司製商品名、平均粒徑〇·5μπι之二氧化矽塡充劑） 5 〇質量份取代堇青石粒子以外，其餘係與實施例1同樣地 做法’而得到電路構件連接用接著劑片。 (實施例5 ) 除調配「EXL-2655」15質量份取代接著劑清漆調整中 之「KW-4426」、並調配「SE2050」50質量份取代堇青石 粒子以外，其餘係與實施例1同樣地做法，而得到電路構 件連接用接著劑片。 (實施例6 ) 除調配rEXL_2655」15質量份取代接著劑清漆調整中 之「KW-4426」、並調配「SE2050」150質量份取代堇青 -32- 201211187 石粒子以外，其餘係與實施例1同樣地做法，而得到電路 構件連接用接著劑片。 (比較例1 ) 除未調配接著劑清漆調整中之「K W - 4 4 2 6」以外，其 餘係與實施例1同樣地做法，而得到電路構件連接用接著 劑片。 (比較例2 ) 除未調配接著劑清漆調整中之堇青石粒子以外，其餘 係與實施例2同樣地做法，而得到電路構件連接用接著劑 片。 (比較例3 ) 除未調配接著劑清漆調整中之堇青石粒子，而調配「 EXL-2 65 5」35質量份取代rKW-4426」以外，其餘係與實 施例1同樣地做法’而得到電路構件連接用接著劑片。 (比較例4 ) 除未調配接著劑清漆調整中之堇青石粒子與「KW-4426」以外’其餘係與實施例1同樣地做法，而得到電路 構件連接用接著劑片。 [接著劑層之評估] 产· ΰ -33- 201211187 (線膨脹係數測定） 將於實施例及比較例所得到之電路構件連接用接著劑 片設定於180°C之烘箱中放置3小時，進行加熱硬化處理。 使加熱硬化後之接著劑層從支持基材剝離，製作3 0mm X 2mm大小的試驗片^使用Seiko Instrument公司製「 TMA/SS6100」（商品名），將上述試驗片安裝於裝置內 成爲卡盤間20mm，測定溫度範圍：20〜3 00 °C、昇溫速度5 °C/分、荷重條件：對試驗片之截面積，成爲0.5 MPa壓力 之條件，以抗拉試驗模式進行熱機械分析，測定線膨脹係 數。測定後，求取1 〇〇 °C與40 °C之線膨脹差，算出以溫度 差除之値，再形成平均線膨脹係數而使用於比較。 (反應率測定） 將於實施例及比較例所得到之電路構件連接用接著劑 片中之接著劑層於鋁製測定容器量取2〜10mg，使用Perkin Elymer公司製 DSC(Differential Scaning Calorimeter) 「 ?丫^1」（商品名），以昇溫速度20^：/分昇溫至30〜300 °C而測定發熱量，以此作爲初期發熱量。然後，以使熱壓 接裝置之加熱頭挾在分隔膜之熱電偶進行溫度確認而於1〇 秒後設定於達到2 5 0 °C之溫度。以此加熱頭設定，使電路 構件連接用接著劑片挾在分隔膜而加熱20秒，得到經實施 與熱壓接時同等之加熱處理的狀態之接著劑層。對於加熱 處理後之接著劑層亦同樣地測定發熱量，以此作爲加熱後 之發熱量。又，對於使電路構件連接用接著劑片以室溫（ -34- 201211187 2 5 °C )保管1 4日後之接著劑層，亦同樣地測定發熱量，以 此作爲保管後之發熱量。從所得到之發熱量以如下之式算 出反應率（％ )。 反應率（％) =(初期發熱量-加熱後之發熱量或保管後之 發熱量）/(初期發熱量）χ100 <半導體裝置之製作及評估> 使用上述所得到之電路構件連接用接著劑片，依下述 之順序，製作半導體裝置，進行評估。結果表示於表1及 表2中。 (於半導體晶圓之貼黏） 於JCM製之黏晶薄膜固定機被加熱至80 t之吸附台上 ’將形成鍍金凸塊的半導體晶圓（6英吋徑、厚7 2 5 μηι )使 凸塊側朝上而載置。將電路構件連接用接著劑片切割成 200mmx200mm，使除去保護膜之第一薄膜的接著劑層朝向 半導體晶圓的凸塊惻，爲免捲入空氣，從半導體晶圓之端 以:ίώ晶固疋機的貼黏輕押住而積層。積層後，沿著晶圓的 外形而切割接著劑滲出部分。 (半導體晶圓背面的背硏磨及支持基材之剝離） 使上述電路構件連接用接著劑片與半導體晶圓（厚 625μηι)之層合體以股份公司Disc製背硏磨裝置，使半導 體晶圓之背面經背硏磨至厚度成爲1 5 0 μ m後，使經背硏磨 -35- 201211187 之半導體晶圓朝上之狀態設置於JCM製之黏晶薄膜固定機 之吸附台上，在室溫下與切割架同時地貼黏Adeka製切割 膠帶「AD80H」。然後，於支持基材上貼黏日東電工製背 硏磨膠帶剝離膠帶，180度剝離拉撕而只拉撕支持基材。 (切割） 使固定於上述切割架之附有接著劑層的半導體晶圓以 股份公司Disco製全自動切割鋸「DFD 636 1」切割成l〇mm X 1 0mm。切割後，進行洗淨，濺飛水分後，從切割膠帶側 進行UV照射後，拾取被個片化之附接著劑的半導體晶片 (壓接） 使附接著劑的半導體晶片於對向凸塊之位置具有形成 以SnAgCu作爲構成成分之焊錫的電路之玻璃環氧基板， 以松下電氣產業製覆晶黏晶機「FCB 3」進行定位後，以 250°C、0.5MPa熱壓接10秒，得到半導體裝置。 評估如上述做法所製作之半導體裝置中的薄膜狀接著 劑之埋入性及連接阻抗。然後，使所製作之半導體裝置放 置於85°C、60% RH的恆溫恆濕器168小時而吸濕，曝露於 設定在260 °C之回焊爐3次。曝露後，確認出連接阻抗及連 接部分之界面狀態。 <連接阻抗> -36- 201211187 對於所製作之半導體裝置，使用數位萬用計（ Advantest公司製、商品名）而測定壓接後之連接阻抗及回 焊後之連接阻抗，依據以下之基準而進行評估。結果表示 於表1及表2中。 a :可得到適用於試驗之封裝TEG的全端子連結的連接 阻抗。 b:存在斷線不良端子。 <壓接後之埋入性> 以日立建機製超音波探傷裝置（SAT )視察接著劑層 之貼黏狀態，依據以下之基準而進行評估。結果表示於表 1及表2中。 a :未觀察到剝離、氣泡。 b :觀察到剝離、氣泡。 <回焊後之連接性> 以日立建機製超音波探傷裝置（S AT )視察接著劑層 之回焊後之連接狀態’依據以下之基準而進行評估。結果 表示於表1及表2中。 a :未觀察到剝離。 b :觀察到剝離。 -37- 201211187 [表i] 實施例1 實施例2 實施例3 實施例4 實施例5 熱可塑性樹脂 ZX1356-2 25 25 25 25 25 熱硬化性樹脂 1032H60 25 25 25 25 25 Epikote 828 15 15 15 15 15 硬化劑 ΗΧ3Θ41ΗΡ 35 35 35 35 35 無機塡充物 堇青石粒子 100 50 125 - — SE2050 一 — 一 50 50 有機微粒子 KW-4426 10 20 7 — — EXL-2655 — - - 30 15 4〇-100eC之平均線膨脹係數 (xi〇'*/°c) 45 60 42 62 54 壓接後之連接阻抗 a a a a a 壓接後之埋入性 8 a a a a . 回焊後之連接性 a a a a a 回焊後之連接阻抗 a a a a a [表2] 實施例6 比較俐1 比较例2 比餃例3 比較例4 熱可塑性樹脂 2X1356-2 25 25 25 25 25 熱硬化性樹脂 1032Η60 25 Z5 25 25 25 Epikote 828 15 15 15 15 15 硬化劑 HX3941HP 35 35 35 35 35 無機塡充物 堇青石粒子 » 100 一 - — SE2050 150 一 - - 一 有機微粒子 KW-4426 一 — 20 一 — EXL-2655 15 — — 35 — 40-100¾之平均線膨脹係數 (XIO'V^) 42 40 70 7β 70 壓接後之連接阻抗 a a a a a 壓接後之埋入性 a b b b b 回焊後之連接性 a b b b b 回焊後之連接阻抗 a b b b b 如表1、表2所示般，使用於實施例1〜6所得到之電路 構件連接用接著劑片時，連接阻抗優異’無氣泡發生’回 焊後亦顯示良好的連接性。但’使用於比較例1〜4所得到 之電路構件連接用接著劑片時，產生氣泡’回焊後剝離’ 可確認出連接信賴性差。 -38- 201211187 【圖式簡單說明】 圖1係表不本發明之電路構件連接用接著劑片的適宜 之一實施形態的模式剖面圖。 圖2係表示本發明之電路構件連接用接著劑片的適宜 之一實施形態的模式剖面圖。 圖3係用以說明本發明之半導體裝置的製造方法之一 實施形態的模式剖面圖。 圖4係用以說明本發明之半導體裝置的製造方法之一 實施形態的模式剖面圖。 圖5係用以說明本發明之半導體裝置的製造方法之一 實施形態的模式剖面圖。 圖6係用以說明本發明之半導體裝置的製造方法之一 實施形態的模式剖面圖。 圖7係用以說明本發明之半導體裝置的製造方法之一 實施形態的模式剖面圖。 【主要元件符號說明】 1 :保護膜 2 :接著劑層 3 :支持基材 3 a :黏著劑層 3b :塑質薄膜 4 :硏磨機 5 :切割膠帶 -39- 201211187 6 :切割鋸 7 :吸引收集器 8:半導體元件載持用支持構件 1 〇 :電路構件連接用接著劑片 11:電路構件連接用接著劑片 1 2 :附薄膜狀接著劑的半導體元件 20 :電路電極 30 :半導體裝置 A :半導體晶圓 -40-The amount of the component (D) is preferably from 25 to 200 parts by mass, more preferably from 50 to 150 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C) of the resin component. It is 75 to 125 parts by mass. When the amount of the component (D) is less than 25 parts by mass, the linear expansion coefficient of the adhesive layer formed from the adhesive composition is decreased and the modulus of elasticity is lowered, so that the connection between the semiconductor wafer and the substrate after crimping is caused. The reliability is easily lowered, and further, it is difficult to obtain the bubble suppression effect at the time of connection. In addition, when the compounding amount of the component (D) exceeds 200 parts by mass, the melt viscosity of the adhesive composition increases, and the wettability of the interface between the semiconductor wafer and the adhesive layer or the interface between the circuit substrate and the adhesive layer is lowered to cause peeling or Insufficient embedding can cause residual bubbles. -16- 201211187 (E) The organic fine particle system may, for example, contain an acrylic resin, a polyoxynylene resin, a butadiene rubber, a polyester, a polyurethane, a polyvinyl butyral, a polyacrylate, a polymethyl group. A copolymer of methyl acrylate, acrylic rubber, polystyrene, NBR, SBR, polyoxymethylene modified resin or the like as a component. The organic fine particles are preferably organic fine particles having a molecular weight of 1,000,000 or more or organic fine particles having a three-dimensional crosslinked structure. Such organic fine particles are highly dispersible in the composition of the adhesive. Further, the adhesive composition containing such organic fine particles is more excellent in stress relaxation property after adhesion and hardening. Further, the term "having a three-dimensional crosslinked structure" herein means that the polymer chain has a three-dimensional network structure, and the organic fine particle having such a structure is, for example, such that a polymer having a complex reaction point can be combined with the reaction point. It is obtained by treating two or more functional groups of a functional group. Any of organic fine particles having a molecular weight of 100,000 or more and organic fine particles having a three-dimensional crosslinked structure may have low solubility in a solvent. The organic fine particles having such a low solubility in a solvent can more effectively obtain the above effects. Further, from the viewpoint that the above effects can be more remarkably obtained, the organic fine particles having a molecular weight of 1,000,000 or more and the organic fine particles having a three-dimensional crosslinked structure are preferably (meth)acrylic acid alkyl ester-polyoxynoxy copolymer, poly An organic fine particle composed of a neon-(meth)acrylic acid copolymer or a composite of these. Further, organic fine particles such as polyamic acid particles or polyamidene particles described in JP-A No. 200 8- 1 50 5 7 3 can also be used. For the component (E), it is also possible to use an organic fine particle having a core-shell type and a core layer and a shell layer. Specific examples of the core-shell type organic fine particles include particles obtained by grafting acrylic acid -17-201211187 resin with a polyfluorene-acrylic rubber as a core, particles obtained by grafting an acrylic resin with an acrylic copolymer as a core, and the like. Further, the core-shell type polyoxynene fine particles described in WO 2009/051067, or the alkyl (meth)acrylate-butadiene-styrene copolymer or composite as described in WO 2009/020005, ( Organic fine particles such as an alkyl acrylate-polyoxyalkylene copolymer or a composite, a polyfluorene-oxygen (meth)acrylic acid copolymer or a composite, or a core-shell structure polymerization as described in JP-A-2002- 25603 The particles of the particles or the rubber particles of the core-shell structure described in JP-A-2004-1 8 803. These core-shell type organic fine particle systems may be used singly or in combination of two or more. When the component (E) is an organic fine particle having a molecular weight of 10,000 or more and an organic fine particle having a three-dimensional crosslinked structure, the solubility in the organic solvent is low, so that the particle shape can be maintained and directly formulated in the adhesive composition. Therefore, the organic fine particles in the adhesive layer 2 after hardening are dispersed in an island shape, and the strength of the bonded body is improved. Further, the component (E) has a function as an impact-relieving agent containing stress relaxation properties. The (E) component preferably has an average particle diameter of 〇.1 to 2 μιη. More preferably 0.1~0·9μηι. When the average particle diameter of the (Ε) component is less than 0.1 μm, the melt viscosity of the adhesive composition increases, and when solder is used for connecting the circuit members, the solder wettability tends to be prevented. If the thickness exceeds 2 μm, the effect of lowering the melt viscosity is When the connection is small, it is difficult to obtain a bubble suppressing effect at the time of connection. The (Ε) component is a bubble suppression at the time of connection to the adhesive layer 2 and a stress relaxation effect after the connection, and is preferably 5 parts by mass based on 100 parts by mass of the components (A), (B), and (C). 30 parts by mass. When the amount of the component (E) is less than 5 parts by mass, it is difficult to exhibit the effect of suppressing the bubbles at the time of connection. -18·201211187 'At the same time, it is difficult to show the tendency of the stress relaxation effect, and if it exceeds 3 parts by mass, the fluidity When the soldering property is lowered, the solder wettability is lowered to cause residual bubbles, and the elastic modulus of the cured product is too low, and the connection reliability tends to be lowered. The stress relaxation effect after the connection of the bubbles is sufficiently suppressed, and the total content of the components (A), (B), and (C) is 100% from the viewpoint of lowering the moisture absorption rate, the coefficient of linear expansion, and the modulus of elasticity. The content of the component (D) is preferably 5 to 150 parts by mass 'the content of the component (E) is 5 to 30 parts by mass' and the total content of the component (D) and the component (E) is 65 to 165 mass. Share. More preferably, the content of the component (D) is $0430 parts by mass, and the amount of the component (E) is 7 to 20 parts by mass ', and the total of the contents of the component (D) and the component (E) is 65 to 132 parts by mass. The content of the component (D) is 50 to 110 parts by mass, and the content of the component (E) is 1 to 20 parts by mass, and the total content of the components (D) and (E) is 65 to 110 parts by mass. When the amount of the component (D) is less than 50 parts by mass, the block strength of the adhesive layer formed from the adhesive composition is low, and the connection reliability in the heat resistance test is lowered, and the amount of the component (D) is adjusted. When the amount is more than 150 parts by mass, the thixotropy of the adhesive composition is too high, and there is a tendency that the peeling failure is increased. In addition, if the total content of the component (D) and the component (E) is 65 parts by mass or more, the effect of suppressing the bubble is further improved, and it is preferably 165 parts by mass or less. The adhesive composition is maintained as a circuit member. The wettability of the interface for fluidity is improved, and the peeling failure suppressing effect is more excellent, which is preferable. Further, if the total content of the components (D) and (E) is more than 165 parts by mass, the connection resistance tends to deteriorate. Further, the content of the '(E) component is preferably 5 to 100 parts by mass, more preferably 5 to 60 parts by mass, more preferably 1 to 10 parts by mass, based on 1 part by mass of the component (D), -19 to 201211187. Share. When the content of the component (E) is 5 parts by mass or more based on 1 part by mass of the component (D), the deformability of the adhesive composition is improved, and the peeling failure suppressing effect at the adherend interface is excellent. Further, when the amount is more than 100 parts by mass, the thermal expansion suppressing effect by the inorganic ruthenium cannot be obtained, and the connection reliability is deteriorated. Further, when the component (D) is excessively present, the thixotropy is too high, so that the wetting at the interface of the adherend is insufficient, and the connectivity is lowered. In the adhesive composition of the present embodiment, the surface of the inorganic filler is modified to enhance the interfacial bonding between the dissimilar materials, and the bonding strength is increased, and various coupling agents may be added. The coupling agent may, for example, be a decane-based, titanium-based or aluminum-based coupling agent. Among them, a decane-based coupling agent is preferred because of its high effect. The decane coupling agent may, for example, be γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane or γ-hydrothiopropyltrimethoxydecane. γ-Hetthiopropyltriethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxydecane. These may be used singly or in combination of two or more. In the adhesive composition of the present embodiment, ionic impurities are adsorbed to improve the insulation reliability during moisture absorption, and an ion scavenger may be added. The ion scavenger is not particularly limited, and is, for example, a compound known as a copper-protecting agent, a zirconium-based or a lanthanum, which is known to prevent the copper from being ionized by a triazine thiol compound or a bisphenol-based reducing agent. It is an inorganic ion adsorbent such as a magnesium-aluminum compound. The composition of the subsequent composition is such that the temperature of the semiconductor wafer and the circuit board is changed to -20-201211187, or the expansion due to heat absorption and the like is suppressed, and in order to achieve high connection reliability, the adhesive layer 2 after hardening is preferably 40~ The coefficient of linear expansion at 100 °C is 60xl0_6/°C or less, more preferably 55xlO_6/°C or less, and most preferably 50χ 1CT6/°C or less. If the linear expansion coefficient of the adhesive layer 2 after hardening exceeds 60 χ 1 (T6/°c, sometimes due to temperature change after packaging or expansion due to heat absorption and moisture, between the connection terminal of the semiconductor wafer and the wiring of the circuit substrate Further, the electrical connection of the adhesive composition of the present invention contains conductive particles to form an anisotropic conductive adhesive film (ACF), but it is preferred that the conductive particles are not contained to form a non-conductive adhesive film (NCF). The adhesive layer 2 formed of the adhesive composition of the present embodiment is heated at 250 ° C for 1 〇 second, and the reaction rate measured by differential scanning calorimetry (hereinafter referred to as "DSC") is 60%. More preferably, it is 70% or more. Further, after storing the circuit member connecting composition sheet at room temperature for one day, the reaction rate of the adhesive layer 2 which is preferably measured by DSC is less than 10%. The adhesive composition of the embodiment can provide a film-like adhesive which is excellent in reactivity at the time of joining and which is excellent in storage stability. The visible light transmittance of the adhesive layer 2 is preferably 5% or more, which is more preferably 5%. Visible light The pass rate is 8% or more, and the visible light transmittance is preferably 10% or more. When the visible light transmittance is less than 5%, the identification of the identification mark of the flip chip machine is difficult to perform, and there is a tendency that the positioning operation cannot be performed. The upper limit of the visible light transmittance is not particularly limited. The visible light transmittance can be measured using a Hitachi U-3 3 10-type spectrophotometer, for example, a DuPont PET film having a film thickness of 5 〇 μηη ( Pyrex, 5 5 5 nm transmittance: 86.03%) Baseline compensation as a reference material - 201211187 After the positive measurement, the transmittance of the visible light transmittance of 400 to 80 nm was measured after the PET film was formed into the adhesive layer 2 at a thickness of 25 μm. The relative intensity of the wavelength of the halogen light source and the light guide used in the crystal bond crystal machine is the strongest in the range of 550 to 6,000 nm. Therefore, in the present specification, the transmittance of the adhesive layer 2 is compared using the transmittance in 550 nm. In the adhesive layer 2, the above-described adhesive composition of the present invention can be dissolved or dispersed in a solvent to form a varnish, and the varnish is applied to a protective film (hereinafter, referred to as "first film" hereinafter). , The solvent is formed by heating and removing the solvent. Thereafter, the laminate support substrate 3' is laminated on the adhesive layer 2 at a normal temperature to 60 ° C to obtain the adhesive member for connecting the circuit member of the present invention. Further, the adhesive layer 2 may be used. The varnish is applied to the support substrate 3, and the solvent is removed by heating. The solvent to be used is not particularly limited, and is preferably determined from the viewpoint of the volatility at the time of formation of the binder layer by the boiling point. Specifically, for example, methanol or ethanol. a solvent having a relatively low boiling point such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene or xylene, when the adhesive layer is formed It is better to harden the hardening of the agent layer. These solvents may be used singly or in combination of two or more. As the protective film 1, a plastic film such as polyethylene terephthalate, a polytetrafluoroethylene film 'polyethylene film, a polypropylene film, a polymethylpentene film or the like can be used. From the viewpoint of release property, it is also preferable to use a film having a low surface energy composed of a fluororesin such as a polytetrafluoroethylene film for protecting the film. In order to improve the release property of the protective film 1, it is preferable to form a protective film 1 by a release agent such as a polyfluorene-based release agent, a fluorine-22-201211187 release agent, or a long-chain alkyl acrylate release agent. The face of the adhesive layer 2 is. For the marketer, for example, "A-63" (release agent: modified polyoxane) manufactured by Teijin Dupont Film Co., Ltd., or "A-3" (release agent: P t Condensed in the oxygen system). The protective film 1 is preferably 10 to ΙΟΟμηι, more preferably 1 to 75 μm, and particularly preferably 25 to 5 μm. When the thickness is less than ημηι, the protective film tends to be broken during coating, and if it exceeds ΙΟΟμπι, there is a tendency for the inexpensiveness to be poor. The method of applying the above varnish to the protective film 1 (or the support substrate 3) may, for example, be a blade coating method, a roll coating method, a spray coating method, a gravure coating method, a rod coating method, or a curtain coating method. Methods. The thickness of the layer 2 is not particularly limited, but is preferably 5 to 2 ΟΟμηι, and more preferably 7 to 150 μηα' is preferably 10 to ΙΟΟμπι. When the thickness is less than 5 μm, it is difficult to ensure a sufficient adhesion force, and there is a tendency that the convex electrode of the circuit board cannot be buried. If the thickness is more than 200 μm, it becomes uneconomical, and it is difficult to meet the requirements for miniaturization of the semiconductor device. The support substrate 3 may, for example, be a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyvinyl acetate film, or a polyvinyl chloride film. , plastic film such as polyimide film. Further, the support substrate 3 may be selected from two or more of the above materials, or the film may be stratified. The thickness of the support substrate 3 is not particularly limited, but is preferably 5 to 25 μm. If the thickness is thinner than 5 μm, it is possible to cut the support substrate during boring (back honing) of the semiconductor wafer. If it is thicker than 250 μm, it is uneconomical, so it is not good. The support substrate 3 is preferably light transmissive, and specifically has a minimum light transmittance of 10% or more in the wavelength range of -23 to 201211187 of 500 to 8 〇〇 nm. Further, the support substrate 3 can be used for the above-mentioned plastic film (hereinafter, referred to as "second film" as the case may be). Fig. 2 is a schematic cross-sectional view showing an embodiment of a suitable adhesive sheet for connecting circuit members of the present invention. The circuit member connecting adhesive sheet 11 shown in FIG. 2 includes a support substrate 3 having a plastic film 3b and an adhesive layer 3a provided on the plastic film 3b, and is provided on the adhesive layer 3a. The adhesive layer 2 composed of the adhesive composition of the present invention and the protective film 1 covering the adhesive layer 2 are provided. In order to improve the adhesion between the second film 3b and the adhesive layer 3a, the surface of the second film may be subjected to chromic acid treatment, exposure to ozone, exposure to flame, exposure to high voltage electric shock, ionizing radiation treatment, etc. Chemical or physical treatment. The adhesive layer 3a preferably has an adhesive force at room temperature, has a necessary adhesion to the adherend, and preferably has a property of hardening (i.e., lowering the adhesive force) by a high-energy line or heat such as a radiation. The adhesive layer 3a can be formed using, for example, an acrylic resin, various synthetic rubbers, natural rubber, or a polyimide resin. The thickness of the adhesive layer 3a is generally about 5 to 25 μm. The above-described circuit member connecting adhesive sheets 10 and 11 are interposed between or between the circuit members having the opposite and joined circuit electrodes or between the semiconductor elements for following the circuit member and the semiconductor element or the semiconductor element Use between. At this time, by thermocompression bonding the circuit member to the semiconductor element or the semiconductor element, it is possible to suppress the occurrence of bubbles while adhering with a sufficient subsequent force, and to bond the circuit electrodes well. In this way, you can get a connection with excellent reliability from -24 - 201211187. Further, the circuit member connecting adhesive sheets 10 and 11 can also be used as a subsequent tablet in a lamination technique using a tantalum through electrode. Next, a method of manufacturing a semiconductor device using the bonding material sheet 10 for circuit member connection will be described. 3 to 7 are schematic cross-sectional views showing a preferred embodiment of a method of fabricating a semiconductor device of the present invention. The method of manufacturing a semiconductor device according to the present embodiment includes: (a) a semiconductor wafer having a plurality of circuit electrodes on a principal surface of one of the semiconductor wafers, and a surface of the semiconductor wafer on which a circuit electrode is provided a step of forming an adhesive layer formed by the adhesive composition; (b) a step of boring the opposite side of the surface side of the semiconductor wafer on which the circuit electrode is provided to thin the semiconductor wafer; (c) cutting the warp a thinned semiconductor wafer and an adhesive layer, a step of dicing a semiconductor element with a film-like adhesive; and (d) bonding a circuit electrode of a semiconductor element with a film-like adhesive to a semiconductor element carrier The step of supporting the circuit electrode of the member. In the step (a) of the present embodiment, the adhesive layer 2 of the above-mentioned adhesive sheet 1 is adhered to the side of the semiconductor wafer on which the circuit electrode is provided, and an adhesive layer is provided. Further, in the step (d) of the present embodiment, solder bonding is performed by heating, and the film-like adhesive interposed between the semiconductor element and the semiconductor element supporting substrate is also cured. Hereinafter, each step will be described with reference to the drawings. -25-201211187 (a) Step First, the adhesive sheet 10 is placed in a specific device, and the protective film 1 is peeled off. Then, the semiconductor wafer A having a plurality of circuit electrodes 20 is prepared on one side of the main surface, and the adhesive layer 2' is attached to the side of the semiconductor wafer A on which the circuit electrodes are provided. The support substrate 3/adhesive layer 2/ is obtained. A laminate in which the semiconductor wafer A is laminated (see Fig. 3). The circuit electrode 20 may be provided with a bump of solder for solder bonding. Further, solder may be provided on the circuit electrode of the semiconductor element supporting member. The circuit electrode 20 may be a gold bump 'copper bump, a nickel bump, or the like formed by using a spatula, a steamed shovel or a metal wire. . Further, the conductive resin bump formed of a resin or the resin core bump which is a core of a resin and a metal core deposited on the surface may not be formed of a single metal, and may also contain gold. A plurality of metal components such as silver, copper, nickel, indium, palladium, tin, antimony, or the like may be formed in the form of a metal layer laminated. In the above step (a), a method of obtaining a laminate of the support substrate 3 / adhesive layer 2 / semiconductor wafer A laminate can be carried out using a commercially available film sticking device or laminator. In order to prevent air bubbles from being trapped in the semiconductor wafer A, the adhesive layer 2' is preferably provided with a heating mechanism and a pressurizing mechanism, and more preferably has a vacuum suction mechanism. Further, the shape of the adhesive sheet 10 may be a shape that can be adhered to the bonding apparatus, and may be in the form of a roll or a sheet, or may be processed in conformity with the shape of the semiconductor wafer A. The laminate of the semiconductor wafer A and the adhesive layer 2 is preferably carried out at a temperature at which the adhesive layer 2 is softened, and the laminate temperature is preferably 40 to 80 ° C, more preferably 50 to 8 (TC, most preferably 60 to 80 ° C). When the layer is laminated at a temperature that does not reach the softening of the adhesive layer 2, -26-201211187, the periphery of the circuit electrode 20 protruding from the semiconductor wafer A is insufficiently embedded, and is in a state of being trapped in a bubble, which is likely to cause an adhesive layer during dicing. The peeling, the deformation of the adhesive layer at the time of picking up, the poor recognition of the identification mark at the time of positioning, and the further reduction of the reliability of the connection due to the bubble. (b) The second step, as shown in Fig. 4, by the honing machine 4 The semiconductor wafer a is provided on the opposite side to the surface side of the circuit electrode 20 to thin the semiconductor wafer. The thickness of the semiconductor wafer can be, for example, 10 to 3 ΟΟμπι. From the viewpoint of miniaturization and thinning of the semiconductor device, it is preferable to make the semiconductor wafer The thickness of the semiconductor wafer is 20 〜1 〇〇μΐΏ. In the step (b), the boring of the semiconductor wafer raft can be performed using a general back honing (B/G) device. In the B/G step Uniformly thinning semiconductor wafer A without thickness unevenness In the step (a), no air bubbles are entangled and the adhesive layer 2 is uniformly adhered. (c) Step Next, as shown in Fig. 5 (a), the semiconductor wafer A of the laminate is adhered to the dicing tape 5 Further, the support substrate 3 is peeled off by disposing it in a specific device. At this time, the support substrate 3 is provided with the adhesive layer 3 a, and when the adhesive layer 3 a is _ ray curable, the radiation is irradiated from the support substrate 3 side. The wire can harden the adhesive layer 3a and reduce the adhesion between the adhesive layer 2 and the support substrate 3. Here, the radiation used may be, for example, ultraviolet rays, electron beams, infrared rays, wires, or the like. The support substrate 3 is easily peeled off. After the support substrate 3 is peeled off, as shown in FIG. 5(b), the semiconductor wafer a and the adhesive layer 2 -27-201211187 are cut by the dicing saw 6. Thus, the semiconductor crystal The circle A is divided into a plurality of semiconductor elements A', and the adhesive layer 2 is divided into a plurality of film-like adhesives 2a. Next, as shown in Fig. 6, by cutting the dicing tape 5, the above-mentioned cutting station is used. The obtained semiconductor elements A' are separated from each other while being half protruding from the side of the dicing tape 5 by the thimble The semiconductor element 12 with the film-like adhesive formed by the conductor element A' and the film-like adhesive 2a is sucked by the suction collector 7. The semiconductor element 12 with the film-like adhesive can be placed in a tray for recycling. It can be directly packaged on the circuit substrate by a flip chip bonding machine. In the step (c), the dicing tape 5 is bonded to the diced semiconductor wafer A, and a general wafer fixing machine can be used to The fixing of the cutting frame is carried out in the same step. The cutting tape 5 can be applied to commercially available cutting tape, which can be UV curing type or pressure sensitive type. (d) Step, next, as shown in Fig. 7, the film is attached The circuit electrode 20 of the semiconductor element A' of the adhesive 2a and the circuit electrode 22 of the semiconductor element supporting member 8 are positioned, and the semiconductor element 12 and the semiconductor element supporting member 8 are bonded by a film adhesive. . By the thermocompression bonding, the circuit electrode 20 is bonded to the circuit electrode 22, electrically and mechanically connected, and a cured film-like adhesive 2a is formed between the semiconductor element A' and the semiconductor element supporting member 8. . The temperature at the time of thermocompression bonding is preferably 200 ° C or more, and more preferably 220 to 260 ° C from the viewpoint of solder bonding. The hot crimping time can be from 1 to 20 seconds. The pressure of the thermocompression bonding may be 0.1 to 5 MPa. -28-201211187 In the package of the circuit board using the flip chip bonding machine, the alignment mark formed on the circuit surface of the semiconductor wafer is transmitted through the adhesive layer 2a formed on the circuit surface of the semiconductor wafer, and is confirmed in the circuit. The substrate is held at the carrying position. Through the above steps, the semiconductor device 3 can be obtained. The film-like adhesive composition composed of the adhesive composition of the present embodiment is excellent in embedding property and adhesion after curing. Therefore, in the semiconductor device 30, the occurrence of bubbles can be sufficiently suppressed, and the circuit electrodes can be well bonded, and the semiconductor element A can be brought back to the semiconductor element supporting member with a sufficient adhesion force, thereby being resistant to reflow cracking or Connect to those who have excellent reliability. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. For example, in the above embodiment, the adhesive sheet for connecting the circuit member is formed. However, the adhesive sheet of the present invention may be an adhesive sheet for forming a bottom lubricant. In the above embodiment, the adhesive sheet for connecting a circuit member is formed and described. The adhesive sheet of the present invention is less likely to generate bubbles during pressure bonding and has excellent embedding property. Therefore, for example, when the adhesive sheet of the present invention is used for the connection between the substrate and the wafer, a sufficiently filled bottom smear is formed in the gap between the wafer and the substrate. According to such a bottom sizing agent, the thermal stress derived from the difference in thermal expansion coefficient between the wafer and the substrate is dispersed, so that the connection reliability due to thermal stress can be prevented from being lowered. The adhesive sheet for forming a bottom sizing agent of the present invention may be in the same form as the appropriate embodiment of the above-mentioned adhesive member for connecting circuit members. -29-201211187 [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. However, the present invention is not limited to the embodiments described herein. (Preparation of Supporting Substrate) First, acrylic acid is synthesized by a solution polymerization method using 2-ethylhexyl acrylate and methyl methacrylate as main monomers and using hydroxyethyl acrylate and acrylic acid as functional monomers. Copolymer. The obtained acrylic acid copolymer had a weight average molecular weight of 40,000 and a glass transition point of -38 r. To 100 parts by mass of the acrylic copolymer, 10 parts by mass of a polyfunctional isocyanate crosslinking agent (trade name "Coronate HL", manufactured by Polyurethane Industries, Ltd., Japan) was blended to adjust the adhesive composition solution. The obtained adhesive composition solution was applied to a polyolefin film (thickness: ΙΟΟμηη) so as to have a thickness of the adhesive layer when dried, and dried. Further, a biaxially stretched polyester film surface-treated with a polyfluorene-based release agent (manufactured by Teijin DuPont Co., Ltd., trade name: 3170, thickness: 2 5 μη deposited layer on the adhesive layer. Lamination of the adhesive layer) After standing at room temperature for one week and fully aging, the peeled polyolefin film was used as a support substrate. (Example 1) <Preparation of the composition of the adhesive agent> 25 parts by mass of "ΖΧ 1 356-2" (trade name of Toyo Kasei Co., Ltd., benzene-30-201211187 oxy-resin), and "1032H60" (product of Japan Epoxy Resin Co., Ltd.) 25 parts by weight, epoxy resin, "Epikote 82 8" (trade name, liquid epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.), 15 parts by mass, and "HX 3941 HP" (product name, micro of Asahi Kasei Electronics Co., Ltd.) The capsule type latent hardener) 35 parts by mass is dissolved in a mixed solvent of toluene and ethyl acetate. In this solution, "KW - 4 4 2 6" (trade name of the Mitsubishi Rayon Co., Ltd., core-shell type organic fine particles) mass fraction, average particle size of 5 μm η, and Cordierite particles (2Mg〇· 2Α12〇3 · 5Si02, specific gravity 2.4, linear expansion coefficient: 1.5 X 1 (Γ6 / °C, refractive index: 1 · 5 7 ) 100 parts by mass was dispersed to obtain an adhesive varnish. <Preparation of adhesive sheet for connecting circuit members> The obtained adhesive varnish was applied to a polyethylene terephthalate (PET) film using a roll coater (manufactured by Teijin Dupont Film Co., Ltd., trade name " AH-3", thickness: 50 μm) was dried in an oven at 70 ° C for 1 minute to form an adhesive layer having a thickness of 25 μm. Next, the adhesive layer is bonded to the adhesive layer in the above-mentioned supporting substrate at a normal temperature to obtain a subsequent tablet for connecting the circuit members. (Example 2) The same procedure as in Example 1 was carried out except that the amount of the "KW-4426" in the adjustment of the adhesive varnish was 20 parts by mass, and the amount of the cordierite particles was 50 parts by mass. The circuit member is connected with an adhesive sheet. -31, 201211187 (Example 3) In the same manner as in Example 1, except that the blending amount of "KW-4426" in the adjustment of the adhesive varnish was 7 parts by mass, and the blending amount of cordierite particles was 125 parts by mass. In the same manner, an adhesive sheet for connecting circuit members was obtained (Example 4). In addition to "EXL-2655" (trade name manufactured by Rohm & Hass Japan Co., Ltd., core-shell type organic fine particles), 3 parts by mass of the replacement adhesive varnish was prepared. "KW-4426" is adjusted, and "SE2050" (trade name of Admatech Co., Ltd., average particle size 〇·5μπι2 cerium oxide filling agent) is added. 5 〇 mass parts are substituted for cordierite particles, and other systems are implemented. In the same manner as in Example 1, an adhesive sheet for connecting a circuit member was obtained. (Example 5) The same procedure as in Example 1 was carried out except that 15 parts by mass of "EXL-2655" was replaced with "KW-4426" in the adhesive varnish adjustment, and 50 parts by mass of "SE2050" was used instead of cordierite particles. In this way, an adhesive sheet for connecting circuit members is obtained. (Example 6) Example 1 except that 15 parts by mass of rEXL_2655" was used to replace "KW-4426" in the adhesive varnish adjustment, and 150 parts by mass of "SE2050" was substituted for the indigo-32-201211187 stone particles. In the same manner, an adhesive sheet for connecting circuit members is obtained. (Comparative Example 1) A circuit board connecting adhesive sheet was obtained in the same manner as in Example 1 except that "K W - 4 4 2 6" in the adjustment of the adhesive varnish was not prepared. (Comparative Example 2) An adhesive sheet for connecting a circuit member was obtained in the same manner as in Example 2 except that the cordierite particles in the adhesive varnish adjustment were not prepared. (Comparative Example 3) A circuit was obtained in the same manner as in Example 1 except that the cordierite particles in the adhesive varnish adjustment were not prepared, and the "EXL-2 65 5" 35 parts by mass was substituted for rKW-4426". The component is joined with an adhesive sheet. (Comparative Example 4) The cordierite particles were adjusted in the same manner as in Example 1 except that the cordierite particles were not blended in the adhesive varnish adjustment, and an adhesive sheet for connecting a circuit member was obtained. [Evaluation of the adhesive layer] Production and production ΰ -33-201211187 (Measurement of coefficient of linear expansion) The adhesive sheet for connecting the circuit member obtained in the examples and the comparative examples was placed in an oven at 180 ° C for 3 hours. Heat hardening treatment. The adhesive layer after heat hardening was peeled off from the support substrate, and a test piece of a size of 30 mm X 2 mm was produced. Using "TMA/SS6100" (trade name) manufactured by Seiko Instrument Co., Ltd., the test piece was mounted in the apparatus to become a chuck. 20mm, measuring temperature range: 20~3 00 °C, heating rate 5 °C / min, load conditions: the cross-sectional area of the test piece, the condition of 0.5 MPa pressure, thermomechanical analysis in the tensile test mode, determination Linear expansion coefficient. After the measurement, the linear expansion difference between 1 〇〇 ° C and 40 ° C was calculated, and the enthalpy was divided by the temperature difference, and the average linear expansion coefficient was formed and used for comparison. (Reaction Rate Measurement) The adhesive layer in the adhesive sheet for connecting the circuit member obtained in the examples and the comparative examples was measured in an aluminum measuring container to measure 2 to 10 mg, and a DSC (Differential Scaning Calorimeter) manufactured by Perkin Elymer Co., Ltd. was used.丫^1" (trade name), the calorific value was measured by raising the temperature to 30 to 300 °C at a heating rate of 20^:/min, and this was used as the initial calorific value. Then, the temperature of the thermocouple of the thermocompression bonding apparatus was set to a thermocouple of the separator to confirm the temperature, and after 1 second, the temperature was set to a temperature of 250 °C. With the heating head setting, the circuit member connecting adhesive sheet was heated on the separator film for 20 seconds to obtain an adhesive layer in a state in which heat treatment was performed in the same manner as in the thermocompression bonding. The calorific value of the adhesive layer after the heat treatment was also measured in the same manner as the calorific value after heating. In addition, the amount of heat generation was measured in the same manner as the adhesive layer after storage of the adhesive sheet for connecting the circuit member at room temperature (-34 - 201211187 2 5 °C) for 14 days, and the heat amount after storage was used. From the obtained calorific value, the reaction rate (%) was calculated by the following formula. Reaction rate (%) = (initial calorific value - calorific value after heating or calorific value after storage) / (initial calorific value) χ 100 <Production and Evaluation of Semiconductor Device> Using the above-described adhesive sheet for connecting circuit members, a semiconductor device was produced and evaluated in the following order. The results are shown in Tables 1 and 2. (Adhesive on semiconductor wafer) The JCM-made die-bonding film holder is heated to 80 t on the adsorption stage. 'The gold-plated bump semiconductor wafer (6-inch diameter, thickness 7 2 5 μηι) will be formed. The bumps are placed side up and placed. The circuit member connecting adhesive sheet is cut into 200 mm x 200 mm, so that the adhesive layer of the first film from which the protective film is removed is directed toward the bump of the semiconductor wafer, so as to avoid entrapment of air, from the end of the semiconductor wafer: The sticking of the machine is lightly pressed and stacked. After lamination, the adhesive bleed portion is cut along the outer shape of the wafer. (Back honing of the back surface of the semiconductor wafer and peeling of the supporting substrate) The laminate of the above-mentioned circuit member connecting adhesive sheet and the semiconductor wafer (thickness 625 μm) is used as a back honing device by the company Disc to make the semiconductor wafer After the back surface is honed to a thickness of 150 μm, the semiconductor wafer with the back honing-35-201211187 is placed on the adsorption stage of the JCM-made viscous film fixing machine. Adhesive cutting tape "AD80H" is attached to the cutting frame at the same time. Then, the backing honing tape peeling tape of Nitto Denko is adhered to the support substrate, and the support substrate is pulled and peeled at 180 degrees. (Cut) The semiconductor wafer with the adhesive layer attached to the above-mentioned dicing frame was cut into a 10 mm x 10 mm by a fully automatic cutting saw "DFD 636 1" manufactured by the company Disco. After the dicing, the surface is washed, splashed with water, and after UV irradiation from the side of the dicing tape, the semiconductor wafer of the diced adhesive is picked up (crimped) to bond the semiconductor wafer of the adhesive to the opposite bump. A glass epoxy substrate having a circuit for forming a solder having SnAgCu as a constituent component, and positioning was carried out by a Panasonic Electric Industrial Industrial Folding Machine "FCB 3", and then thermocompression-bonded at 250 ° C and 0.5 MPa for 10 seconds. Semiconductor device. The embedding property and connection resistance of the film-like adhesive in the semiconductor device fabricated as described above were evaluated. Then, the fabricated semiconductor device was placed in a constant temperature and humidity apparatus at 85 ° C and 60% RH for 168 hours to absorb moisture, and exposed to a reflow furnace set at 260 ° C for 3 times. After the exposure, the connection impedance and the interface state of the connection portion are confirmed. <Connection resistance> -36-201211187 The semiconductor device to be fabricated is connected to a connection measuring impedance after crimping and a connection resistance after reflow using a digital multimeter (manufactured by Advantest Co., Ltd.). And evaluate. The results are shown in Tables 1 and 2. a : The connection resistance of the full-terminal connection of the packaged TEG for the test can be obtained. b: There is a broken terminal. <Embeddedness after crimping> The adhesion state of the adhesive layer was inspected by the Hitachi Construction Mechanism Ultrasonic Flaw Detector (SAT), and evaluated based on the following criteria. The results are shown in Tables 1 and 2. a : No peeling or air bubbles were observed. b: Peeling and air bubbles were observed. <Connectivity after reflowing> The connection state after the reflow of the adhesive layer was inspected by the Hitachi Construction Mechanism Ultrasonic Flaw Detector (S AT ) was evaluated based on the following criteria. The results are shown in Tables 1 and 2. a : No peeling was observed. b: Peeling was observed. -37-201211187 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Thermoplastic resin ZX1356-2 25 25 25 25 25 Thermosetting resin 1032H60 25 25 25 25 25 Epikote 828 15 15 15 15 15 Hardener ΗΧ3Θ41ΗΡ 35 35 35 35 35 Inorganic ruthenium cordierite particles 100 50 125 - — SE2050 One - one 50 50 Organic granules KW-4426 10 20 7 — — EXL-2655 — - - 30 15 4〇-100eC Average linear expansion coefficient (xi〇'*/°c) 45 60 42 62 54 Connection resistance after crimping aaaaa Implantability after crimping 8 aaaa . Connectivity after reflow soldering aaaaa Connection resistance after reflow aaaaa [ Table 2] Example 6 Comparative 俐 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Thermoplastic Resin 2X1356-2 25 25 25 25 25 Thermosetting Resin 1032 Η 60 25 Z5 25 25 25 Epikote 828 15 15 15 15 15 Hardener HX3941HP 35 35 35 35 35 Inorganic ruthenium cordierite particles » 100 A - SE2050 150 One - - One organic microparticle KW-4426 One - 20 One - EXL-2655 15 - 35 - 40-1003⁄4 average linear expansion coefficient ( XIO'V^) 42 40 70 7β 70 pressure After the connection resistance aaaaa, the buried abbb after the crimping, the connectivity after the reflow, the abbbb, the connection resistance after the reflow, the abbbb, and the circuit components obtained in Examples 1 to 6, as shown in Tables 1 and 2. When the adhesive sheet was connected, the connection resistance was excellent, and "no bubble generation" showed good connectivity after reflow. However, when the adhesive sheets for connection of circuit members obtained in Comparative Examples 1 to 4 were used, it was confirmed that the bubbles were peeled off after reflow, and it was confirmed that the connection reliability was poor. -38-201211187 [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing an embodiment of a suitable adhesive sheet for connecting circuit members of the present invention. Fig. 2 is a schematic cross-sectional view showing an embodiment of a suitable adhesive sheet for connecting circuit members of the present invention. Fig. 3 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 4 is a schematic cross-sectional view for explaining an embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 5 is a schematic cross-sectional view for explaining an embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 6 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 7 is a schematic cross-sectional view for explaining an embodiment of a method of manufacturing a semiconductor device of the present invention. [Description of main component symbols] 1 : Protective film 2 : Adhesive layer 3 : Support substrate 3 a : Adhesive layer 3 b : Plastic film 4 : Honing machine 5 : Cutting tape - 39 - 201211187 6 : Cutting saw 7 : Suction collector 8: semiconductor element supporting member 1 〇: circuit member connecting adhesive sheet 11: circuit member connecting adhesive sheet 1 2: film element-attached semiconductor element 20: circuit electrode 30: semiconductor device A: Semiconductor Wafer-40-

Claims (1)

201211187 七、申請專利範圍： 1 . 一種接著劑組成物’其特徵爲含有（A )熱可塑性 樹脂、（B )熱硬化性樹脂、（C )潛在性硬化劑、（D ) 無機塡充物、與（E)有機微粒子。 2 ·如申請專利範圍第1項之接著劑組成物，其中對於 前述（A)熱可塑性樹脂、前述（B )熱硬化性樹脂及前述 (C )潛在性硬化劑之總含有量1 〇〇質量份而言，前述（〇 )無機塡充物的含有量爲5〇〜150質量份，前述（E)有機 微粒子的含有量爲5〜30質量份，且前述（D)無機塡充物 及前述（E)有機微粒子的含有量之合計爲65〜165質量份 〇 3 ·如申請專利範圍第1項或第2項之接著劑組成物，其 爲介在相對向的電路構件間，用於將前述電路構件彼此接 著。 4. 一種接著劑片，其特徵爲具備支持基材、及設置於 該支持基材上之如申請專利範圍第1項至第3項中任一項之 接著劑組成物所成的接著劑層。 5 ·如申請專利範圍第4項之接著劑片，其中前述支持 基材爲具備塑質薄膜與設置於該塑質薄膜上的黏著劑層， 前述接著劑層設置於前述黏著劑層上。 6 .如申請專利範圍第4項或第5項之接著劑片，其爲介 在相對向的電路構件間，用於將前述電路構件彼此接著。 7.—種半導體裝置之製造方法，其特徵爲具備 準備於一方之主面具有複數電路電極的半導體晶圓， 5 -41 - 201211187 於該半導體晶圓之設有前述電路電極的面側上，設置由如 申請專利範圍第1項至第3項中任一項之接著劑組成物所成 的接著劑層之步驟、 將前述半導體晶圓之設有前述電路電極的面側之相反 側進行硏削，使前述半導體晶圓薄化的步驟、 切割前述經薄化的半導體晶圓及前述接著劑層，使附 有薄膜狀接著劑的半導體元件個片化的步驟、與 將前述附有薄膜狀接著劑之半導體元件的前述電路電 極接合於半導體元件載持用支持構件之電路電極的步驟。 -42-201211187 VII. Patent application scope: 1. An adhesive composition characterized by containing (A) thermoplastic resin, (B) thermosetting resin, (C) latent curing agent, (D) inorganic filling, With (E) organic microparticles. 2. The adhesive composition of claim 1, wherein the total content of the (A) thermoplastic resin, the (B) thermosetting resin, and the (C) latent curing agent is 1 〇〇 The content of the (〇) inorganic enthalpy is 5 〇 to 150 parts by mass, the content of the (E) organic fine particles is 5 to 30 parts by mass, and the (D) inorganic entangled material and the aforementioned (E) the total content of the organic fine particles is 65 to 165 parts by mass. 接着3. The adhesive composition of the first or second aspect of the patent application is interposed between the opposing circuit members for the aforementioned The circuit components follow each other. An adhesive sheet characterized by comprising a support substrate, and an adhesive layer formed on the support substrate, which is an adhesive composition according to any one of claims 1 to 3 of the patent application. . 5. The adhesive sheet of claim 4, wherein the support substrate is provided with a plastic film and an adhesive layer provided on the plastic film, and the adhesive layer is provided on the adhesive layer. 6. An adhesive sheet according to item 4 or item 5 of the patent application, which is disposed between opposing circuit members for adhering the aforementioned circuit members to each other. 7. A method of manufacturing a semiconductor device, comprising: providing a semiconductor wafer having a plurality of circuit electrodes on one main surface, and 5 - 41 - 201211187 on a surface side of the semiconductor wafer on which the circuit electrode is provided; Providing a step of forming an adhesive layer formed of the adhesive composition according to any one of claims 1 to 3, and performing the opposite side of the surface side of the semiconductor wafer on which the circuit electrode is provided. a step of thinning the semiconductor wafer, a step of dicing the thinned semiconductor wafer and the adhesive layer, and a step of forming a semiconductor element with a film-like adhesive, and attaching the film to the film The step of bonding the circuit electrode of the semiconductor element of the subsequent device to the circuit electrode of the semiconductor element supporting member. -42-
TW099130500A 2010-09-09 2010-09-09 Adhesive composition, method for manufacturing connection of circuit member and semiconductor device TWI509043B (en)

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