201211188 六、發明說明： 【發明所屬之技術領域】 本發明係關於接著劑組成物、電路構件連接用接著劑 薄片及半導體裝置之製造方法。 【先前技術】 近年來，隨著電子設備之小型化、薄型化，電路構件 中所形成之電路高密度化獲得進展，與鄰接電極之間隔或 電極之寬度有變極爲狹窄之傾向。伴隨於此，亦高度要求 對應於半導體封裝之薄型化或小型化。因此，作爲半導體 晶粒之安裝方式，代替使用金屬線連接之過去之金線黏合 (wire-bonding )方式，而於晶粒電極上形成稱爲凸塊之 突起電極，透過凸塊使基板電極與晶粒電極直接連接之覆 晶（F1 i p C h i p )連接方式受到矚目。 至於覆晶連接方式已知有使用焊錫凸塊之方式、使用 金凸塊與導電性接著劑之方式、熱壓著方式、超音波方式 等。該等方式均有因晶粒與基板之熱膨脹係數差所導致之 熱應力集中於連接部份而造成連接信賴性降低之問題。爲 防止該種信賴性降低，一般係利用樹脂形成充塡晶粒與基 板之間隙之底部塡充（underfill )。由於利用朝底部塡充 之分散而緩和熱應力，故可改善連接信賴性。 形成底部塡充之方法一般已知有使晶粒與基板連接後 ’將液狀樹脂注入於晶粒與基板之間隙中之方法（參照專 利文獻1 )。又，亦已知在使用異向性導電性接著薄膜（ -5- 201211188 以下稱爲ACF)或非導電性接著薄膜（以下稱爲NCF)等 薄膜狀樹脂連接晶粒與基板之步驟中，亦完成底部塡充形 成之方法（參照專利文獻2 ) » 另一方面，近年來作爲可進一步高功能化、高速動作 者之以最短距離連接晶粒間之三次元安裝技術的矽貫穿電 極（TSV:Through Silicon Via)受到矚目（參照非專利文 獻Ο 。結果，要求半導體晶圓之厚度儘可能地薄，且不 降低機械強度。 又，隨著半導體裝置之更薄型化要求，爲了使半導體 晶圓更薄，而進行硏削晶圓背面之所謂背面硏磨（back grinding )，使半導體裝置之製造步驟變得煩雜。因此， 提案有在背面硏磨時可兼顧保持半導體晶圓之功能及底部 塡料功能之樹脂作爲適於步驟簡化之方法（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2003-142529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 Technology 2007 年 10 月 /第 211 號 Vol. 74 No· 3 -6 - 201211188 【發明內容】 [發明欲解決之課題] 然而，隨著半導體裝置之薄膜化，連接部之空隙或端 子間之間距變得更爲狹窄。因此，連接時由於薄膜狀樹脂 之流動不足造成界面之潤濕不足或因薄膜狀樹脂發泡產生 孔洞等，使薄膜狀樹脂朝間距間之塡充變得不充分，而有 連接信賴性降低之虞。因此，電路構件之連接所用之薄膜 狀接著劑，就確保連接信賴性之觀點而言，需要具有壓著 時難以產生孔洞之優異埋入性或硬化後之接著力充分高。 且，在半導體晶粒之電極部分形成焊錫凸塊，藉由焊 接接合直接將半導體晶粒連接於電路基板上之面固晶方式 ，爲了獲得良好之電性接合，而要求去除焊錫表面及連接 端子部份之金屬表面上形成之氧化皮膜。然而，過去之接 著劑以短時間加熱進行焊接接合時，無法獲得用以去除焊 錫表面及連接端子部分之金屬表面的氧化膜之助焊劑活性 ’而有使焊錫潤濕性變得不足，造成連接信賴性下降之情 況。 本發明係有鑒於上述問題而完成者，其目的係提供一 種作成薄膜狀時埋入性仍相當優異，且可製作連接信賴性 優異之半導體裝置之接著劑組成物，使用彼等之電路構件 連接用接著劑薄片，及半導體裝置之製造方法。 [用以解決課題之手段] 爲解決上述課題，本發明提供一種接著劑組成物，其 201211188 含有（A )熱可塑性樹脂、 在性硬化劑、（D )無機塡 )室溫中爲固體之最大粒徑 且（F)成分爲選自具有羧 合物及醯肼化合物之至少一 依據本發明之接著劑組 (B)、( C )、（D)及（ 異，可充分減低孔洞發生， 去除焊錫表面及連接端子部 膜，可改善焊錫潤濕性而形 又，本發明之接著劑組 性之觀點而言，（B )成分i 本發明之接著劑組成物 之電路電極之電路構件間， 該情況，藉由使電路構件彼 可以充分接著力接著，且可 合。因此，可獲得連接信賴 本發明之電路構件連接 撐基材及設置於該基材上之 所組成之接著劑層。 上述支撐基材具備有塑 之黏著劑層，而上述接著劑 此，本發明之電路構件連接 背面硏磨時，可穩定地保持 (B )熱硬化性樹脂、（C )潛 料、（E)有機微粒子、及（F 爲25μπι以下之粉體化合物， 基之化合物、具有羥甲基之化 種化合物。 L成物，藉由含有上述（Α)、 Ε )成分，連接時之埋入性優 進而藉由調配（F)成分，可 分之金屬表面上形成之氧化皮 成薄膜狀接著劑。 成物中，就改善耐熱性及接著 晈好含有環氧樹脂。 係介隔在具有相對向焊接接合 可用於使電路構件彼此接著。 此熱壓著，可抑制孔洞發生且 使電路電極彼此良好地焊接接 性優異之連接體。 用接著劑薄片之特徵爲具備支 由上述本發明之接著劑組成物 膠薄膜及設置於該塑膠薄膜上 層較好設置於黏著劑層上。據 用接著劑薄片在半導體晶圓之 半導體晶圓。 • 8 - 201211188 另外，本發明之電路構件連接用接著劑薄片係介隔在 具有相對向之焊接接合之電路電極之電路構件間’可用於 使電路構件彼此接著。該情況’藉由使電路構件彼此熱壓 著，可抑制孔洞發生且以充分接著力接著’且可使電路電 極彼此良好地焊接接合。據此，可獲得連接信賴性優異之 連接體。 本發明另提供一種半導體裝置之製造方法，該方法具 備下列步驟：準備於主面之一方上具有複數電路電極之半 導體晶圓，在該半導體晶圓之設有電路電極之側，設置由 本發明之接著劑組成物所構成之接著劑層之步驟，將半導 體晶圓之設置有電路電極側之相反側予以硏削並進行薄化 半導體晶圓之步驟，切割經薄化之半導體晶圓及接著劑層 並將附有薄膜狀接著劑之半導體元件予以單片化之步驟， 與將附有薄膜狀接著劑之半導體元件之電路電極焊接接合 於半導體元件搭載用支撐構件之電路電極上之步驟。 [發明效果] 依據本發明可提供一種成爲薄膜狀時之埋入性足夠優 異，同時可製作連接信賴性優異之半導體裝置之接著劑組 成物及使用其之電路構件連接用接著劑薄片。且，依據本 發明之半導體裝置之製造方法，可提供連接信賴性優異之 半導體裝置。 【實施方式】 -9- 201211188 圖1爲顯示本發明之電路構件連接用接著劑薄片之較 佳實施形態之模式剖面圖。圖1中所示之電路構件連接用 接著劑薄片10具備支撐基材3、設置於該支撐基材3上 且由本發明之接著劑組成物所構成之接著劑層2,及被覆 接著劑層2之保護薄膜1。 首先，針對構成接著劑層2之本發明接著劑組成物加 以說明。 本發明之接著劑組成物包含（A)熱可塑性樹脂、（ B)熱硬化性樹脂、（C)潛在性硬化劑、（D)無機塡料 、（E)有機微粒子、及（F)室溫中爲固體之最大粒徑爲 25μιη以下之粉體化合物。 至於（A )熱可塑性樹脂列舉爲聚酯樹脂、聚醚樹脂 、聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚醯亞胺樹脂、聚丁 酸乙烯酯樹脂、聚乙烯基甲醛樹脂、苯氧樹脂、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。該等可單獨使用或混 合兩種以上使用。 (A )成分可使接著劑組成物之薄膜形成性變良好》 所謂薄膜形成性表示使接著劑組成物成爲薄膜狀時，不容 易破裂、碎裂、黏糊之機械特性者。在通常狀態（例如常 溫）下若薄膜之處理容易則稱爲薄膜成形性良好。上述之 熱可塑性樹脂中，就耐熱性及機械強度優異而言，較好使 用聚醯亞胺樹脂或苯氧樹脂。 -10- 201211188 (A )成分之調配量相對於樹脂成分的（A ) 、( B ) 及（C )成分之合計100質量份，較好爲1~50質量份， 更好爲15〜40質量份，又更好爲20〜35質量份。（A)成 分之調配量在該範圍內時，接著劑組成物之薄膜形成性變 良好，且熱壓著時顯示流動性，可使凸塊與電路電極間之 樹脂排除性良好。（A )成分之調配量未達1 0質量份時 ，薄膜形成性降低，且有自支撐基材與保護薄膜之旁邊滲 出之傾向。另一方面，（A)成分之調配量超過50質量 份時，熱壓著時之流動性下降，有自凸塊與電極間之排除 性降低之傾向。 (A)成分之重量平均分子量較好爲2萬~80萬，更 好爲3萬〜50萬，又更好爲3.5萬〜1〇萬，最好爲4萬〜8 萬。重量平均分子量在該範圍時，由於作成薄片狀或薄膜 狀之接著劑層2之強度、可撓性易良好地均衡同時接著劑 層2之流動性良好，故可充分確保配線之電路充塡性（埋 入性）。又，本說明書中，所謂重量平均分子量係表示以 凝膠滲透層析儀測定，使用標準聚苯乙烯檢量線換算之値 〇 且，就一方面維持薄膜形成性，一方面賦予硬化前之 接著劑層2黏接著性之觀點而言，（A )成分之玻璃轉移 溫度較好爲20〜170 °C，更好爲25〜120 °C。（A)成分之玻 璃轉移溫度未達2 0 °C時室溫之薄膜形成性低，背面硏磨步 驟之半導體晶圓之加工中接著劑層2有容易變形之傾向， 超過1 7〇°C時將接著劑層2貼合於半導體晶圓時之貼合溫 -11 - 201211188 度需要比170°C更高之高溫度，故有進行（B)成分之熱 硬化反應，接著劑層2之流動性降低而容易發生連接不良 之傾向。 (B)熱硬化性樹脂列舉爲例如環氧樹脂、不飽和聚 酯樹脂、三聚氰胺樹脂、脲樹脂、苯二甲酸二烯丙酯樹脂 、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、 間苯二甲酚樹脂、二甲苯樹脂、苯并胍樹脂、矽氧樹脂、 矽氧烷改質之環氧樹脂及矽氧烷改質之聚醯胺醯亞胺樹脂 。該等可單獨使用或混合兩種以上使用。就改善耐熱性及 接著性之觀點而言，較好含有環氧樹脂作爲（B)成分。 至於上述環氧樹脂只要是具有硬化接著作爲者即無特 別限制，例如可廣泛使用環氧樹脂手冊（新保正樹編，曰 刊工業新聞社）等所記載之環氧樹脂。具體而言，可使用 例如雙酚 A型環氧樹脂等二官能基環氧樹脂、酚酚醛樹 脂型環氧樹脂或甲酚酚醛樹脂型環氧樹脂之酚醛樹脂型環 氧樹脂、參酚甲烷型環氧樹脂。又，多官能基環氧樹脂可 使用縮水甘油基胺型環氧樹脂、含雜環之環氧樹脂或脂環 式環氧樹脂等一般已知者。 (B)成分之調配量，爲了維持硬化後之接著劑之耐 熱性、接著性，且展現高信賴性，相對於樹脂成分的（A )、（B)及（C)成分之合計100質量份，較好爲5〜88 質量份，更好爲20~50質量份，又更好爲20〜40質量份。 (B)成分之調配量未達5質量份時，硬化物之凝聚力下 -12- 201211188 降’容易造成連接信賴性下降。另一方面，（B)成分之 調配量超過88質量份時，硬化前之薄膜狀態中之低分子 量成分變得過多導致不易維持薄膜狀形體。 至於（C )潛在性硬化劑可列舉爲例如酚系、咪唑系 、醯肼系、硫醇系、苯并噁嗪、三氟化硼-胺錯合物、锍 鹽、胺醯亞胺、聚胺之鹽、二氰二醯胺及有機過氧化物系 之硬化劑。不過，電路構件連接用接著劑薄片1 0，在使 用於對半導體晶圓之貼合、半導體晶圓硏削時之電路電極 之保護、半導體晶圓之切割、及對所得半導體元件之電路 電極之接合等半導體裝置之製造之一連串步驟中時，必須 保持可於長時間暴露於常溫環境下，不受製造步驟中之熱 、溫度、光等影響之對電路電極之接合時可使用之特性。 除該方面以外，就可延長可使用期間之觀點而言，（C ) 之潛在性硬化劑較好爲微膠囊型之潛在性硬化劑。 微膠囊型之潛在性硬化劑列舉爲聚胺基甲酸酯、聚苯 乙烯、明膠及聚異氰酸酯等高分子物質、矽酸鈣或沸石等 無機物，或利用鎳或銅等金屬薄膜之被膜實質上覆蓋由上 述硬化劑所成之核者。 微膠囊型之潛在性硬化劑之平均粒徑，就確保反應起 始點之均勻分散與薄膜平坦性之觀點而言，較好爲1 〇μη 以下，更好爲5 μπι以下。又，平均粒徑之下限値’就對 於薄膜形成時之漆料所使用之溶劑確保耐溶劑性之觀點而 言，較好爲1 μ m以上。 (B ) (C )成分之調配量相對於樹脂成分的（A )、 -13- 201211188 及（C)成分之合計100質量份，較好爲2〜45質量份’ 更好爲1 〇~40質量份，又更好爲22-40質量份。（C )成 分之調配量未達2質量份時，會有硬化反應難以進行之傾 向。另一方面，（C)成分之調配量超過45質量份時，由 於接著劑組成物之硬化劑比例太多，相對地熱硬化性樹脂 之比例變少，而有耐熱性或接著性等特性下降之傾向。 藉由使接著劑組成物含有（D)無機塡料，由於可降 低硬化後之接著劑層2之吸濕率及線膨脹係數，且提高彈 性率，故可改善製作之半導體裝置之連接信賴性。且，爲 了防止接著劑層2中之可見光之散射且改善可見光之透過 率’故（D)成分可選擇不降低可見光透過率之無機塡料 。較好選擇具有比可見光之波長更細之粒徑之無機塡料作 爲可抑制可見光透過率下降之（D)成分，或者較好選擇 具有近似於由樹脂成分的（A) 、（B)及（C)成分所組 成之術之組成物（以下有時稱爲「樹脂組成物」）之折射 率之折射率的無機塡料。 具有比可見光之波長更細之粒徑的無機塡料，只要是 具有透明性之塡料則塡料之組成無特別限制，較好平均粒 徑未達〇.3μπι ’更好爲〇·1μίη以下。且，該無機塡料之折 射率較好爲1.46~1.7。 具有近似於樹脂組成物折射率之折射率的無機塡料可 在製作由（A ) 、（ Β )及（c )所組成之樹脂組成物並測 疋折射率後，選定具有近似於該折射率之折射率的無機塡 料。至於該無機塡料，就對接著劑層2之半導體晶粒與電 -14- 201211188 路基板之空隙之塡充性之觀點及抑制連接步驟中孔洞發生 之觀點而言’較好使用微細塡料。該種無機塡料之平均粒 徑較好爲〇.〇1〜5μηι’更好爲〇.1〜2μπι，又更好爲0.3〜Ιμιη 。平均粒徑未達Ο.ΟΙμηϊ時，粒子之被覆表面積變大使接 著劑組成物之黏度增加’會有無機塡料難以塡充之傾向。 具有近似於樹脂組成物折射率之折射率的無機塡料之 折射率較好爲樹脂組成物之折射率±0.06之範圍。例如， 樹脂組成物之折射率爲1 · 6 0時，可使用折射率爲 1· 54〜1.66之無機塡料。折射率可使用Abbe折射計，以鈉 D線（5 8 9nm )作爲光源測定。至於該種無機塡料列舉爲 複合氧化物塡料、複合氫氧化物塡料、硫酸鋇及黏土礦物 ’具體而言可使用堇青石、鎂橄欖石、莫來石（Mullite) 、硫酸鋇、氫氧化鎂、硼酸鋁、鋇或二氧化矽氧化鈦。 又’上述兩類之無機塡料亦可組合使用。但，爲了不 影響接著劑組成物之黏度增加’具有比可見光之波長更細 之粒徑之無機塡料的添加量以（D )成分作爲基準，較好 爲未達1 0質量。/。。 又’ （D )成分，就改善接著劑層2之彈性率之觀點 而言’線膨脹係數在0〜700°C之溫度範圍較好爲7xl(T6/t 以下，更好爲3x1 (T6/°C以下。 (D)成分之調配量相對於樹脂成分的（a) 、 ( B ) 及（C)成分之合計1〇〇質量份，較好爲25〜200質量份 ’更好爲50〜150質量份，又更好爲75〜125質量份。（D )成分之調配量未達25質量份時，容易導致由接著劑組[Technical Field] The present invention relates to an adhesive composition, an adhesive sheet for connecting a circuit member, and a method of manufacturing a semiconductor device. [Prior Art] In recent years, with the miniaturization and thinning of electronic devices, the density of circuits formed in circuit members has progressed, and the interval between adjacent electrodes or the width of electrodes has become extremely narrow. Along with this, it is also highly demanded to be thinner or smaller in size than the semiconductor package. Therefore, as a mounting method of the semiconductor die, instead of using a conventional wire-bonding method in which a metal wire is connected, a bump electrode called a bump is formed on the die electrode, and the substrate electrode is formed by the bump. The flip chip (F1 ip C hip ) connection method in which the die electrodes are directly connected is attracting attention. As the flip chip connection method, a solder bump is used, a gold bump and a conductive adhesive are used, a hot press method, an ultrasonic method, and the like are known. In these methods, there is a problem that the thermal stress caused by the difference in thermal expansion coefficient between the crystal grains and the substrate concentrates on the connection portion, resulting in a decrease in connection reliability. In order to prevent such a decrease in reliability, a resin is generally used to form a bottom underfill of the gap between the filled crystal grains and the substrate. Since the thermal stress is alleviated by the dispersion to the bottom, the connection reliability can be improved. In the method of forming the bottom charge, a method of injecting a liquid resin into the gap between the crystal grain and the substrate after the die is connected to the substrate is generally known (refer to Patent Document 1). Further, it is also known that in the step of connecting a crystal grain and a substrate using a film-like resin such as an anisotropic conductive adhesive film (hereinafter referred to as ACF), or a non-conductive adhesive film (hereinafter referred to as NCF), The method of forming the underfill is completed (see Patent Document 2). On the other hand, in recent years, the 矽-through electrode (TSV: which is a three-dimensional mounting technique for connecting the inter-die at the shortest distance as a further high-performance and high-speed actor) Through Silicon Via) (see Non-Patent Document 。. As a result, the thickness of the semiconductor wafer is required to be as thin as possible without deteriorating the mechanical strength. Moreover, as semiconductor devices are required to be thinner, in order to make semiconductor wafers more Thin, and the so-called back grinding of the back side of the wafer is boring, making the manufacturing steps of the semiconductor device complicated. Therefore, it is proposed to maintain the function of the semiconductor wafer and the bottom material during back honing. A functional resin is a method suitable for step simplification (refer to Patent Documents 3 and 4). [Prior Art Document] [Patent Document] [Patent Document 1] JP-A-2000-1008 [Non-patent Document 1] [Non-Patent Document 1] [Patent Document 1] [Non-Patent Document 1] [Non-Patent Document 1] OKI Technology October 2007 / No. 211 Vol. 74 No. 3 -6 - 201211188 [Summary of the Invention] However, with the thinning of a semiconductor device, the gap between the terminals or the distance between the terminals In the case of the connection, the insufficient wettability of the interface due to insufficient flow of the film-like resin or the formation of voids due to foaming of the film-like resin causes insufficient filling of the film-like resin toward the gap. Therefore, the film-like adhesive used for the connection of the circuit members needs to have excellent embedding property or hardening adhesion after hardening, in terms of ensuring connection reliability. Further, a solder bump is formed on the electrode portion of the semiconductor die, and the semiconductor die is directly bonded to the circuit substrate by solder bonding, in order to obtain good electrical properties. In combination, it is required to remove the oxide film formed on the surface of the solder and the metal surface of the connection terminal portion. However, when the past adhesive is heated and soldered for a short time, the metal surface for removing the solder surface and the connection terminal portion cannot be obtained. The flux activity of the oxide film is insufficient to cause the solder wettability to be insufficient, and the reliability of the connection is lowered. The present invention has been made in view of the above problems, and an object thereof is to provide a film-formed embedding property. It is still excellent, and it is possible to produce an adhesive composition for connecting a semiconductor device having excellent reliability, using an adhesive sheet for connecting circuit members thereof, and a method for manufacturing a semiconductor device. [Means for Solving the Problems] In order to solve the above problems, the present invention provides an adhesive composition comprising 20121188 which contains (A) a thermoplastic resin, a curing agent, and (D) an inorganic cerium; The particle size and the component (F) are selected from at least one of the adhesive groups (B), (C), (D) and (different according to the present invention) having a carboxylate compound and a bismuth compound, which can sufficiently reduce pore occurrence and removal. The surface of the solder and the film for connecting the terminal portions can improve the solder wettability and shape. In terms of the adhesive composition of the present invention, (B) component i is between the circuit components of the circuit electrodes of the adhesive composition of the present invention. In this case, the circuit member can be sufficiently adhered to and can be joined. Therefore, it is possible to obtain a bonding agent layer which is connected to the circuit member of the present invention and which is provided on the substrate. The support substrate is provided with a plastic adhesive layer, and the above-mentioned adhesive agent can stably hold (B) thermosetting resin, (C) latent material, and (E) organic when the circuit member of the present invention is connected to the back surface honing. Microparticles, (F is a powder compound of 25 μm or less, a compound of a base, and a compound of a compound having a methylol group. The L-form, by containing the above (Α), Ε) component, is excellent in embedding at the time of connection and is prepared by blending (F) component, which can be divided into oxide film formed on the surface of the metal to form a film-like adhesive. The heat resistance of the product is improved, and then the epoxy resin is contained. The spacer can be used for the purpose of making the solder joint. The circuit members are bonded to each other. This heat-pressing can suppress the occurrence of voids and provide excellent bonding properties between the circuit electrodes. The adhesive sheet is characterized in that it has a film of the adhesive composition of the present invention and The upper layer of the plastic film is preferably disposed on the adhesive layer. The adhesive wafer is used on the semiconductor wafer of the semiconductor wafer. 8 - 201211188 In addition, the adhesive member for connecting the circuit member of the present invention is interposed The circuit member between the circuit electrodes that are soldered to the opposite ends can be used to cause the circuit members to follow each other. In this case, by heating the circuit members to each other, The hole is formed and the electrode electrodes are soldered to each other with sufficient adhesion. Thus, a connector having excellent connection reliability can be obtained. The present invention further provides a method of manufacturing a semiconductor device, which has the following steps a semiconductor wafer having a plurality of circuit electrodes on one side of a main surface, and a step of forming an adhesive layer composed of the adhesive composition of the present invention on a side of the semiconductor wafer on which the circuit electrodes are provided, and a semiconductor crystal The circle is provided with a step of boring and thinning the semiconductor wafer on the opposite side of the circuit electrode side, cutting the thinned semiconductor wafer and the adhesive layer, and singulating the semiconductor element with the film-like adhesive The step of soldering and bonding the circuit electrode of the semiconductor element with the film-like adhesive to the circuit electrode of the semiconductor element mounting support 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 a film form, and which can be used in a semiconductor device having excellent connection reliability, and an adhesive sheet for connecting circuit members using the same. Further, according to the method of manufacturing a semiconductor device of the present invention, it is possible to provide a semiconductor device excellent in connection reliability. [Embodiment] -9-201211188 Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members of the present invention. The circuit member connection adhesive sheet 10 shown in FIG. 1 includes a support substrate 3, an adhesive layer 2 provided on the support substrate 3 and composed of the adhesive composition of the present invention, and an adhesive layer 2 Protective film 1. First, the adhesive composition of the present invention which constitutes the adhesive layer 2 will be described. The adhesive composition of the present invention comprises (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic coating, (E) an organic fine particle, and (F) room temperature. The powder is a solid compound having a maximum particle diameter of 25 μm or less. As for the (A) thermoplastic resin, it is exemplified by a polyester resin, a polyether resin, a polyamide resin, a polyamidimide resin, a polyimide resin, a polyvinyl butyrate resin, a polyvinyl formaldehyde resin, and a benzene. Oxygen 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 singly or in combination of two or more. The component (A) can improve the film formability of the adhesive composition. The film formability is a property in which the adhesive composition is not easily broken, broken, or sticky when the adhesive composition is formed into a film. When the film is easily handled in a normal state (e.g., normal temperature), it is said that the film formability is good. Among the above thermoplastic resins, a polyimide or a phenoxy resin is preferably used because of its excellent heat resistance and mechanical strength. -10- 201211188 The amount of the component (A) is preferably from 1 to 50 parts by mass, more preferably from 15 to 40 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 preferably 20 to 35 parts by mass. When the amount of the component (A) is within this range, the film formation property of the adhesive composition becomes good, and fluidity is exhibited at the time of hot pressing, and the resin-removing property between the bump and the circuit electrode can be improved. When the amount of the component (A) is less than 10 parts by mass, the film formability is lowered and there is a tendency for the self-supporting substrate to bleed out beside the protective film. On the other hand, when the amount of the component (A) is more than 50 parts by mass, the fluidity at the time of hot pressing is lowered, and the exclusion between the bump and the electrode tends to be lowered. 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, still more preferably from 35,000 to 1,000,000, and most preferably from 40,000 to 80,000. When the weight average molecular weight is in this range, the strength and flexibility of the adhesive layer 2 which is formed into a sheet or a film form are easily balanced and the fluidity of the adhesive layer 2 is good, so that the circuit chargeability of the wiring can be sufficiently ensured. (buried). In the present specification, the weight average molecular weight is measured by a gel permeation chromatograph and converted to a standard polystyrene calibration line, and the film formation property is maintained on the one hand, and the hardening is performed on the other hand. The glass transition temperature of the component (A) is preferably from 20 to 170 ° C, more preferably from 25 to 120 ° C, from the viewpoint of adhesion of the agent layer 2. When the glass transition temperature of the component (A) is less than 20 ° C, the film formation property at room temperature is low, and the adhesive layer 2 tends to be easily deformed during the processing of the semiconductor wafer in the back honing step, exceeding 1 7 ° C. When the adhesive layer 2 is bonded to the semiconductor wafer, the bonding temperature is -11 - 201211188, which requires a higher temperature than 170 ° C, so that the thermal hardening reaction of the component (B) is performed, and the adhesive layer 2 is The fluidity is lowered and the tendency to cause poor connection tends to occur. (B) The thermosetting resin is exemplified by, for example, an epoxy resin, an unsaturated polyester resin, a melamine resin, a urea resin, a diallyl phthalate resin, a bismaleimide resin, a triazine resin, a polyamine group. Formate resin, phenol resin, cyanoacrylate resin, polyisocyanate resin, furan resin, meta-xyl phenol resin, xylene resin, benzopyrene resin, oxime resin, oxime modified epoxy resin And a polyamine amidoxime resin modified by a siloxane. These may be used alone or in combination of two or more. From the viewpoint of improving heat resistance and furtherness, an epoxy resin is preferably contained as the component (B). The epoxy resin described above is not particularly limited as long as it has a hardening work, and for example, an epoxy resin described in the epoxy resin manual (Xin Bao Zheng Shu, ed.) is widely used. Specifically, for example, a difunctional epoxy resin such as a bisphenol A epoxy resin, a phenol novolac resin epoxy resin, a phenolic phenol resin epoxy resin phenol resin epoxy resin, or a phenol methane type can be used. Epoxy resin. Further, as the polyfunctional epoxy resin, a glycidylamine type epoxy resin, a hetero ring-containing epoxy resin or an alicyclic epoxy resin can be generally used. In order to maintain the heat resistance and adhesion of the adhesive after curing, and to exhibit high reliability, the blending amount of the component (B) is 100 parts by mass based on the total of the components (A), (B), and (C) of the resin component. It is preferably 5 to 88 parts by mass, more preferably 20 to 50 parts by mass, still more preferably 20 to 40 parts by mass. When the amount of the component (B) is less than 5 parts by mass, the cohesive force of the cured product is -12-201211188, which is likely to cause a decrease in connection reliability. On the other hand, when the amount of the component (B) is more than 88 parts by mass, the low molecular weight component in the film state before curing becomes too large, so that it is difficult to maintain the film-like body. The (C) latent curing agent may, for example, be a phenol type, an imidazole type, an anthraquinone type, a thiol type, a benzoxazine, a boron trifluoride-amine complex, an onium salt, an amine imide, a poly A salt of an amine, a dicyanodiamide and an organic peroxide-based hardener. However, the circuit member connection adhesive sheet 10 is used for bonding a semiconductor wafer, protecting a circuit electrode when a semiconductor wafer is diced, cutting a semiconductor wafer, and circuit electrodes of the obtained semiconductor element. In the series of steps of manufacturing a semiconductor device such as bonding, it is necessary to maintain characteristics that can be used when the circuit electrodes are bonded to each other without being affected by heat, temperature, light, or the like in a normal temperature environment for a long period of time. In addition to this aspect, the latent curing agent of (C) is preferably a microcapsule-type latent curing agent from the viewpoint of extending the usable period. The microcapsule-type latent curing agent is exemplified by a high molecular weight material such as polyurethane, polystyrene, gelatin or polyisocyanate, an inorganic substance such as calcium citrate or zeolite, or a film using a metal film such as nickel or copper. Covering the core formed by the above hardener. The average particle diameter of the microcapsule-type latent curing agent is preferably 1 〇μη or less, more preferably 5 μπι or less from the viewpoint of ensuring uniform dispersion at the starting point of the reaction and film flatness. Further, the lower limit 値' of the average particle diameter is preferably 1 μm or more from the viewpoint of ensuring solvent resistance in the solvent used for the paint at the time of film formation. (B) The amount of the component (C) is preferably from 2 to 45 parts by mass, more preferably from 1 to 45 parts by mass, based on 100 parts by mass of the total of the components (A) and -13 to 201211188 and (C) of the resin component. The mass fraction is more preferably 22-40 parts by mass. When the amount of the component (C) is less than 2 parts by mass, there is a tendency that the hardening reaction is difficult to proceed. On the other hand, when the amount of the component (C) is more than 45 parts by mass, the ratio of the curing agent to the adhesive composition is too large, and the ratio of the thermosetting resin is small, and the properties such as heat resistance and adhesion are deteriorated. tendency. By including the (D) inorganic coating material in the adhesive composition, the moisture absorption rate and the linear expansion coefficient of the adhesive layer 2 after curing can be lowered, and the elastic modulus can be improved, so that the connection reliability of the fabricated semiconductor device can be improved. . Further, in order to prevent scattering of visible light in the adhesive layer 2 and to improve the transmittance of visible light, the component (D) may be selected from inorganic materials which do not lower the visible light transmittance. It is preferable to select an inorganic pigment having a particle diameter smaller than the wavelength of visible light as the component (D) capable of suppressing a decrease in visible light transmittance, or preferably (A), (B) and (similar to the resin component). C) An inorganic material having a refractive index of a composition of a composition (hereinafter sometimes referred to as "resin composition"). The inorganic material having a particle diameter smaller than the wavelength of visible light is not particularly limited as long as it is transparent, and the average particle diameter is preferably less than 3.3μπι 'better than 〇·1μίη. . Further, the refractive index of the inorganic pigment is preferably from 1.46 to 1.7. The inorganic tantalum having a refractive index close to the refractive index of the resin composition may be selected to have a refractive index after the refractive index of the resin composition composed of (A), ( Β ), and (c ) The inorganic pigment of the refractive index. As for the inorganic pigment, the viewpoint of the adhesion of the semiconductor crystal grains of the adhesive layer 2 to the voids of the dielectric-14-201211188 substrate and the viewpoint of suppressing the occurrence of voids in the bonding step are better. . The average particle size of the inorganic mash is preferably 〇. 〇1~5μηι' is preferably 〇.1~2μπι, and more preferably 0.3~Ιμιη. When the average particle diameter is less than Ο.ΟΙηη, the surface area of the particles is increased to increase the viscosity of the composition of the adherends, and there is a tendency that the inorganic mash is difficult to be filled. The refractive index of the inorganic tantalum having a refractive index close to the refractive index of the resin composition is preferably in the range of the refractive index of the resin composition ± 0.06. For example, when the refractive index of the resin composition is 1600, an inorganic cerium having a refractive index of 154 to 1.66 can be used. The refractive index can be measured using an Abbe refractometer using sodium D line (589 μm) as a light source. As for the inorganic cerium, it is exemplified as composite oxide cerium, composite hydroxide cerium, barium sulphate and clay minerals. Specifically, cordierite, forsterite, mullite, barium sulfate, hydrogen can be used. Magnesium oxide, aluminum borate, barium or titanium dioxide dioxide. Further, the above two types of inorganic materials can also be used in combination. However, in order not to affect the viscosity increase of the adhesive composition, the amount of the inorganic fine material having a particle diameter smaller than the wavelength of visible light is preferably less than 10% based on the component (D). /. . Further, the component (D) has a linear expansion coefficient of from 7 to 700 ° C in a temperature range of from 0 to 700 ° C from the viewpoint of improving the elastic modulus of the adhesive layer 2 (T6/t or less, more preferably 3 x 1 (T6/). The amount of the component (D) is 1 part by mass based on the total of the components (a), (B) and (C) of the resin component, preferably 25 to 200 parts by mass. 150 parts by mass, more preferably 75 to 125 parts by mass. When the amount of the component (D) is less than 25 parts by mass, it is likely to result from the adhesive group
C -15- 201211188 成物形成之接著劑層2之線膨脹係數增大及彈性率下降。 據此，容易使壓著後之半導體晶粒與基板之連接信賴性下 降，而且，亦難以獲得連接時之孔洞抑制效果。另一方面 ，（D)成分之含量超過20 0質量份時，由於接著劑組成 物之熔融黏度增加，且半導體晶粒與接著劑層2之界面或 電路基板與接著劑層2之界面之潤濕性下降，因剝離或埋 入不足而容易引起孔洞殘留。 (E )有機微粒子列舉爲含有例如丙烯酸樹脂、矽氧 樹脂、丁二烯橡膠、聚酯、聚胺基甲酸酯、聚乙烯縮丁醛 、聚芳酯、聚甲基丙烯酸甲酯、丙烯酸橡膠、聚苯乙烯、 NBR、SBR、矽氧烷改質之樹脂等作爲成分之共聚物。至 於有機微粒子，就對接著劑組成物之分散性、應力緩和性 、接著性提高之觀點而言，較好爲分子量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。該等有機 微粒子列舉爲選自（甲基）丙烯酸烷酯-丁二烯-苯乙烯共 聚物、（甲基）丙烯酸烷酯-矽氧共聚物、矽氧-(甲基） 丙烯酸共聚物或複合物之一種以上。此處，所謂「分子量 1〇〇萬以上之有機微粒子或具有三次元交聯構造之有機微 粒子」爲超高分子量故對溶劑缺乏溶解性者，或者具有三 次元網目構造故對溶劑缺乏溶解性者。又，亦可使用具有 芯殼型之構造，芯層與殼層之組成不同之有機微粒子作爲 (E)成分。至於芯殼型有機微粒子具體而言列舉爲以矽 氧-丙烯酸橡膠作爲芯，以丙烯酸樹脂作爲殻之粒子，於 丙烯酸共聚物上接枝丙烯酸樹脂之粒子。 -16- 201211188 (E) 成分由於具有交聯構造，或爲超高分子量樹脂 ，故不溶解於有機溶劑中，因此可維持粒子形狀就此調配 於接著劑組成物中。因此，可使（E )成分島狀地分散於 硬化後之接著劑層2中，可高度保持連接體之強度。（e )成分爲具有作爲含有應力緩和性之耐衝擊緩和劑之功能 者。 (E )成分之平均粒徑較好爲0.1〜2μιη。（Ε)成分之 平均粒徑未達0 . 1 μηι時有接著劑組成物之熔融黏度增加， 妨礙連接時之焊錫潤濕性之傾向，超過2 μιη時會使熔融 黏度之減低效果減少，而有連接時難以獲得孔洞抑制效果 之傾向。 (Ε )成分之調配量，爲了賦予接著劑層2在連接時 之孔洞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，較好爲5〜20質量份 。（E )成分之調配量未達5質量份時會有難以達到抑制 連接時之孔洞之效果，同時亦難以展現應力緩和效果之傾 向，超過2 0質量％時由於流動性低，故有焊錫之潤濕性 下降而成爲殘留孔洞原因且硬化物之彈性率過低而有連接 信賴性下降之傾向。 (F) 室溫中爲固體之最大粒徑爲25 μηι以下之粉體 化合物爲含有選自具有羧基之化合物、具有羥甲基之化合 物及醯肼化合物之至少一種之化合物。（F )成分具有作 爲焊錫潤濕性改質劑之功能（以下稱（F )成分爲「焊錫 潤濕性改質劑」）。亦即’ （F )成分具有比焊錫之熔點 -17- 201211188 低溫度之熔點，熔融後藉由去除焊錫表面及電路電極等之 金屬表面之氧化物，可改善接著劑層2之焊錫潤濕性。至 於（F)成分列舉爲例如乙醯基水楊酸、苯甲酸、二苯乙 醇酸（benzilic acid)、己二酸、壬二酸、苄基苯甲酸、 丙二酸、2,2-雙（羥基甲基）丙酸、水楊酸、間-羥基苯甲 酸、琥珀酸、2,6-二甲氧基甲基對甲酚、苯甲酸醯肼、羧 醯胼、丙二酸二醯肼、琥珀酸二醯肼、葡糖酸二醯肼、水 楊酸醯肼、亞胺二乙酸二醯肼、衣康酸二醯肼、檸檬酸三 醯肼、硫代羧醯肼、二苯甲酮腙、4,4’-氧基雙苯磺醯肼及 己二酸二醯肼。然而，只要在室溫爲固體，具有羧基之化 合物、具有羥甲基之化合物或醯肼化合物，則不限於該等 者。就改善對接著劑層2之分散性之觀點而言，較好使用 以硏缽將該等化合物粉碎，經微粉化後，以至少25 μιη之 過濾器去除粒徑大者。（F )成分之最大粒徑較好爲20 μιη 以下。又，（F)成分之最小粒徑爲Ο.ΟΙμιη左右。 (F)成分之熔點較好爲l〇〇°C以上更好爲130〜200t ，又更好爲140〜180°C。 （F)成分之熔點未達lOOt：時， 會有在薄膜形成時之乾燥溫度粉體溶解，與熱硬化性成分 反應，而損及保存性之傾向。 (F)成分之調配量相對於接著劑組成物1〇〇質量份 ，較好爲1〜2 0質量份，更好爲1〜10質量份。（F)成分 之調配量未達1質量份時，改善潤濕性之效果不足，即使 調配超過20質量份，由於焊錫潤濕性改善效果達飽和故 使成分變得過剩。 -18- 201211188 接著劑組成物中，爲了將無機塡料之表面改質而改善 異種材料間之界面結合並增大接著強度，亦可添加各種偶 合劑。至於偶合劑列舉爲例如矽烷系、鈦系及鋁系之偶合 劑，其中就效果高之方面而w較好爲砂院系偶合劑。 砂院系偶合劑列舉爲例如γ -甲基丙烧醯氧基丙基三甲 氧基矽烷、γ -甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-锍基丙基三甲氧基矽烷、γ-锍基丙基三乙氧基矽院、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。該等可單獨使用或組合兩種以上 使用。 接著劑組成物中’爲了吸附離子性雜質，改善吸濕時 之絕緣信賴性’亦可添加離子捕捉劑。該種離子捕捉劑並 無特別限制。列舉爲例如三嗪硫醇化合物、雙酚系還原劑 等之用以防止銅離子化溶出之已知作爲銅害防止劑之化合 物、鍩系、銻鉍系鎂鋁化合物等無機離子吸附劑。 接著劑組成物，爲了抑制半導體晶粒與電路基板連接 後之因溫度變化或因加熱吸濕造成之膨脹等，而達成高連 接信賴性，其硬化後之接著劑層2之於4 0〜1 0 〇。(：的線膨脹 係數較好爲60xl0'6/°C以下，更好爲55xl(T6/t：以下，又 更好爲5 0 X 1 0 _6 / °C以下’硬化後之接著劑層2之線膨脹係 數超過60xl(T6/°C時’有因安裝後之溫度變化或因加熱吸 濕造成之膨漲而無法維持半導體晶粒之連接端子與電路基 板之配線間之電性連接之情況。另外，電路構件連接用接 著劑薄片1 0可於構成接著劑層2之接著劑組成物中含有 -19- 201211188 導電粒子而成爲異向性導電性接著薄膜（ACF )，但較好 不含導電性粒子成爲非導電性接著薄膜（NCF )。 由接著劑組成物形成之接著劑層2在2 5 0。(：加熱1 〇秒 後，以示差掃描熱量測定（以下稱爲「DSC」）測定之反 應率較好在60%以上，更好爲70%以上。又，將電路構件 連接用組成物薄片在室溫放置1 4天後，以D S C測定之接 著劑層2之反應率較好未達1 〇%。據此，使用本發明之接 著劑組成物可獲得連接時之反應性相當優異且保存安定性 亦優異之薄膜狀接著劑。 接著劑層2未硬化時之可見光透過率較好爲5%以上 ’更好可見光透過率爲8 %以上，又更好可見光透過率爲 10%以上。可見光透過率未達5%時，無法進行以覆晶固 晶之辨識標示識別，而有無法進行位置對位作業之傾向。 另一方面，可見光透過率之上限並無特別限制。 可見光透過率可使用日立製造之U-3310型分光光度 計測定。例如，以膜厚50μιη之帝人杜邦製造之PET薄膜 (Purex’於555nm之透過率86.03%)爲基準進行基準線 校正測定後，以25 μπι之厚度在PET薄膜上形成接著劑層 2後’測定400〜80〇nm之可見光區域之透過率。由於覆 晶固晶所使用之鹵素光源與光導之波長相對強度中以 5 50~600nm最強，故本說明書中使用5 5 5 nm之透過率進 行接著劑層2之透過率比較。 接著劑層2可使上述本發明之接著劑組成物溶解或分 散於溶劑中作成漆料，將該漆料塗佈於保護薄膜（以下有 -20- 201211188 時稱爲「第一薄膜」）1上，藉由利用加熱去除溶劑而形 成。隨後，在常溫至60°c將支撐基材3層合於接著劑層2 上，可獲得本發明之電路構件連接用接著劑薄片1 〇。又 ，接著劑層2亦可藉由將上述漆料塗佈於支撐基材3，利 用加熱去除溶劑而形成。 使用之溶劑並無特別限制，但較好考慮接著劑層形成 時之揮發性等由沸點加以決定。具體而言，就接著劑層形 成時難以促進接著劑層硬化之方面而言，以例如甲醇、乙 醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇、甲基 乙基酮、丙酮、甲基異丁基酮、甲苯、二甲苯等比較低沸 點之溶劑較佳。該等溶劑可單獨使用一種或組合兩種以上 〇 保護薄膜1可使用例如聚對苯二甲酸乙二醋、聚四氟 乙烯薄膜、聚乙烯薄膜、聚丙烯薄膜、聚甲基戊稀薄膜等 塑膠薄膜。就剝離性之觀點而g，亦較好使用如聚四氣乙 烯薄膜之由氟樹脂所構成之表面能量低之薄膜作爲保護薄 膜1。 爲了提局保護薄膜1之剝離性，保護薄膜1之形成接 著劑層2之面較好以矽氧系剝離劑、氟系剝離劑、長鏈丙 烯酸烷酯系剝離劑等脫模劑處理。至於市售者，可購自帝 人杜邦薄膜公司製造之「A-63」（脫模處理劑：改質砂氧 系）及「A-3 1」（脫模處理劑：Pt系矽氧系）。 保護薄膜1之厚度較好爲10~100μιη，更好爲 10〜75μπι，最好爲25〜50μιη。該厚度未達1〇μιη時，塗佈 -21 - 201211188 時有保護薄膜破裂之傾向，超過ΙΟΟμιη時會有廉價性變 差之傾向。 將上述漆料塗佈於保護薄膜1(或支撐基材3)上之 方法列舉爲刮刀塗佈法、輥塗佈法、噴霧塗佈法、凹版塗 佈法、棒塗佈法、簾流塗佈法等一般習知之方法。 接著劑層2之厚度並無特別限制，較好爲5〜200μηι， 更好爲7〜150μηι，又更好爲10〜ΙΟΟμιη。厚度小於5μιη時 ，難以確保充分之接著力，而有無法使電路基板之凸電極 埋入之傾向，比200μιη厚時不僅不經濟且難以符合半導 體裝置之小型化要求。 支撐基材3列舉爲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、聚乙酸乙烯酯薄膜、聚氯乙烯薄膜、聚醯亞胺薄膜等 塑膠薄膜。另外’支撐基材3可爲使選自上述材料之兩種 以上混合而成者，或亦可爲上述之薄膜經多層化者。 支撐基材3之厚度並無特別限制，較好爲5〜2 5 0μιη。 厚度比5 μπι薄時’半導體晶圓硏削（背面硏磨）時會有 切到支撐基材之可能性，厚度超過250m時不經濟故不佳 〇 支撐基材3較好爲光透過性高者，具體而言較好爲於 5 00〜8 0 Onm之波長區域之最小透過率爲1〇%以上。 又，亦可使用於上述塑膠薄膜（以下有時稱爲「第二 薄膜」）上層合黏著劑層者作爲支撐基材3。 圖2顯示本發明之電路構件連接用接著劑薄片之較佳 -22- 201211188 實施形態之模式剖面圖。圖2所示之電路構件連接用接著 劑薄片11具備具有塑膠薄膜3b與設置於該塑膠薄膜3b 上之黏者劑層3a之支撐基材3’及設置於該黏著劑層3a 上之由本發明之接著劑組成物所組成之接著劑層2，及被 覆接著劑層2之保護薄膜1。 爲了提高第二薄膜3b與黏著劑層3a之密著性，第二 薄膜之表面亦可經鉻酸處理、臭氧暴露、火焰暴露、高壓 電擊暴露' 離子化輻射線處理等化學或物理性處理。 黏著劑層3a較好在室溫下具有黏著力，且對被著體 具有必要之密著力’且較好爲具備藉由輻射線等高能量線 或熱而硬化（亦即，降低黏著力）特性者。黏著劑層3 a 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之厚度通常爲5〜2 Ομπι 左右。 上述之電路構件連接用接著劑薄片10及11可介隔在 於具有相對向焊接接合而成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，用於使電路構件與半 導體元件或半導體元件彼此接著用。該情況下，藉由使電 路構件與半導體元件或半導體元件彼此熱壓著，可抑制孔 洞發生同時以充分接著力接著，且可良好地使電路電極彼 此焊錫接合。據此，可獲得連接信賴性優異之連接體。又 ’電路構件連接用接著劑薄片10及11亦可在使用矽貫通 電極之層合技術中作爲接著劑使用。 以下針對使用電路構件連接用接著劑薄片1 0製造半 -23- 201211188 導體裝置之方法加以說明。 圖3〜圖7爲說明使用本發明之半導體裝置之製造方 法之實施形態之模式剖面圖。本實施形態之半導體裝置之 製造方法具備有下列步驟： (a)準備於主面之一方上具有複數電路電極之半導 體晶圓，在該半導體晶圓之設有電路電極之側設置由本發 明之接著劑組成物所組成之接著劑層之步驟，（b )將半 導體晶圓之設置有電路電極側之相反側予以硏削並進行薄 化半導體晶圓之步驟， (c )切割經薄化之半導體晶圓及接著劑層並將附有 薄膜狀接著劑之半導體元件予以單片化之步驟，與 (d)將附有薄膜狀接著劑之半導體元件之電路電極 焊接接合於半導體元件搭載用支撐構件之電路電極之步驟 〇 本實施形態中之（a )步驟係藉由將上述電路構件連 接用接著劑薄片10之接著劑層2貼合於半導體晶圓之設 有電路電極側上，而設置接著劑層。且，本實施形態之（ d )步驟係利用加熱進行焊接接合，同時亦進行使介隔在 半導體元件與半導體元件搭載用支撐構件之間之薄膜狀接 著劑之硬化。以下參照圖面針對各步驟加以說明。 (a)步驟 胃先’將電路構件連接用接著劑薄片1 0配置在特定 之裝置上’剝離保護薄膜〗。接著，準備於主面之—方上 -24- 201211188 具有複數電路電極20之半導體晶圓A，在該半導體晶圓 A之設有電路電極之側貼合接著劑層2，獲得以支撐基材 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2〇上塗佈焊接接合用焊錫並設置凸塊。又， 亦可在半導體元件搭載用支撐構件之電路電極上設置焊錫 〇 上述（a)步驟中，獲得以支撐基材3/接著劑層2/半 導體晶圓A層合之層合體之方法可使用市售之薄膜貼合 裝置或層合機。爲了在不將孔洞捲入半導體晶圓A中而 貼合接著劑層2，較好於貼合裝置上具備加熱機構及加壓 機構，更好具備真空吸引機構。又電路構件連接用接著劑 薄片1 〇之形狀只要可藉貼合裝置作業之形狀即可，可爲 輥狀或薄片狀，亦可配合半導體晶圓A之外形而加工者 〇 半導體晶圓A與接著劑層2之層合較好在使接著劑 層2軟化之溫度進行。層合溫度較好爲40〜80。(：，更好爲 50〜80°C，又更好爲60~80°C。以未達使接著劑層2軟化之 溫度進行層合時，會發生半導體晶圓A之突出且對電路 電極2 0周邊之埋入不足，成爲捲入孔洞之狀態。該情況 下’容易產生切割時之接著劑層之剝離、拾取時接著劑層 之變形、位置對準時辨識標記之辨識不良、進而因孔洞造 成連接信賴性降低。 (b )步驟 -25- 201211188 接著，如圖4所示，將半導體晶圓A之設置有電路 電極20側之相反側藉由硏削機4予以硏削’使半導體晶 圓薄化。半導體晶圓之厚度可爲例如1〇~300μιη。就半導 體裝置之小型化、薄型化之觀點而言，半導體晶圓之厚度 較好爲 20~100 μιη。 (b)步驟中，半導體晶圓Α之硏削可使用一般背面 硏磨（B/G)裝置進行。於B/G步驟爲了不會厚度不均而 可均勻硏削半導體晶圓A，較好將（a)步驟中之接著劑 層2以不捲入孔洞之方式均勻貼合。 (c )步驟 接著，如圖5(a)所示，將切割之膠帶5貼合於層 合體之半導體晶圓A上，將其配置於特定裝置上並剝離 支撐基材3。此時，支撐基材3具備有黏著劑層3a’且黏 著劑層3 a爲輻射線硬化性時，藉由自支撐基材3側照射 輻射線，使黏著劑層3 a硬化可降低接著劑層2與支撐基 材3之間之接著力。此處，使用之輻射線列舉爲例如紫外 線、電子束、紅外線等。據此可容易地剝離支撐基材3。 支撐基材3剝離後，如圖5 ( b )所示’利用切割鋸6切 割半導體晶圓A及接著劑層2。如此’可將半導體晶圓A 分割成複數之半導體元件A’，將接著劑層2切割成複數 之薄膜狀接著劑2a。 接著，如圖6所示，藉由使切割膠帶5擴張，一邊使 上述切割獲得之半導體元件A ’相互分離’ 一邊以吸附套 -26- 201211188 爪7自切割膠帶5側以針吸附拾取 A’及薄膜狀接著劑2a所組成之貼附 體元件1 2。貼附薄膜狀接著劑之半|| 盤中回收，亦可直接以覆晶固晶安裝 (c )步驟中’將切割膠帶5貼 晶圓A上之作業係使用一般之晶圓 導線架之固定以相同之步驟進行。切 之切割膠帶，亦可使用UV硬化型，： (d )步驟 接著，如圖7所示，使附著薄膜 體元件A ’之電路電極20與搭載半導 8之電路電極22位置對準，使貼附 體元件12與搭載半導體元件用之支; 由該熱壓著，可利用焊接接合使電路 22電性且機械地連接，同時在半導律 體元件用支撐構件8之間形成薄膜狀 〇 熱壓著時之溫度就焊接接合之 200°C以上，更好爲220〜260°C。熱壓 。熱壓著之壓力可爲〇.l〜5MPa。 使用覆晶固晶對電路基板之安裝 電路面上形成之薄膜狀接著劑層2a 粒之電路面上之對準標記，可確認電 突起之由半導體元件 薄膜狀接著劑之半導 !體元件1 2可置於拖 於電路基板上。 合於經硏削之半導體 載置，且可與對切割 割膠帶5可使用市售 亦可爲感壓型。 丨狀接著劑2a之半導 體元件用之支撐構件 薄膜狀接著劑之半導 擦構件8熱壓著。藉 電極20與電路電極 |元件A’與搭載半導 :接著劑2a之硬化物 .觀點而言，較好爲 著時間可爲1〜20秒 可透過半導體晶粒之 確認形成於半導體晶 路基板之搭載位置而 -27- 201211188 實施。 經由以上步驟，獲得半導體裝置3 0。由本發明之接 著劑組成物組成之薄膜狀接著劑之埋入性及硬化後之接著 力優異，同時即使以短時間焊接接合亦可去除焊錫表面上 形成之氧化皮膜，可改善焊錫之潤濕性。據此，半導體裝 置3 0可充分抑制孔洞發生，使電路電極彼此良好地焊接 接合，以充分接著力接著半導體元件A ’與搭載半導體元 件用之支撐構件，獲得耐回焊龜裂性及連接信賴性優異者 [實施例] 以下列舉實施例及比較例更具體說明本發明。但，本 發明並不受限於該等實施例。 (支撐基材之準備） 首先，使用丙烯酸2·乙基己酯與甲基丙烯酸甲酯作 爲主單體，使用丙烯酸羥基乙酯與丙烯酸作爲官能基單體 ，利用溶液聚合法合成丙烯酸共聚物。所得丙烯酸共聚物 之重量平均分子量爲40萬，玻璃轉移溫點爲-3 8°C。相對 於該丙基酸共聚物1〇〇質量份，調配多官能基異氰酸酯交 聯劑（日本Polyurethan工業股份有限公司製造，商品名 「CORONETO HL」）10質量份，調製黏著劑組成物溶液 〇 將所得黏著劑組成物溶液以乾燥時之黏著劑層厚度成 -28- 201211188 爲ΙΟμηι之方式塗佈於聚嫌烴薄膜（〇kamoto股份 司製造，商品名「WNH-2110」，厚度：ΙΟΟμηι) 燥。接著，將第二薄膜的經矽氧系脫模劑表面處理 延伸聚酯薄膜（帝人杜邦薄膜公司製造，商品名「 ’厚度：2 5 μιη」層合於黏著劑層面上。將該貼附 層之層合體於室溫放置一週進行充分老化後，使用 烯烴者作爲支撐基材。 (實施例1 ) <接著劑組成物之調製> 將「ΖΧ 1 3 5 6-2」（東都化成股份有限公司製造 名，苯氧樹脂）100質量份，「1032Η60」（日本 脂股份有限公司製造之商品名，環氧樹脂）1 0 0質 「EPICOTE 82 8」（曰本環氧樹脂公司製造之商品 狀環氧樹脂）60質量份及「ΗΧ3 94 1 ΗΡ」（旭化成 份有限公司製造之商品名，微膠囊型潛在性硬化I 質量份溶解於甲苯與乙酸乙酯之混合溶劑中。將 4 426」（三菱嫘縈股份有限公司製造之商品名，芯 機微粒子）40質量份、進行5μιη分級處理之平 Ιμιη之堇青石粒子（2Mg0.2Al203.5Si02，比重： 膨脹係數：1.5xl(T6/°C，折射率：1.5 7 ) 40 0質量份 ΙΟμιη分級處理之「ADH」（大塚化學公司製造之 ，己二酸二醯肼）40質量份分散於該溶液中，獲 劑漆料。 有限公 上並乾 之二軸 A3 1 70 黏著劑 剝離聚 之商品 環氧樹 量份， 名，液 電子股 y ) mo 「KW- 殼型有 均粒徑 L4，線 、進行 商品名 得接著 -29- 201211188 <電路構件連接用接著劑薄片之製備> 使用輥塗佈器將所得接著劑漆料塗佈於 對苯二甲酸乙二酯（PET )薄膜（帝人杜邦 ’商品名「AH-3」，厚度：50μιη)上，以. 10分鐘’形成厚度25/zm之接著劑層。接 合接著劑層與上述支撐基材中之黏著劑層面 件連接用接著劑薄片。 (實施例2) 除調配「EXL2655」（羅門哈斯公司製 代替接著劑漆料之調製中之「KW-4426」以 例1同樣，獲得電路構件連接用接著劑薄片 (實施例3 ) 除調配「2,2-雙（羥基甲基）丙酸」（ 公司製造，以下簡稱爲「B ΗΡΑ」）代替接 製中之「ADH」以外，餘與實施例1同樣， 連接用接著劑薄片。 (實施例4)C -15- 201211188 The adhesive layer 2 of the formed article has an increased linear expansion coefficient and a decreased elastic modulus. As a result, it is easy to reduce the reliability of connection between the semiconductor die after pressing and the substrate, and it is also difficult to obtain a hole suppressing effect at the time of connection. On the other hand, when the content of the component (D) exceeds 200 parts by mass, the melt viscosity of the adhesive composition increases, and the interface between the semiconductor crystal grains and the adhesive layer 2 or the interface between the circuit substrate and the adhesive layer 2 The wetness is lowered, and the pores are likely to be left due to insufficient peeling or embedding. (E) organic fine particles are listed as containing, for example, an acrylic resin, a decyloxy resin, a butadiene rubber, a polyester, a polyurethane, a polyvinyl butyral, a polyarylate, a polymethyl methacrylate, an acrylic rubber A copolymer of a polystyrene, NBR, SBR, a siloxane 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 from the viewpoint of dispersibility, stress relaxation, and adhesion of the adhesive composition. The organic fine particles are exemplified by an alkyl (meth)acrylate-butadiene-styrene copolymer, an alkyl (meth)acrylate-oxime copolymer, a oxime-(meth)acrylic copolymer or a composite. More than one kind of thing. Here, the "organic fine particles having a molecular weight of 1,000,000 or more or the organic fine particles having a three-dimensional crosslinked structure" are ultrahigh molecular weight, so that they lack solubility in a solvent, or have a three-dimensional network structure, so that they lack solubility in a solvent. . Further, as the (E) component, an organic fine particle having a core-shell type structure and a core layer and a shell layer composition may be used. As the core-shell type organic fine particles, specifically, particles of an acrylic resin are grafted onto an acrylic copolymer by using a ruthenium-acrylic rubber as a core and an acrylic resin as a shell particle. -16- 201211188 (E) Since the component has a crosslinked structure or an ultrahigh molecular weight resin, it is not dissolved in an organic solvent, so that the particle shape can be maintained in the adhesive composition. Therefore, the component (E) can be dispersed in an island shape in the cured adhesive layer 2, and the strength of the bonded body can be maintained at a high level. The component (e) is a function as an impact-relieving agent containing stress relaxation properties. The average particle diameter of the component (E) is preferably from 0.1 to 2 μm. When the average particle diameter of the (Ε) component is less than 0.1 μm, the melt viscosity of the adhesive composition increases, which hinders the solder wettability at the time of joining, and when it exceeds 2 μm, the effect of reducing the melt viscosity is reduced. It is difficult to obtain a hole suppression effect when it is connected. The amount of the (Ε) component to be added is preferably 100 parts by mass based on the total of the components (A), (B) and (C) in order to impart a stress relaxation effect to the adhesion of the adhesive layer 2 at the time of connection. It is 5 to 20 parts by mass. When the amount of the component (E) is less than 5 parts by mass, it is difficult to achieve the effect of suppressing the pores at the time of connection, and it is also difficult to exhibit the tendency of the stress relaxation effect. When the content exceeds 20% by mass, the fluidity is low, so that the solder is used. The wettability is lowered to cause residual pores, and the elastic modulus of the cured product is too low, and the connection reliability tends to decrease. (F) The powder having a maximum particle diameter of 25 μηη or less in a solid at room temperature is a compound containing at least one compound selected from the group consisting of a compound having a carboxyl group, a compound having a methylol group, and a hydrazine compound. The component (F) has a function as a solder wettability modifier (hereinafter, the component (F) is a "solder wettability modifier"). That is, the '(F) component has a melting point lower than the melting point of the solder -17-201211188, and the solder wettability of the adhesive layer 2 can be improved by removing the oxide of the metal surface of the solder surface and the circuit electrode after melting. . The component (F) is exemplified by, for example, acetyl salicylic acid, benzoic acid, benzilic acid, adipic acid, sebacic acid, benzyl benzoic acid, malonic acid, 2,2-dual ( Hydroxymethyl)propionic acid, salicylic acid, m-hydroxybenzoic acid, succinic acid, 2,6-dimethoxymethyl-p-cresol, bismuth benzoate, carboxyindole, diammonium malonate, Diterpenic succinate, diterpene gluconate, bismuth salicylate, diammonium diamine diacetate, diterpenic itaconate, triterpenoid citrate, thiocarboxylate, benzophenone Bismuth, 4,4'-oxybisbenzenesulfonate and diammonium adipate. However, as long as it is a solid at room temperature, a compound having a carboxyl group, a compound having a methylol group or a hydrazine compound, it is not limited to these. From the viewpoint of improving the dispersibility of the adhesive layer 2, it is preferred to use the ruthenium to pulverize the compounds, and after micronizing, the particles having a large particle size are removed by a filter of at least 25 μm. The maximum particle diameter of the component (F) is preferably 20 μηη or less. Further, the minimum particle diameter of the component (F) is about Ο.ΟΙμιη. The melting point of the component (F) is preferably from 10 ° C to more preferably from 130 to 200 t, more preferably from 140 to 180 ° C. When the melting point of the component (F) is less than 100 t:, the powder is dissolved at a drying temperature at the time of film formation, and reacts with the thermosetting component to impair the preservability. The amount of the component (F) to be added is preferably from 1 to 20 parts by mass, more preferably from 1 to 10 parts by mass, per part by mass of the adhesive composition. When the amount of the component (F) is less than 1 part by mass, the effect of improving the wettability is insufficient, and even if the amount is more than 20 parts by mass, the effect of improving the solder wettability is saturated, so that the component becomes excessive. -18- 201211188 In the following composition, various coupling agents may be added in order to improve the surface bonding of the dissimilar materials and increase the bonding strength in order to modify the surface of the inorganic tanning material. The coupling agent is exemplified by, for example, a decane-based, titanium-based or aluminum-based coupling agent. Among them, the effect is high, and w is preferably a sand-system coupling agent. The sanding system coupling agent is exemplified by, for example, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, and γ-mercaptopropyltrimethoxy. Baseline, γ-mercaptopropyltriethoxyphthalate, 3-aminopropylmethyldiethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxy Decane. These may be used alone or in combination of two or more. An ion scavenger may be added to the subsequent composition "in order to adsorb ionic impurities and improve the insulating reliability at the time of moisture absorption". The ion trapping agent is not particularly limited. An inorganic ion adsorbent such as a compound known as a copper damage preventive agent, a lanthanide-based or a lanthanide-based magnesium aluminum compound, which is used to prevent copper ionization and elution, such as a triazine thiol compound or a bisphenol-based reducing agent, is exemplified. In order to suppress temperature change due to temperature change or expansion due to heat absorption and the like after the connection of the semiconductor crystal grains and the circuit board, the adhesive composition achieves high connection reliability, and the cured adhesive layer 2 is at 40 to 1 0 〇. The linear expansion coefficient of (: is preferably 60xl0'6/°C or less, more preferably 55xl (T6/t: below, more preferably 5 0 X 1 0 _6 / °C or less) 'hardened adhesive layer 2 The coefficient of linear expansion exceeds 60xl (at the time of T6/°C, there is a possibility that the connection between the connection terminal of the semiconductor die and the wiring of the circuit board cannot be maintained due to temperature change after mounting or swelling due to heat absorption and moisture absorption. Further, the adhesive member sheet 10 for circuit member connection may contain -19-201211188 conductive particles in the adhesive composition constituting the adhesive layer 2 to form an anisotropic conductive adhesive film (ACF), but preferably contains no conductive material. The particles are a non-conductive adhesive film (NCF). The adhesive layer 2 formed of the adhesive composition is at 250. (: After heating for 1 sec, it is measured by differential scanning calorimetry (hereinafter referred to as "DSC"). The reaction rate is preferably 60% or more, more preferably 70% or more. Further, after the substrate member composition sheet is placed at room temperature for 14 days, the reaction rate of the adhesive layer 2 measured by DSC is better. Up to 1%. According to this, the adhesive composition of the present invention can be used for connection. A film-like adhesive which is excellent in reactivity and excellent in stability and stability. The visible light transmittance of the adhesive layer 2 is preferably 5% or more when it is not cured, and the visible light transmittance is better than 8%, and the visible light is better. The transmittance is 10% or more. When the visible light transmittance is less than 5%, the identification of the crystal-clearing crystal cannot be recognized, and there is a tendency that the position alignment operation cannot be performed. On the other hand, the upper limit of the visible light transmittance is not The visible light transmittance can be measured using a U-3310 spectrophotometer manufactured by Hitachi. For example, the baseline correction is based on a PET film manufactured by DuPont DuPont (Purex's transmittance at 555 nm of 86.03%) with a film thickness of 50 μm. After the measurement, the adhesion layer in the visible light region of 400 to 80 Å was measured after forming the adhesive layer 2 on the PET film at a thickness of 25 μm. The relative intensity of the wavelength of the halogen light source and the light guide used in the flip chip solidification was 5 50~600nm is the strongest, so the transmittance of the adhesive layer 2 is compared using the transmittance of 550 nm in the present specification. The second layer 2 can dissolve the above-mentioned adhesive composition of the present invention. Or it is dispersed in a solvent to form a paint, and the paint is applied to a protective film (hereinafter referred to as "first film" on -20 to 201211188) 1 and formed by removing the solvent by heating. Subsequently, at room temperature The support substrate 3 is laminated on the adhesive layer 2 to 60 ° C to obtain the adhesive member sheet 1 for circuit member connection of the present invention. Further, the adhesive layer 2 can also be applied by applying the above-mentioned paint to the adhesive layer 2 The support substrate 3 is formed by removing the solvent by heating. The solvent to be used is not particularly limited, but it is preferably determined by the boiling point in consideration of the volatility at the time of formation of the adhesive layer. Specifically, in terms of difficulty in promoting hardening of the adhesive layer at the time of formation of the adhesive layer, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl A solvent having a relatively low boiling point such as ethyl ketone, acetone, methyl isobutyl ketone, toluene or xylene is preferred. These solvents may be used singly or in combination of two or more kinds of ruthenium protective films. For example, plastics such as polyethylene terephthalate, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethyl pentylene film, etc. may be used. film. From the viewpoint of the releasability, a film having a low surface energy composed of a fluororesin such as a polytetraethylene film is preferably used as the protective film 1. In order to improve the releasability of the protective film 1, the surface of the protective film 1 on which the adhesive layer 2 is formed is preferably treated with a release agent such as a ruthenium-based release agent, a fluorine-based release agent or a long-chain alkyl acrylate release agent. As for the marketer, "A-63" (release agent: modified sand oxide) manufactured by Teijin DuPont Film Co., Ltd. and "A-3 1" (release agent: Pt system) . The thickness of the protective film 1 is preferably from 10 to 100 μm, more preferably from 10 to 75 μm, most preferably from 25 to 50 μm. When the thickness is less than 1 μm, the protective film tends to be cracked when -21 - 201211188 is applied, and the price tends to be deteriorated when it exceeds ΙΟΟμηη. The method of applying the above paint to the protective film 1 (or the support substrate 3) is exemplified by a doctor blade coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. A commonly known method such as cloth method. The thickness of the layer 2 is not particularly limited, and is preferably 5 to 200 μm, more preferably 7 to 150 μm, still more preferably 10 to ΙΟΟμηη. When the thickness is less than 5 μm, it is difficult to secure sufficient adhesion, and the convex electrode of the circuit board cannot be buried. When it is thicker than 200 μm, it is not uneconomical and it is difficult to meet the requirements for miniaturization of the semiconductor device. The support substrate 3 is exemplified by, for example, a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyvinyl acetate film, a polyvinyl chloride film, and a poly Plastic film such as yttrium imide film. Further, the support substrate 3 may be a mixture of two or more selected from the above materials, or may be a multilayered film. The thickness of the support substrate 3 is not particularly limited, but is preferably 5 to 2 50 μm. When the thickness is thinner than 5 μπι, the semiconductor wafer is diced (back honing), and the substrate may be cut to the support substrate. When the thickness exceeds 250 m, it is uneconomical. Therefore, the support substrate 3 preferably has high light transmittance. Specifically, it is preferable that the minimum transmittance in the wavelength region of 500 to 80 Onm is 1% or more. Further, as the support substrate 3, a laminate film of the above-mentioned plastic film (hereinafter sometimes referred to as "second film") may be used. Fig. 2 is a schematic cross-sectional view showing an embodiment of the adhesive member for connecting circuit members of the present invention, which is preferably a -22-201211188 embodiment. The circuit member connecting adhesive sheet 11 shown in FIG. 2 is provided with a support substrate 3' having a plastic film 3b and an adhesive layer 3a provided on the plastic film 3b, and the present invention is provided on the adhesive layer 3a. The adhesive layer 2 composed of the adhesive composition and the protective film 1 coated with the adhesive layer 2. In order to improve the adhesion of the second film 3b to the adhesive layer 3a, the surface of the second film may be subjected to chemical or physical treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment or the like. The adhesive layer 3a preferably has an adhesive force at room temperature and has a necessary adhesion to the object', and preferably has a high energy line or heat by radiation or the like (ie, reduces adhesion). Characteristic. The adhesive layer 3 a 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 usually about 5 to 2 Ομπι. The above-described circuit member connecting adhesive sheets 10 and 11 may be interposed between the circuit member having the oppositely soldered and joined circuit electrodes and the semiconductor element or between the semiconductor elements for making the circuit member and the semiconductor element or The semiconductor elements are used next to each other. In this case, by heating the circuit member and the semiconductor element or the semiconductor element with each other, it is possible to suppress the occurrence of the hole while sufficiently adhering the force, and it is possible to satisfactorily solder the circuit electrodes to each other. According to this, a connector having excellent connection reliability can be obtained. Further, the adhesive member sheets 10 and 11 for connecting the circuit members can also be used as an adhesive in a lamination technique using a through-electrode. Hereinafter, a method of manufacturing a semi--23-201211188 conductor device using the adhesive member sheet 10 for circuit member connection will be described. 3 to 7 are schematic cross-sectional views illustrating an embodiment of a method of fabricating a semiconductor device of the present invention. The method of manufacturing a semiconductor device of the present embodiment includes the following steps: (a) preparing a semiconductor wafer having a plurality of circuit electrodes on one side of the main surface, and providing a circuit electrode on the side of the semiconductor wafer. a step of forming an adhesive layer of the composition of the agent, (b) a step of dicing the semiconductor wafer on the opposite side of the circuit electrode side and thinning the semiconductor wafer, and (c) cutting the thinned semiconductor a step of singulating a wafer and an adhesive layer with a semiconductor element having a film-like adhesive, and (d) soldering and bonding a circuit electrode of a semiconductor element with a film-like adhesive to a supporting member for mounting the semiconductor element Step of the circuit electrode, in the step (a) of the present embodiment, by attaching the adhesive layer 2 of the above-mentioned circuit member connecting adhesive sheet 10 to the circuit electrode side of the semiconductor wafer, and then providing Agent layer. In the step (d) of the present embodiment, the film-like adhesive interposed between the semiconductor element and the supporting member for mounting the semiconductor element is cured by solder bonding. The steps will be described below with reference to the drawings. (a) Step First, the circuit member connecting adhesive sheet 10 is placed on a specific device to peel off the protective film. Next, the semiconductor wafer A having the plurality of circuit electrodes 20 is prepared on the main surface, and the adhesive layer 2 is bonded to the side of the semiconductor wafer A on which the circuit electrodes are provided to obtain the support substrate. 3/Bladding layer 2/Semiconductor wafer A laminated laminate (see Fig. 3). A solder for solder bonding is applied to the circuit electrode 2A and a bump is provided. Further, it is also possible to provide a solder crucible on the circuit electrode of the semiconductor element mounting support member. In the above step (a), a method of obtaining a laminate in which the support substrate 3 / the adhesive layer 2 / the semiconductor wafer A is laminated can be used. A commercially available film bonding apparatus or laminator. In order to bond the adhesive layer 2 without entanglement of the holes in the semiconductor wafer A, it is preferable to provide a heating mechanism and a pressurizing mechanism to the bonding apparatus, and it is preferable to provide a vacuum suction mechanism. Further, the shape of the adhesive member sheet 1 电路 for the circuit member connection may be a shape of a roll-on or a sheet, and may be a shape of a roll or a sheet, and may be combined with a shape of the semiconductor wafer A to process the semiconductor wafer A and The lamination of the layer 2 is preferably carried out at a temperature at which the adhesive layer 2 is softened. The lamination temperature is preferably from 40 to 80. (:, preferably 50 to 80 ° C, more preferably 60 to 80 ° C. When lamination is performed at a temperature at which the adhesive layer 2 is not softened, the semiconductor wafer A is protruded and the circuit electrode is formed In the case where the periphery is insufficiently buried, the hole is entangled in the hole. In this case, it is easy to cause peeling of the adhesive layer during dicing, deformation of the adhesive layer at the time of picking, identification of the identification mark at the time of alignment, and further, the hole is formed. (b) Step -25 - 201211188 Next, as shown in FIG. 4, the opposite side of the side of the semiconductor wafer A on which the circuit electrode 20 is provided is boring by the boring machine 4 to make the semiconductor crystal The thickness of the semiconductor wafer may be, for example, 1 to 300 μm. The thickness of the semiconductor wafer is preferably 20 to 100 μm from the viewpoint of miniaturization and thinning of the semiconductor device. (b) In the step, The boring of the semiconductor wafer can be performed using a general back honing (B/G) device. In the B/G step, the semiconductor wafer A can be uniformly punctured in order not to have uneven thickness, preferably in step (a). The adhesive layer 2 is uniformly bonded so as not to be entangled in the holes. Step Next, as shown in FIG. 5(a), the cut tape 5 is bonded to the laminated semiconductor wafer A, placed on a specific device, and the support substrate 3 is peeled off. At this time, the support substrate is supported. 3, when the adhesive layer 3a' is provided and the adhesive layer 3a is radiation curable, the adhesive layer 3a is hardened by the radiation from the side of the support substrate 3 to lower the adhesive layer 2 and the support substrate. Here, the radiation used is exemplified by ultraviolet rays, electron beams, infrared rays, etc. According to this, the support substrate 3 can be 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 are cut by the dicing saw 6. Thus, the semiconductor wafer A can be divided into a plurality of semiconductor elements A', and the adhesive layer 2 can be cut into a plurality of film-like adhesives 2a. As shown in FIG. 6, by expanding the dicing tape 5, the semiconductor element A' obtained by the dicing is separated from each other, and the accommodating sleeve -26-201211188 is used to pick up A' from the side of the dicing tape 5 by the needle. Attachment element 1 2 composed of film-like adhesive 2a. Half of the film-like adhesive || Recycling in the tray, or directly in the flip-chip mounting (c) step - The operation of attaching the dicing tape 5 to the wafer A is the same as that of the conventional wafer lead frame. The step of cutting. The dicing tape is cut, and a UV curing type can also be used. (d) Step Next, as shown in FIG. 7, the circuit electrode 20 of the attached film body member A' and the circuit electrode 22 on which the semiconductor guide 8 is mounted are placed. Alignment, the attached body element 12 and the support for mounting the semiconductor element; by the heat pressing, the circuit 22 can be electrically and mechanically connected by solder bonding, and between the support member 8 for the semi-guide body element When the film is formed, the temperature at the time of hot pressing is 200 ° C or more, more preferably 220 to 260 ° C. Hot pressing. The pressure of the hot pressing can be 〇.l~5MPa. The semi-conducting element 1 of the semiconductor element film-like adhesive can be confirmed by the alignment mark on the circuit surface of the film-like adhesive layer 2a formed on the mounting circuit surface of the circuit board by the flip chip bonding. 2 can be placed on the circuit board. It can be used in conjunction with boring semiconductors, and can be used with the cut-cut tape 5 or commercially available or pressure-sensitive. The support member for the semiconductor element of the bismuth adhesive 2a The semi-conductive member 8 of the film-like adhesive is heat-pressed. By means of the electrode 20 and the circuit electrode | the element A' and the mounted semiconductor: the cured material of the adhesive 2a, it is preferably formed in the semiconductor crystal substrate by the confirmation of the semiconductor crystal by a time of 1 to 20 seconds. The mounting position is -27-201211188. Through the above steps, the semiconductor device 30 is obtained. The film-like adhesive composed of the adhesive composition of the present invention is excellent in embedding property and adhesion after curing, and the oxide film formed on the surface of the solder can be removed even by soldering for a short time, thereby improving the wettability of the solder. . As a result, the semiconductor device 30 can sufficiently suppress the occurrence of voids, and the circuit electrodes can be soldered and joined to each other with good adhesion, and the semiconductor element A' and the supporting member for mounting the semiconductor element can be sufficiently adhered to obtain reflow-resistant cracking resistance and connection reliability. The present invention is more specifically described below by way of examples and comparative examples. However, the invention is not limited to the embodiments. (Preparation of support substrate) First, acrylic acid copolymer was 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 group monomers. The obtained acrylic copolymer had a weight average molecular weight of 400,000 and a glass transition temperature of -38 °C. 10 parts by mass of a polyfunctional isocyanate crosslinking agent (manufactured by Polyurethan Industrial Co., Ltd., trade name "CORONETO HL") was prepared in an amount of 1 part by mass based on the propyl acid copolymer, and a solution of the adhesive composition was prepared. The obtained adhesive composition solution is applied to a polyaniline film (manufactured by 〇kamoto Co., Ltd., trade name "WNH-2110", thickness: ΙΟΟμηι) by drying the adhesive layer thickness to -28-201211188 as ΙΟμηι. . Next, the surface-treated stretched polyester film of the second film was coated with a polyester film (manufactured by Teijin DuPont Film Co., Ltd., trade name "Thickness: 25 μm" to be laminated on the adhesive layer. The laminate was allowed to stand at room temperature for one week and sufficiently aged, and an olefin was used as a support substrate. (Example 1) <Preparation of an adhesive composition> " 将1 3 5 6-2" (Dongdu Chemical Co., Ltd.) Ltd. Manufacturing name, phenoxy resin) 100 parts by mass, "1032Η60" (trade name manufactured by Nippon Fatty Co., Ltd., epoxy resin) 100 quality "EPICOTE 82 8" (product of 环氧树脂本树脂树脂公司) 60 parts by mass of epoxy resin and "ΗΧ3 94 1 ΗΡ" (trade name manufactured by Asahi Kasei Co., Ltd., microcapsule type latent curing I mass part is dissolved in a mixed solvent of toluene and ethyl acetate. 4 426 (Mercury name, core machine microparticles manufactured by Mitsubishi Rayon Co., Ltd.) 40 parts by mass of cordierite particles of 5 μm η graded treatment (2Mg0.2Al203.5SiO2, specific gravity: expansion coefficient: 1.5xl (T6/) C, refractive index: 1.5 7 ) 40 parts by mass of ADμιη classified "ADH" (manufactured by Otsuka Chemical Co., Ltd., diammonium adipate) 40 parts by mass dispersed in the solution to obtain a paint. And the dry two-axis A3 1 70 adhesive peeling off the product of the epoxy tree, the name, the liquid electron stock y) mo "KW- shell type has an average particle size L4, the line, the trade name is followed by -29- 201211188 <Preparation of adhesive sheet for connecting circuit members> The obtained adhesive paint was applied to a polyethylene terephthalate (PET) film (manufactured by DuPont's trade name "AH-3" using a roll coater. Thickness: 50 μm), forming an adhesive layer having a thickness of 25/zm in 10 minutes. Bonding the adhesive layer to the adhesive sheet for bonding the adhesive layer member in the above supporting substrate. (Example 2) "EXB2655" ("KW-4426" in the preparation of the adhesive paint of Rohm and Haas Company) was obtained in the same manner as in Example 1 except that the adhesive sheet for connecting the circuit member was obtained (Example 3) except that "2,2-bis(hydroxyl) was formulated. Methyl)propionic acid (manufactured by the company, hereinafter referred to as "B Η Instead of the bonding system in "ADH" Α ") except that in Example 1 with the remainder, connecting adhesive sheet (Example 4)
除分別調配「EXL2655」代替接著劑漆 「KW-4426」，調配「ΒΗΡΑ」代替「ADH 實施例1同樣，獲得電路構件連接用接著劑 第一薄膜的聚 薄膜公司製造 70°C烘箱乾燥 著，於常溫貼 ，獲得電路構 造之商品名） 外，餘與實施 東京化成工業 著劑漆料之調 獲得電路構件 料之調製中之 」以外，餘與 薄片。 •30- 201211188 (實施例5 ) 除調配「2,6-二甲氧基甲基對甲酚」（旭有機材料公_ 司製造之商品名，「26DMPC」）代替接著劑漆料之調製 中之「AD Η」以外，餘與實施例1同樣，獲得電路構件連 接用接著劑薄片。 (實施例6) 除調配「EXL265 5」代替接著劑漆料之調製中之「 KW-4426」，以「260DMPC」代替「ADH」以外，餘與實 施例1同樣，獲得電路構件連接用接著劑薄片。 (比較例1 ) 除未調配接著劑漆料之調製中之「ADH」以外，餘與 實施例1同樣，獲得電路構件連接用接著劑薄片。 (比較例2) 除調配「EXL2 65 5」代替接著劑漆料之調製中之「 KW-4426」，且未調配「ADH」以外，餘與實施例1同樣 ’獲得電路構件連接用接著劑薄片。 [接著劑層之評價] (線膨脹係數測定） 將實施例及比較例中獲得之電路構件連接用接著劑薄 片放置於設定爲18(TC之烘箱中3小時，進行加熱硬化。 -31 - 201211188 自支撐基材剝離加熱硬化後之接著劑層，製作30mmx2mm 大小之試驗片。使用 Seiko Instrument公司製造之「 TMA/SS6100」（商品名），將上述試驗片以夾具間成爲 20mm之方式裝設於裝置內，以測定溫度範圍：20~3 00°C ，升溫速度：5 °C /分鐘，荷重條件：對試驗片之剖面積爲 0.5 MPa之壓力之條件，以拉伸試驗模式進行熱機械分析 ，測定線膨脹係數。 (反應率測定） 於鋁製測定容器中稱量2〜10mg之實施例及比較例中 獲得之電路構件連接用接著劑薄片中之接著劑層，使用 Perkin Elmer公司製造之DSC (差分掃描卡計）「Pylisl 」（商品名），測定以升溫速度 20°C/分鐘升溫至 3 0〜3 0 0°C之發熱量，以此作爲初期發熱量。接著，以夾持 於分離器之熱電偶對熱壓著裝置之加熱頭進行溫度確認， 設定成在1 〇秒後達到25 0°C之溫度。以該加熱頭設定，將 電路構件連接用接著劑薄片夾持在分離器中並加熱20秒 ，獲得施以與熱壓著時同樣之加熱處理之狀態的接著劑層 。亦對加熱處理後之接著劑層同樣測定發熱量，以其作爲 加熱後之發熱量。且，亦同樣測定電路構件連接用接著劑 薄片在室溫（20〜25 °C )下保存14天後之接著劑層之發熱 量，以其作爲保存後之發熱量。由所得發熱量以下式計算 出反應率（％)。 -32- 201211188 反應率（％)=(初期發熱量-加熱後之發 後之發熱量）/(初期發熱量）XI 〇〇 <半導體裝置之製作及評價> 使用上述獲得之電路構件連接用接著劑薄 順序製作半導體裝置且進行評價。結果示於表 (對半導體晶圓之貼合） 使形成鍍金凸塊之半導體晶圓（直徑6 725 μη〇 ，以使凸塊側朝上搭載於JCM製造力 Attach)薄膜安裝機之加熱至80°C之吸附台上 件連接用接著劑薄片切斷成2 OOmmx 2 00mm， 薄膜的第一薄膜之接著劑層朝向半導體晶圓之 不使空氣捲入之方式自半導體晶圓端以貼晶安 輥擠出並層合。經層合後，沿著晶圓之外形切 露出部分。 (半導體晶圓背面之背面硏磨及支撐基材之剝 以DISCO股份有限公司製造之背面硏磨 述電路構件連接用接著劑薄片與半導體晶圓（ )之層合體進行半導體晶圓背面之背面硏磨 1 5 0 μπι爲止。隨後，以使經背面硏磨之半導體 狀態設置於JCM製造之貼晶薄膜安裝機之吸 室溫與切割導線架同時貼附Adeca製切割膠帶 熱量或保存 片，以下列 英吋，厚度 L貼晶（D i e 。將電路構 以去除保護 凸塊側，以 裝機之貼附 斷接著劑之 離） 裝置，將上 厚度6 2 5 μ m 至厚度成爲 晶圓向上之 附台上，在 r AD80H」 -33- 201211188 。接著，將日東電工製造之背面硏磨膠帶剝離膠帶貼附於 支撐基材上，以1 80度剝離拉開僅剝離支撐基材。 (切割） 以 DISCO股份有限公司製造之全自動切割鋸「 DFD636 1」將固定於上述切割導線架上之貼附接著劑層之 半導體晶圓切割成l〇mmxlOmm。切割後，經洗淨且甩開 水分後，自切割膠帶側進行UV照射後，拾取經單片化之 貼附接著劑之半導體晶粒。 (壓著） 使貼附接著劑之半導體晶粒，以松下電器產業製之覆 晶黏合機「FCB3」於在與凸塊對向之位置具有形成有以 SnAgCu作爲構成成分之電路的玻璃環氧樹脂基板上進行 定位後，在250t：、〇.5MPa熱壓著10秒，獲得半導體裝 置。 評價如上述製作之半導體裝置中之薄膜狀接著劑之埋 入性及連接電阻。接著，將製作之半導體裝置於85°C、 60%RH之恆溫恆濕器中放置168小時使吸濕，且暴露於 設定在260°C之回焊爐中三次。暴露後，確認連接電阻及 連接部份之界面狀態。 <壓著後之埋入性> 以曰立建機製超音波.探傷裝置（SAT)視察接著劑層 -34- 201211188 之貼合狀態，基於下列基準進行評價。 A :未觀察到剝離、孔洞 B :觀察到剝離、孔洞 <回焊後之連接性> 以日立建機製超音波探傷裝置（SAT )視察接著劑層 之回焊後之連接狀態，基於下列基準進行評價。 A :未觀察到剝離 B :觀察到剝離 <連接電阻> 針對製作之半導體裝置，使用數位多功能計（In addition, "EXL2655" was added instead of the adhesive paint "KW-4426", and "ΒΗΡΑ" was added instead of "ADH. In the same manner as in Example 1, the first film of the adhesive for connecting the circuit components was obtained, and the oven was dried at 70 ° C. In addition to the use of the Tokyo Chemical Industry Industrial Coatings to obtain the circuit component materials, the balance and the sheet are obtained. •30-201211188 (Example 5) In addition to the preparation of "2,6-dimethoxymethyl-p-cresol" (trade name manufactured by Asahi Organic Materials Co., Ltd., "26DMPC") instead of the adhesive paint In the same manner as in Example 1, except for "AD Η", an adhesive sheet for connecting a circuit member was obtained. (Example 6) An adhesive for connecting a circuit member was obtained in the same manner as in Example 1 except that "EXB265 5" was used instead of "KW-4426" in the preparation of the adhesive paint, and "260DMPC" was used instead of "ADH". Sheet. (Comparative Example 1) An adhesive sheet for connecting a circuit member was obtained in the same manner as in Example 1 except that "ADH" in the preparation of the adhesive paint was not prepared. (Comparative Example 2) The same procedure as in Example 1 was carried out except that "EXL2 65 5" was used instead of "KW-4426" in the preparation of the adhesive paint, and the adhesive sheet for connecting the circuit member was obtained. . [Evaluation of the adhesive layer] (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 set to 18 (TC for 3 hours, and heat-hardened. -31 - 201211188 The self-supporting substrate was peeled off from the adhesive layer after heat curing to prepare a test piece having a size of 30 mm x 2 mm. The test piece was set to 20 mm between the jigs using "TMA/SS6100" (trade name) manufactured by Seiko Instrument Co., Ltd. In the device, the temperature range is 20~3 00 °C, the heating rate is 5 °C / min, the load condition is: the condition of the pressure of the test piece is 0.5 MPa, and the thermomechanical analysis is carried out in the tensile test mode. (Measurement of the coefficient of linear expansion) (Measurement of the reaction rate) The adhesive layer in the adhesive sheet for connecting the circuit member obtained in the examples and the comparative examples obtained by weighing 2 to 10 mg in an aluminum measuring container was manufactured by Perkin Elmer Co., Ltd. DSC (Differential Scanning Card Meter) "Pylisl" (trade name), measured as the initial calorific value by heating up to 30 °C to 30 °C at a temperature increase rate of 20 °C / min. The temperature of the heating head of the hot pressing device is confirmed by the thermocouple clamped on the separator, and is set to reach a temperature of 25 ° C after 1 〇 second. The circuit head is connected by the heating head setting. The sheet was held in a separator and heated for 20 seconds to obtain an adhesive layer in the same state as in the heat treatment at the time of hot pressing. The calorific value was also measured for the adhesive layer after the heat treatment, and was used as a heating. In the same manner, the calorific value of the adhesive layer after storage of the adhesive sheet for connecting the circuit member at room temperature (20 to 25 ° C) for 14 days was measured as the calorific value after storage. The obtained calorific value is calculated by the following formula: -32 - 201211188 Reaction rate (%) = (initial calorific value - calorific value after heating) / (initial calorific value) XI 〇〇 <Semiconductor device Production and Evaluation> The semiconductor device was fabricated and evaluated in the order of the thinner for connecting the circuit member to be obtained as described above. The results are shown in the table (bonding to the semiconductor wafer). The semiconductor wafer on which gold-plated bumps are formed (diameter 6) 725 μ 〇 搭载 搭载 搭载 搭载 搭载 搭载 搭载 搭载 搭载 搭载 搭载 搭载 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) J J J J J J J The layer of the agent is extruded and laminated from the end of the semiconductor wafer to the semiconductor wafer by means of a wafer roll. After lamination, the exposed portion is formed along the outside of the wafer. The back surface honing and the support substrate are peeled off by the back side of the DISCO Co., Ltd. The circuit member is connected with the laminate of the semiconductor wafer ( ) and the back surface of the semiconductor wafer is honed 1 5 0 μπι until. Subsequently, the Adeca dicing tape heat or the holding sheet is attached to the room temperature and the cut lead frame of the paste film mounting machine manufactured by JCM in the semiconductor state of the back honing, and the thickness is L in the following inches. (Die. The circuit is configured to remove the protective bump side, and the attached device is attached to the adhesive.) The device has an upper thickness of 6 2 5 μm to the thickness of the wafer on the attached stage, at r AD80H" -33- 201211188. Next, the back honing tape peeling tape manufactured by Nitto Denko was attached to the support substrate, peeled off at 180 degrees, and only the support substrate was peeled off. (Cut) The semiconductor wafer attached to the adhesive layer fixed to the above-mentioned cutting lead frame was cut into l〇mmxlOmm by a fully automatic cutting saw "DFD636 1" manufactured by DISCO Co., Ltd. After the dicing, after washing and rinsing the water, after UV irradiation from the side of the dicing tape, the singulated semiconductor granules of the affixing adhesive are picked up. (Crimping) The semiconductor die to which the adhesive is attached is a glass epoxy having a circuit formed with SnAgCu as a constituent component at a position opposed to the bump at a position of the flip chip bonding machine "FCB3" manufactured by Matsushita Electric Industrial Co., Ltd. After positioning on the resin substrate, it was heat-pressed at 250 t:, 〇. 5 MPa for 10 seconds to obtain a semiconductor device. The embedding property and the connection resistance of the film-form adhesive in the semiconductor device produced as described above were evaluated. Next, the fabricated semiconductor device was placed in a thermo-hygrostat at 85 ° C, 60% RH for 168 hours to absorb moisture, and exposed to a reflow furnace set at 260 ° C three times. After exposure, confirm the connection resistance and the interface state of the connection part. <Embeddedness after pressing> The evaluation state of the ultrasonic layer. flaw detection device (SAT) inspection adhesive layer -34-201211188 was evaluated based on the following criteria. A: no peeling was observed, hole B: peeling was observed, hole <connectivity after reflowing> The connection state of the adhesive layer after the reflow was inspected by the Hitachi Construction Mechanism Ultrasonic Flaw Detector (SAT), based on the following Benchmarks are evaluated. A: no peeling was observed B: peeling was observed <connection resistance> For the fabricated semiconductor device, a digital multimeter was used (
Advantest公司製造，商品名）測定壓著後之連接電阻及 回焊後之連接電阻，基於下列基準進行評價。 (壓著後之連接電阻） A :試驗所使用之安裝TEG之全部端子（176端子） 連結之電阻値爲7〜10Ω B :未獲得全部端子連結之電阻，或全部端子連結之 電阻値大於1 〇 Ω (回焊後之連接電阻） A :相對於壓著後之連接電阻値爲20%以內之電阻上 升 ς -35- 201211188 B:相對於壓著後之連接電阻超過20 %之電阻上升 <溫度循環試驗> 將上述回焊後之半導體裝置以-55°C歷時30分鐘及在 125t歷時30分鐘作爲一次循環投入於溫度循環試驗’評 價在試驗機內有無連接電阻維持。可通電之循環數示於表 [表1] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 比較例 1 比較例 2 熱可塑性 樹脂 ZX1356—J2 100 100 100 100 100 100 100 100 熱硬化性 樹脂 1032H60 100 100 100 100 100 100 100 100 60 60 60 60 60 60 60 60 硬化劑 HX3941HP t40 140 140 140 140 140 140 140 嫌糖 400 400 400 400 400 400 400 400 有機微粒子 KW4426 40 一 40 — 40 — 40 - BTA751J - 40 — 40 — 40 — 40 凸塊潤濕性 改質劑 ADH 40 AO — — 一 一 一 — BHPA 一 — 40 40 — — - 一 26DMPC — — 一 - 40 40 一 - 線膨膜係數(xl〇-6/°C) 45 53 43 52 45 54 47 57 250。。10秒之反應率(％) 80 80 85 85 80 80 70 70 14天後之反應率(％) 7 7 8 8 5 5 5 5 壓著後之連接電阻 A A A A A A A A 壓著後之埋入性 A A A A A A A A 回焊後之連接電阻 A A A A A A A A 回焊後之連接性 A A A A A A A A 可導通之循環次數 1000S 1000^ 1000客 1000^ 1000^ 1000^ 300 300 如表1所示，使用實施例1〜6獲得之電路構件連接用 接著劑薄片時，沒有產生孔洞’回焊後仍顯示良好之連接 性，而且在溫度循環試驗中經1 000次循環以上仍可導通 。相對於此，使用比較例1、2獲得之電路構件連接用接 著劑薄片時，雖然沒有產生孔洞，且回焊後亦顯示良好之 -36- 201211188 連接性，但溫度循環試驗於3 0 0次循環產生連接不良，且 凸塊潤濕性不足，故確認焊接接合不充分且連接信賴性差 【圖式簡單說明】 圖1爲顯示本發明之電路構件連接用接著劑薄片之較 佳實施形態之模式剖面圖。 圖2爲顯示本發明之電路構件連接用接著劑薄片之較 佳實施形態之模式剖面圖。 圖3爲說明本發明之半導體裝置之製造方法之一實施 形態之模式剖面圖。 圖4爲說明本發明之半導體裝置之製造方法之一實施 形態之模式剖面圖。 圖5爲說明本發明之半導體裝置之製造方法之一實施 形態之模式剖面圖。 圖6爲說明本發明之半導體裝置之製造方法之一實施 形態之模式剖面圖。 圖7爲說明本發明之半導體裝置之製造方法之一實施 形態之模式剖面圖。 【主要元件符號說明】 1 :保護薄膜 2 :接著劑層 3 :支撐基材 -37- 201211188 3 a :黏著劑層 3b :塑膠薄膜 4 :硏磨機 5 :切割膠帶 6 :切割鋸 7 :吸附套爪 8:搭載半導體元件用之支撐構件 10:電路構件連接用接著劑薄片 11:電路構件連接用接著劑薄片 1 2 :貼附薄膜狀接著劑之半導體元件 20 :電路電極 30 :半導體裝置 A :半導體晶圓 -38-The connection resistance manufactured by Advantest Co., Ltd., and the connection resistance after reflow were measured and evaluated based on the following criteria. (Connecting resistance after pressing) A : All the terminals (176 terminals) for mounting TEG used in the test. The connected resistors are 7 to 10 Ω. B: The resistors that do not have all the terminals are connected, or the resistance 全部 of all the terminals is greater than 1. 〇Ω (connection resistance after reflow) A: The resistance rises within 20% with respect to the connection resistance 压 after pressing ς -35- 201211188 B: The resistance rises over 20% with respect to the connection resistance after pressing Temperature Cycling Test> The semiconductor device after the above reflow was placed in a temperature cycle test at -55 ° C for 30 minutes and at 125 t for 30 minutes as a single cycle to evaluate whether or not the connection resistance was maintained in the test machine. The number of cycles that can be energized is shown in the table [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Thermoplastic resin ZX1356-J2 100 100 100 100 100 100 100 100 Thermosetting resin 1032H60 100 100 100 100 100 100 100 100 60 60 60 60 60 60 60 60 Hardener HX3941HP t40 140 140 140 140 140 140 140 Suspected sugar 400 400 400 400 400 400 400 400 Organic microparticles KW4426 40 A 40-40 — 40 — BTA751J - 40 — 40 — 40 — 40 Bump Wetting Modifier ADH 40 AO — — 一一一 — BHPA 一 — 40 40 — — — A 26DMPC — — — — — — — — — — — — — — — — — Coefficient (xl 〇 -6 / ° C) 45 53 43 52 45 54 47 57 250. . Reaction rate of 10 seconds (%) 80 80 85 85 80 80 70 70 Reaction rate after 14 days (%) 7 7 8 8 5 5 5 5 Connection resistance after pressing AAAAAAAA Embedding AAAAAAAA reflow after pressing After the connection resistance AAAAAAAA, the connectivity after reflow soldering AAAAAAAA The number of cycles that can be turned on 1000S 1000^1000 guest 1000^1000^ 1000^ 300 300 As shown in Table 1, the connecting members for circuit components obtained using Examples 1 to 6 In the case of flakes, no voids were formed. After reflow, good connectivity was observed, and it was turned on after more than 1 000 cycles in the temperature cycle test. On the other hand, when the adhesive sheets for connection of circuit members obtained in Comparative Examples 1 and 2 were used, no holes were formed, and after the reflow, a good -36 - 201211188 connectivity was exhibited, but the temperature cycle test was performed 300 times. In the cycle, the connection is poor, and the wettability of the bump is insufficient. Therefore, it is confirmed that the solder joint is insufficient and the connection reliability is poor. [Brief Description] FIG. 1 is a view showing a preferred embodiment of the adhesive sheet for connecting the circuit member of the present invention. Sectional view. Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of the 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 showing an embodiment of a method of manufacturing a semiconductor device of the present invention. Fig. 5 is a schematic cross-sectional view showing 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 showing an embodiment of a method of manufacturing a semiconductor device of the present invention. [Main component symbol description] 1 : Protective film 2 : Adhesive layer 3 : Support substrate -37 - 201211188 3 a : Adhesive layer 3b : Plastic film 4 : Honing machine 5 : Cutting tape 6 : Cutting saw 7 : Adsorption Collet 8: Support member 10 for mounting a semiconductor element: Adhesive sheet for circuit member connection 11: Adhesive sheet for circuit member connection 1 2: Semiconductor element 20 to which a film-like adhesive is attached: Circuit electrode 30: Semiconductor device A :Semiconductor Wafer-38-