TW200919657A - Adhesive for circuit member connection - Google Patents

Adhesive for circuit member connection Download PDF

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Publication number
TW200919657A
TW200919657A TW097126483A TW97126483A TW200919657A TW 200919657 A TW200919657 A TW 200919657A TW 097126483 A TW097126483 A TW 097126483A TW 97126483 A TW97126483 A TW 97126483A TW 200919657 A TW200919657 A TW 200919657A
Authority
TW
Taiwan
Prior art keywords
adhesive
circuit
resin
wafer
composite oxide
Prior art date
Application number
TW097126483A
Other languages
Chinese (zh)
Other versions
TWI425598B (en
Inventor
Akira Nagai
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of TW200919657A publication Critical patent/TW200919657A/en
Application granted granted Critical
Publication of TWI425598B publication Critical patent/TWI425598B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • H01L24/80—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
    • H01L24/83—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Wire Bonding (AREA)
  • Adhesive Tapes (AREA)
  • Combinations Of Printed Boards (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

Disclosed is a thermosetting adhesive for circuit member connection, which is composed of a resin composition containing a thermally crosslinkable resin and a curing agent reactive with the thermally crosslinkable resin and complex oxide particles dispersed in the resin composition.

Description

200919657 九、發明說明 【發明所屬之技術領域] 本發明係關於電路構件連接用黏著劑及半導體裝置。 【先前技術】 作爲由倒裝焊接（face down bonding)方式直接封裝 半導體晶片於電路基板之方式，已知於半導體晶片之電極 ηβ份’形成錫焊凸塊（s ο 1 d e r b u m p )，焊接連接於電路晶 板之方式，或塗佈導電性黏著劑於半導體晶片設有之突起 電極’進行電連接於電路基板電極之方法。 此等方法中，因爲暴露於各種環境下時，基於連接晶 片與基板之熱膨脹係數差之壓力發生於連接界面，所以有 連接信賴性降低之問題。因此，緩和連接界面的壓力之目 的下’檢討一般塡充環氧樹脂等之底部塡充 （Underfill )材料於晶片與基板間隙之方式。 作爲底部塡充材料之塡充方式，有連接晶片與基板後 ’注入低黏度之液狀樹脂之方式，及設置底部塡充材料於 » f反上後搭載晶片之方式。另外，作爲設置底部塡充材料 方令基板上後搭載晶片之方式，有塗佈液狀樹脂之方法及黏 貼薄膜狀樹脂之方法。 然而，塗佈液狀樹脂時，難以由分散器控制精密的塗 佈量’因爲近年來晶片之薄型化，塗佈量過多時，接合時 滲出的樹脂沾上晶片的側面，污染接合工具，所以必須洗 淨工具’此成爲量產時步驟成爲煩雜的原因。另外’黏貼 -4- 200919657 薄膜狀樹脂時，由控制樹脂厚度，容易決定最適合 ’但相反地’黏貼薄膜於基板用之稱爲假壓著步驟 步驟係必要的。 假壓著步驟中，使用縱切寬度比成爲對象晶片 大之卷軸狀膠帶，因應晶片尺寸，半切基材上之黏 於黏著劑不反應程度之溫度，由熱壓著黏貼基板。 爲確保生產率，於假壓著步驟所黏貼之薄膜， 比晶片尺寸大。然而，薄膜比晶片尺寸大時，因必 鄰零件保持距離，將阻礙高密度化封裝。因此，作 與晶片尺寸同樣尺寸的黏著劑之方法，揭示以黏貼 給黏者劑於晶圓後，由進fj切割（d i c i n g )等之晶 ’亦同時進行黏著劑加工，得到附有黏著劑之晶片 〇 例如專利文獻1之方法係黏貼薄膜狀黏著劑於 ，以切割個片化，得到附有黏著薄膜之晶片之方法 法係製作晶圓/黏著劑/分離片之層合體，將其切斷 離分離片，得到附有黏著劑之晶片。然而，此方法 斷層合體時，剝離黏著劑及分離片之結果，有個片 體晶片飛散之虞。 專利文獻2係關於具有黏著材料層及黏著劑層 加工用膠帶之方法’揭示黏貼晶圓於晶圓加工用膠 切割及選取’覆晶連接個片化晶片於基板之方法。 一般覆晶封裝係連接晶片電路面之稱爲凸塊之 相對的基板側之端子，將晶片側之位置核對記號與 樹脂量 之追加 之寬度 著劑， 一般係 須與相 爲供給 狀態供 片加工 之方法 晶圓後 。此方 後，剝 中，切 化半導 之晶圓 帶後， 端子與 基板側 -5- 200919657 之位置核對記號’以覆晶黏著機核對位置’將此等黏貼。 黏貼黏著劑於晶片電路面時’因黏者劑覆盖電路面之位置 核對記號，所以必須透過黏著劑’確認位置核對記號。 爲透過黏著劑以確認晶片電路面之位置核對記號’考 量提升黏著劑之透過率作爲解決手段。一般配合成份之相 溶性高、形態（m 〇 r p h ο 1 〇 g y )均句的樹脂組成物之透過率 高。另一方面，因爲發生相分離之樹脂組成物於樹脂內部 光散射，所以透過率變低。因此’爲形態均勻之組成’可 構築容易辨別位置核對記號之黏著劑。 另一方面，半導體用之黏著劑係要求對應基於晶片與 基板之熱膨脹係數差所發生應力用之高黏著性、對應回焊 溫度用之高耐熱性、對應高溫環境下用之低熱膨脹性、對 應商溫局濕環境下用之低吸濕性％之商信賴性。作爲提升 特性之手法’檢討可達成高耐熱性及高黏著性之添加線膨 脹係數小之二氧化矽塡料於環氧樹脂之組成。然而，混合 二氧化矽塡料於環氧樹脂時，因塡料與環氧樹脂之界面發 生散射’所以透過率差，難以得到透明性。 在此’專利文獻3中記載作爲添加塡料於樹脂時之得 到透明性之方法，含有絕緣性黏著劑及黏著劑中所分散之 導電粒子及透明玻璃粒子之各向異性導電膜。 專利文獻1 :特許2 8 3 3 1 1 1號公報 專利文獻2:特開2006-049482號公報 專利文獻3 :特許3 4 0 8 3 0 1號公報 200919657 【發明內容】 發明之揭示 發明所欲解決之課題 然而，即使玻璃粒子爲透明時，因爲與使分散玻璃粒 子之樹脂之折射率有差異時發生光散射，所以因分散玻璃 粒子而損害透明性。因此，混合粒子以得到透明性係僅粒 子本身爲透明仍不能達成。如此地前述專利文獻1〜3之 晶圓先置型之底部塡充方法係因爲各有課題，所以未於市 場一般化。 因此，本發明係提供進行連接電路構件時，透過電路 構件連接用黏著劑，可辨別晶片電路面之認識記號，同時 連接電路構件後，不發生通電不良以及可得到安定的低連 接電阻之電路構件連接用黏著劑爲課題。 課題之解決手段 本發明係提供由含有熱交聯性樹脂及與該熱交聯性樹 脂反應之硬化劑之樹脂組成物，與分散於該樹脂組成物中 之複合氧化物粒子，所形成之熱硬化型電路構件連接用黏 著劑。 使用本發明之電路構件連接用黏著劑，進行連接電路 構件時，連接時，可透過電路構件連接用黏著劑，辨別晶 片電路面之認識記號，同時連接電路構件後，不發生通電 不良，可得到安定的低連接電阻。 複合氧化物粒子之平均粒徑係以〇 · 1 μιη〜0.5 μηι爲宜 200919657 。於上述範圍時，複合氧化物粒子分散於該樹脂組成 ，補強樹脂組成物。另外，提升連接安定性。 電路構件連接用黏著劑係相對於樹脂組成物100 份，複合氧化物粒子係以含有2 〇〜1 5 0重量份爲宜。 氧化物粒子若爲2 0重量份以上時，因爲電路構件連 黏著劑之線膨脹係數降低，彈性率上升，所以壓著後 導體晶片與基板之連接信賴性更加提升。複合氧化物 若未滿1 5 0重量份時，與超過1 5 0重量份時比較，因 構件連接用黏著劑之溶融黏度降低，所以容易連接半 之突出電極與基板之電路。 電路構件連接用黏著劑，以未硬化時具有1 5〜 可見光並行透過率爲宜。具有上述範圍之可見光並行 率，另外，容易辨別晶片電路面之認識記號。 複合氧化物粒子之折射率係以1 . 5〜1 _ 7爲宜。折 若於上述範圍時，電路構件連接用黏著劑之可見光並 過率上升，另外，容易辨別晶片電路面之認識記號。 樹脂組成物係以含有於支鏈上至少包含1個可與 劑或熱交聯性樹脂反應之官能基的共聚合性樹脂爲宜 電路構件連接用黏著劑於1 8(TC下加熱20秒鐘後 差示掃描熱量計所得之發熱量所算出之電路構件連接 著劑的反應率係以8 0 %以上爲宜。反應率若爲8 0 %以 ，連接安定性提升。 電路構件連接用黏著劑硬化後之4 0〜1 0 0 t下之 脹係數係以70 X 1 (T6/°C以下爲宜。硬化後之線膨脹係 物中 重量 複合 接用 之半 粒子 電路 導體 1 0 0 % 透過 射率 行透 硬化 〇 ，以 用黏 上時 線膨 數若 -8 - 200919657 超過70x1 0_6/°C時，因封裝後之溫度變化或加熱吸濕之膨 脹，有難以保持半導體晶片之連接端子與電路基板之配線 間之電連接之趨勢。 本發明之電路構件連接用黏著劑係可使具有突出連接 端子之半導體晶片與具有配線圖型之電路基板，以連接端 子與配線圖型電連接的方式黏著時所使用。 本發明係提供具備有具有配線圖型之電路基板，與安 裝於電路基板之具有突出連接端子之半導體晶片，與介於 電路基板與半導體晶片之間並予連接之黏著層，連接端子 與配線圖型爲電連接，黏著劑層爲由上述本發明之電路構 件連接用黏著劑所形成之半導體裝置。本發明之半導體裝 置係不發生通電不良，保持安定的低連接電阻。 發明之功效 依據本發明，可提供進行連接電路構件時，透過電路 構件連接用黏著劑，可辨別晶片電路面之認識記號，並且 連接電路構件後，不發生通電不良及可得到安定的低連接 電阻之電路構件連接用黏著劑。另外，可提供使用上述電 路構件連接用黏著劑所得之半導體裝置。 用以實施發明之最佳型態 以下係因應需要，參考圖式下，詳細地說明本發明適 合之實施型態。另外，圖式中，給予相同符號於相同要素 ，省略重複說明。另外，上下左右等之位置關係除非例外 -9- 200919657 ，皆基於圖式表示之位置關係者。另外，圖式之尺寸比率 並非局限於圖示之比率者。 有關本實施型態之電路構件連接用黏著劑係由含有熱 交聯性樹脂及與該熱交聯性樹脂反應之硬化劑之樹脂組成 物，與分散於該樹脂組成物中之複合氧化物粒子，所形成 之熱硬化型黏著劑。 圖1係表示具備電路構件連接用黏著劑之電路連接材 料之一種實施型態之斷面圖。圖1所示之電路連接材料1 係具備薄膜狀之電路構件連接用黏著劑4 0、電路構件連接 用黏著劑4 0之兩側所配置之2個分離片1 0。電路構件連 接用黏著劑40係具有含球狀之複合氧化物粒子層20、及 其上所層合之含球狀之複合氧化物粒子及導電粒子層30。 含複合氧化物粒子層20係由樹脂組成物2 1及分散於樹脂 組成物2 1中之複合氧化物粒子2 2所形成。含複合氧化物 粒子及導電粒子層3 0係由樹脂組成物3 1及分散於樹脂組 成物3 1中之複合氧化物粒子22及導電粒子3 3所形成。 分離片1 〇係剝離性樹脂薄膜。 樹脂組成物2 1及3 1係分別含熱交聯性樹脂及硬化劑 之熱硬化性樹脂組成物。構成含複合氧化物粒子22層20 之樹脂組成物2 1，及構成含複合氧化物粒子2 2及導電粒 子3 3層3 0之樹脂組成物3 1係可爲相同，亦可爲相異。 樹脂組成物2 1及/或3 1所含之熱交聯性樹脂係與硬 化劑反應，形成交聯結構之樹脂。作爲熱交聯性樹脂係以 環氧樹脂爲宜。尤其’因爲要求透過性升高及高Tg化、 -10- 200919657 低線膨脹係數化，所以以萘酚漆用酚醛型固體環氧樹脂、 含有芴骨架之液體或固體環氧樹脂爲宜。除了環氧樹脂以 外，作爲樹脂組成物2 1及/或31所含之熱交聯性樹脂， 可使用雙馬來酸酐縮亞胺樹脂、三嗪樹脂、聚醯亞胺樹脂 、聚醯胺樹脂、氰基丙烯酸酯樹脂、酚醛樹脂、不飽和聚 酯樹脂、三聚氰胺樹脂、尿素樹脂、聚胺基甲酸乙酯樹脂 、聚異氰酸酯樹脂、呋喃樹脂、間苯二酚樹脂、二甲苯樹 脂、苯幷鳥糞胺樹脂、苯二酸二烯丙酯樹脂、矽氧樹脂、 聚乙烯丁縮醛樹脂、矽氧烷改性聚醯胺醯亞胺樹脂、丙烯 酸酯樹脂等。此等係可單獨或組合2種以上使用。 熱交聯性樹脂可爲含有於支鏈上至少包含1個可與硬 化劑或上述熱交聯性樹脂反應之官能基的共聚合性樹脂。 作爲如此之共聚合性樹脂，以於支鏈上包含可與上述熱交 聯性樹脂反應之官能基之環氧基、羧基、或羥基的丙烯基 共聚物爲宜。尤其，以含有使用縮水甘油丙烯酸酯、縮水 甘油甲基丙烯酸酯等作爲共聚合成份所得之含有環氧基之 丙烯基共聚物爲宜。其他亦可使用羥乙基（甲基）丙烯酸 酯、羥丙基（甲基）丙烯酸酯、羥丁基（甲基）丙烯酸酯 等之羥烷基（甲基）丙烯酸酯、及甲基丙烯酸甲酯、丁基 (甲基）丙烯酸酯、2·乙基己基（甲基）丙烯酸酯、環己 基甲基丙烯酸酯、糠基甲基丙烯酸酯、月桂基（甲基）丙 烯酸醋、硬脂醯基（甲基）丙稀酸酯、三甲基環己基甲基 丙烯酸酯、三環癸基甲基丙烯酸酯、四環十二烷基_3_丙烯 酸醋等之（甲基）丙烯酸醋、苯乙嫌、乙稀基甲苯、聚丙 -11 - 200919657 二醇單甲基丙烯酸酯、羥乙基丙烯酸酯、丙烯腈、苯甲基 甲基丙烯酸酯、環己基馬來酸酐縮亞胺等作爲共聚合成份 用之共聚合性樹脂。 與熱交聯性樹脂反應之硬化劑係可選自酚系、咪唑系 、醯肼系、硫醇系、苯幷噁嗪、三氟化硼-胺配位化合物 、鎏鹽、胺醯亞胺、多胺的鹽、雙氰胺（dicyandiamide ) 、及有機過氧化物系之硬化劑。 爲延長可使用時間，可以上述硬化劑爲微膠囊型硬化 劑。微膠囊型硬化劑係以硬化劑爲核，由聚胺基甲酸乙酯 、聚苯乙烯、果膠及聚異氰酸酯等之高分子物質、或矽酸 鈣、沸石等之無機物、及鎳、銅等之金屬薄膜等之被膜實 質上被覆。微膠囊型硬化劑之平均粒徑爲1〇μιη以下，以 5 μ m以下爲宜。 爲增大黏著強度，樹脂組成物21及/或31亦可含交 聯劑。爲輔助薄膜形成性，亦可含聚酯、聚胺基甲酸乙酯 、聚乙烯基丁縮醛、聚丙烯酸酯、聚甲基丙烯酸甲酯、丙 烯酸橡膠、聚苯乙烯、苯氧樹脂、NBR (丙烯晴-丁二烯 橡膠）、SBR (苯乙烯-丁二烯橡膠）、聚醯亞胺或聚矽 氧烷改性樹脂（丙烯基聚矽氧烷、環氧基聚矽氧烷、聚醯 亞胺聚矽氧烷）等之熱可塑性樹脂亦可包含於樹脂組成物 2 1及/或3 1。另外，於改質複合氧化物粒子表面之目的下 ，亦可含矽油、聚矽氧烷、聚矽氧烷低聚物、交聯劑。 樹脂組成物2 1及/或3 1之硬化後折射率係以1 . 5〜1 . 7 爲宜。爲使硬化後之折射率於上述範圍，未硬化狀態之折 -12- 200919657 射率係以1 · 5〜1 . 7爲宜。使未硬化狀態之折射率爲丨· 5以 上’可使高折射率成份分散於樹脂組成物2 1及/或3 1。作 爲如此高折射率成份’可舉例如作爲環氧樹脂之硬化觸媒 所使用之咪唑化合物及胺系之硬化劑等之分子內含氮原子 之化合物。另一方面’使未硬化狀態之折射率爲1.7以下 ’可含有低折射率成份於樹脂組成物2 1及/或31中。若 使低折射率成份分散於樹脂組成物2 1及/或3 1中，樹脂 組成物2 1及/或3 1之折射率有變低之趨勢。作爲如此低 折射率成份，可提升高分子量之熱可塑性樹脂。作爲高分 子量之熱可塑性樹脂，可舉例如苯氧樹脂或丙烯酸之共聚 物。藉由使樹脂組成物2 1及/或3 1中含有高折射率成份 及低折射率成份，可使未硬化狀態之樹脂組成物2 1及/或 3 1之折射率爲1 . 6左右。樹脂組成物2 1及3 1之折射率係 可使用阿貝折射計（Abbe refractometer)，以鈉 D線（ 5 8 9 nm )爲光源而測定。 複合氧化物粒子22之折射率爲1.5〜1.7，並且樹脂 組成物21及/或31之折射率差係以±0.1以內爲宜’ ±0.05 以內尤佳。折射率差若超出±0. 1以內時，藉由添加複合氧 化物粒子22於樹脂組成物2 1及/或3 1，有減少透過率之 趨勢。尤其電路構件連接用黏著劑40之膜厚度大時’透 過半導體晶片之具有突出連接端子的面所黏貼之電路構件 連接用黏著劑40，辨別半導體晶片之電路面所形成之位置 核對記號，有困難之趨勢。依貝克（Becke )法使用顯微 鏡測定複合氧化物粒子2 2之折射率。 -13- 200919657 複合氧化物粒子22係以含2種以上之金屬，由可結 晶化之金屬氧化物或結晶化金屬氧化物所形成爲宜。作爲 如此之金屬氧化物’以含有至少1種選自鋁、鎂及鈦之金 屬、及2種以上之其他金屬之複合氧化物爲宜。含鈦及矽 之複合氧化物尤佳’就容易由組成比調整折射率之點上， 以含二氧化矽及二氧化鈦者尤佳。含二氧化矽及二氧化鈦 之二氧化矽二氧化鈦粒子係可由溶膠凝膠法製作，就亦可 使用市售品，以複合氧化物粒子2 2爲宜。 複合氧化物粒子22之平均粒徑係以0.1〜0.5 μιη爲宜 。平均粒徑若未滿0 · 1 μ m時，與0 . 1 μ m以上時相比較，因 粒子之比表面積大，所以表面能量亦變大。該結果係粒子 彼此之相互作用變大，發生凝聚體，有分散性降低之趨勢 。另外’即使分散性良好時，因爲比表面積大，分散於樹 脂組成物2 1及/或3 1時增黏而成形性變得容易降低。 複合氧化物粒子22之平均粒徑若超過0.5μιη時，與 0.5 μιη以下時相比較，因粒子之比表面積小，樹脂組成物 2 1及/或3 1之流動性變大，成形時容易發生空隙。另外， 因爲粒徑變大，以相同添加量分散複合氧化物粒子22時 ’比粒徑小時，粒子數量變少。該結果係分散複合氧化物 粒子22之目的之一，樹脂組成物2丨及/或3丨之補強效果 有變少之趨勢。另外，複合氧化物粒子22之粒徑大時， 因複合氧化物粒子22包圍晶片之凸塊與電路基板之電極 間而容易發生阻礙電特性。尤其，以低壓封裝時或凸塊係 由鎳等之硬質材料所形成時，複合氧化物粒子22變得難 -14- 200919657 以埋入連接知子。該結果係進行連接時，妨礙凸塊與電路 基板電極間之接觸、或電路構件連接用黏著劑40含導電 粒子3 3時，導電粒子3 3扁平而成阻礙，電連接容易受到 阻礙。另外’複合氧化物粒子22之最大粒徑爲40μιη以上 時，複合氧化物粒子22之粒徑比晶片與基板之間隙大。 此時，因封裝時之加壓，複合氧化物粒子2 2可能傷害晶 片之連接端子或基板之電路。 複合氧化物粒子2 2係比重爲5以下者爲宜，以2〜5 者尤佳，比重爲2〜3 · 2者更好。比重若超過5時，添加 於樹脂組成物2 1及/或31之清漆時，比重差大時，清漆 中容易發生沈澱。該結果將難以得到複合氧化物粒子22 均勻分散之電路構件連接用黏著劑40。 複合氧化物粒子22之線膨脹係數係於0〜700 °C以下 之溫度範圍，以 7xl〇_6/°C以下爲宜，以 3xl(T6/°C以下尤 佳。複合氧化物粒子22之線膨脹係數若小時，爲降低電 路構件連接用黏著劑40之線膨脹係數，可減少添加複合 氧化物粒子22的量。 電路構件連接用黏著劑40係相對於樹脂組成物2 1及 /或31之100重量份，以含有20〜150重量份之複合氧化 物粒子22爲宜，以含有25〜1〇〇重量份尤佳，以含有50 〜1 0 0重量份尤佳。複合氧化物粒子2 2若未滿2 0重量份 時，有電路構件連接用黏著劑4 0之線膨脹係數增大及彈 性率降低之趨勢。該結果係壓著後之半導體晶片與基板之 連接信賴性變得容易降低。另一方面’配合量若超過1 5 0 -15- 200919657 重量份時，電路構件連接用黏著劑4 0之溶融黏度有增加 的趨勢。其結果係半導體之突出電極與基板電路變得非常 難以連接。 本發明之電路構件連接用黏著劑40爲吸收連接晶片 之凸塊或基板電極等之高度不齊，積極給予各向異性導電 性之目的下，可具備除了複合氧化物粒子22之外，混入 及分散導電粒子33之含複合氧化物粒子22及導電粒子33 之層30。作爲導電粒子33，爲含Au、Ag、Ni、Cu、銲錫 等金屬之粒子或碳粒子等，平均粒徑係以1〜1 Ομιη之粒子 爲宜。其中，爲得到充份的可操作期（Pot life )，導電粒 子33之表層非Ni及Cu等之過渡金屬，以由Au、Ag、鈾 屬之貴金屬形成爲宜，以由Au形成尤佳。或導電粒子33 亦可爲以Au等貴金屬被覆Ni等過渡金屬之表面者。導電 粒子3 3係以上述金屬被覆非導電性之玻璃、陶瓷、塑膠 等，最外層爲貴金屬時，及熱溶融金屬粒子時，藉由加熱 加壓所得之導電子具有變形性，吸收電極高度之不齊。該 結果係連接時，與電極之接觸面積增加，信賴性上升，所 以適宜。爲得到良好的電阻，如此之導電粒子3 3之貴金 屬類之被覆層厚度係以100A以上爲宜。然而，於Ni等過 渡金屬上設置貴金屬類層時，混合分散導電粒子3 3時發 生的貴金屬類層缺損時，將容易引起氧化還原作用。該結 果係因爲發生的游離自由基引起保存性降低，所以貴金屬 類之被覆層厚度係以300A以上爲宜。貴金屬類之被覆層 厚度若變厚時，因爲此等效果飽和，所以最大以Ιμπι爲宜 -16 - 200919657 ，但並非局限於此者。 導電粒子3 3係相對於1 0 0體積份之樹脂組成物3 1 ’ 於0.1〜3 0體積份之範圍，依用途調整。爲防止過剩的導 電粒子33所引起之鄰接電路短路，以0.1〜1〇體積份尤 佳。電路構件連接用黏著劑40亦可不具有含複合氧化物 粒子22及導電粒子33之層30。 電路構件連接用黏著劑40係以未硬化時具有1 5〜 100 %之可見光並行透過率爲宜，以具有 18〜100 %可見光 並行透過率尤佳，以具有25〜100%可見光並行透過率最 好。可見光並行透過率若未滿1 5%時，將難以以覆晶式黏 晶機（flip chip bonder )辨別認識符號，位置核對作業變 得困難。 可見光並行透過率係可以日立製作股份有限公司製， 商品名U-3310型分光光度計測定。例如以膜厚爲50μ:η之 帝人 DuPont Film股份有限公司製PET薄膜（商標名 Purex，5 5 5 nm透過率8 6.03 )爲基準物質，進行基線修正 測定，以25μιη厚度塗佈電路構件連接用黏著劑40於PET 基材’可測定4〇〇nm〜800 nm之可見光範圍之並行透過率 。覆晶式黏晶機所使用之鹵素光源與導光之波長相對強度 中，因爲5 5 5 nm〜60 0 nm最強，所以本發明中以5 5 5mm 之透過率，可進行可見光並行透過率之測定。 將電路構件連接用黏著劑4 0，於1 8 0 °C下加熱2 0秒 後’以差示掃描熱量計（DSC )所得之發熱量所算出之反 應率係以80%以上爲宜。在此，電路構件連接用黏著劑之 -17- 200919657 反應率（單位：％)係對加熱前之電路構件連接用黏 ’進行DSC測定所得之發熱量作爲初期發熱量，對 後之電路構件連接用黏著劑，進行D S C測定所得之 量作爲加熱後發熱量，由下述式（1)所算出。 反應率=(初期發熱量-加熱後發熱量）/初期發熱量X1 〇〇 ( 於1 8 0 °C下加熱2 0秒後之電路構件連接用黏著； 之反應率爲80%以上，可使連接端子與配線圖型進行 及機械的連接。另外，於連接後之冷卻收縮時，亦可 連接端子與配線圖型之連接。 電路構件連接用黏著劑4 0硬化後之4 0〜1 0 0 °C下 膨脹係數係以70xl(T6/°C以下爲宜，以60xl〇-6/〇C以 佳’以50xl(T0/t：以下更好。硬化後之線膨脹係數若 7〇xlO_6/°C時，因封裝後之溫度變化或加熱吸濕之膨 難以保持半導體晶片之連接端子與電路基板之配線圖 之電連接。 電路構件連接用黏著劑40係可使具有突出連接 之半導體晶片與具有配線圖型之電路基板，以上述連 子與上述配線圖型電連接的方式黏著時所使用。 上述連接端子係可使用金線所形成之柱形金凸 Gold Stud Bump)、由熱壓著或超音波併用熱壓著機 金屬球於半導體晶片之電極者及由電鍍或蒸著所形成 另外，上述連接端子係無須以單一金屬所構成，亦可 著劑 加熱 發熱 fll 4 0 電的 保持 之線 下尤 超過 脹， 型間 端子 接端 塊（ 固定 者。 含金 -18- 200919657 、銀、銅、鎳、銦、鈀、錫、鉍等多數之金屬成份，亦可 爲層合此等金屬成份層之形式。另外，上述具有連接端子 之半導體晶片亦可爲具有突出連接端子之半導晶圓之狀態 〇 爲黏著以使上述半導體晶片之突出連接端子與上述配 線圖型所形成之基板電連接，以配置上述連接端子與上述 配線圖型成對向爲宜。因此，半導體晶片係與突出連接端 子於同一面位置具有核對記號爲宜。 上述配線圖型所形成之電路基板係可爲通常的電路基 板’亦可爲半導體晶片。電路基板時，上述配線圖型係可 將於含浸環氧樹脂或具有苯幷三嗪骨架之樹脂於玻璃布或 不織布而形成之基板、具有增層（Build Up)之基板、或 聚醯亞胺、玻璃、陶瓷等之絕綠基板之表面上所形成之銅 等金屬層之不需要部份，蝕刻除去以形成。另外，於絕緣 基板表面，藉由電鍍亦可形成，藉由蒸著等亦可形成。 上述配線圖型係無須以單一的金屬所形成，亦可含有 金、銀、銅、鎳、銦、IS、錫、鉍等多數之金屬成份，亦 可爲層合此等金屬成份的層之形態。另外，基板爲半導體 晶片時’配線圖型通常以鋁所構成，但亦可於該表面形成 金、銀、銅、鎳、銦、紀、錫、秘等之金屬層。 黏貼電路構件連接用黏著劑4 0於半導體晶片之具有 連接端子的面之狀態係如下述所得。（1 )製作以晶片化 前之具有突出連接端子之半導體晶圓、配置於半導體晶圓 之突出連接端子面之電路構件連接用黏著劑4〇、設置黏著 -19- 200919657 層於半導體晶圓側之由UV照射而硬化之切割膠帶的順序 所層合之層合體。（2 )由切割切斷成個片。（3 )自切割 膠帶剝離個片化之附有電路構件連接用黏著劑40之半導 體晶片。 (1 )由半導體晶圓、電路構件連接用黏著劑40、切 割膠帶所構成之層合體係準備層合電路構件連接用黏著劑 40及切割膠帶之層合體後，由具有加熱機構及加壓滾輪之 晶圓貼片機（wafer mounter)或具有加熱機構及真空加壓 機構之晶圓貼片機，層合於半導體晶圓而可得。層合體中 ，電路構件連接用黏著劑40係與半導體晶圓同等面積， 切割膠帶係具有比半導體晶圓及電路構件連接用黏著劑大 的面積，比切割架之內尺寸大，比外尺寸小的面積。 上述層合係於電路構件連接用黏著劑40軟化之溫度 下進行爲宜，例如加熱成4 0〜8 0 °C下進行爲宜，以加熱成 60〜8 (TC下進行尤佳，以加熱成70〜80 °C下層合更好。於 電路構件連接用黏著劑40之軟化溫度以下層合時，發生 半導體晶圓之突出連接端子周圍之埋入不足，成爲空隙捲 入之狀態，有成爲切割時之剝離、取出（Pick Up )時電 路構件連接用黏著劑4〇之變形、位置核對時之認識符號 辨別不佳、進而因空隙而引起連接信賴性降低等原因之虞 〇 (2 )切割由半導體晶圚、電路構件連接用黏著劑4 0 、切割膠帶所構成之上述層合體時，由使用IR (紅外線） 辨別相機，透過晶圓，認識半導體晶圓之配線圖型或切割 -20- 200919657 用之位置核對記號，可進行切割線（scribe line )之位置 核對。 上述層合體中，切斷半導體晶圓及電路構件連接用黏 著劑40之步驟係可使用通常的切割器進行。由切割器切 斷係可適合於一般稱爲切割之步驟。切割係以僅切斷晶圓 作爲第1階段，切斷至第1階段之切斷溝內之剩餘晶圓及 電路構件連接用黏著劑40與切割膠帶之界面或切割膠帶 內部之階段切斷之切割爲宜。切割亦可適用使用雷射之切 割。切割後，以通常之曝光機等，以1 5〜3 0 m W，1 5 0〜 3 0 0mJ程度之UV照射切割膠帶側。 (3 )自切割膠帶剝離個片化附有電路構件連接用黏 著劑40之半導體晶片之步驟係由與半導體晶片層合面之 相反面壓住，以壓推切割膠帶，使於電路構件連接用黏著 劑40與UV照射後之切割膠帶之界面剝離撕下而可進行 〇 電路構件連接用黏著劑40係對UV照射之切割膠帶 之黏著力爲1 ΟΝ/m以下，而且對半導體晶圓之黏著力係以 7 ΟΝ/m以上爲宜。對UV照射之切割膠帶之黏著力若超過 1 ON/m時’自切割膠帶剝離切割後個片化之附有電路構件 連接用黏著劑40之半導體晶片之作業，有發生晶片破壞 或發生電路構件連接用黏著劑層變形之虞。另一方面，對 半導體晶圓之黏著力若未滿7 ON/m時，因切割時切板的旋 轉切削所引起之衝擊及水壓的影響，晶片與電路構件連接 用黏著劑40之界面有發生剝離之虞。 -21 - 200919657 電路構件連接用黏著劑4〇與UV照射後之切割膠帶 之黏著力係可如下述測定。由設定加熱溫度成80t;之層合 機層合電路構件連接用黏著劑40於晶圓，將UV照射前 之切割膠帶之黏著面朝向電路構件連接用黏著劑40，以 4 0 °C進行層合後，於切割膠帶側，以1 5 m W，3 0 0 m J程度 ’進行UV照射。將UV照射後之切割膠帶，切入丨〇mm 寬度之切口，準備拉伸測定用之短片。強壓晶圓於台上， 固定成短片之切割膠帶的一端於拉伸測定機之拉伸治具， 進行90 °剝離試驗，剝離電路構件連接用黏著劑40與 UV照射後切割膠帶。如此可測定剝離電路構件連接用黏 著劑40與UV照射後切割膠帶之黏著力。 電路構件連接用黏著劑4 0與半導體晶圓之黏著力係 可如下述測定。由設定加熱溫度成8 (TC之層合機層合電路 構件連接用黏著劑40於晶圓，朝向黏著面，黏貼Kapton Tape (日東電工股份有限公司製，寬 1 〇mm，厚25μιη ) 於電路構件連接用黏著劑40，使充份密合。之後’沿著 Kapton Tape的端面，切入10mm寬度之切口於電路構件 連接用黏著劑4 0。將此電路構件連接用黏著劑4 0與 Kapton Tape層合體之一端，自晶圓剝離，固定於拉伸測 定機之拉伸治具。強壓晶圓於台上’將短片上拉’進行 9 0。剝離試驗，自晶圓剝離電路構件連接用黏著劑4 0。如 此操作而可測定電路構件連接用黏著劑4 0與半導體晶圓 之黏著力。 附電路構件連接用黏著劑40之吸引步驟、位置核對 -22- 200919657 步驟、加熱加壓步驟係可以通常的覆晶式黏晶機進行。本 說明書中，可辨別位置核對記號係指使用覆晶式黏晶機之 晶片辨別用裝置，所拍取位置核對記號的影像及所登記之 位置核對記號的影像之整合性良好，可進行核對位置的作 業。此辨別裝置通常係由具有鹵素燈之鹵素光源、光導管 (Light Guide )、照射裝置、CCD ( Charge-Coupled Device,電荷藕合元件）相機所構成。判斷以CCD相機所 拍取影像與由影像處理裝置所預先登記之位置核對用之影 像圖型之整合性，進行位置核對作業。 例如使用 AthleteFA股份有限公司製，商品名覆晶式 黏晶機C B - 1 0 5 0，電路構件連接用黏著劑4 0係與黏著於 具有突出連接端子的面之層合體之連接端子面相反面，吸 引層合體於覆晶式黏晶機之吸附噴嘴後，以裝置內之辨別 裝置，透過電路構件連接用黏著劑層，拍攝半導體晶片表 面所形成之辨別記號，取得與預先拍取於影像處理裝置之 半導體晶片之辨別記號之整合性，可判斷可核對位置者作 爲可辨別電路構件連接用黏著劑，不能核對位置者作爲不 能辨別電路構件連接用黏著劑。 進行吸引步驟、位置核對步驟，假固定位置核對後之 半導體晶片於基板後，亦可以僅進行壓著之壓著機加熱加 壓以連接。另外，不僅加熱加壓，亦可外加超音波下進行 連接。 以下係由實施例說明本發明。 -23- 200919657 【實施方式】 實施例 (實施例1 ) (1 -1)製作樹脂組成物清漆 將作爲熱交聯性樹脂之1 5重量份之環氧樹脂（大阪 GAS化學製，商品名EX- 1 020 )及20重量份之含有環氧 基之丙烯酸橡膠（Nagase Chemtex股份有限公司製，商品 名XTR-8 6 0P-3 ’重量平均分子量爲30萬）、作爲硬化劑 之3 0重量份之苯酚芳烷基樹脂（三井化學股份有限公司 製，商品名XL C-LL )及35重量份之微膠囊型硬化劑（旭 化成股份有限公司製，商品名HX-3 94 1 HP )、以及1重量 份之砂院交聯劑（T 0 r a y D 〇 w C 〇 r n i n g s i 1 i c ο n e s股份有限 公司製，商品名SH6040 )，溶解於甲苯及醋酸乙酯之混 合溶劑，得到樹脂組成物清漆。 (1 -2 )測定樹脂組成物之折射率 使用滾輪塗佈機塗佈（1 -1 )所得之部份樹脂組成物 清漆於分離薄膜（p E T薄膜）上後，以7 0 °c之烤箱乾燥 1 〇分鐘’得到於分離薄膜上厚度爲25 μπι之樹脂組成物膜 。以此爲折射率測定用膜。設置所得之折射率測定用膜於 阿貝折射計（鈉D線）試料台，剝離分離薄膜，滴下1滴 匹配油（matching oil ) ’放上折射率爲1 _74之試驗片， 測定折射率。此結果係樹脂組成物之折射率爲1 . 5 9 ( 2 5 T： -24- 200919657 (1 - 3 )確認含複合氧化物粒子層之透過性 秤量（1 -1 )所得之樹脂組成物清漆，加入5 0重量份 之平均粒徑爲0.1 μηι之二氧化矽二氧化鈦粒子1 ( Tokuyama股份有限公司製，折射率爲1.58)，攪拌使分 散。接著，使用滾輪塗佈機塗佈清漆於分離薄膜（PET薄 膜）上後，以70 °C之烤箱乾燥1 〇分鐘’得到於分離片上 厚度爲25μιη的膜，以此爲透過性確認用薄膜。使用UV-V I S分光光度計’以波長爲5 5 5 nm ’測定上述透過性確認 用薄膜之可見光並行透過率之結果’可見光並行透過率爲 40%。 (1 - 4 )製作含複合氧化物粒子層 秤量（1 -1 )所得之樹脂組成物清漆，加入5 0重量份 之作爲複合氧化物粒子之平均粒徑爲0.1 μ®之二氧化矽二 氧化鈦粒子1，攪拌使分散。接著’使用滾輪塗佈機塗佈 清漆於分離薄膜（PET薄膜）上後’藉由以70 °C之烤箱乾 燥1〇分鐘，製作於分離片上含複合氧化物粒子之厚度爲 2 0 μιη之樹脂組成物層。含複合氧化物粒子層之材料組成 係以重量份爲基準，如表1所示。 (1 -5 )製作含複合氧化物粒子及導電粒子層 於以聚苯乙嫌爲核之粒子表面，設置厚度爲〇.2μιη之 鎳層，於鎳層的外側，設置厚度爲〇.〇4μιη之金層，製作 -25- 200919657 平均粒徑爲3 μιη之導電粒子。除了加入此導電粒子以外 與（1 -4 )製作含複合氧化物粒子層相同的步驟，製作 分離片上含複合氧化物粒子及導電粒子之厚度爲5μπι之 脂組成物層。含複合氧化物粒子及導電粒子層之材料組 係以重量份爲基準，如表2所示。 (1 -6 )製作電路構件連接用黏著劑 以層合機黏著上述之含複合氧化物粒子層，以及上 之含複合氧化物粒子及導電粒子層，製作厚度爲25μηι 電路構件連接用黏著劑。 (實施例2 ) 除了使用平均粒徑爲〇 · 3 μηι之二氧化矽二氧化鈦粒 2 ( Tokuyama股份有限公司製，折射率爲1 .59 )作爲複 氧化物粒子以外，與實施例1同樣地以表1及表2所示 成，製作含複合氧化物粒子層以及含複合氧化物粒子及 電粒子層，使用此等與實施例1同樣地製作電路構件連 用黏著劑。 (實施例3 ) 除了使用平均粒徑爲0 · 1 μιη之二氧化矽二氧化鈦粒 3 (Tokuyama股份有限公司製，折射率爲1.60)作爲複 氧化物粒子以外，與實施例1同樣地以表1及表2所示 成，製作含複合氧化物粒子層以及含複合氧化物粒子及 於 樹 成 述 之 子 合 組 導 接 子 合 組 導 -26- 200919657 電粒·子層’使用此等與貫施例1同樣地製作電路構件連接 用黏著劑。 (實施例4 ) 除了使用平均粒徑爲0 · 3 μχη之二氧化矽二氧化鈦粒子 2 ( Tokuyama股份有限公司製，折射率爲159)作爲複合 氧化物粒子以外’與實施例1同樣地以表1及表2所示組 成’製作含複合氧化物粒子層以及含複合氧化物粒子及導 電粒子層’使用此等與實施例1同樣地製作電路構件連接 用黏著劑。 (實施例5 ) (5 - 1 )製作樹脂組成物清漆 將作爲熱交聯性樹脂之2 0重量份之環氧樹脂（J ap an Epoxy Resins股份有限公司製，商品名EP 1 03 2H60)及15 重量份之環氧樹脂（大阪GAS化學製，商品名EX- 1 020 ) 、2 5重量份之苯氧樹脂（東都化成股份有限公司製，商品 名FX2 93 )、40重量份之微膠囊型硬化劑（旭化成股份有 限公司製，商品名XP-3 94 1 HP )以及1重量份之矽烷交聯 劑（Toray Dow Corning silicones股份有限公司製，商品 名SH6040 )，溶解於甲苯及醋酸乙酯之混合溶劑中，得 到樹脂組成物清漆。 (5-2 )測定樹脂組成物之折射率 -27- 200919657 使用滾輪塗佈機塗佈（5 - 1 )所得之部份樹 清漆於分離薄膜（PET薄膜）上後，以7(TC之 1 〇分鐘，得到於分離薄膜上厚度爲2 5 μιη之樹脂 。以此爲折射率測定用。設置所得之折射率測定 貝折射計（鈉D線）試料台，剝離分離薄膜，滴 配油（matching oil)，放上折射率爲1.74之試 定折射率。此結果係樹脂組成物之折射率爲1 . 5 9 (5 -3 )確認含複合氧化物粒子層之透過性 坪量（5 -1 )所得之樹脂組成物清漆，加入 份之作爲複合氧化物粒子之平均粒徑爲0.3 μιη之 二氧化鈦粒子 2 ( Tokuyama股份有限公司製， 1.59)，攪拌使分散後，使用滾輪塗佈機塗佈於 (PET薄膜）上後，以70 °C之烤箱乾燥1 0分鐘 分離片上厚度爲2 5 μιη的膜。以此爲透過性確認 使用UV-VIS分光光度計，以波長爲5 5 5nm測定 性確認用薄膜之透過率之結果，透過率爲70%。 (5 _ 4 )製作含複合氧化物粒子層 秤量（5 - 1 )所得之樹脂組成物清漆，加入 份之作爲複合氧化物粒子之平均粒徑爲0.3μιη之 二氧化鈦粒子2，攪拌使分散後，使用滾輪塗佈 分離薄膜（PET薄膜）上後，藉由以70°C之烤f 脂組成物 烤箱乾燥 組成物膜 用膜於阿 下1滴匹 驗片，測 (25°c ) 10 0重量 二氧化矽 折射率爲 分離薄膜 ，得到於 用薄膜。 上述透過 1 0 0重量 二氧化矽 機塗佈於 乾燥10 -28- 200919657 分鐘，製作於分離片上含複合氧化物粒子之厚度爲20μπι 之樹脂組成物層。含複合氧化物粒子膜之材料組成係以重 量份爲基準，如表1所示。 (5 - 5 )製作含複合氧化物粒子及導電粒子層 於以聚苯乙烯爲核之粒子表面，設置厚度爲〇.2μιη之 鎳層，於鎳層的外側，設置厚度爲〇.〇4μιη之金層，製作 平均粒徑爲3 μιη之導電粒子。除了加入此導電粒子以外， 與（5 -4 )製作含複合氧化物粒子層相同的步驟，製作於 分離片上含複合氧化物粒子及導電粒子之厚度爲5μπι之樹 脂組成物層。含複合氧化物粒子及導電粒子層之材料組成 係以重量份爲基準，如表2所示。 (5-6 )製作電路構件連接用黏著劑 以層合機黏合上述之含複合氧化物粒子層，以及上述 之含複合氧化物粒子及導電粒子層，製作厚度爲25μπι之 電路構件連接用黏著劑。 (實施例6 ) 與實施例5同樣地得到樹脂組成物清漆。秤量清漆， 加入1 00重量份之作爲複合氧化物粒子之平均粒徑爲 〇·3μιη之二氧化砂二氧化鈦粒子2 (Tokuyama股份有限公 司製，折射率爲1 . 5 9 )，攪拌分散，使用滾輪塗佈機塗佈 於分離薄膜（PET薄膜）上後，以70°C之烤箱乾燥1 〇分 -29- 200919657 鐘，得到於分離片薄膜上厚 黏著劑。 爲45 μιη之電路構件連接用 (比較例1 ) 除了改變實施例1之二壽 徑爲0·2μιη之二氧化矽粒子 S Ε 1 0 5 0，折射率爲1.4 6 )以夕 及表2所示組成製作含複合_ 粒子及導電粒子層，使用此等 化矽二氧化鈦粒子成平均粒 (Admatechs社製，商品名 ，與實施例1同樣地以表1 化物粒子層與含複合氧化物 製作電路構件連接用黏著劑 (比較例2 ) 除了改變實施例1之二_ 徑爲〇.5μιη之二氧化矽粒子 SE2050，折射率爲1.46)以外 及表2所示組成製作含複合孽 物粒子及導電粒子層，使用此 劑。 (比較例3 ) (3 ’ -1 )製作樹脂組成物清漆 混合作爲熱交聯性樹脂之 型環氧樹脂（東都化成股 YDCN700- 1 0 )及50重量份之 化矽二氧化鈦粒子成平均粒 (Admatechs社製，商品名 ，與實施例1同樣地以表1 化物粒子層以及含複合氧化 等製作電路構件連接用黏著 5 〇重量份之甲酚漆用酚醛 份有限公司製，商品名 含有環氧基之丙烯酸橡膠（ -30- 200919657200919657 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to an adhesive for connecting circuit members and a semiconductor device. [Prior Art] As a method of directly packaging a semiconductor wafer on a circuit substrate by face down bonding, it is known that an electrode ηβ part of a semiconductor wafer forms a solder bump (s ο 1 derbump ), and the solder is connected to A method of electrically connecting a circuit board to a circuit substrate electrode by applying a conductive adhesive to a bump electrode provided in the semiconductor wafer. In these methods, since the pressure due to the difference in thermal expansion coefficient between the bonded wafer and the substrate occurs at the connection interface when exposed to various environments, there is a problem that the connection reliability is lowered. Therefore, the review of the purpose of easing the pressure of the connection interface generally fills the gap between the wafer and the substrate at the bottom of the epoxy resin or the like. As a charging method of the bottom charging material, there is a method of injecting a low-viscosity liquid resin after connecting the wafer and the substrate, and a method of mounting the wafer by placing the bottom filling material on the opposite side of the f. Further, there is a method of applying a liquid resin and a method of adhering a film-like resin as a method of mounting a wafer on a substrate. However, when a liquid resin is applied, it is difficult to control a precise coating amount by a disperser. In recent years, when the amount of coating is too large, the amount of coating is too large, and the resin oozing out during bonding contaminates the side surface of the wafer and contaminates the bonding tool. The cleaning tool must be cleaned. This becomes a cause of cumbersome steps in mass production. Further, in the case of the adhesive film -4-200919657 film-like resin, it is easy to determine the optimum thickness by controlling the thickness of the resin, but it is necessary to say that the film is applied to the substrate in a pseudo-pressure step. In the squeezing step, a reel-shaped tape having a slitting width ratio larger than that of the target wafer is used, and the substrate is embossed by heat pressing in accordance with the wafer size and the temperature at which the adhesive is not reacted on the half-cut substrate. To ensure productivity, the film adhered to the dummy pressing step is larger than the wafer size. However, when the film is larger than the wafer size, the distance between the adjacent parts is kept, which hinders the high-density package. Therefore, the method of making an adhesive of the same size as the wafer reveals that after the adhesive is applied to the wafer, the crystal is diced by fj, and the adhesive is processed at the same time to obtain an adhesive. For example, in the method of Patent Document 1, a film-like adhesive is adhered to a sheet to obtain a wafer with an adhesive film, and a laminate of a wafer/adhesive/separator is formed and cut. The separator was separated to obtain a wafer with an adhesive attached thereto. However, when the method is combined, the adhesive and the separator are peeled off, and a wafer is scattered. Patent Document 2 relates to a method of using an adhesive material layer and an adhesive layer processing tape to disclose a method in which a paste wafer is diced in a wafer processing paste and a flip chip is bonded to a wafer. Generally, the flip chip package is connected to a terminal on the substrate side of the wafer circuit surface, which is called a bump, and the width of the wafer side is checked and the resin amount is added. Generally, the film is processed in a supply state. The method is after the wafer. After this, after stripping and cutting the semi-conductive wafer strip, the terminal and the substrate side -5-200919657 are checked at the position 'with the flip-chip bonding machine check position'. When the adhesive is applied to the surface of the chip, the position is checked by the position of the adhesive covering the circuit surface, so the position check mark must be confirmed by the adhesive. In order to confirm the position of the circuit surface of the wafer by the adhesive, it is considered as a solution to increase the transmittance of the adhesive. Generally, the compatibility of the components with high compatibility is high, and the resin composition of the morphology (m 〇 r p h ο 1 〇 g y ) is high. On the other hand, since the resin composition in which phase separation occurs is light-scattered inside the resin, the transmittance is lowered. Therefore, the composition of the uniform shape can be used to construct an adhesive which can easily distinguish the position check mark. On the other hand, an adhesive for a semiconductor is required to have high adhesion for stress generated by a difference in thermal expansion coefficient between a wafer and a substrate, high heat resistance for a reflow temperature, and low thermal expansion for a high temperature environment, and corresponding The commercial reliability of the low moisture absorption rate used in the wet environment of the commercial temperature bureau. As a means of improving the characteristics, it is possible to achieve a high heat resistance and high adhesion with a composition having a small coefficient of expansion of the cerium oxide added to the epoxy resin. However, when the cerium oxide is mixed with the epoxy resin, the interface between the cerium and the epoxy resin scatters, so the transmittance is poor, and it is difficult to obtain transparency. Patent Document 3 describes a method for obtaining transparency when a resin is added to a resin, and comprises an insulating adhesive and an anisotropic conductive film of conductive particles and transparent glass particles dispersed in the adhesive. Patent Document 1: Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. 2006-049482. Patent Document 3: Patent No. 3 4 0 8 3 0 No. 200919657 [Description of the Invention] Problem to be Solved However, even when the glass particles are transparent, light scattering occurs when the refractive index of the resin that disperses the glass particles is different. Therefore, the transparency is impaired by dispersing the glass particles. Therefore, it is still not possible to mix the particles to obtain transparency, and only the particles themselves are transparent. The bottom-filling method of the wafer-pre-type type of the above-mentioned Patent Documents 1 to 3 is not generalized in the market because of various problems. Therefore, the present invention provides a circuit member for connecting a circuit member, which can recognize the identification mark of the circuit surface of the wafer, and which can be connected to the circuit member without electrical conduction failure and a stable low connection resistance. Adhesives for connection are the subject. Solution to Problem The present invention provides a heat of a resin composition containing a heat-crosslinkable resin and a curing agent reactive with the heat-crosslinkable resin, and a composite oxide particle dispersed in the resin composition. Adhesive for connecting a hardened circuit member. When the circuit member is connected by using the adhesive for connecting the circuit member of the present invention, the adhesive for connecting the circuit member can be transmitted through the connection, and the identification mark of the surface of the chip can be discriminated, and the connection of the circuit member can be performed without causing a failure of the current. Stable low connection resistance. The average particle size of the composite oxide particles is 〇 · 1 μιη~0. 5 μηι is suitable for 200919657. In the above range, the composite oxide particles are dispersed in the resin composition to reinforce the resin composition. In addition, improve connection stability. The adhesive for connecting the circuit member is 100 parts by weight with respect to the resin composition, and the composite oxide particles are preferably contained in an amount of 2 Torr to 150 parts by weight. When the amount of the oxide particles is 20 parts by weight or more, the linear expansion coefficient of the circuit member-bonding agent is lowered, and the modulus of elasticity is increased. Therefore, the reliability of connection between the conductor wafer and the substrate after pressing is further improved. When the amount of the composite oxide is less than 150 parts by weight, the melt viscosity of the adhesive for component connection is lowered as compared with the case of more than 150 parts by weight, so that it is easy to connect the circuit of the projecting electrode and the substrate. The adhesive for connecting the circuit member has a parallel transmittance of 1 5 to visible light when it is not hardened. The visible light parallel ratio in the above range is also easy to discern the recognition mark of the wafer circuit surface. The refractive index of the composite oxide particles is 1 .  5~1 _ 7 is appropriate. When the value is within the above range, the visible light of the adhesive for connecting the circuit member increases, and the probability of the chip circuit surface is easily recognized. The resin composition is preferably a copolymerizable resin containing at least one functional group reactive with a solvent or a thermally crosslinkable resin in a branch, and is preferably heated at 18 (TC) for 20 seconds. The reaction rate of the circuit member connecting agent calculated by the calorific value of the post-difference scanning calorimeter is preferably 80% or more. When the reaction rate is 80%, the connection stability is improved. The expansion coefficient of 40 0 to 1 0 0 t after hardening is 70 X 1 (T6/° C or less is preferred. The weight of the semi-particle circuit conductor in the linear expansion system after hardening is 100% transmitted through When the firing rate is hardened, the expansion ratio of the semiconductor wafer is -8 - 200919657. When the temperature exceeds 70x1 0_6/°C, it is difficult to maintain the connection terminals of the semiconductor wafer due to temperature change after packaging or expansion of heat absorption and moisture absorption. The tendency of the electrical connection between the wirings of the circuit board. The adhesive for connecting the circuit components of the present invention is such that the semiconductor wafer having the protruding connection terminals and the circuit substrate having the wiring pattern can be electrically connected by the connection terminals and the wiring pattern. Adhesive The present invention provides a semiconductor substrate having a wiring pattern, a semiconductor wafer having a protruding connection terminal mounted on the circuit substrate, and an adhesive layer interposed between the circuit substrate and the semiconductor wafer, and connected. The terminal and the wiring pattern are electrically connected, and the adhesive layer is a semiconductor device formed by the above-described adhesive for connecting circuit members of the present invention. The semiconductor device of the present invention does not cause an electric conduction failure, and maintains a stable low connection resistance. According to the present invention, it is possible to provide a circuit for connecting a circuit member, a sensor for connecting a circuit member, a discriminating mark of a circuit surface of the chip, and a circuit for connecting a circuit member without a power failure and a stable low connection resistance. An adhesive for connecting components. A semiconductor device obtained by using the above-described adhesive for connecting circuit members can be provided. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, suitable implementation of the present invention will be described in detail with reference to the drawings. Type. In addition, in the schema, the same symbol is given to the same In addition, the positional relationship of up, down, left, and right, etc., unless otherwise the exception -9-200919657, is based on the positional relationship represented by the schema. In addition, the size ratio of the drawing is not limited to the ratio shown in the figure. The adhesive for connecting circuit members is formed of a resin composition containing a heat crosslinkable resin and a curing agent reactive with the thermally crosslinkable resin, and a composite oxide particle dispersed in the resin composition. Fig. 1 is a cross-sectional view showing an embodiment of a circuit connecting material including an adhesive for connecting circuit members. The circuit connecting material 1 shown in Fig. 1 is provided with a film-like circuit member for bonding. The agent 40 and the two separators 10 disposed on both sides of the adhesive for bonding the circuit member 40. The circuit member connecting adhesive 40 has a spherical composite oxide particle layer 20, and spherical composite oxide particles and a conductive particle layer 30 laminated thereon. The composite oxide-containing particle layer 20 is formed of the resin composition 21 and the composite oxide particles 2 2 dispersed in the resin composition 21. The composite oxide-containing particles and the conductive particle layer 30 are formed of the resin composition 31 and the composite oxide particles 22 and the conductive particles 33 dispersed in the resin composition 31. Separator 1 A ruthenium-peelable resin film. The resin compositions 2 1 and 3 1 each contain a thermosetting resin composition of a heat crosslinkable resin and a curing agent. The resin composition 2 1 constituting the layer 20 containing the composite oxide particles 22 and the resin composition 3 1 constituting the composite oxide particles 2 2 and the conductive particles 3 3 may be the same or different. The heat crosslinkable resin contained in the resin composition 2 1 and/or 31 is reacted with a hardener to form a resin having a crosslinked structure. As the heat crosslinkable resin, an epoxy resin is preferred. In particular, it is preferable to use a phenolic solid epoxy resin for naphthol paint, a liquid containing a fluorene skeleton, or a solid epoxy resin because it requires high permeability and high Tg, and -10-200919657 low linear expansion coefficient. In addition to the epoxy resin, as the thermal crosslinkable resin contained in the resin composition 21 and/or 31, a bismaleimide resin, a triazine resin, a polyimide resin, a polyamide resin can be used. , cyanoacrylate resin, phenolic resin, unsaturated polyester resin, melamine resin, urea resin, polyurethane resin, polyisocyanate resin, furan resin, resorcinol resin, xylene resin, benzoquinone A fecal amine resin, a diallyl phthalate resin, a decyloxy resin, a polyvinyl butyral resin, a decane-modified polyamidoximine resin, an acrylate resin, or the like. These may be used alone or in combination of two or more. The heat crosslinkable resin may be a copolymerizable resin containing at least one functional group reactive with a hardener or the above thermally crosslinkable resin in a branched chain. As such a copolymerizable resin, a propylene-based copolymer containing an epoxy group, a carboxyl group or a hydroxyl group which is a functional group reactive with the above-mentioned thermally crosslinkable resin is preferably used. In particular, an epoxy group-containing propylene-based copolymer obtained by using a glycidyl acrylate, glycidyl methacrylate or the like as a copolymerization component is preferred. Others may also use hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. Ester, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl methacrylate, mercapto methacrylate, lauryl (meth) acrylate, stearin (Meth)acrylic acid vinegar, trimethylcyclohexyl methacrylate, tricyclodecyl methacrylate, tetracyclododecyl _3_acrylic acid vinegar, etc. Aliphatic, ethylbenzene toluene, polypropyl-11 - 200919657 diol monomethacrylate, hydroxyethyl acrylate, acrylonitrile, benzyl methacrylate, cyclohexyl maleic anhydride imine, etc. as a copolymerization component A copolymer resin used. The hardener reactive with the thermally crosslinkable resin may be selected from the group consisting of phenolic, imidazole, lanthanide, thiol, benzoxazine, boron trifluoride-amine complex, sulfonium salt, amine sulfimine A polyamine salt, a dicyandiamide, and an organic peroxide-based hardener. In order to prolong the usable time, the above hardener may be a microcapsule type hardener. The microcapsule-type hardener is made of a hardener as a core, a polymer material such as polyurethane, polystyrene, pectin or polyisocyanate, or an inorganic substance such as calcium citrate or zeolite, or nickel or copper. The film such as the metal thin film is substantially covered. The average particle diameter of the microcapsule-type hardener is 1 μm or less, and preferably 5 μm or less. In order to increase the adhesion strength, the resin compositions 21 and/or 31 may also contain a crosslinking agent. To aid film formation, it may also contain polyester, polyurethane, polyvinyl butyral, polyacrylate, polymethyl methacrylate, acrylic rubber, polystyrene, phenoxy resin, NBR ( Acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), polyamidene or polyoxyalkylene modified resin (propylene polyoxyalkylene, epoxy polyoxyalkylene, polyfluorene) A thermoplastic resin such as an imine polysiloxane may be contained in the resin composition 21 and/or 31. Further, for the purpose of modifying the surface of the composite oxide particles, an eucalyptus oil, a polyoxyalkylene oxide, a polyoxyalkylene oligomer or a crosslinking agent may be contained. The refractive index of the resin composition 2 1 and/or 3 1 after hardening is 1.  5~1.  7 is appropriate. In order to make the refractive index after hardening in the above range, the uncured state is -12-200919657 and the radiance is 1 · 5~1 .  7 is appropriate. The refractive index of the uncured state is 丨·5 or more to disperse the high refractive index component in the resin composition 2 1 and/or 31. As such a high refractive index component, for example, a compound containing a nitrogen atom in a molecule such as an imidazole compound and an amine-based curing agent used as a curing catalyst for an epoxy resin can be mentioned. On the other hand, the refractive index of the uncured state is 1. 7 or less ' may contain a low refractive index component in the resin composition 21 and/or 31. When the low refractive index component is dispersed in the resin composition 2 1 and/or 3 1 , the refractive index of the resin composition 2 1 and/or 3 1 tends to be low. As such a low refractive index component, a high molecular weight thermoplastic resin can be improved. The thermoplastic resin having a high molecular weight may, for example, be a copolymer of phenoxy resin or acrylic acid. By including the high refractive index component and the low refractive index component in the resin composition 2 1 and/or 3 1 , the refractive index of the resin composition 2 1 and/or 3 1 in the uncured state can be made 1.  6 or so. The refractive index of the resin compositions 2 1 and 3 1 can be measured using an Abbe refractometer using a sodium D line (589 μm) as a light source. The refractive index of the composite oxide particles 22 is 1. 5~1. 7, and the refractive index difference between the resin compositions 21 and/or 31 is ±0. Within 1 is appropriate '±0. Especially within 05. If the refractive index difference exceeds ±0.  When the inside of 1 is added, the composite oxide particles 22 are added to the resin composition 2 1 and/or 3 1 to have a tendency to reduce the transmittance. In particular, when the film thickness of the adhesive for connecting the circuit member 40 is large, it is difficult to discriminate the position check mark formed by the circuit surface of the semiconductor wafer by the adhesive for connecting the circuit member to which the surface of the semiconductor wafer having the protruding connection terminal is adhered. The trend. The refractive index of the composite oxide particles 2 2 was measured using a microscope by the Becke method. -13- 200919657 The composite oxide particles 22 are preferably composed of a metal oxide or a crystallized metal oxide which contains two or more kinds of metals. As such a metal oxide, a composite oxide containing at least one metal selected from the group consisting of aluminum, magnesium, and titanium, and two or more other metals is preferable. A composite oxide containing titanium and ruthenium is particularly preferable because it is easy to adjust the refractive index from the composition ratio, and it is particularly preferable to contain cerium oxide and titanium dioxide. The cerium oxide-containing cerium oxide particles containing cerium oxide and titanium dioxide can be produced by a sol-gel method, and a commercially available product can also be used, and the composite oxide particles 2 2 are preferably used. The average particle diameter of the composite oxide particles 22 is 0. 1~0. 5 μιη is suitable. If the average particle size is less than 0 · 1 μ m, it is 0.  When the surface area is larger than 1 μm, the surface energy is also increased because the specific surface area of the particles is large. As a result, the interaction between the particles becomes large, and aggregates occur, and the dispersion tends to decrease. Further, even when the dispersibility is good, the specific surface area is large, and when it is dispersed in the resin composition 2 1 and/or 3 1 , the viscosity is increased, and the moldability is liable to lower. The average particle diameter of the composite oxide particles 22 exceeds 0. When 5μιη, with 0. When the ratio is 5 μm or less, the flow ratio of the resin composition 2 1 and/or 3 1 is large due to the small specific surface area of the particles, and voids are likely to occur during molding. Further, when the particle diameter is increased, when the composite oxide particles 22 are dispersed in the same amount of addition, the particle diameter is small, and the number of particles is small. This result is one of the purposes of dispersing the composite oxide particles 22, and the reinforcing effect of the resin composition 2丨 and/or 3丨 tends to be small. Further, when the particle diameter of the composite oxide particles 22 is large, the composite oxide particles 22 surround the bumps of the wafer and the electrodes of the circuit board, and the electrical characteristics are likely to be hindered. In particular, when the package is formed by a low-voltage package or when the bump is formed of a hard material such as nickel, the composite oxide particles 22 become difficult to be immersed in the connection. As a result, when the connection is made, the contact between the bump and the electrode of the circuit board is hindered, or when the conductive member 3 for the circuit member connection contains the conductive particles 3 3, the conductive particles 3 3 are flattened, and the electrical connection is easily hindered. When the maximum particle diameter of the composite oxide particles 22 is 40 μm or more, the particle diameter of the composite oxide particles 22 is larger than the gap between the wafer and the substrate. At this time, the composite oxide particles 22 may damage the circuit of the connection terminal of the wafer or the substrate due to the pressurization at the time of packaging. The composite oxide particles 2 2 are preferably those having a specific gravity of 5 or less, preferably 2 to 5, and more preferably 2 to 3 · 2 . When the specific gravity exceeds 5, when the varnish is added to the resin composition 2 1 and/or 31, when the specific gravity difference is large, precipitation is likely to occur in the varnish. As a result, it is difficult to obtain the circuit member connecting adhesive 40 in which the composite oxide particles 22 are uniformly dispersed. The coefficient of linear expansion of the composite oxide particles 22 is in a temperature range of 0 to 700 ° C or less, preferably 7 x 1 〇 6 / ° C or less, preferably 3 x 1 (more preferably T6 / ° C or less. Composite oxide particles 22 When the coefficient of linear expansion is small, the amount of the composite oxide particles 22 to be added can be reduced in order to reduce the coefficient of linear expansion of the adhesive 40 for connecting the circuit members. The adhesive for connecting the circuit members 40 is based on the resin composition 2 1 and/or 31. 100 parts by weight, preferably 20 to 150 parts by weight of the composite oxide particles 22, particularly preferably 25 to 1 part by weight, particularly preferably 50 to 100 parts by weight. Composite oxide particles 2 2 When the amount is less than 20 parts by weight, the linear expansion coefficient of the adhesive for connecting the circuit components 40 increases and the elastic modulus decreases. This results in the reliability of the connection between the semiconductor wafer and the substrate after pressing. On the other hand, when the amount of the compound exceeds 1 50 -15 to 2009 19657 parts by weight, the melt viscosity of the adhesive for connecting the circuit components 40 tends to increase. As a result, the protruding electrode and the substrate circuit of the semiconductor become very large. Difficult to connect. The invention The adhesive for connecting the circuit member 40 can absorb and disperse the conductive particles in addition to the composite oxide particles 22 in order to absorb the unevenness of the bumps or the substrate electrodes of the bonded wafers and positively impart anisotropic conductivity. The layer 30 containing the composite oxide particles 22 and the conductive particles 33. The conductive particles 33 are particles containing metal such as Au, Ag, Ni, Cu, or solder, or carbon particles, and the average particle diameter is 1 to 1 Ο μιη. Preferably, in order to obtain a sufficient pot life, the surface layer of the conductive particles 33 is not a transition metal such as Ni or Cu, and is preferably formed of a noble metal such as Au, Ag or uranium. The Au layer may be formed by coating a surface of a transition metal such as Ni with a noble metal such as Au. The conductive particles 3 3 are coated with a non-conductive glass, ceramic, plastic, or the like, and the outermost layer is a noble metal. When the metal particles are thermally melted, the conductive particles obtained by heating and pressurizing have deformability, and the height of the absorption electrode is not uniform. As a result, the contact area with the electrode increases, and the reliability increases. In order to obtain a good electrical resistance, the thickness of the coating layer of the noble metal of the conductive particles 3 3 is preferably 100 A or more. However, when a noble metal layer is provided on a transition metal such as Ni, mixing and dispersing the conductive particles 3 3 occurs. When the noble metal layer is defective, the redox effect is likely to occur. This result is due to the decrease in storage stability due to free radicals generated, so the thickness of the coating layer of the noble metal is preferably 300 A or more. The thickness of the coating layer of the noble metal is changed. When thick, because these effects are saturated, the maximum is Ιμπι is appropriate-16 - 200919657, but it is not limited to this. The conductive particles 3 3 are relative to 100 parts by volume of the resin composition 3 1 ' at 0. The range of 1 to 30 parts by volume is adjusted according to the use. In order to prevent the adjacent circuit short circuit caused by the excess conductive particles 33, the voltage is 0. 1 to 1 part by volume is particularly preferred. The circuit member connecting adhesive 40 may not have the layer 30 containing the composite oxide particles 22 and the conductive particles 33. The adhesive for connecting the circuit member 40 has a visible light transmittance of 15 to 100% when uncured, and has a parallel transmittance of 18 to 100% of visible light, and has a parallel transmittance of 25 to 100% of visible light. it is good. If the parallel transmittance of visible light is less than 1 5%, it will be difficult to discriminate the recognition symbol by the flip chip bonder, and the position matching operation becomes difficult. The visible light parallel transmittance system can be measured by Hitachi Manufacturing Co., Ltd., and the product name is U-3310 spectrophotometer. For example, a PET film made by Teijin DuPont Film Co., Ltd. with a film thickness of 50 μ: η (trade name Purex, 5 5 5 nm transmittance 8 6. 03) Baseline correction was performed for the reference material, and the parallel transmittance of the visible light range of 4 〇〇 nm to 800 nm was measured by coating the circuit member bonding adhesive 40 to the PET substrate at a thickness of 25 μm. In the relative intensity of the wavelength of the halogen light source and the light guide used in the flip chip type crystal machine, since the 5 5 5 nm to 60 0 nm is the strongest, in the present invention, the parallel transmittance of visible light can be performed at a transmittance of 5 5 5 mm. Determination. When the circuit member connecting adhesive 40 is heated at 180 ° C for 20 seconds, the reaction rate calculated by the differential calorimeter (DSC) is preferably 80% or more. Here, the -17-200919657 reaction rate (unit: %) of the adhesive for connecting the circuit components is the initial heat generation by DSC measurement of the adhesion of the circuit member before heating, and the subsequent circuit components are connected. The amount obtained by DSC measurement using an adhesive is calculated as the calorific value after heating, and is calculated by the following formula (1). Reaction rate = (initial calorific value - calorific value after heating) / initial calorific value X1 〇〇 (adhesion of circuit member after heating for 20 seconds at 180 ° C; the reaction rate is 80% or more, The connection terminal is connected to the wiring pattern and mechanically. In addition, when the connection is cooled and contracted, the connection between the terminal and the wiring pattern can be connected. The circuit component is connected with the adhesive 40 and the cured 4 0~1 0 0 The coefficient of expansion at °C is 70xl (T6/°C or less, 60xl〇-6/〇C is better than 50xl (T0/t: better). The linear expansion coefficient after hardening is 7〇xlO_6/ At ° C, it is difficult to maintain the electrical connection between the connection terminals of the semiconductor wafer and the wiring pattern of the circuit substrate due to the temperature change after the package or the heat absorption and moisture absorption. The circuit member connection adhesive 40 can be used to connect the semiconductor wafer with the protruding connection. A circuit board having a wiring pattern is used when the connection is electrically connected to the wiring pattern. The connection terminal is formed by a gold-plated gold stud bump formed by a gold wire. Or supersonic and use a hot metal ball in the heat The electrode of the body wafer is formed by electroplating or evaporation, and the connection terminal does not need to be composed of a single metal, and the heating can be heated by the agent fll 4 0. Block (fixed. Gold-18-200919657, silver, copper, nickel, indium, palladium, tin, antimony, etc., can also be laminated in the form of such metal component layers. In addition, the above has a connection terminal The semiconductor wafer may be in a state of a semi-conductive wafer having a protruding connection terminal, such that the protruding connection terminal of the semiconductor wafer is electrically connected to the substrate formed by the wiring pattern to configure the connection terminal and the wiring pattern. Preferably, the semiconductor wafer is provided with a check mark at the same surface position as the protruding connection terminal. The circuit board formed by the wiring pattern may be a normal circuit substrate 'or a semiconductor wafer. In the case of a substrate, the wiring pattern may be formed by impregnating an epoxy resin or a resin having a benzotriazine skeleton into a glass cloth or a non-woven fabric. An unnecessary portion of a metal layer such as copper formed on the surface of the substrate, the substrate having the build up, or the green substrate such as polyimide, glass, ceramic, or the like, is removed by etching to form. The surface of the insulating substrate can be formed by electroplating, and can be formed by evaporation or the like. The wiring pattern does not need to be formed of a single metal, and may also contain gold, silver, copper, nickel, indium, IS, tin. Most of the metal components, such as ruthenium, may also be in the form of a layer in which the metal components are laminated. When the substrate is a semiconductor wafer, the wiring pattern is usually made of aluminum, but gold or silver may be formed on the surface. A metal layer of copper, nickel, indium, bismuth, tin, or the like. The state in which the adhesive member 40 for bonding the circuit member is bonded to the surface of the semiconductor wafer having the connection terminal is as follows. (1) A semiconductor wafer having a protruding connection terminal before wafer formation, an adhesive for connecting a circuit member disposed on a protruding connection terminal surface of the semiconductor wafer, and an adhesive layer -19-200919657 are formed on the semiconductor wafer side. A laminate in which the dicing tape hardened by UV irradiation is laminated in the order of the dicing tape. (2) Cut into pieces by cutting. (3) The semiconductor wafer with the adhesive for bonding the circuit member 40 is peeled off from the dicing tape. (1) A laminate system comprising a semiconductor wafer, a circuit member connecting adhesive 40, and a dicing tape, and a laminated body of the laminated circuit member connecting adhesive 40 and the dicing tape, and having a heating mechanism and a pressure roller A wafer mounter or a wafer mounter having a heating mechanism and a vacuum pressurizing mechanism is available for lamination to a semiconductor wafer. In the laminate, the adhesive for bonding the circuit member 40 is the same area as the semiconductor wafer, and the dicing tape has a larger area than the adhesive for connecting the semiconductor wafer and the circuit member, and is larger than the inner size of the dicing frame and smaller than the outer size. Area. The lamination is preferably carried out at a temperature at which the circuit member connecting adhesive 40 is softened, for example, heating to 40 to 80 ° C is preferably carried out to heat to 60 to 8 (more preferably at TC for heating). It is better to laminate at 70 to 80 ° C. When laminating at a softening temperature of the adhesive for bonding the circuit member 40, the embedding around the protruding connection terminals of the semiconductor wafer is insufficient, and the voids are entangled. When peeling at the time of cutting, picking up (Pick Up), deformation of the adhesive for connecting the circuit member 4, poor recognition of the position when the position is checked, and deterioration of the connection reliability due to the gap (2) cutting When the laminate is composed of a semiconductor wafer, an adhesive for connecting circuit members, and a dicing tape, an IR (infrared) camera is used to recognize the wiring pattern or cut of the semiconductor wafer through the wafer. 200919657 The position check mark can be used to check the position of the scribe line. In the above laminate, the step of cutting the semiconductor wafer and the circuit member connecting adhesive 40 can be used. The conventional cutter is used. The cutter cutting system can be adapted to a step generally called cutting. The cutting is performed by cutting only the wafer as the first stage, and cutting off the remaining wafer in the cutting groove of the first stage. And the circuit member connection adhesive 40 and the cutting tape interface or the cutting tape inside the cutting stage is preferably cut. The cutting can also be applied to the use of laser cutting. After cutting, the usual exposure machine, etc., 1 5~ 3 0 m W, 1 5 0 to 3 0 0 M of the degree of UV irradiation of the dicing tape side. (3) The step of peeling off the dicing tape from the semiconductor wafer with the circuit member connecting adhesive 40 is performed by the semiconductor wafer layer The opposite surface of the joint surface is pressed, and the dicing tape is pressed to peel off the interface between the circuit member connecting adhesive 40 and the dicing tape after UV irradiation, and the adhesive for bonding the circuit member 40 can be irradiated to the UV. The adhesive tape has an adhesive force of 1 ΟΝ/m or less, and the adhesion to the semiconductor wafer is preferably 7 ΟΝ/m or more. When the adhesion of the UV-irradiated dicing tape exceeds 1 ON/m, the self-cutting is performed. Tape peeling and cutting The operation of the semiconductor wafer with the adhesive for connecting the circuit member 40 causes deformation of the wafer or deformation of the adhesive layer for connecting the circuit member. On the other hand, if the adhesion to the semiconductor wafer is less than 7 ON/m At the time of the impact caused by the rotary cutting of the cutting plate during cutting and the influence of the water pressure, the interface between the wafer and the circuit member connecting adhesive 40 is peeled off. -21 - 200919657 The adhesive for connecting the circuit components 4〇 The adhesive force of the dicing tape after UV irradiation can be measured as follows: The set heating temperature is set to 80 t; the laminator laminated circuit member is connected to the adhesive 40 on the wafer, and the adhesive face of the dicing tape before UV irradiation is oriented. The adhesive for bonding the circuit member 40 was laminated at 40 ° C, and then irradiated with UV on the side of the dicing tape at a level of 15 m W, 300 m J. The dicing tape after UV irradiation was cut into a slit having a width of 丨〇mm to prepare a short film for tensile measurement. The wafer is strongly pressed on the stage, and one end of the dicing tape fixed in a short piece is stretched on the tensile tester of the tensile measuring machine, and subjected to a 90° peeling test. The peeling circuit member is bonded with the adhesive 40 and the UV-cut dicing tape. Thus, the adhesive force of the peeling circuit member connecting adhesive 40 and the dicing tape after UV irradiation can be measured. The adhesion of the circuit member connecting adhesive 40 to the semiconductor wafer can be measured as follows. By setting the heating temperature to 8 (TC laminate laminating circuit member bonding adhesive 40 on the wafer, facing the adhesive surface, pasting Kapton Tape (made by Nitto Denko Co., Ltd., width 1 〇mm, thickness 25 μιη) on the circuit The member-bonding adhesive 40 is used to make a sufficient adhesion. Then, along the end face of the Kapton Tape, a 10 mm-wide slit is cut into the circuit member connecting adhesive 40. This circuit member is bonded with the adhesive 40 and Kapton Tape. One end of the laminate, which is peeled off from the wafer and fixed to the tensile jig of the tensile measuring machine. The strong pressed wafer is pulled up on the stage to perform the 90. Peel test, and the adhesion of the circuit member from the wafer is adhered. In this way, the adhesion between the adhesive for bonding the circuit member 40 and the semiconductor wafer can be measured. The suction step and position check of the adhesive for connecting the circuit member 40 - 200919657 Step, heating and pressurizing step It can be carried out by a conventional flip-chip type die bonder. In the present specification, the position-recognizable mark is a wafer discriminating device using a flip-chip type die-cutting machine, and the image of the position check mark is taken. The image of the registered position check mark has good integration and can be used for checking the position. The identification device is usually a halogen light source with a halogen lamp, a light guide, an illumination device, and a CCD (Charge-Coupled Device).藕 元件 ) 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The flip-chip type bonding machine CB - 1 0 50, the adhesive for connecting the circuit components 40 is opposite to the connection terminal surface of the laminate adhered to the surface of the surface having the protruding connection terminal, and the laminate is attracted to the flip chip. After the adsorption nozzle of the machine, the identification device formed in the device is used to connect the adhesive layer for connecting the circuit member to capture the identification mark formed on the surface of the semiconductor wafer, and the integration with the identification mark of the semiconductor wafer previously captured by the image processing device is obtained. It can be judged that the position can be checked as an adhesive for distinguishing circuit members, and the position cannot be checked. In order to discriminate the adhesive for connecting the circuit components, the suction step and the position collation step are performed, and after the semiconductor wafer after the pseudo-fixed position is collated on the substrate, the pressing and pressing machine may be used only for heating and pressing to connect. Pressurization may be carried out by adding an ultrasonic wave. The present invention will be described by way of examples. -23- 200919657 [Embodiment] Example (Example 1) (1 -1) Preparation of a resin composition varnish will be used as heat 15 parts by weight of an epoxy resin (manufactured by Osaka GAS Chemical Co., Ltd., trade name EX-1 020) and 20 parts by weight of an epoxy resin containing an epoxy group (manufactured by Nagase Chemtex Co., Ltd., trade name XTR-8) 6 0P-3 'weight average molecular weight is 300,000), 30 parts by weight of phenol aralkyl resin (manufactured by Mitsui Chemicals, Inc., trade name XL C-LL) and 35 parts by weight of microcapsule type as a curing agent A hardener (manufactured by Asahi Kasei Co., Ltd., trade name HX-3 94 1 HP), and 1 part by weight of a sandstone crosslinker (T 0 ray D 〇w C 〇rningsi 1 ic ο nes Co., Ltd., Name SH6040), was dissolved in toluene, and a mixed solvent of ethyl acetate to obtain a resin composition varnish. (1 - 2 ) Determining the refractive index of the resin composition Using a roller coater to coat a portion of the resin composition varnish obtained by (1 -1 ) on a separation film (p ET film), an oven at 70 ° C was used. Drying for 1 ' minutes' obtained a resin composition film having a thickness of 25 μm on the separation film. This is used as a film for refractive index measurement. The obtained film for measuring the refractive index was placed on an Abbe refractometer (sodium D line) sample stage, and the separation film was peeled off, and one drop of matching oil was dropped. A test piece having a refractive index of 1 to 74 was placed, and the refractive index was measured. This result is that the refractive index of the resin composition is 1.  5 9 ( 2 5 T: -24- 200919657 (1 - 3 ) The resin composition varnish obtained by the permeability measurement (1 -1 ) containing the composite oxide particle layer was confirmed, and the average particle diameter of 50 parts by weight was 0. . 1 μηι of cerium oxide titanium dioxide particles 1 (made by Tokuyama Co., Ltd., refractive index is 1. 58), stirring to disperse. Then, the varnish was applied onto a separation film (PET film) using a roller coater, and then dried in an oven at 70 ° C for 1 ’ minutes to obtain a film having a thickness of 25 μm on the separator, which was used as a film for transparency confirmation. The visible light parallel transmittance of the film for the above-mentioned transparency was measured by a UV-V I S spectrophotometer at a wavelength of 5 5 5 nm. The visible light parallel transmittance was 40%. (1 - 4 ) A resin composition varnish obtained by weighing (1 -1 ) of a composite oxide particle layer was prepared, and 50 parts by weight of the composite oxide particles were added as an average particle diameter of 0. 1 μ® of cerium oxide titanium dioxide particles 1 is stirred to disperse. Then, after applying the varnish to the separation film (PET film) using a roller coater, the resin having a thickness of 20 μm of the composite oxide particles on the separator was dried by drying in an oven at 70 ° C for 1 minute. Composition layer. The material composition of the composite oxide-containing particle layer is based on parts by weight, as shown in Table 1. (1 -5 ) Prepare a layer containing composite oxide particles and conductive particles on the surface of particles with polystyrene benzene as the core, and set the thickness to 〇. 2μηη nickel layer, on the outside of the nickel layer, set the thickness to 〇. 〇4μιη gold layer, made -25- 200919657 conductive particles with an average particle size of 3 μηη. The same steps as in the production of the composite oxide-containing particle layer were carried out except for the addition of the conductive particles, and a lipid composition layer having a thickness of 5 μm of the composite oxide particles and the conductive particles on the separator was produced. The material composition containing the composite oxide particles and the conductive particle layer is based on parts by weight, as shown in Table 2. (1 -6) The adhesive for connecting the circuit member was bonded to the above-mentioned composite oxide-containing particle layer and the above-mentioned composite oxide-containing particles and the conductive particle layer by a laminator to prepare an adhesive for connecting a circuit member having a thickness of 25 μm. (Example 2) In addition to the use of cerium oxide titanium dioxide particles 2 having an average particle diameter of 〇·3 μηι (manufactured by Tokuyama Co., Ltd., the refractive index was 1. In the same manner as in Example 1, except that the composite oxide particles were used, the composite oxide particle-containing layer and the composite oxide-containing particles and the electrodeposited layer were produced, and the same as in Example 1 was used. Similarly, the circuit member is used in combination with an adhesive. (Example 3) In addition to the use of cerium oxide titanium dioxide particles 3 having an average particle diameter of 0 · 1 μηη (manufactured by Tokuyama Co., Ltd., the refractive index was 1. 60) In the same manner as in Example 1, except that the composite oxide particles were formed as shown in Table 1 and Table 2, the composite oxide-containing layer and the composite oxide-containing particles and the sub-group of the group were formed. -26-200919657 Electric Particles and Sublayers The adhesive for connecting circuit members was produced in the same manner as in Example 1 using these. (Example 4) In the same manner as in Example 1, except that cerium oxide titanium dioxide particles 2 (having a refractive index of 159, manufactured by Tokuyama Co., Ltd.) having an average particle diameter of 0·3 μχη were used. In the same manner as in Example 1, the composition shown in Table 2 was used to produce a composite oxide particle-containing layer and a composite oxide-containing particle and a conductive particle layer. (Example 5) (5 - 1 ) A resin composition varnish was prepared as 20 parts by weight of an epoxy resin (manufactured by J ap an Epoxy Resins Co., Ltd., trade name EP 1 03 2H60) as a heat crosslinkable resin. 15 parts by weight of epoxy resin (manufactured by Osaka GAS Chemical Co., Ltd., trade name EX- 1 020), 25 parts by weight of phenoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name FX2 93), and 40 parts by weight of microcapsule type A hardener (manufactured by Asahi Kasei Co., Ltd., trade name XP-3 94 1 HP) and 1 part by weight of a decane crosslinker (manufactured by Toray Dow Corning Silicons Co., Ltd., trade name SH6040), dissolved in toluene and ethyl acetate In the mixed solvent, a resin composition varnish was obtained. (5-2) Determination of Refractive Index of Resin Composition -27- 200919657 After coating (5 - 1 ) of the obtained partial tree varnish on a separation film (PET film) using a roller coater, 7 (TC 1) In a minute, a resin having a thickness of 25 μm on the separation film was obtained, which was used for the measurement of the refractive index. The obtained refractive index measurement refractometer (sodium D line) sample stage, peeling separation film, and dispensing oil (matching) were obtained. Oil), put a refractive index of 1. Test the refractive index of 74. This result is that the refractive index of the resin composition is 1.  5 9 (5 -3 ) The resin composition varnish obtained by the permeability of the composite oxide particle layer (5 -1 ) was confirmed, and the average particle diameter of the composite oxide particles was 0. 3 μιη of titanium dioxide particles 2 (made by Tokuyama Co., Ltd., 1. 59) After stirring, the mixture was applied to a (PET film) using a roller coater, and then dried in an oven at 70 ° C for 10 minutes to separate a film having a thickness of 25 μm on the sheet. As a result of the transparency, the transmittance of the film for the measurement of the wavelength of 550 nm was measured using a UV-VIS spectrophotometer, and the transmittance was 70%. (5 _ 4 ) A resin composition varnish obtained by weighing (5 - 1 ) of a composite oxide particle layer is prepared, and the average particle diameter of the composite oxide particles is 0. 3μηη of the titanium dioxide particles 2, after stirring to disperse, after coating the separation film (PET film) with a roller, the film of the composition film was dried in a oven at 70 ° C to form a film for the test. Sheet, measured (25 ° c) 10 0 weight of cerium oxide refractive index is a separation film, obtained a film. The above was applied to a dry 10 -28 to 2009 19657 minutes by a 100 liter weight of a cerium oxide machine to prepare a resin composition layer having a thickness of 20 μm containing composite oxide particles on the separator. The material composition of the composite oxide-containing particle film is based on the weight fraction as shown in Table 1. (5 - 5) The composite oxide particles and the conductive particle layer are formed on the surface of the particles with polystyrene as the core, and the thickness is set to 〇. 2μηη nickel layer, on the outside of the nickel layer, set the thickness to 〇. A gold layer of 4 μm was used to prepare conductive particles having an average particle diameter of 3 μm. In addition to the addition of the conductive particles, the same procedure as in the production of the composite oxide particle-containing layer was carried out in (5 - 4 ), and a resin composition layer containing a composite oxide particle and a conductive particle having a thickness of 5 μm was formed on the separator. The material composition of the composite oxide-containing particles and the conductive particle layer is based on parts by weight, as shown in Table 2. (5-6) The adhesive layer for connecting circuit members is bonded to the above-mentioned composite oxide-containing particle layer by a laminator, and the above-mentioned composite oxide-containing particles and conductive particle layer are used to form an adhesive for connecting circuit members having a thickness of 25 μm. . (Example 6) A resin composition varnish was obtained in the same manner as in Example 5. Weigh the varnish and add 100 parts by weight of the silica dioxide dioxide 2 as an average particle diameter of the composite oxide particles of 〇·3μιη (Tokuyama Co., Ltd., with a refractive index of 1.  5 9 ), stirring and dispersing, coating on a separation film (PET film) using a roller coater, and drying in an oven at 70 ° C for 1 〇 -29 - 2009 19 657, to obtain a thick adhesive on the separator film. For connection of a circuit member of 45 μm (Comparative Example 1), the refractive index was 1. except that the cerium oxide particle S Ε 1 0 5 0 of the second embodiment having a life of 0·2 μηη was changed. 4 6 ) The composite-containing particles and the conductive particle layer were prepared in the composition shown in Table 2, and the cerium-doped titanium oxide particles were used as an average particle (trade name, manufactured by Admatech Co., Ltd., and the same as in Example 1 The layer and the composite oxide-containing circuit member bonding adhesive (Comparative Example 2) except that the second embodiment was changed to 〇. 5μιη of cerium oxide particles SE2050, refractive index of 1. 46) Other than the composition shown in Table 2, a composite ruthenium-containing particle and a conductive particle layer were produced, and this agent was used. (Comparative Example 3) (3 '-1) A resin composition varnish was mixed as a heat-crosslinkable resin type epoxy resin (Dongdu Chemical Co., Ltd. YDCN700-10) and 50 parts by weight of ruthenium dioxide particles were averaged ( Manufactured by Admatech Co., Ltd., the product name is made of phenolic phenolic phenolic acid co., Ltd. Base of acrylic rubber ( -30- 200919657

Nagase Chemtex股份有限公司製，商品名HTR-860P-3， 重量平均分子量爲3 0萬）、作爲硬化劑之咪唑化合物（ 四國化成工業股份有限公司製，商品名2PHZ )、1重量份 之砂院交聯劑（Toray Dow Corning silicones股份有限公 司製，商品名SH6040 )以及平均粒徑爲〇.〇ΐ2μιη之二氧 化矽微粒子（日本Aerosil股份有限公司製，商品名R805 )，溶解於甲苯及醋酸乙酯之混合溶劑中，得到樹脂組成 物清漆。 (3 ’ -2 )測定樹脂組成物之透過率 使用滾輪塗佈機塗佈部份上述樹脂組成物清漆於分離 薄膜（PET薄膜）上後，以70 °C之烤箱乾燥〗〇分鐘，得 到於分離薄膜上厚度爲2 5 μ m的膜。以此爲透過性確認用 薄膜。使用UV-VIS分光光度計，以波長爲5 5 5 nm測定上 述透過性確認用薄膜之透過率之結果’透過率爲9 % ° (3’_3 )製作樹脂組成物膜 使用滾輪塗佈機塗佈（3 ’ -1 )所得之樹脂組成物清漆 於分離薄膜（P E T薄膜）上後’以7 0 °C之烤箱乾燥1 0分 鐘，得到於分離片上厚度爲20Pm的膜。該膜之組成如表 1所示。 (3 ’-4 )製作含導電粒子層 於以聚苯乙烯爲核之粒子表面’設置厚度爲〇·2μηΊ之 -31 - 200919657 鏡層，於鎳層的外側’設置厚度爲〇. 〇4 μ m之金層，製作 平均粒徑爲3 μ m之導電粒子。除了導電粒子以外，與製作 (3，-3 )的膜相同的步驟’以表2記載之組成’製作薄膜 ，製作於分離片上含導電粒子之厚度爲5 μιη之樹脂組成物 層。 (3，- 5 )製作電路構件連接用黏著劑 以層合機黏合上述（3’-4)所得的膜，及上述之含導 電粒子層，製作厚度爲2 5 μιη之電路構件連接用黏著劑。 -32- 200919657 表1 表1 .含複合氧化物粒子層之組成 材料名 商品名 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 比較例3 EX1020 15 15 15 15 15 15 15 15 環氧樹脂 EP1032H60 20 20 YDCN700-10 50 苯氧樹脂 FX293 25 25 共聚合性樹脂 HTR-860P-3 20 20 20 20 20 20 50 XLC-LL 30 30 30 30 30 30 硬化劑 2PHZ 1.25 微膠囊型硬化劑 HX-3941HP 35 35 35 35 40 40 35 35 矽烷交聯劑 SH6040 1 I 1 1 1 1 1 1 1 粒子1 (折射率1.58) 50 - - - - - - - - 二氧化矽 二氧化鈦粒子 粒子2 (折射率1.59) - 50 - 100 100 100 - - - 粒子3 (折射率1.60) - - 50 - - - - - - SE1050 (折射率1.46) - - - - - - 50 - - 二氧化石夕 粒子 SE2050 (折射率1.46) - - - - - - - 50 - R805 . . 誉 . . 15 -33- 200919657 表2.含複合氧化物粒子及導電粒子層之組成 材料名 商品名 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例2 比較例3 環氧樹脂 EX1020 15 15 15 15 15 15 15 EP1032H60 20 YDCN700-10 50 苯氧樹脂 FX293 25 共聚合性樹脂 HTR-860P-3 20 20 20 20 20 20 50 硬化劑 XLC-LL 30 30 30 30 30 30 2PHZ 1.25 微膠囊型硬化劑 HX-3941HP 35 35 35 35 40 35 35 矽烷交聯劑 SH6040 1 1 1 1 1 1 1 1 二氧化砂 二氧化鈦粒子 粒子1 (折射率1.58) 50 - - - - - - - 粒子2 (折射率】.59) - 50 - 100 100 - - - 粒子3 (折射率1.60) - - 50 - - - - - 二氧化矽 粒子 SEI050 (折射率1.46) - - - - - 50 - - SE2050 (折射率1.46) - - - - - - 50 - R805 浙射率） - - - - - - - 15 導電粒子 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (製作實施例1〜5及比較例1〜3之半導體裝置、確認特 性） (A ) 製作半導體晶圓/電路構件連接用黏著劑/切割膠帶 層合體 加熱黏晶薄膜貼片機（Die Attach Film Mounter)( -34- 200919657 JCM製）之吸附台成8(TC後，將形成鍍金! 15 0μιη，直徑爲6吋之半導體晶圓，以凸塊側 吸附台上。 將實施例1〜5及比較例1〜3記載之電路 黏著劑，連同分離片，切斷成200mmx200mm 電粒子之膜側朝向半導體晶圓之凸塊側，於不 ，自半導體晶圓端以黏晶薄膜貼片機之黏著滾 行層合。層合後，沿著晶圓外形，切斷電路構 著劑滲出部份。切斷後，剝離分離片。接著， 片後之晶圓及電路構件連接用黏著劑之層合體 黏著面朝上，搭載於設定台溫度爲4 (TC之黏晶 之吸附台，另外，設置12吋晶圓用之切割架 〇 將UV硬化型切割膠帶（古河電氣工業股 製，商品名 UC-3 3 4EP-110)之黏著面朝向半 ，於不捲入氣體下，自切割架端以黏晶薄膜貼 滾輪強壓，進行層合。層合後，於切割架外圍 間附近切斷切割膠帶，製作固定於切割架之^ 電路構件連接用黏著劑/切割膠帶層合體。 (B )切割 將固定於切割架之半導體晶圓/電路構件 劑/切割膠帶層合體，以半導體晶圓之本底（B 面朝上搭載於全自動切割機（Fully Automatic 2塊之厚度 朝上搭載於 構件連接用 ，將未含導 捲入氣體下 輪強壓，進 件連接用黏 將剝離分離 ，以黏著劑 薄膜貼片機 於晶圓外圍 份有限公司 導體晶圓側 片機之黏著 及內圍之中 2導體晶圓/ 連接用黏著 ickground ) Dicing Saw -35- 200919657 )(Disco社製，商品名DFD63 6 1 )。由IR相機透過晶圓 ’進行切割線之位置核對。 第1段係自本底面切斷至ΙΟΟμπι ’以長邊側15.1mm 間隔，短邊側1 . 6mm間隔，切斷至剩餘半導體晶圓及電路 構件連接用黏著劑及切割膠帶內。切斷後，洗淨、吹乾使 水份飛散後，自切割膠帶側進行UV照射。之後，自切割 膠帶側，突起於半導體晶圓側，得到電路構件連接用黏著 劑形成於凸塊側之1 5 · 1 m m X 1 . 6 m m之半導體晶片。 (C)連接電路構件 使附電路構件連接用黏著劑之半導體晶圓之本底面， 朝向超音波覆晶式黏晶機（ALTECS社製，商品名SH-5 0ΜΡ )之吸附頭側，吸引晶片，由鹵素光源與導光（ MORI TEX社製），自電路構件連接用黏著劑層照射光， 辨別於半導體晶片表面所形成之鋁製之位置核對記號。 另一方面’辨別於厚度爲〇.7mm之無鹼玻璃上，以 1 400A之膜厚’形成銦-錫氧化物（IT〇 )電極之基板之 ΙΤΟ製之位置核對記號，與上述半導體晶片表面之位置核 對記號’進行位置核對。之後，無加熱，以1秒鐘 0.5 MPa強壓晶片於玻璃基板，於玻璃基板上，介由電路 構件連接用黏著劑假固定半導體晶片。接著，以2 i ， 5 0 Μ P a強壓晶片於玻璃5秒鐘的同時，使黏著劑硬化，凸 塊與ITO電極之連接及晶片與玻璃基板之黏著完成。 -36- 200919657 (D )測定連接電阻値（壓著後、高溫高濕試驗後、溫度 循環試驗後） 壓著後，進行確認半導體晶片-玻璃基板連接體之連 接電阻値。另外’爲確認電路構件連接用黏著劑之連接信 賴性，放入半導體晶片-玻璃基板連接體於60 °C ’相對濕 度爲9 0 %之高溫高濕裝置，或-4 0 °C、1 5分鐘及1 〇 〇 °C、 1 5分鐘之溫度循環試驗機，觀測一定時間後之連接電阻値 變化。 (製作實施例6之半導體裝置，確認特性） (6-A) 製作電路構件連接用黏著劑/半導體晶圓/切割膠 帶層合體 加熱黏晶薄膜貼片機（JCM製）之吸附台成8 0 °C後 ，將形成鍍金凸塊之厚度150μιη，直徑爲6吋之半導體晶 圓，以凸塊側朝上搭載於吸附台上。 將實施例6記載之電路構件連接用黏著劑，連同分離 片，切斷成 200mmx200mm，將未含導電粒子之膜側朝向 半導體晶圓之凸塊側，於不捲入氣體下，自半導體晶圓端 以黏晶薄膜貼片機之黏著滾輪強壓，進行層合。層合後， 沿著晶圓外形，切斷電路構件連接用黏著劑滲出部份。將 半導體晶圓及電路構件連接用黏著劑之層合體，以黏著劑 黏著面朝下’搭載於設定台溫度爲4 0 °C之黏晶薄膜貼片機 之吸附台，另外，設置1 2吋晶圓用之切割架於晶圓外圍 -37- 200919657 將UV硬化型切割膠帶（古河電氣工業股份有限公司 製，商品名u C - 3 3 4 E P -1 1 〇 )之黏著面朝向半導體晶圓側 ’於不捲入氣體下，自切割架端以黏晶薄膜貼片機之黏著 滾輪強壓，進行層合。層合後’於切割架外圍及內圍之中 間附近切斷切割膠帶，剝離電路構件連接用黏著劑之分離 片，製作固定於切割架之電路構件連接用黏著劑/半導體 晶圓/切割膠帶層合體。 (6-B )切割 將固定於切割架之電路構件連接用黏著劑/半導體晶 圓/切割膠帶層合體，以電路構件連接用黏著劑側朝向切 割刀片側，搭載於全自動切割機（Fully Automatic Dicing Saw ) ( Disco 社製，商品名 DFD63 6 1 )。 透過黏著劑，核對晶圓切斷位置後，第1段係自本底 面自表面切斷至1 ΟΟμιη，第2段以長邊側、短邊側皆爲 1 0mm間隔，1 0mm間隔切斷至剩餘晶圓及切割膠帶內。切 斷後，洗淨、吹乾使水份飛散後，自切割膠帶側進行UV 照射。之後，自切割膠帶側，突起於半導體晶圓側’得到 電路構件連接用黏著劑形成於凸塊側之1 1 0mm之半 導體晶片。 (6-C )連接電路構件 使附有電路構件連接用黏著劑之半導體晶圓之本底面 ，朝向超音波覆晶式黏晶機（ALTECS社製，商品名SH- -38- 200919657 5 OMP )之吸附頭側，吸引晶片，由鹵素光源與導光（ MORITEX社製），自電路構件連接用黏著劑層照射光， 辨別於半導體晶片表面所形成之鋁製之位置核對記號。接 著，與Au/Ni電鍍Cu電路印刷基板進行位置核對，進行 連接，得到半導體裝置。 (6-D )測定連接電阻値 所得之半導體裝置之176凸塊連接菊鏈（Daisy-chain )之連接電阻爲8.6 Ω，確認爲良好的連接狀態。另外， 放置半導體裝置於30°C，相對濕度爲60%之槽內192小時 後，進行紅外線迴焊（IR Reflow)處理（最大26 5 °C ) 3 次之結果，未發生晶片剝離或通電不良。 另外，放置紅外線迴焊後之半導體裝置於溫度循環試 驗機（-5 5 °C 3 0分鐘，室溫（2 5 °C ) 5分鐘，1 2 5 °C 30 分鐘）內，進行槽內之連接電阻測定，經600次循環後， 確認未發現通電不良。 (確認實施例1〜6及比較例1〜3之電路構件連接用黏著 劑之特性） (E )測定線膨脹係數 將實施例1〜6及比較例1〜3之電路構件連接用黏著 劑，與分離片一同放置於設定成1 80 °C之烤箱3小時，進 行加熱硬化處理。自分離片剝離加熱硬化後之薄膜，切斷 成30mmx30mm大小。使用Seiko Instruments社製，商品 -39- 200919657 名 TMA/SS6 100，進行薄膜之熱機械分析。設定夾具間 2 0 m m後，測定温度範圍爲2 0 °C〜3 0 0 °C，升溫速度爲5 °C /min，對於斷面積，壓力爲〇.5MPa之荷重條件’以拉伸 試驗模式，進行熱機械分析，求出線膨脹係數。 (F )測定反應率 秤量2〜10mg之實施例1〜6及比較例1〜3記載之電 路構件連接用黏著劑於鋁製測定容器後，於熱量測定裝置 (PerkinElmer 社製，商品名 D S C ( Di fferential ScaningNagase Chemtex Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 300,000), imidazole compound as a curing agent (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: 2PHZ), 1 part by weight of sand A cross-linking agent (manufactured by Toray Dow Corning Silicons Co., Ltd., trade name: SH6040) and cerium oxide microparticles (manufactured by Nippon Aerosil Co., Ltd., trade name R805) having an average particle diameter of 〇.〇ΐ2μιη, dissolved in toluene and acetic acid A resin composition varnish was obtained in a mixed solvent of ethyl ester. (3 ' -2 ) Measure the transmittance of the resin composition. Apply a part of the above resin composition varnish to a separation film (PET film) using a roller coater, and then dry it in an oven at 70 ° C for 〇 minutes to obtain A film having a thickness of 25 μm on the separation film was separated. This is used as a film for transparency confirmation. The transmittance of the above-mentioned film for transparency confirmation was measured by a UV-VIS spectrophotometer at a wavelength of 5 5 5 nm. The transmittance was 9 % (3'_3 ). The resin composition film was coated with a roller coater. The resin composition varnish obtained by the cloth (3'-1) was dried on a separation film (PET film) and dried in an oven at 70 ° C for 10 minutes to obtain a film having a thickness of 20 Pm on the separator. The composition of the film is shown in Table 1. (3 '-4 ) Produce a layer containing conductive particles on the surface of particles with polystyrene as the core 'Set the thickness of 〇·2μηΊ -31 - 200919657 Mirror layer, set the thickness on the outside of the nickel layer 〇. 〇4 μ A gold layer of m is used to produce conductive particles having an average particle diameter of 3 μm. In the same procedure as in the production of (3, -3) film, except for the conductive particles, a film was produced by the composition shown in Table 2, and a resin composition layer having a thickness of 5 μm of conductive particles on the separator was produced. (3, - 5) A film obtained by bonding the above-mentioned (3'-4) and a conductive particle-containing layer are bonded by a laminator to prepare a circuit member connecting adhesive having a thickness of 25 μm. . -32- 200919657 Table 1 Table 1. Composition of composite oxide particle-containing layer Name of material name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 EX1020 15 15 15 15 15 15 15 15 Epoxy Resin EP1032H60 20 20 YDCN700-10 50 Phenoxy Resin FX293 25 25 Copolymerizable Resin HTR-860P-3 20 20 20 20 20 20 50 XLC-LL 30 30 30 30 30 30 Hardener 2PHZ 1.25 microcapsule type hardener HX-3941HP 35 35 35 35 40 40 35 35 decane crosslinker SH6040 1 I 1 1 1 1 1 1 1 Particle 1 (refractive index 1.58) 50 - - - - - - - - Dioxide Bismuth titanium dioxide particles 2 (refractive index 1.59) - 50 - 100 100 100 - - - Particle 3 (refractive index 1.60) - - 50 - - - - - - SE1050 (refractive index 1.46) - - - - - - 50 - - Separate sulphur dioxide particles SE2050 (refractive index 1.46) - - - - - - - 50 - R805 . . . 15 -33- 200919657 Table 2. Composition of composite oxide particles and conductive particle layers Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Epoxy Resin EX1020 15 15 15 15 15 15 15 EP1032H60 20 YDCN700-10 50 Phenoxy Resin FX293 25 Copolymerizable Resin HTR-860P-3 20 20 20 20 20 20 50 Hardener XLC-LL 30 30 30 30 30 30 2PHZ 1.25 Microcapsule type hardener HX-3941HP 35 35 35 35 40 35 35 decane crosslinker SH6040 1 1 1 1 1 1 1 1 Titanium dioxide titanium dioxide particle 1 (refractive index 1.58) 50 - - - - - - - Particle 2 (refractive index) .59) - 50 - 100 100 - - - Particle 3 (refractive index 1.60) - - 50 - - - - - Ceria particle SEI050 (refractive index 1.46) - - - - - 50 - - SE2050 (refractive index 1.46) - - - - - - 50 - R805 射射率) - - - - - - - 15 Conductive particles 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (Production Examples 1 to 5 and Comparative Example 1 (3) Semiconductor device and confirming characteristics) (A) A semiconductor wafer/circuit member bonding adhesive/cut tape laminated body (Die Attach Film Mounter) (-34-200919657 JCM system) After the adsorption stage is 8 (TC, gold plating will be formed! 15 0μιη, semiconductor crystal with a diameter of 6吋) To the bump side of the adsorption stage. The circuit adhesives described in Examples 1 to 5 and Comparative Examples 1 to 3, together with the separator, were cut into the film side of the 200 mm x 200 mm electrode particles toward the bump side of the semiconductor wafer, and were not adhered from the semiconductor wafer end. Adhesive rolling lamination of the crystal film placement machine. After lamination, the circuit builder bleeds off the wafer profile. After cutting, the separator was peeled off. Then, the laminate of the adhesive for the wafer and the circuit member after the film is adhered face up, and is mounted on the adsorption stage with a temperature of 4 (TC), and a 12-inch wafer cutting frame. The adhesive surface of the UV-curable dicing tape (Fuji Electric Industry Co., Ltd., trade name UC-3 3 4EP-110) is oriented toward the half, and is not entangled in the gas, and the layer is pressed by the adhesive film at the end of the cutting frame to carry out the layer. After lamination, the dicing tape is cut near the periphery of the dicing frame to form an adhesive/cutting tape laminate for the circuit member connection fixed to the dicing frame. (B) The semiconductor wafer to be fixed to the dicing frame is cut/ Circuit component/cut tape laminate, which is mounted on a semiconductor wafer base (B face up on a fully automatic cutter (Fully Automatic 2 blocks are mounted upwards for component connection, and no guide is entrained under gas) The wheel is pressed and the adhesive is peeled and separated. The adhesive film mounter is used in the adhesion and inner circumference of the wafer wafer peripheral machine. 2 conductor wafer / connection adhesive ickground ) DicingSaw -35- 200919657 ) (Disco 63, manufactured by Disco, Ltd.). The position of the cutting line is checked by the IR camera through the wafer. The first stage is cut from the bottom surface to ΙΟΟμπι '15.1mm on the long side. Interval, short-side side 1. 6mm interval, cut into the remaining semiconductor wafer and circuit member bonding adhesive and dicing tape. After cutting, washing and drying to scatter water, UV irradiation from the cutting tape side Then, from the side of the dicing tape, the semiconductor wafer is protruded from the semiconductor wafer side, and a semiconductor wafer of 1 5 · 1 mm × 1.6 mm formed on the bump side by the adhesive for connecting the circuit member is obtained. (C) Connecting the circuit member The bottom surface of the semiconductor wafer to which the circuit member is bonded is attached to the adsorption head side of the ultrasonic flip chip type crystallizer (trade name: SH-5 0 by ALTECS Co., Ltd.) to attract the wafer, and the halogen light source and the light guide ( MORI TEX Co., Ltd.) irradiates light from the adhesive layer for connecting circuit members, and discriminates the position check mark of aluminum formed on the surface of the semiconductor wafer. On the other hand, it is distinguished from the alkali-free glass having a thickness of 〇7 mm. 1 400A film thickness 'The position check mark of the substrate forming the indium-tin oxide (IT〇) electrode is aligned with the position check mark ' on the surface of the semiconductor wafer. Then, without heating, the wafer is pressed at 0.5 MPa for 1 second. The glass substrate is pseudo-fixed on the glass substrate via an adhesive for connecting the circuit members. Then, the wafer is pressed against the glass for 5 seconds at 2 i , 50 Μ P a to harden the adhesive, and the bumps are bonded. The connection of the ITO electrodes and the adhesion of the wafer to the glass substrate are completed. -36- 200919657 (D) Measurement of connection resistance 値 (after pressing, after high temperature and high humidity test, after temperature cycle test) After pressing, the connection resistance 値 of the semiconductor wafer-glass substrate connector was confirmed. In addition, in order to confirm the connection reliability of the adhesive for connecting the circuit components, a semiconductor wafer-glass substrate connector is placed at a temperature of 60 ° C and a relative humidity of 90%, or a temperature of -40 ° C, 1 5 The temperature and cycle tester at 1 〇〇 ° C and 15 minutes was used to observe the change in the connection resistance 一定 after a certain period of time. (Production of the semiconductor device of Example 6 to confirm the characteristics) (6-A) Preparation of an adhesive for a circuit member connection/semiconductor wafer/cut tape laminated body, a heat-adhesive film mounter (JCM system) After ° C, a gold-plated bump having a thickness of 150 μm and a semiconductor wafer having a diameter of 6 Å was formed, and the bump was mounted on the adsorption stage with the bump side facing up. The adhesive for connecting the circuit member described in Example 6 was cut into 200 mm x 200 mm together with the separator, and the film side containing no conductive particles was directed toward the bump side of the semiconductor wafer, and the semiconductor wafer was not entrapped under the gas. The end is pressed by the adhesive roller of the die-bonding film placement machine to perform lamination. After lamination, the adhesive exudation portion of the circuit member connection is cut along the outer shape of the wafer. The laminate of the adhesive for connecting the semiconductor wafer and the circuit member is mounted on the adsorption stage of the die-bonding film placement machine at a setting temperature of 40 ° C with the adhesive adhered face down, and 1 2 设置 is set. Wafer cutting frame on the periphery of the wafer -37- 200919657 Adhesive surface of UV-curable dicing tape (manufactured by Furukawa Electric Co., Ltd., trade name u C - 3 3 4 EP -1 1 朝向) toward the semiconductor wafer The side is not entangled in the gas, and is laminated at the end of the cutting frame by the adhesive roller of the die-bonding film placement machine. After laminating, the cutting tape is cut near the middle of the periphery of the cutting frame and the inner circumference, and the separator for connecting the adhesive for the circuit member is peeled off, and the adhesive for bonding the circuit member to be attached to the cutting frame/semiconductor wafer/cut tape layer is formed. Fit. (6-B) The adhesive/semiconductor wafer/cut tape laminate for circuit member connection to be fixed to the dicing frame, and the adhesive side of the circuit member is oriented toward the dicing blade side, and is mounted on a fully automatic cutting machine (Fully Automatic) Dicing Saw ) (produced by Disco, trade name DFD63 6 1 ). After the wafer is cut by the adhesive, the first stage is cut from the bottom surface to 1 ΟΟμιη from the bottom surface, and the second section is separated by 10 mm on both the long side and the short side, and the interval is cut to 10 mm. Remaining wafer and cutting tape inside. After cutting, after washing and drying to scatter the water, UV irradiation is performed from the side of the cutting tape. Thereafter, from the side of the dicing tape, the semiconductor wafer side was protruded to obtain a semiconductor wafer in which the circuit member bonding adhesive was formed on the bump side by 110 mm. (6-C) Connecting the circuit member so that the bottom surface of the semiconductor wafer with the adhesive for connecting the circuit member is directed to the ultrasonic flip chip type crystal bonding machine (manufactured by ALTECS, trade name SH--38-200919657 5 OMP) On the side of the adsorption head, the wafer was attracted, and a halogen light source and a light guide (manufactured by MORITEX Co., Ltd.) were used to irradiate light from the adhesive layer for connection of the circuit member, and the position check mark of aluminum formed on the surface of the semiconductor wafer was identified. Then, the Au/Ni plated Cu circuit printed substrate was subjected to position collation and connected to obtain a semiconductor device. (6-D) Measurement of the connection resistance 値 The connection resistance of the 176-bump daisy-chain of the obtained semiconductor device was 8.6 Ω, which was confirmed to be a good connection state. Further, after the semiconductor device was placed in a bath at 30 ° C and a relative humidity of 60% for 192 hours, IR reflow treatment (maximum 26 5 ° C) was performed three times, and wafer peeling or poor electrification did not occur. . In addition, the semiconductor device after the infrared reflow is placed in a temperature cycle tester (-5 5 ° C for 30 minutes, room temperature (25 ° C) for 5 minutes, 1 2 5 ° C for 30 minutes), in the tank The connection resistance was measured, and after 600 cycles, it was confirmed that no power failure was observed. (Characteristics of the adhesives for connecting circuit members of Examples 1 to 6 and Comparative Examples 1 to 3) (E) Measurement of coefficient of linear expansion The adhesives for connecting circuit members of Examples 1 to 6 and Comparative Examples 1 to 3, The mixture was placed in an oven set at 180 ° C for 3 hours together with the separator, and subjected to heat hardening treatment. The heat-hardened film was peeled off from the separator and cut into a size of 30 mm x 30 mm. Thermomechanical analysis of the film was carried out using Seiko Instruments, product -39-200919657 TMA/SS6 100. After setting the clamp between 20 mm, the measurement temperature range is 20 °C~3 0 0 °C, the heating rate is 5 °C /min, and for the sectional area, the pressure is 〇5 MPa load condition 'in tensile test mode Thermomechanical analysis was performed to determine the coefficient of linear expansion. (F) Measurement of the reaction rate: 2 to 10 mg of the adhesives for the circuit members described in Examples 1 to 6 and Comparative Examples 1 to 3 were measured in an aluminum measuring container, and then subjected to a calorimeter (trade name DSC (manufactured by PerkinElmer Co., Ltd.) Di fferential Scaning

Calorimeter) Pylis 1)，以 20 °C /min 之升溫速度至 30 〜 3 〇〇 °C，進行發熱量測定，將此作爲初期發熱量。 接著，夾著熱壓著裝置於分離片之熱電偶，進行溫度 確認，設定於20秒後達成1 80度之溫度。以加熱頭設定 ，加熱包夾於分離片之電路構件連接用黏著劑20秒’得 到被施以與熱壓著時相同之加熱處理狀態之薄膜。秤量2 〜1 0 m g之加熱處理後之薄膜，放入鋁製測定容器’以上 述熱量測定裝置’以20 °C /min之升溫速度至30〜300 °C ’ 進行發熱量測定，將此作爲加熱後發熱量。所得之發熱量 係由下述式（1 )算出反應率（％ )。 反應率=(初期發熱量·加熱後發熱量）/ (初期發熱量）x10〇 ( 1 ) 作爲電路構件連接用黏著劑之特性’可見光並行透過 率、硬化後之線膨脹係數、可不可辨別覆晶式黏晶機之定 -40- 200919657 位點（alignment mark)、反應率以及壓著後之連接電阻 値及信賴性試驗後之連接電阻値如表3所示。 表3 表3確認電路構件連接用黏著劑夕特性 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 比較例3 可見光並行透過率（％) 40 70 30 50 70 70 13 3 9 線膨脹係數（40-】00〇C) (ΧΙΟ"4) 66 67 69 47 40 40 64 69 170 辨別晶片定位點 可能 可能 可能 可能 可能 可能 不可 不可 不可 反應率（％) 89 88 89 86 89 89 88 86 0 壓著後之連續電阻（Ω ) 1.7 0.3 1.8 0.6 0.6 8.6 導電不良 導電不良 導電不良 高溫高濕試驗200h後之連續 電阻（Ω) 8.1 2.6 13.2 2.7 2.6 - - - 溫度循環試驗200次循環後之連續 電阻（Ω ) 2.1 0.4 2.2 0.7 0.7 - - - - 如表3所示，使用作爲複合氧化物粒子之二氧化矽二 氧化鈦之實施例1〜6之電路構件連接用黏著劑係（1 )因 可見光並行透過率爲3 0 %以上，所以使用覆晶式黏晶機之 辨別系統，透過黏著劑，可辨別晶片電路面之認識記號， (2 )減低硬化後之線膨脹係數成70χ 1 0_6/°C，連接信賴 性試驗中不發生導電不良，（3 )以熱壓時之加熱條件達 成80%以上之反應率，顯示安定的低連接電阻。尤其，使 用平均粒徑爲〇.3μιη之二氧化矽二氧化鈦粒子之實施例2 、4、5及6之電路構件連接用黏著劑係優異的，可見光並 行透過率高，壓著後、高溫高濕試驗後及温度循環試驗後 之連接電阻値低。 另一方面，比較例1及2之電路構件連接用黏著劑， -41 - 200919657 因使用二氧化矽粒子而與樹脂組成物之折射率 生散射，可見光並行透過率小。因此，不能由 位點記號以核對位置，不能確保半導體裝置之 另外，比較例3之電路構件連接用黏著劑之反 速硬化性。因此，黏著劑不凝固，不能保持壓 ，發生半導體裝置導電不良。不能測定壓著後 値。 【圖式簡單說明】 [圖丨]表示有關本發明之一種實施型態之 件連接用黏著劑之電路連接材料之斷面圖。 【主要元件符號說明】 1:電路連接材料、1〇:分離片、20:含 粒子層、2 1 :樹脂組成物、2 2 :複合氧化物粒 複合氧化物粒子及導電粒子層、3 1 :樹脂組成 電粒子、4 0 :電路構件連接用黏著劑。 大，所以發 辨別晶片定 初期導電。 應率低，無 著後之狀態 之連接電阻 使用電路構 複合氧化物 子、30 :含 物、33 :導 -42-Calorimeter) Pylis 1), measured at a temperature rise rate of 20 °C /min to 30 〜 3 〇〇 °C, used as the initial calorific value. Next, the thermocouple of the separator was pressed against the thermocouple, and the temperature was confirmed. After 20 seconds, the temperature was set to 180 °C. With the heating head set, the adhesive for connecting the circuit member to the separator was heated for 20 seconds to obtain a film which was subjected to the same heat treatment state as that at the time of hot pressing. The heat-treated film was weighed in an amount of 2 to 10 mg, and placed in an aluminum measuring container, and the calorific value was measured at a temperature rising rate of 20 ° C / min to 30 to 300 ° C. Heat after heating. The calorific value obtained was calculated from the following formula (1) to calculate the reaction rate (%). Reaction rate = (initial calorific value, calorific value after heating) / (initial calorific value) x10 〇 (1) Characteristics of the adhesive for connecting circuit members 'Visible parallel transmittance, linear expansion coefficient after hardening, and indistinguishable The crystal bonder--40-200919657 alignment mark, reaction rate and connection resistance after crimping and the connection resistance after the reliability test are shown in Table 3. Table 3 Table 3 Confirmation of Adhesives for Connecting Circuit Member Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Visible light parallel transmittance (%) 40 70 30 50 70 70 13 3 9 Linear expansion coefficient (40-]00〇C) (ΧΙΟ"4) 66 67 69 47 40 40 64 69 170 Identifying wafer positioning points may or may not be impossible. (%) 89 88 89 86 89 89 88 86 0 Continuous resistance after pressing (Ω) 1.7 0.3 1.8 0.6 0.6 8.6 Poor Conductivity Poor Conduction Poor Conduction High Temperature and Humidity Test Continuous Resistance after 200h (Ω) 8.1 2.6 13.2 2.7 2.6 - - - Temperature Continuous resistance after the 200-cycle cycle test (Ω) 2.1 0.4 2.2 0.7 0.7 - - - - As shown in Table 3, the circuit members used in Examples 1 to 6 as the composite oxide particles of ruthenium dioxide dioxide were bonded. The agent system (1) has a visible light transmittance of more than 30%, so the discriminating system of the flip chip type microcutter can be used to discriminate the recognition mark of the circuit surface of the chip through the adhesive, and (2) reduce the linear expansion after hardening. The coefficient was 70 χ 1 0_6/°C, and no conduction failure occurred in the connection reliability test, and (3) the reaction rate at 80% or more by the heating condition at the time of hot pressing showed a stable low connection resistance. In particular, the electrode member for connection of circuit members of Examples 2, 4, 5 and 6 having an average particle diameter of 〇.3 μm is excellent in the parallel transmission of visible light, and after pressing, high temperature and high humidity. The connection resistance after the test and after the temperature cycle test was low. On the other hand, the adhesives for connecting circuit members of Comparative Examples 1 and 2, -41 - 200919657, were scattered by the refractive index of the resin composition by using the cerium oxide particles, and the visible light transmittance was small. Therefore, the position cannot be checked by the dot mark, and the retardation hardenability of the adhesive for connecting the circuit member of Comparative Example 3 cannot be ensured. Therefore, the adhesive does not solidify, the pressure cannot be maintained, and the semiconductor device is poorly conductive. It is not possible to measure the 値 after pressing. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 丨] shows a cross-sectional view of a circuit connecting material for a bonding adhesive for an embodiment of the present invention. [Description of main component symbols] 1: Circuit connection material, 1〇: separator, 20: particle-containing layer, 2 1 : resin composition, 2 2 : composite oxide particle composite oxide particle and conductive particle layer, 3 1 : Resin-constituting electric particles, 40: an adhesive for connecting circuit members. Large, so the identification of the chip is initially conductive. The response rate is low, and there is no connection state after the use of the circuit structure composite oxide, 30: inclusion, 33: conduction -42-

Claims (1)

200919657 十、申請專利範圍 1. 一種電路構件連接用黏著劑，其特徵爲，由含有熱 交聯性樹脂及與該熱交聯性樹脂反應之硬化劑之樹脂組成 物’與分散於該樹脂組成物中之複合氧化物粒子，所形成 之熱硬化型電路構件連接用黏著劑。 2 _如申請專利範圍第1項之電路構件連接用黏著劑， 其中’前述複合氧化物粒子之平均粒徑爲0.1 μηι 〜0 _ 5 μιη 〇 3 .如申請專利範圍第1項之電路構件連接用黏著劑， 其中，相對於前述樹脂組成物1 0 0重量份，前述複合氧化 物粒子爲含有2 0〜1 5 0重量份。 4 ·如申請專利範圍第1項之電路構件連接用黏著劑， 其中，未硬化時具有15〜100%可見光並行透過率。 5 _如申請專利範圍第1項之電路構件連接用黏著劑， 其中，前述複合氧化物粒子之折射率爲1 . 5〜1 . 7。 6. 如申請專利範圍第1項之電路構件連接用黏著劑， 其中，前述樹脂組成物爲含有於支鏈上至少包含1個可與 前述硬化劑或前述熱交聯性樹脂反應之官能基的共聚合，丨生 樹脂。 7. 如申請專利範圍第1項之電路構件連接用黏著劑， 其中，前述電路構件連接用黏著劑於1 80 °C下加熱20秒鐘 後，以差示掃描熱量計所得之發熱量所算出之前述電路構 件連接用黏著劑的反應率爲8 0 %以上。 -43- 200919657 8. 如 其中，前 之線膨脹 9. 如 其爲使具 電路基板 黏著時所 1 0. — 型之電路 之半導體 間並予連 電連接， 一項之電 申請專利範圍第1項之電路構件連接用黏著劑， 述電路構件連接用黏著劑硬化後之4 0〜1 0 〇 t下 係數爲70χ 1 〇_6/。(：以下。 申請專利範圍第1項之電路構件連接用黏著劑， 有突出連接端子之半導體晶片與具有配線圖型之 ’以前述連接端子與前述配線圖型電連接的方式 使用之電路構件連接用黏著劑。 -種半導體裝置，其特徵爲，具備有具有配線圖 基板，與安裝於該電路基板之具有突出連接端子 晶片’與介於前述電路基板與前述半導體晶片之 接之黏著層’且前述連接端子與前述配線圖型爲 前述黏著劑層爲由申請專利範圍第1至9項中任 路構件連接用黏著劑所形成。 -44-200919657 X. Patent application scope 1. An adhesive for connecting circuit members, characterized in that a resin composition containing a heat-crosslinkable resin and a hardener reactive with the heat-crosslinkable resin is dispersed and dispersed in the resin composition The composite oxide particles in the product are formed of an adhesive for bonding a thermosetting circuit member. 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the adhesive composition, the composite oxide particles are contained in an amount of 20 to 150 parts by weight based on 100 parts by weight of the resin composition. 4. The adhesive for connecting circuit members according to item 1 of the patent application, wherein the unbonded has a parallel transmittance of 15 to 100% of visible light. 5〜1. 7。 The _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 6. The adhesive for connecting circuit members according to claim 1, wherein the resin composition contains at least one functional group reactive with the hardener or the thermally crosslinkable resin. Copolymerization, twinning resin. 7. The adhesive for connecting circuit members according to the first aspect of the invention, wherein the adhesive for connecting the circuit members is heated at 180 ° C for 20 seconds, and then calculated by the calorific value obtained by the differential scanning calorimeter. The reaction rate of the above-mentioned adhesive for connecting circuit members is 80% or more. -43- 200919657 8. If the front line expands. 9. If it is to connect the semiconductors of the circuit of the type 1 to the circuit board, the electric power of the patent application is the first item. The adhesive for connecting the circuit members is 70 〜 1 〇 _6/ at a coefficient of 40 1 1 0 〇t after the circuit member is bonded with an adhesive. (The following is the adhesive for connecting circuit members of the first application of the patent application, the semiconductor wafer having the protruding connection terminal and the circuit member having the wiring pattern type which is electrically connected to the wiring pattern by the connection terminal; A semiconductor device comprising: a wiring pattern substrate; and an adhesive layer having a protruding connection terminal wafer 'attached to the circuit substrate and the semiconductor wafer; The connection terminal and the wiring pattern described above are formed by the adhesive for connecting the road member in the first to ninth aspects of the patent application.
TW097126483A 2007-07-11 2008-07-11 Adhesive for connection of circuit components TWI425598B (en)

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