TW201235395A - Film-like resin composition for sealing and filling semiconductor, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Film-like resin composition for sealing and filling semiconductor, method for manufacturing semiconductor device, and semiconductor device Download PDF

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Publication number
TW201235395A
TW201235395A TW100142344A TW100142344A TW201235395A TW 201235395 A TW201235395 A TW 201235395A TW 100142344 A TW100142344 A TW 100142344A TW 100142344 A TW100142344 A TW 100142344A TW 201235395 A TW201235395 A TW 201235395A
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Taiwan
Prior art keywords
resin composition
film
semiconductor
resin
acid
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TW100142344A
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Chinese (zh)
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TWI462959B (en
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Tetsuya Enomoto
Akira Nagai
Emi Miyazawa
Kazutaka Honda
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Hitachi Chemical Co Ltd
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Publication of TWI462959B publication Critical patent/TWI462959B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
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    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
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    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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    • H01L2924/151—Die mounting substrate
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    • H01L2924/351—Thermal stress

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Wire Bonding (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed is a film-like resin composition for sealing and filling a semiconductor, which is provided with a first layer composed of a first resin composition containing a thermosetting resin and a filler, and a second layer composed of a second resin composition containing a flux agent. The mass ratio of the filler in the second resin composition to the total quantity of the second resin composition is smaller than the mass ratio of the filler in the first resin composition to the total quantity of the first resin composition.

Description

201235395 六、發明說明： 【發明所屬之技術領域】 本發明係關於半導體密封塡充用薄膜狀樹脂組成物、 半導體裝置之製造方法及半導體裝置。 ' 【先前技術】 近年來，隨著電子設備之小型化、高功能化之進展， 對半導體裝置要求小型化、薄型化及電特性之提升（對高 頻傳輸之對應等）。伴隨於此，而自以往之以線黏合（ wire bonding)將半導體晶片安裝於基板上之方式，開始 朝於半導體晶片上形成稱爲突出物之導電性突起電極且與 基板電極直接連接之覆晶連接方式進行。 至於在半導體晶片上形成之突出物雖係使用以焊料或 金構成之突出物，但爲對應近年來之微細連接化，已變成 使用在銅柱之前端形成焊料層或錫層而成之構造之突出物 〇 又，爲了高信賴性化，而要求利用金屬接合而連接， 不僅採用使用了焊料突出物的焊料接合或利用於銅柱之前 端形成有焊料層或錫層之構造之突出物之金屬接合，於使 ' 用金突出物時，亦已採用於基板電極側形成焊料層或錫層 ，而進行金屬接合之連接方法。 再者，覆晶連接方式由於會有源自半導體晶片與基板 之熱膨脹係數差之熱應力集中於連接部而破壞連接部之虞 • ，故爲了分散該熱應力並提高連接信賴性，有必要以樹脂 -5- 201235395 密封塡充半導體晶片與基板間之空隙。一般’利用樹脂密 封塡充係採用使用焊料等將半導體晶片與基板連接後，利 用毛細管現象於空隙中注入液狀密封樹脂之方式。 於使晶片與基板連接之際，爲使焊料等之表面氧化膜 還原除去而使金屬接合變容易，而使用由松香或有機酸等 所成之助焊劑。此處，若殘留助焊劑殘渣，則注入液狀樹 脂時會造成稱爲孔隙之氣泡發生，或會因酸成分會發生配 線腐蝕，使連接信賴性降低，故必須進行洗淨殘渣之步驟 。然而，近年來，隨著連接間隙之窄間距化，半導體晶片 與基板間之空隙變得狹小，故有助焊劑殘渣之洗淨變困難 之情況。再者，於半導體晶片與基板間之狹小空隙中注入 液狀樹脂需要長時間，而有生產性降低之問題。 爲解決此種液狀密封樹脂之問題，已提出有使用具備 將焊料等之表面之氧化膜還原去除之性質（助焊劑活性） 之密封樹脂’對基板供給密封樹脂後，使半導體晶片與基 板連接之同時’以樹脂密封塡充半導體晶片及基板間之空 隙’而可省略助焊劑殘渣之洗淨之稱爲先供給方式之連接 方法（例如參考專利文獻1〜5 )。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2006-143795號公報 [專利文獻2]日本特開2007-107006號公報 [專利文獻3]日本特開2008-294382號公報 [專利文獻4]日本特開2009_239138號公報 201235395 [專利文獻5]日本特開200 5 -2 8 73 4號公報 【發明內容】 [發明欲解決之課題] '然而，以往之先供給方式爲了減低密封樹脂之熱膨脹 係數而調配之塡料會夾在突出物與基板電極之間而發生稱 爲凹陷（trapping )之連接不良，而引起導電不良，有以 夾入之塡料爲起點而於突出物或基板電極上產生龜裂而使 連接信賴性下降之問題。 本發明之目的係提供一種作爲先供給方式用之密封樹 脂使用時，可充分抑制凹陷之產生，且獲得具有良好導電 性及連接信賴性之半導體裝置之半導體密封塡充用薄膜狀 樹脂組成物，以及使用其之半導體裝置及其製造方法。 [解決課題之手段] 本發明係提供一種半導體密封塡充用薄膜狀樹脂組成 物’其係具備··由含有熱硬化性樹脂及塡料之第1樹脂組 成物所構成的第1層、與含有助焊劑之第2樹脂組成物所 構成的第2層’且相對於前述第2樹脂組成物總量之前述 第2樹脂組成物中的塡料之質量比率，比相對於前述第1 樹脂組成物總量之前述第1樹脂組成物中的塡料之質量比 率更小。 依據本發明，可防止在突出物與基板電極之間夾入塡 ' 料，可形成良好之連接部。亦即，依據本發明之半導體密 201235395 封塡充用薄膜狀樹脂組成物，可充分抑制 凹陷之產生，且可獲得具有良好導電性及 導體裝置。 又，依據本發明之半導體密封塡充用 物，以連接半導體晶片與基板時之加熱加 成物硬化，使硬化後之第1樹脂組成物補 電極之連接部。據此，在連接結束後之冷 體晶片與基板之熱膨脹係數差所造成之熱 部及產生龜裂等連接不良之生成可充分受 依據此種半導體密封塡充用薄膜狀樹脂組 接信賴性更優異之半導體裝置。 本發明之半導體密封塡充用薄膜狀樹 上述第2樹脂組成物進一步含有熱可塑性 該半導體密封塡充用薄膜狀樹脂組成 組成物構成之第2層之表面黏附力低。因 半導體製造方法中，具有於將貼附有半導 膜狀樹脂組成物之半導體晶圓單粒化成半 止所產生之切削層附著於第2層表面上之 本發明另提供半導體裝置之製造方法 形成有複數個突出物之突出物形成面之半 有設有複數個電極之電極面的基板之半導 法，其特徵在於具備：將如上述本發明之 用薄膜狀樹脂組成物，以使前述第2層相 配置於前述基板側之方式，貼附於前述基 先供給方式中之 連接信賴性之半 薄膜狀樹脂組成 壓使第1樹脂組 強突出物與基板 卻過程中，半導 應力集中於連接 到抑制。亦即， 成物，可獲得連 脂組成物，較好 樹脂。 物，由第2樹脂 此，例如後述之 體密封塡充用薄 導體晶片時，防 效果。 ，其係具備具有 導體晶片、與具 體裝置之製造方 半導體密封塡充 對於前述第1層 板之前述電極面 -8- 201235395 上的第1步驟、與將經前述第1步驟之前述基板與前述半 導體晶片，配置成爲使前述電極面與前述突出物形成面介 隔著前述半導體密封塡充用薄膜狀樹脂組成物而互相對向 ，且進行加熱加壓以使前述基板之電極與前述半導體晶片 之突出物電連接之第2步驟；且在於前述第2步驟連接之 前述電極及前述突出物當中至少一者的表面，存在有錫或 焊料。如此藉由將本發明之薄膜狀樹脂組成物配置於基板 表面上，使半導體晶片之突出物與基板之電極在塡料之質 量比率較小之第2層中接觸，可抑制塡料之夾入，同時藉 由第2層中之助焊劑還原去除突出物前端之氧化膜，使與 基板電極之金屬接合變得容易。 本發明另提供一種半導體裝置之製造方法，其係具備 具有形成有複數個突出物之突出物形成面的半導體晶片、 與具有設有複數個電極之電極面的基板之半導體裝置之製 造方法，其特徵在於具備：將上述本發明之半導體密封塡 充用薄膜狀樹脂組成物，以使前述第1層相對於前述第2 層配置於前述半導體晶圓側的方式貼附於具有形成有複數 個突出物之突出物形成面之半導體晶圓的該突出物形成面 上的第1步驟、將經前述第1步驟之前述半導體晶圓單粒 化’得到貼附有前述半導體密封塡充用薄膜狀樹脂組成物 之半導體晶片的第2步驟、與將於前述第2步驟得到之前 述半導體晶片與前述基板，配置成爲使前述突出物形成面 與前述電極面介隔著前述半導體密封塡充用薄膜狀樹脂組 成物而互相對向，且進行加熱加壓以使前述半導體晶片之 -9- 201235395 突出物與前述基板之電極電連接的第3步驟；且在於前述 第3步驟連接之前述電極及前述突出物當中至少一者的表 面，存在有錫或焊料。如此藉由將本發明之薄膜狀樹脂組 成物配置於半導體晶片表面，使半導體晶片之突出物與基 板之電極在塡料之質量比率較小之第2層中接觸，可抑制 塡料之夾入，同時藉由第2層中之助焊劑還原去除突出物 前端之氧化膜，使與基板電極之金屬接合變得容易。 依據本發明之半導體裝置之製造方法，由於使用上述 本發明之半導體密封塡充用薄膜狀樹脂組成物，故可充分 抑制凹陷之產生，可製造具有良好導電性及連接信賴性之 半導體裝置。 本發明進而提供以上述本發明之半導體裝置之製造方 法製造之半導體裝置。該半導體裝置由於以上述本發明之 半導體密封塡充用薄膜狀樹脂組成物密封塡充，故抑制了 因凹陷之發生引起之連接不良或龜裂之產生，而具有良好 之導電性及連接信賴性。 [發明效果] 依據本發明，可提供作爲先供給方式用之密封樹脂使 用時，可充分抑制凹陷之產生，獲得具有良好導電性及連 接信賴性之半導體裝置之半導體密封塡充用薄膜狀樹脂組 成物，以及使用其之半導體裝置及其製造方法。 【實施方式】 -10- 201235395 針對本發明之較佳實施形態說明於下。 本實施形態之半導體密封塡充用薄膜狀樹脂組成物爲 具備有由含有塡料之第1樹脂組成物所構成的第1層、與 含有助焊劑之第2樹脂組成物所構成的第2層’且相對於 第2樹脂組成物總量之第2樹脂組成物中的塡料之質量比 率，比相對於第1樹脂組成物總量之第1樹脂組成物中的 塡料之質量比率更小者。 此處，第2樹脂組成物可含有塡料亦可不含。亦即， 「相對於第2樹脂組成物總量之第2樹脂組成物中的塡料 之質量比率」亦可爲〇質量％。 依據本實施形態之半導體密封塡充用薄膜狀樹脂組成 物，可充分抑制先供給方式中凹陷之產生。爲此，藉由使 用本實施形態之半導體密封塡充用薄膜狀樹脂組成物，可 獲得具有良好導電性及連接信賴性之半導體裝置。 (第1層） 第1層爲由含有塡料之第1樹脂組成物所構成之層。 至於塡料較好使用無機塡料。使用無機塡料時，由於 第1樹脂組成物（或其硬化物）之熱膨脹係數更低，故使 利用半導體密封塡充用薄膜狀樹脂組成物密封塡充之半導 體裝置之連接信賴性變更良好。 至於無機塡料列舉爲玻璃、二氧化矽（Silica )、氧 化銘（alumina)、氧化欽（titania)、氧化鎂（magnesia )、碳黑、雲母、硫酸鋇等。該等可單獨使用或混合兩種 -11 - 201235395 以上使用。 又，作爲無機塡料亦可使用含兩種以上金屬 化物（並非單純混合兩種以上之金屬氧化物者， 氧化物彼此經化學鍵結成爲無法分離之狀態者） 機塡料列舉爲例如含有由矽、鈦、鋁、硼及鎂所 選出之至少兩種元素之複合氧化物。更具體而言 例如二氧化砂與氧化鈦之複合氧化物、由二氧化 鋁構成之複合氧化物、由氧化硼與氧化鋁所構成 化物' 由二氧化矽與氧化鋁及氧化鎂所構成之複 等。該等複合氧化物可單獨使用或混合兩種以上 可與上述之無機塡料混合使用。 又，本實施形態中，爲了孔隙抑制效果或應 亦可組合孔隙無機塡料與有機塡料作爲塡料使用 有機塡料列舉爲例如由丙烯酸樹脂、聚矽氧 二烯橡膠、聚酯、聚胺基甲酸酯、聚乙烯縮丁醛 酸酯、聚甲基丙烯酸甲酯、丙烯酸橡膠、聚苯乙 、SBR、聚矽氧改質之樹脂等樹脂成分所構成之每 至於有機塡料較好爲含有分子量100萬以上 有機微粒子或具有三次元交聯構造之有機微粒子 微粒子對樹脂組成物之分散性高。且，含有該有 之薄膜狀樹脂組成物之接著性與硬化後之應力緩 異。又，此處所謂「具有三次元交聯構造」係表 機微粒子之樹脂之聚合物鏈具有三次元網目構造 該構造之樹脂係藉由例如具有複數個反應點之聚 之複合氧 而是金屬 。該種無 組成群組 ，列舉爲 矽與氧化 之複合氧 合氧化物 使用，亦 力緩和， 〇 樹脂、丁 、聚丙烯 烯、NBR I料。 之樹脂之 。該有機 機微粒子 和性更優 示構成有 ，且具有 合物以具 -12- 201235395 有兩個以上之可與該反應點鍵結之官能基之交聯劑處理而 獲得。含有分子量爲1〇〇萬以上之樹脂之有機微粒子及具 有三次元交聯構造之有機微粒子對任何溶劑之溶解性均低 之方面而言係較佳。對溶劑之溶解性低之該等有機微粒子 可更顯著地獲得上述效果。另外，就更顯著地獲得上述效 果之觀點而言，上述有機微粒子較好爲由（甲基）丙烯酸 烷酯-聚矽氧共聚物、聚矽氧-(甲基）丙烯酸共聚物或該 等之複合物所構成之有機微粒子。 至於有機塡料可使用具有蕊殻（core-shell)型構造， 且蕊層與殻層中之組成不同之有機微粒子。蕊殻型有機微 粒子具體而言列舉爲以聚矽氧-丙烯酸橡膠爲蕊而接枝丙 烯酸樹脂之粒子，以丁二烯橡膠爲蕊而接枝丙烯酸樹脂或 苯乙烯樹脂之粒子等。 使用含有分子量爲1〇〇萬以上之樹脂之有機微粒子或 具有三次元交聯構造之有機微粒子作爲有機塡料時，由於 對有機溶劑之溶解性低，故容易以維持粒子形狀之狀態直 接含於薄膜狀樹脂組成物中。據此，有機微粒子在薄膜狀 樹脂組成物中可分散成島狀，可進一步提高硬化後之薄膜 狀樹脂組成物之強度。 瑱料之形狀並無特別限制，列舉爲破碎狀、針狀、鱗 片狀、球狀等。該等中，塡料之形狀較好爲球狀。球狀之 塡料由於在樹脂組成物中之分散性良好，故可防止塡料集 中於樹脂組成物之特定部位而容易夾入突出物與基板電極 之間，可獲得連接信賴性更優異之半導體裝置。又，塡料 -13- 201235395 爲球狀時，會有樹脂組成物之黏度控制變容易之傾向。又 ，此處所謂球狀未必一定爲真球，亦可爲略球狀。 塡料之尺寸只要是比覆晶連接時之半導體晶片與基板 間之空隙小者即可。塡料之平均粒徑就可提高塡充密度， 使樹脂組成物之黏度控制變容易之觀點而言，較好爲 1 Ομιη以下，更好爲5μιη以下，又更好爲3μηι以下。又， 塡料之平均粒徑之下限値並無特別限制，例如可使用平均 粒徑爲0.01 μηι以上之塡料。又，爲了更顯著地獲得本實 施形態之半導體密封塡充用薄膜狀樹脂組成物中之效果（ 良好之導電性及連接信賴性），塡料之平均粒徑可設爲 0.05〜0·9μιη，亦可爲 0.1~0.8μηι。 又，此處所謂平均粒徑爲可利用雷射光繞射法之粒度 分布測定裝置以中値直徑求得者。所謂中値直徑係表示個 數基準之粒度分布中之累積率成爲50%之粒徑（D50)之 値。 相對於第1樹脂組成物總量之第1樹脂組成物中之塡 料的質量比率，就使第1樹脂組成物（或其硬化物）之熱 膨脹係數更低之觀點而言，較好爲20質量％以上，就進一 步提高第1樹脂組成物（或其硬化物）之機械強度之觀點 而言，更好爲3 0質量％以上，就進一步降低第1樹脂組成 物（或其硬化物）之吸水率之觀點而言，又更好爲40質 量％以上。 相對於第1樹脂組成物總量之第1樹脂組成物中之塡 料的質量比率之上限値並無特別限制，例如可設爲70質 -14- 201235395 量％以下，亦可設爲60質量％以下，超過70質量％時第1 樹脂組成物變脆，有操作性降低之傾向。 有機塡料與無機塡料倂用時，有機塡料之質量比率相 對於第1樹脂組成物宜爲1~10質量％。爲1質量％以上時 ，可顯著獲得由有機塡料所致之孔隙抑制效果或應力緩和 效果，爲1 〇質量％以下時，樹脂組成物之增黏獲得抑制， 可減低薄膜狀樹脂組成物表面之凹凸，更抑制孔隙之發生 ，且更提高接著性。 第1樹脂組成物較好含有熱硬化性樹脂。 藉此，在連接半導體晶片與基板時之加熱加壓下使第 1樹脂組成物硬化，且經硬化之第1樹脂組成物可補強突 出物與基板電極之連接部。因此，連接完成後之冷卻過程 中’可充分抑制起因半導體晶片與基板之熱膨脹係數差異 所致之熱應力集中於連接部而造成龜裂等連接不良。亦即 ’藉由使第1樹脂組成物含有熱硬化性樹脂，所得之半導 體裝置之連接信賴性會變得更優異。 至於熱硬化性樹脂列舉爲酚樹脂、氰酸酯樹脂、苯并 環丁烯樹脂、丙烯酸酯樹脂、甲基丙烯酸酯樹脂、環氧樹 脂等。基於耐熱性優異及使作業性變良好，第一樹脂組成 物較好含有環氧樹脂作爲熱硬化性樹脂。 例如使用2官能基以上之環氧樹脂（分子中具有2個 以上環氧基之環氧樹脂）作爲環氧樹脂。該環氧樹脂可使 用例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型 環氧樹脂、酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧 -15- 201235395 樹脂、聯苯型環氧樹脂、氫醌型環氧樹脂、含有二苯基硫 醚骨架之環氧樹脂、酚芳烷基型多官能基環氧樹脂、含有 萘骨架之多官能基環氧樹脂、含有二環戊二烯骨架之多官 能基環氧樹脂、含有三苯基甲烷骨架之多官能基環氧樹脂 、胺基酚型環氧樹脂、二胺基二苯基甲烷型環氧樹脂、其 他各種多官能基環氧樹脂等。 該等環氧樹脂中，就可容易地實現樹脂組成物之低黏 度化、降低樹脂組成物（或其硬化物）之吸水率且更難產 生尺寸變化'進一步提高樹脂組成物（或其硬化物）之耐 熱性等之觀點而言，較好使用雙酚A型環氧樹脂、雙酚F 型環氧樹脂、含有萘骨架之多官能基環氧樹脂、含有二環 戊二烯之多官能基環氧樹脂、含有三苯基甲烷骨架之多官 能基環氧樹脂等。 至於環氧樹脂之性狀在25 t下爲液狀或爲固態均無妨 。且，該等環氧樹脂可單獨使用或混合兩種以上使用。 第1樹脂組成物可進而含有硬化劑。硬化劑可依據熱 硬化性樹脂之種類適當選擇。例如，第1樹脂組成物含有 環氧樹脂作爲熱硬化性樹脂時，可使用咪唑類、酸酐類、 胺類、酚類、聯胺類、聚硫醇類、路易斯酸-胺錯合物等 作爲硬化劑。該等硬化劑中，就可容易地實現樹脂組成物 之低黏度化、儲存安定性優異、更提高樹脂組成物之硬化 物之耐熱性等觀點而言，較好使用咪唑類、酸酐類、胺類 、酚類。且，以聚胺基甲酸酯系、聚酯系之高分子物質等 被覆並經微膠囊化者作爲硬化劑由於可延長可使用時間故 -16- 201235395 較佳。 上述咪唑類列舉爲2 -甲基咪唑、2 -十一烷基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、1-苄 基-2-甲基咪唑、卜苄基-2-苯基咪唑、1-氰乙基-2 -甲基咪 唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-乙基-4-甲基 咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑 鎗偏苯三酸鹽、1-氰乙基-2-苯基咪唑鎗偏苯三酸鹽、2,4-二胺基-6-[2’-甲基咪唑基-(1’）]-乙基-3-三嗪、2,4-二胺 基-6-[2，-十一烷基咪唑基-(1’）]-乙基-s-三嗪、2,4-二胺 基-6-[2’-乙基- 4’-甲基咪唑基-(1，）]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1，）]-乙基-s-三聚異氰酸加成 物、2,4-二胺基-6-[2’-甲基咪唑基-(1’）]-乙基-3-三聚異 氰酸加成物、2-苯基咪唑三聚異氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等。又 ，亦可使用將環氧樹脂加成於該等咪唑類而成之化合物。 該等咪唑類可使用例如 2ΜΖ、Cl 1Ζ、2ΡΖ ' 2Ε4ΜΖ、 2Ρ4ΜΖ、1Β2ΜΖ、1Β2ΡΖ、2MZ-CN、2E4MZ-CN、2PZ-CN 、C11Z-CN、2PZ-CNS、C11Z-CNS、2ΜΖ-Α、C11Z-A、 2Ε4ΜΖ-Α、2Ρ4ΜΗΖ、2ΡΗΖ、2ΜΑ-ΟΚ、2ΡΖ-ΟΚ (均爲四 國化成工業股份有限公司製造，製品名）等。又，上述咪 唑類可單獨使用或混合兩種以上使用。 第1樹脂組成物中之咪唑類之調配量相對於第1樹月旨 組成物中之環氧樹脂之總量100質量份，較好爲0.1~1Q 質量份，更好爲0.5〜10質量份，又更好爲1〜10質量份。 -17- 201235395 調配量爲ο. 1質量份以上時，環氧樹脂之硬化充分進 可更確實發揮上述效果（連接信賴性更優異等）。又 由使調配量成爲10質量份以下，使儲存安定性變得 好。 上述酸酐類可使用例如馬來酸酐、琥珀酸酐、十 基琥珀酸酐、苯二甲酸酐、四氫苯二甲酸酐、甲基四 二甲酸酐、六氫苯二甲酸酐、甲基六氫苯二甲酸酐 亞甲基四氫苯二甲酸酐、甲基橋-亞甲基四氫苯二甲 甲基腐植酸酐 '均苯四甲酸二酐、二苯甲酮四羧酸二 聚壬二酸二酐、烷基苯乙烯-馬來酸酐共聚物、3,4-基- 6-( 2 -甲基-1-丙烯基）-4 -環己烯-1,2 -二羧酸酐、 丙基-4-甲基-雙環[2.2.2]辛-5-烯-2,3-二羧酸酐、乙二 偏苯三酸酯、丙三醇叁偏苯三酸酐等》 該等中，就使樹脂組成物（或其硬化物）之耐熱 耐濕性變得更好之觀點而言，較好使用甲基四氫苯二 酐、甲基六氫苯二甲酸酐、橋-亞甲基四氫苯二甲酸 基橋-亞甲基四氫苯二甲酸、3,4-二甲基-6-(2-甲基-烯基）-4-環己烯-l，2-二羧酸酐、l-異丙基-4-甲基-[2.2·2]辛-5-烯·2,3-二羧酸酐、乙二醇雙偏苯三酸酯 三醇叁偏苯三酸酐酯等。該等可單獨使用或混合兩種 使用8 第1樹脂組成物中之酸酐類之調配量較好爲使第 脂組成物中之環氧樹脂所具有之環氧基之數，與 調配於第1樹脂組成物中之酸酐產生之羧基之數n2 行， ，藉 更良 二烯 氫苯 、橋_ 酸、 酐、 二甲 1-異 醇雙 性及 甲酸 、甲 .1 -丙 雙環 、丙 以上 1樹 可自 之比 -18- 201235395 (N1/N2)成爲〇·5〜1.5之調配量。上述比（N1/N2)更好 爲0.7〜1.2。比（Ν,/Ν：!)小於0.5時，羧基過量而殘留於 樹脂組成物之硬化物中’會有樹脂組成物之硬化物之耐濕 信賴性下降之情況。亦即，比（Ν! /Ν2 )爲0 · 5以上時，樹 脂組成物之硬化物之耐濕信賴性變得更良好。又，比（ Ni/lSh)爲1.5以下時，環氧樹脂之硬化充分地進行，而更 確實發揮上述效果（連接信賴性更優異等）。 上述胺類列舉爲分子內具有至少一個以上之一級或二 級胺基之化合物。至於胺類，就儲存安定性優異、使樹脂 組成物之硬化物之耐熱性變得更好等之觀點而言，較好使 用芳香族胺類。 至於芳香族胺類列舉爲例如二胺基二苯基甲烷、二胺 基二苯基颯、二胺基二苯基硫醚、間二甲苯二胺、3,3’-二 乙基-4,4’-二胺基二苯基甲烷、3,3’，5,5’-四乙基-4,4’-二胺 基二苯基甲烷、4,4’-二胺基二苯基颯、4,4’-二胺基二苯基 硫醚、2,2-雙-[4- (4-胺基苯氧基）苯基]-六氟丙烷、2，2-雙（4-胺基苯基）-六氟丙烷、2,4-二胺基甲苯、1，4-二胺 基苯、1，3-二胺基苯、二乙基甲苯二胺、二甲基甲苯二胺 、苯胺類、烷基化苯胺類、N-烷基化苯胺類等。該等可單 獨使用或混合兩種以上使用。 第1樹脂組成物中之二胺類之調配量較好爲使第1樹 脂組成物中之環氧樹脂所具有之環氧基之數N,，與調配 於第1樹脂組成物中之胺類之胺基上之活性氫之數N3之 比（ISh/lSh)成爲0.5〜1.5之調配量。上述比（Ν,/Ν3)更 201235395 好爲0.7〜1.2。比（Ν,/Α)小於〇·5時， 過量而殘留於樹脂組成物之硬化物中，會 硬化物之耐濕性下降之情況。亦即，比（ 上時，樹脂組成物之硬化物之耐濕信賴性 ，比（Ni/Nh )爲1.5以下時，環氧樹脂之 ，更確實發揮上述效果（連接信賴性更優 至於上述酚類，可使用雙酚樹脂、酚 萘酚酚醛清漆樹脂、烯丙基化酚酚醛清漆 、甲酣酚醛清漆樹脂、酚芳烷基樹脂、甲 合物、三苯基甲烷型多官能基酚樹脂、二 醛清漆樹脂、二甲苯改質之萘酚酣醛清漆 能基酚樹脂等。該等可單獨使用一種或以 物使用。 第1樹脂組成物中之酚類之調配量較 組成物中之環氧樹脂所具有之環氧基之婁 第1樹脂組成物中之酚類所具有之酚性超 (Ni/N*)成爲 0.5〜1 .5之調配量。上述i 爲0.7〜1.2。比（NWN4 )小於0.5時，酣 留於樹脂組成物之硬化物中，會有樹脂組 耐濕性降低之情況。亦即，比（N i /N4 ) Μ 脂組成物之硬化物之耐濕信賴性變得更 Ni/NO爲1.5以下時，環氧樹脂之硬化充 實發揮上述效果（連接信賴性更優異等） 又，倂用酸酐類、胺類及酚類中之兩 胺基上之活性氫 有樹脂組成物之 N】/N3 )爲0.5以 變得更良好。且 ，硬化充分地進行 異等）。 酚醛清漆樹脂、 樹脂、雙酚樹脂 酚萘酚甲醛聚縮 甲苯改質之酚酚 樹脂、各種多官 兩種以上之混合 好爲使第1樹脂 N i，與調配於 S基之數N4之比 :匕（NWN4 )更好 性羥基過量而殘 成物之硬化物之 丨〇. 5以上時，樹 良好。又，比（ 分地進行，更確 〇 種以上時，較好 -20- 201235395 以使比[Νι/ ( Ν〗+Ν3+Ν4 )]成爲0.5〜1 .5之方式調配 以成爲2之方式調配。 使用酸酐類、胺類、酚類作爲硬化劑時，亦可 外之硬化促進劑。例如’上述咪唑類可與作爲硬化 之酸if類、胺類、酚類一起使用。又’至於硬化促 使用三級胺類；1,8-二氮雜雙環（5.4.0 )十一碳火 1,5-二氮雜雙環（4.3.0)壬烯-5等環狀胺類：三級 環狀胺類之四苯基硼酸鹽；三丁基膦等之三烷基膦 苯基膦等三芳基膦類；四丁基鱗三苯基硼酸鹽或四 四苯基硼酸鹽等鱗鹽等。硬化促進劑之調配量係考 化時間或儲存安定性而適當設定。 第1樹脂組成物亦可含有熱可塑性樹脂。藉由 可塑性樹脂而提高薄膜形成性。 至於熱可塑性樹脂列舉爲苯氧樹脂、聚醯亞胺 聚醯胺樹脂、聚碳二醯亞胺樹脂、丙烯酸樹脂、聚 、聚乙烯樹脂、聚醚颯樹脂 '聚醚醯亞胺樹脂、聚 酸酯醯亞胺樹脂、聚乙烯乙縮醛樹脂、聚乙烯丁縮 、胺基甲酸酯樹脂、丙烯酸橡膠等。該等中，基於 及薄膜形成性優異，宜爲苯氧樹脂、聚醯亞胺樹脂 二醯亞胺樹脂、聚胺基甲酸酯醯亞胺樹脂，更好爲 脂、聚醯亞胺樹脂。 熱可塑性樹脂之重量平均分子量較好爲5000 更好爲10000以上，又更好爲20000以上。重量平 量爲5000以上時，可充分獲得提高薄膜形成性之 ，更好 倂用額 促進劑 進劑可 i -7或 胺類或 類：三 苯基鱗 慮凝膠 含有熱 樹脂、 酯樹脂 胺基甲 醛樹脂 耐熱性 、聚碳 苯氧樹 以上， 均分子 效果。 -21 - 201235395 又，此處之重量平均分子量係使用GPC (凝膠滲透層析法 )，以聚苯乙烯換算測定之値。又，該等熱可塑性樹脂可 單獨使用或亦可以兩種以上之混合物或共聚物使用。 第1樹脂組成物含有熱可塑性樹脂時，其含量以第1 樹脂組成物之總量爲基準，較好爲1〜5 0質量％，更好爲 1〜40質量％，又更好爲5〜30質量％。含量超過50質量％ 時，會有樹脂組成物之硬化物之耐熱性降低之情況。 第1樹脂組成物中，亦可調配矽烷偶合劑、鈦偶合劑 、抗氧化劑、平流劑、離子凹陷劑等添加劑作爲上述以外 之成分。該等添加劑可單獨使用，亦可組合兩種以上使用 。添加劑之調配量只要調整爲展現各添加劑之效果即可。 又，第1樹脂組成物亦可含有後述之助焊劑。 (第2層） 第2層爲由含有助焊劑之第2樹脂組成物構成之層。 第2樹脂組成物中，爲了還原去除焊料等之金屬之表面氧 化膜，以金屬接合形成良好之連接度，而調配助焊劑爲必 須成分。 又，相對於第2樹脂組成物總量之第2樹脂組成物中 之塡料的質量比率，比相對於第1樹脂組成物總量之第1 樹脂組成物中之塡料的質量比更小。藉由具有該構成，而 充分抑制先供給方式中之凹陷發生。又，第2樹脂組成物 可含有塡料亦可不含。 第2樹脂組成物，除塡料之質量比率較小以外，亦可 -22- 201235395 含有與第1樹脂組成物相同之成分，且各成分之調配量可 與上述第1樹脂組成物中之較佳調配量相同。 相對於第2樹脂組成物總量之第2樹脂組成物中之塡 料的質量比率較好爲〇質量％以上未達2 0質量％，更好爲 0〜15質量％，又更好爲0〜10質量％。藉由減少塡料之含量 ，而提高第2樹脂組成物及第2層之光透過性。據此，於 後述之半導體裝置之製造方法中貼合於半導體晶圓上時， 可透過第2層辨識突出物前端部，可獲得使切晶時之位置 對準或連接時與基板之位置對準變容易之效果。又，爲了 使該突出物前端部之辨識成爲可能，第2層之光透過率對 於5 5 5nm之可見光宜爲10%以上，更好爲20%以上，又更 好爲40%以上。又，光透過率對於5 50nm之可見光可爲 95%以下，亦可爲90%以下。 第2樹脂組成物較好含有熱可塑性樹脂。第2樹脂組 成物含有熱可塑性樹脂時，會有第2層之表面黏附力變低 之傾向。因此，例如於後述之半導體之製造方法中，可發 揮防止將貼附有半導體密封塡充用薄膜狀樹脂組成物之半 導體晶圓單粒化成半導體晶片時產生之切削層附著於第2 層表面之效果。 就更顯著獲得該效果之觀點而言，第2樹脂組成物中 之熱可塑性樹脂之含量，以第2樹脂組成物之總量爲基準 ，較好爲5〜99.9質量％，更好爲1 0〜95質量％。 又，就同樣之觀點而言，第2樹脂組成物中之熱可塑 性樹脂及助焊劑之合計含量，以第2樹脂組成物之總量爲 -23- 201235395 基準’較好爲5質量％以上，更好爲1 〇質量％以上。 第2樹脂組成物亦可爲僅由熱可塑性樹脂及助焊劑所 者。 第2樹脂組成物中之助焊劑之調配量，以第2樹 成物之總量爲基準，較好爲0 . 1〜1 0質量％，就進一步 光透過性之觀點而言更好爲0.5〜7質量％，就進而提 存安定性之觀點而言更好爲1〜5質量％。調配量爲〇 量％以上時，由於更顯著發揮以助焊劑去除氧化膜之 ，故使連接信賴性更爲提高。且，助焊劑過量存在時 樹脂組成物之絕緣性降低之情況，但藉由使調配量成: 質量％以下而防止此種絕緣性之降低，獲得絕緣信賴 異之樹脂組成物。 至於助焊劑，就對樹脂組成物中之分散性優異之 而言，較好使用由醇類、酚類及碳酸類所組成群組選 至少一種化合物。 至於上述醇類列舉爲分子內具有兩個以上醇性羥 化合物。至於該醇類可使用1，3-二噁烷-5,5-二甲醇、 戊二醇、2,5 -呋喃二甲醇、二乙二醇、四乙二醇 '五 醇、六乙二醇、1,2,3-己三醇、1，2,4-丁三醇、Ι，2,6-醇、3-甲基戊烷-1,3,5-三醇、丙三醇、三羥甲基乙烷 羥甲基丙烷' 赤癖醇、季戊四醇、核醣醇、山梨糖 2，4-二乙基-1,5-戊二醇、丙二醇單甲基醚、丙二醇單 醚、1，3-丁二醇、2-乙基-1,3-己二醇、Ν-丁基二乙醇 Ν-乙基二乙醇胺、二乙醇胺、三乙醇胺、Ν，.Ν-雙（2_ 又， 構成 脂組 提高 高儲 _1質 效果 會有 U 10 性優 觀點 出之 基之 1,5-乙二 己三 、 三 醇、 乙基 胺、 羥基 -24 - 201235395 乙基）異丙醇胺、雙（2 -羥基甲基）亞胺基叁（羥基甲基 )甲烷、N，N，N’，N’-肆（2-羥基乙基）乙二胺、 1，1’，Γ’，Γ”-(伸乙基二硝基）肆（2-丙醇）等。 該等醇類中，具有三級氮原子之化合物，例如Ν-丁 基二乙醇胺、Ν-乙基二乙醇胺、三乙醇胺、ν，Ν-雙（2-羥 基乙基）異丙醇胺、雙（2-羥基甲基）亞胺基叁（羥基甲 基）甲烷、Ν，Ν，Ν’，Ν’-肆（2-羥基乙基）乙二胺、 1，1 ’，1”，1 (伸乙基二硝基）肆（2-丙醇）等，與其他化 合物相較’顯示良好之助焊劑活性故較佳。顯示良好助焊 劑活性之詳細理雖尙不清楚，但推測係由於醇性羥基之氧 化膜還原能與源自三級氮原子上之未共用（lone pair)電 子之電子供給性所致之還原能一併作用所致。又，該等醇 類可單獨使用，亦可組合兩種以上使用。 上述酚類列舉爲分子內具有2個以上酚性羥基之化合 物。該酚類列舉爲兒茶酚、間苯二甲酚、氫醌、雙酚、二 經基萘、經基氫醒、連苯三酣、叉甲基雙酣（methylidene bisphenol)(亦稱爲「雙酚F」）、叉異丙基雙酚（亦稱 爲「雙酚A」）、叉乙基雙酚（亦稱爲「雙酚AD」）、 1，1，1-三（4-羥基苯基）乙烷、三羥基二苯甲酮、三羥基 苯乙酮、聚對乙烯基酚等。 又’分子內具有2個以上之酚性羥基之化合物可使用 分子內具有酚性羥基之化合物A，及可與該化合物A聚縮 合之化合物B之聚縮合物。此處之化合物B列舉爲二乙烯 基苯；醛類；分子內具有2個以上之鹵甲基、烷氧基甲基 -25- 201235395 或羥基甲基之芳香族化合物等。又，該等酚類可單 亦可組合兩種以上使用。 上述化合物A列舉爲例如酚、烷基酚、萘酚、 兒茶酚、間苯二甲酚、氫醌、雙酚、二羥基萘、羥 、連苯三酚、叉甲基雙酚（亦稱爲「雙酚F」）、 基雙酚（亦稱爲「雙酚A」）、叉乙基雙酚（亦稱 酚AD」）、叁（4-羥基苯基）乙烷、三羥基 酮、三羥基苯乙酮、聚對乙烯基酚等。 上述醛類列舉爲甲醛（爲其水溶液之福馬林） 醛、三噁烷、六亞甲基四胺等。 至於分子內具有兩個以上之鹵甲基、烷氧基甲 基甲基之芳香族化合物，列舉爲例如1，2-雙（氯甲 、1，3-雙（氯甲基）苯、1，4-雙（氯甲基）苯、1，2· 氧基甲基）苯、1，3-雙（甲氧基甲基）苯、1，4-雙 基甲基）苯、1，2-雙（羥基甲基）苯、1，3-雙（羥 )苯、1，4-雙（羥基甲基）苯、雙（氯甲基）聯苯 甲氧基甲基）聯苯等。 亦即，上述聚縮合物列舉爲例如酚與甲醛之聚 之酚酚醛清漆樹脂、甲酚與甲醛之聚縮合物之甲酚 漆樹脂、萘酚類與甲醛之聚縮合物之萘酚酚醛清漆 酚與1，4-雙（甲氧基甲基）苯之聚縮合物之酚芳烷 、雙酚A與甲醛之聚縮合物、酚與二乙烯基苯之聚 、甲酚與萘酚及甲醛之聚縮合物等，亦可爲該等聚 經橡膠改質者或於分子骨架內導入胺基三嗪骨架或 獨使用 甲酚、 基氫醌 叉異丙 爲「雙 二苯甲 、聚甲 基或羥 基）苯 雙（甲 (甲氧 基甲基 、雙（ 縮合物 酚醛清 樹脂、 基樹脂 縮合物 縮合物 二環戊 -26- 201235395 二烯骨架而成者。 再者，至於助焊劑，亦可使用烯丙基化酚酚醛清漆樹 脂、二烯丙基雙酚A、二烯丙基雙酚F、二烯丙基雙酚等 作爲藉由使該等酚類烯丙基化而液狀化而成者。該等化合 物可單獨使用，亦可組合兩種以上使用》 上述羧酸類可爲脂肪族羧酸、芳香族羧酸之任一種， 較好爲在25°C爲固體狀者。 至於脂肪族羧酸列舉爲例如丙二酸、甲基丙二酸、二 甲基丙二酸、乙基丙二酸、烯丙基丙二酸、2，2’-硫基二乙 酸、3,3’-硫基二丙酸、2,2’-(伸乙基二硫基）二乙酸、 3,3’-二硫基二丙酸、2-乙基-2-羥基丁酸、二硫基二乙醇酸 、二乙醇酸、乙炔二羧酸、馬來酸、蘋果酸、2·異丙基蘋 果酸' 酒石酸、衣康酸、1，3-丙酮二羧酸、丙三羧酸、黏 康酸（muconic acid) 、β -氬黏康酸、號珀酸、甲基號拍 酸、二甲基琥珀酸、戊二酸、α-酮戊二酸、2-甲基戊二酸 、3 -甲基戊二酸、2,2-二甲基戊二酸、3，3-二甲基戊二酸 、2,2-雙（羥基甲基）丙酸、檸檬酸、己二酸、3-第三丁 基己二酸、庚二酸、苯基草酸、苯基乙酸、硝基苯基乙酸 、苯氧基乙酸、硝基苯氧基乙酸、苯基硫基乙酸、羥基苯 基乙酸、二羥基苯基乙酸、扁桃酸、羥基扁桃酸、二羥基 扁桃酸、1，2,3,4-丁烷四羧酸、辛二酸、4,4’-二硫基二丁 酸、桂皮酸、硝基桂皮酸、羥基桂皮酸、二羥基桂皮酸、 香豆酸、苯基丙酮酸 '羥基苯基丙酮酸、咖啡酸、均苯二 甲酸、甲苯基乙酸、苯氧基丙酸、羥基苯基丙酸、苄氧基 -27- 201235395 乙酸、苯基乳酸、托品酸（tropic acid ) 、3-(苯基磺醯 基）丙酸、3，3 -四亞甲基戊二酸、5 -氧代壬二酸、壬二酸 、苯基琥珀酸、1，2-伸苯基二乙酸、1，3-伸苯基二乙酸、 1,4-伸苯基二乙酸、苄基丙二酸、癸二酸、十二烷二酸、 十一烷二酸、二苯基乙酸、二苯基乙醇酸、二環己基乙酸 、十四烷二酸、2,2-二苯基丙酸、3,3-二苯基丙酸、4,4-雙 (4-經基苯基）戊酸、海松酸（pimaric acid)、長葉松酸 (palustric acid )、異海松酸（isopimaric acid )、松香 酸（abietic acid )、脫氫松香酸、新松香酸、瑪瑙酸（ Agathic acid )等。 芳香族羧酸列舉爲例如苯甲酸、2-羥基苯甲酸、3-羥 基苯甲酸、4_羥基苯甲酸、2，3-二羥基苯甲酸、2,4-二羥 基苯甲酸、2,5-二羥基苯甲酸、2,6-二羥基苯甲酸、3,4-二 羥基苯甲酸、2,3，4-三羥基苯甲酸、2,4,6-三羥基苯甲酸、 3.4.5- 三羥基苯甲酸、1，2,3·苯三羧酸、1，2,4-苯三羧酸、 1.3.5- 苯三羧酸、2-[雙（4-羥基苯基）甲基]苯甲酸、1-萘 甲酸、2-萘甲酸、1-羥基-2-萘甲酸、2-羥基-1-萘甲酸、3-羥基-2-萘甲酸、6-羥基-2·萘甲酸、1,4-二羥基-2-萘甲酸 、3,5-二羥基-2-萘甲酸、3,7-二羥基-2-萘甲酸、2,3-萘二 羧酸、2,6-萘二羧酸、2-苯氧基苯甲酸、聯苯-4-羧酸、聯 苯-2-羧酸、2_苯甲醯基苯甲酸等。 該等羧酸類中，就儲存安定性優異、取得容易之觀點 而言，較好使用琥珀酸、蘋果酸、衣康酸、2,2-雙（羥基 甲基）丙酸、己二酸、3,3’-硫基二丙酸、二硫基二丙 -28- 201235395 酸、1，2,3,4-丁烷四羧酸、辛二酸、癸二酸、苯基琥珀酸 、十二烷二酸、二苯基乙酸、二苯基乙醇酸、4,4-雙（4-羥基苯基）戊酸、松香酸、2,5 -二羥基苯甲酸、3，4,5 -三羥 基苯甲酸、1,2,4-苯三羧酸、1，3,5-苯三羧酸、2-[雙（4-羥 基苯基）甲基]苯甲酸等。又，該等羧酸類可單獨使用亦 可組合兩種以上使用。 助焊劑在室溫（例如25 °C )可爲液狀亦可爲固體狀， 但第2樹脂組成物含有環氧樹脂時，較好使用在室溫爲固 體狀之助焊劑。由於酚類中存在之酚性羥基或羧酸類中存 在之羧基會與環氧樹脂反應，故使用液狀助焊劑，使環氧 樹脂與助焊劑成均勻相溶狀態時，會有儲存安定性降低之 虞。 第2樹脂組成物亦可含有金屬粒子等導電粒子，但就 藉由突出物與基板電極之金屬接合而獲得優異之連接信賴 性之觀點而言，導電粒子之含量以第2樹脂組成物之總量 爲基準較好爲0〜10質量％，更好爲0〜5質量％，又更好爲 〇質量％ (亦即不含導電粒子）。 (半導體密封塡充用薄膜狀樹脂組成物） 本實施形態之半導體密封塡充用薄膜狀樹脂組成物例 如可在各有機溶劑中，使用行星式混練機或珠粒混練機混 合構成第1層之成分及構成第2層之成分，製作漆料，且 使用刮刀塗佈器或輥塗佈器，將該漆料塗佈於施加脫模處 理之樹脂薄膜基材上後，藉由乾燥去除有機溶劑，分別製 -29- 201235395 作成爲第1層之薄膜狀樹脂組成物及成爲第2層之薄膜狀 樹脂組成物，且使用層合機貼合該等而製造。又，亦可藉 由將含有構成第1層之成分及構成第2層之成分之任一種 成分之漆料塗佈於施以脫模處理之樹脂薄膜基材上並經乾 燥後，再度塗佈含有另一種成分之漆料並乾燥而製造。 上述有機溶劑列舉爲例如乙酸乙酯、甲基乙基酮、環 己酮、N-甲基吡咯烷酮等。且，上述樹脂薄膜基材列舉爲 聚對苯二甲酸乙二酯、聚胺基甲酸酯、聚氯化乙烯、聚乙 酸乙烯酯、聚乙烯基縮丁醛、聚烯烴等。 本實施形態之半導體密封塡充用薄膜狀樹脂組成物中 ，第2層之厚度較好比第1層之厚度小。該半導體密封塡 充用薄膜狀樹脂組成物之熱膨脹係數小而可進一步提高連 接信賴性。第2層之厚度較好爲第1層厚度之0.8倍以下 ，更好爲0.7倍以下。第2層厚度之下限並無特別限制， 可爲第1層厚度之〇.〇5倍以上，亦可爲第1層厚度之0.1 倍以上。 半導體密封用薄膜狀樹脂組成物之厚度可依據用以塡 充半導體晶片與基板之間之空隙所需之樹脂量而適當設定 。例如，半導體密封塡充用薄膜狀樹脂組成物之厚度較好 爲連接前之突出物之高度的0.5〜1.5倍，更好爲0.6〜1.3 倍，又更好爲〇.7~1.2倍。厚度爲突出物之高度的0.5倍 以上時，可充分抑制因樹脂之未塡充造成之孔洞之發生， 使連接信賴性更爲優異。又，厚度超過1.5倍時，於連接 時會自晶片連接區域擠出多餘樹脂組成物，會有樹脂組成 •30- 201235395 物附著於不需要部分上之虞。 使用將半導體密封塡充用薄膜狀樹 備後述之準備步驟A之製造方法時’可 厚度爲 5〜25μιη，第二層之厚度爲 5〜15 μιη)。依據該半導體密封塡充用薄 可進一步防止具備準備步驟Α之製造方 獲得具有更優異導電性及連接信賴性之 第一層及第二層之厚度在上述範圍內時 均粒徑成爲0.1〜0.8 μπι，可更顯著獲得 製造方法中之上述效果。且，第一層及 述範圍內時，半導體密封塡充用薄膜狀 連接突出物高度爲40 μιη之晶片。 且，於將半導體密封塡充用薄膜狀 具備後述準備步驟Β而之製造方法時， 之厚度爲20〜90μηι(更好爲30〜80μηι) 1 ~2 0 μηι (更好爲 5〜15μηι)。依據該 薄膜狀樹脂組成物，可進一步防止具備: 方法中之凹陷發生，獲得具有更優異導 之半導體裝置。又，第一層及第二層之 時，藉由使塡料之平均粒徑成爲0.1〜〇 得具備準備步驟Β之製造方法中之上述 及第二層之厚度在上述範圍內時，半導 狀樹脂組成物適用於連接突出物高度爲 脂組成物使用於具 設爲例如第一層之 1〜20μιη (更好爲 膜狀樹脂組成物， 法中之凹陷發生， 半導體裝置。又， ，藉由使塡料之平 具備準備步驟Α之 第二層之厚度在上 樹脂組成物適用於 樹脂組成物使用於 可設爲例如第一層 ，第二層之厚度爲 半導體密封塡充用 準備步驟B之製造 電性及連接信賴性 厚度在上述範圍內 ·8μιη，可更顯著獲 效果。且，第一層 體密封塡充用薄膜 70μιη左右之晶片 -31 - 201235395 半導體密封塡充用薄膜狀樹脂組成物於250°C之膠凝 化時間較好爲3〜30秒，更好爲3~20秒，又更好爲3〜15 秒。膠凝化時間在上述範圍時，生產性優異，同時連接信 賴性更爲優異。又，所謂25 0°C之膠凝化時間係表示將半 導體密封塡充用薄膜狀樹脂組成物放置於設定在2 50°C之 加熱板上，以湯匙等攪拌直到無法攪拌之時間。 半導體密封塡充用薄膜狀樹脂組成物可藉由貼附於切 成特定大小之半導體晶片、半導體晶圓、基板等而供給。 (半導體裝置之製造方法） 本實施形態之半導體裝置之製造方法具備準備具有電 極之基板、形成突出物之半導體晶片、與貼合於基板或半 導體晶片上之半導體密封塡充用薄膜狀樹脂組成物之準備 步驟，及使基板之電極與半導體晶片之突出物電連接之連 接步驟。 此處，基板之電極及半導體晶片之突出物之至少一表 面上存在焊料或錫。因此，如專利文獻5中所記載之方法 ，作爲防止突出物與基板電極之間之凹陷，若突出物前端 自樹脂組成物露出時，露出之焊料或錫會形成氧化膜而有 導致連接不良之虞。相對於此，依據本實施形態之半導體 裝置之製造方法，由於基板電極與突出物之接合部係位在 第.2層內，故可防止因焊料或錫之氧化膜造成之連接不良 ，且可充分抑制凹陷。 且，由於基板之電極及半導體晶片之突出物之至少一 -32- 201235395 表面上存在焊料或錫’故基板之電極與半導體晶片之突出 物之電連接通常會藉由焊料或錫之金屬接合完成。亦即， 藉由焊料或錫利用連接時之加熱而熔融，使基板之電極與 半導體晶片之突出物透過焊料或錫而接合。藉由進行該金 屬接合’而獲得優異之導電性及連接信賴性。 至於半導體晶片，可使用在複數個電極上形成有複數 個突出物之半導體晶片。半導體晶片之材質並無特別限制 ’可使用矽、鍺等元素半導體；砷化鎵、磷化銦等化合物 半導體等之各種半導體》 至於半導體晶片上形成之突出物列舉爲例如銅突出物 、金突出物、焊料突出物、銅柱之前端形成有焊料或錫層 之構造之突出物等。 焊料可使用Sn-37Pb (熔點183°C).，但考慮對環境 之影響，較好使用Sn-3.5Ag (熔點221°C ) 、Sn-2.5Ag- 0.5Cu-lBi (熔點 214°C) 、Sn-0.7Cu (熔點 227°C) 、Sn-3Ag-0.5Cu (熔點 217°C ) 、Sn-92Zn (熔點 198°C )等之無 鉛銲料。又，就對應於微細連接化之觀點而言，較好爲在 銅柱前端形成焊料或錫層之構造之突出物。 基板具有設置有複數個電極之電極面。至於基板可使 用一般之電路基板，亦可使用不具有突出物之半導體晶片 〇 至於電路基板可使用餽刻去除於玻璃環氧樹脂、聚醯 亞胺、聚酯、陶磁等絕緣基板表面上形成之銅等金屬層之 不需要部位而形成含電極之配線圖型者；藉由於絕緣基板 -33- 201235395 表面上鍍銅等而形成含電極之配線圖型者；將導電性物質 印刷於絕緣基板表面而形成含電極之配線圖型者等。 基板之電極表面上較好形成由金層、焊料層、錫層及 防銹皮膜層選出之至少一種表面處理層。金屬及錫層可藉 由無電解電鍍或電解電鍍形成。另外，焊料層可藉由電鍍 形成，亦可藉由印刷塗佈焊料糊料並經加熱熔融之方法， 亦可藉由將微細之焊料粒子配置於配線圖型上並經加熱熔 融之方法形成。 防銹皮膜層亦稱爲預助焊，係藉由將基板浸漬於專用 之藥液中，去除以銅等形成之配線圖型表面之氧化膜，同 時藉由於該表面上形成由有機成分所構成之防銹皮膜而設 置。該種防銹皮膜層由於可確保對焊料或錫之良好潤濕性 ，同時容易對應於微細連接化故較佳。 爲進行上述之金屬接合，半導體晶片之突出物爲銅突 出物、金突出物等之表面上不具有焊料或錫之突出物時， 選擇表面上形成有焊料層或錫層之電極作爲基板之電極。 另外，基板之電極表面上不存在焊料或錫時，半導體晶片 之突出物係選擇焊料突出物、銅柱之前端形成焊料或錫層 之構造之突出物等。 至於準備步驟，列舉爲例如準備基板、貼附於該基板 上之半導體密封塡充用薄膜狀樹脂組成物及半導體晶片之 準備步驟A;準備半導體晶片、貼附於該半導體晶片上之 半導體密封塡充用薄膜狀樹脂組成物及基板之準備步驟B 等。 -34- 201235395 (準備步驟A ) 準備步驟A係以使第2層配置於基板側之方式，將半 導體密封塡充用薄膜狀樹脂組成物貼附於基板之電極面上 〇 至於於基板之電極面上貼附半導體密封塡充用薄膜狀 樹脂組成物之方法，列舉爲例如使用熱輥層合機或真空層 合機之方法。 (準備步驟B ) 準備步驟係實施在具有形成有複數個突出物之突出物 形成面之半導體晶圓之該突出物形成面上，以使第1層相 對於第2層配置於半導體晶圓側之方式貼附半導體密封塡 充用薄膜狀樹脂組成物之貼合步驟，及使經過第1步驟之 半導體晶圓單粒化，獲得貼附有半導體密封塡充用薄膜狀 樹脂組成物之半導體晶片之單粒化步驟。 準備步驟B由於可一次製作複數個貼附有半導體密封 塡充用薄膜狀樹脂組成物之半導體晶片，故生產性優異。 於半導體晶圓之突出物形成面上貼附半導體密封塡充 用薄膜狀樹脂組成物之方法，列舉爲例如使用熱輥層合機 或真空層合機之方法。 此處，相對於如上述之第2樹脂組成物總量之第2樹 脂組成物中之塡料的質量比率較少（例如未達20質量％ ) 時，第2層由於光透過性優異，故可透過第2層辨識突出 -35- 201235395 物前端。因此，單粒化步驟或後述之連接步驟中，可以突 出物之前端作爲基準進行位置對準，而提高作業性。 半導體晶圓之單粒化可藉由例如刮刀切晶、雷射切晶 、隱形切晶（stealth dicing )等進行。此時，半導體晶圓 可固定於使切片膠帶貼附於半導體晶圓之與突出物形成面 相反側之面上之切晶裝置上，亦可固定於將切晶膠帶貼合 於貼附於半導體晶圓上之半導體密封塡充用薄膜狀樹脂組 成物上之切晶裝置上。 準備步驟B可將半導體密封塡充用薄膜狀樹脂組成物 貼附於經背部硏磨加工而薄化加工至預定厚度之半導體晶 圓上。另外，於施以背部硏磨加工前之半導體晶圓上貼附 半導體密封塡充用薄膜狀樹脂組成物後，亦可以與半導體 密封塡充用薄膜狀樹脂組成物鄰接之方式貼合背部硏磨膠 帶，使突出物形成面與相反側之面經背部硏磨加工薄化加 工成爲特定厚度。 又，準備步驟B亦可針對施以背部硏磨加工前之半導 體晶圓，沿著切晶線，以切晶裝置進行半加工形成溝槽後 ，將半導體密封塡充用薄膜狀樹脂組成物貼附於突出物形 成面上。該情況下，可以與半導體密封塡充用薄膜狀樹脂 組成物鄰接之方式貼合背部硏磨膠帶，自與突出物形成面 相反側之面，藉由背部硏磨使上述溝槽露出，使半導體晶 圓薄化之同時使半導體晶片單粒化。 連接步驟係使基板之電極與半導體晶片之突出物電連 接。連接步驟可例如透過半導體密封塡充用薄膜狀樹脂組 -36- 201235395 成物使半導體晶片與基板成對向配置，邊在焊料或錫之熔 點以上之溫度加熱邊加壓而進行。藉此，焊料或錫之表面 氧化膜可藉由第2層（或第2層及第1層）中所含之助焊 劑去除’同時使焊料或錫快速熔解，使半導體晶片之突出 物與基板之電極金屬接合。 此處’半導體密封塡充用薄膜狀樹脂組成物係分別以 第〗層位在半導體薄膜側，第2層位在基板側之方式配置 。藉此’可充分抑制凹陷之產生，製造具有良好導電性及 連接信賴性之半導體裝置。 加熱加壓時間較好爲0.1〜2 0秒，更好爲0.1〜1 5秒， 又更好爲〇 · 1〜1 〇秒。藉由使加熱加壓時間爲0.1秒以上， 可自突出物與電極間充分排除樹脂組成物，同時均勻地去 除焊料或錫之表面氧化膜，故有進一步提高連接信賴性之 傾向。且，連接時間超過2 0秒時，有生產性下降之虞。 連接步驟可包含在第2層中所含助焊劑之活化溫度以 上、焊料或錫之熔點以下之溫度下加熱加壓之第一加熱步 驟，及在焊料或錫之熔點以上之溫度加熱加壓而使半導體 晶片之突出物與基板之電極金屬接合之第二加熱步驟。 第一加熱步驟爲將藉由加熱而將低黏度化之樹脂組成 物自突出物與基板電極間排除，同時藉由助焊劑去除焊料 或錫之表面氧化膜。第一加熱步驟後之焊料或錫由於以樹 脂組成物被覆故而防止再氧化。且，於第一加熱步驟，使 樹脂組成物中之低分子量成分揮發或高分子化。 依據第一加熱步驟，由於自突出物與基板電極間充分 -37- 201235395 排除樹脂組成物，故可進一步抑制凹陷之產生。又，第一 加熱步驟中由於樹脂組成物中之低分子量成分揮發或高分 子化，故在第二加熱步驟之高溫連接條件下，可抑制低分 子量成分揮發及孔隙產生。 第一加熱步驟之加熱時間通常較好爲0.1〜20秒，更 好爲0.5〜1 5秒，又更好爲1.0〜1 5秒。加熱時間爲〇. 1秒 以上時，可均勻地去除焊料或錫之表面氧化膜，同時充分 地進行突出物與基板電極間之樹脂排除，故有進一步提高 連接信賴性之傾向。又，加熱時間超過2 0秒時，會有生 產性下降之虞。 但，第一加熱步驟中，若半導體密封塡充用薄膜狀樹 脂組成物膠凝化，則第二加熱步驟中，熔融之焊料或錫之 流動因‘膠凝化之樹脂組成物而受阻，有無法發揮充分潤濕 性之虞。據此，加熱時間較好依據所用半導體密封塡充用 薄膜狀樹脂組成物之膠凝化時間而適當設定。 第二加熱步驟係使焊料或錫熔融並使突出物與基板電 極金屬接合。因此加熱溫度設定在焊料或錫之熔點以上。 第一加熱步驟中，由於完成了焊料或錫之表面氧化膜之去 除及突出物與基板電極間之樹脂之排除，故於第二加熱步 驟中，可使焊料或錫加速熔融，而在突出物及基板電極之 表面展現良好之潤濕性》 第二加熱步驟之加熱時間通常較好爲0.1〜20秒，更 好爲0.5〜15秒’又更好爲1.〇〜15秒。藉由使加熱時間爲 〇· 1秒以上，可使焊料或錫充分潤濕突出物及基板電極之 -38- 201235395 表面，故可進一步抑制連接不良。又，加熱時間超過20 秒時，會有生產性降低之虞。 但，第二加熱步驟中，藉由使半導體密封塡充用薄膜 狀樹脂組成物膠凝化，而補強金屬接合之連接部。藉此， 期待可抑制連接結束後之冷卻過程中因半導體晶片與基板 之熱膨脹係數差異造成之熱應力集中於連接部而產生龜裂 等連接不良之效果。因此，第二加熱步驟之加熱時間係依 據半導體密封塡充用薄膜狀樹脂組成物充分膠凝化之膠凝 化時間適當設定。 第一加熱步驟與第二加熱步驟可以單一連接裝置連續 進行，但由於連接裝置需要升溫及冷卻而使作業時間加長 ，而有生產性降低之情況。 另一方面，可分開第一加熱步驟與第二加熱步驟，且 以不同之連接裝置分別進行，可在將連接裝置之設定溫度 保持一定之狀態作業，可實現高的生產性。且，由於不使 用具備升溫或冷卻機構（脈衝加熱機構）之連接裝置，而 以具備可加熱至一定溫度之機構（固定加熱機構）之連接 裝置進行，故可使設備簡化。 另外，亦可在進行第一加熱步驟前，進行半導體晶片 與基板之位置對準，在比助焊劑之活化溫度低，比半導體 密封埏充用薄膜狀樹脂組成物顯示黏著性之溫度高之溫度 下進行將半導體晶片與基板暫時固定之暫時固定步驟。藉 由設置該暫時固定步驟，可對於複數個半導體晶片與基板 一次進行第一加熱步驟及第二加熱步驟，可實現高的生產 -39- 201235395 性。 再者，爲了進一步提高連接信賴性，亦可在連接半導 體晶片與基板後，在加熱烘箱等中進行加熱處理，進一步 進行半導體密封塡充用薄膜狀樹脂組成物之硬化。 以下針對以本實施形態之製造方法製造之半導體裝置 加以說明》 圖1爲顯示本發明之半導體裝置之一實施形態之模式 剖面圖。半導體裝置10具備電路基板7、半導體晶片5、 配置於電路基板7與半導體晶片5之間之密封樹脂6。密 封樹脂6係由本實施形態之半導體密封塡充用薄膜狀樹脂 組成物之硬化物所構成，且密封電路基板7與半導體晶片 5間之空隙。電路基板7具備中介片（interposer)等之基 板，及設置於該基板之一面上之配線4。電路基板之配線 4與半導體晶片5係藉由突出物3而電連接。另外，電路 基板7在與設置配線4之面相反側之面上具有電極焊墊2 與設置於電極焊墊2上之焊料球1，成爲可與其他電路構 件連接。 本發明之半導體裝置列舉爲如圖1所示，於稱爲中介 片之基板上搭載半導體晶片，並經樹脂密封者。具體而言 列舉爲CSP (晶片尺寸封裝）或BGA (球柵陣列）。又， 本發明之其他半導體裝置列舉爲於半導體晶片上搭載其他 半導體晶片之構造之CoC (晶片上搭載晶片）、利用矽貫 穿電極使複數個半導體晶片三次元層合而成之構造之3D 封裝等。 -40- 201235395 又，使用本實施形態之半導體密封塡充用薄膜狀樹脂 組成物之半導體裝置之製造方法並不限於上述之製造方法 ，例如亦可將以使第一層鄰接於半導體晶片之突出物形成 面之方式供給半導體密封塡充用薄膜狀樹脂組成物者，將 二個組合，使突出物彼此連接而製造半導體裝置。 以上，針對本發明之較佳實施形態加以說明，但本發 明並不限於上述實施形態。 [實施例] 以下以實施例更具體說明本發明，但本發明並不受限 於實施例。 (實施例1〜10、比較例1~6)201235395 6. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a film-like resin composition for semiconductor sealing and filling, a method for manufacturing a semiconductor device, and a semiconductor device. [Prior Art] In recent years, with the advancement of miniaturization and high functionality of electronic devices, semiconductor devices have been required to be smaller, thinner, and improved in electrical characteristics (correspond to high-frequency transmission). Along with this, from the conventional method of mounting a semiconductor wafer on a substrate by wire bonding, a flip chip in which a conductive bump electrode called a protrusion is formed on the semiconductor wafer and directly connected to the substrate electrode is started. The connection method is carried out. As for the protrusion formed on the semiconductor wafer, a protrusion made of solder or gold is used. However, in order to achieve fine connection in recent years, a solder layer or a tin layer is formed on the front end of the copper pillar. In order to achieve high reliability, the protrusions are required to be joined by metal bonding, and not only solder joints using solder bumps but also metal using protrusions in which a solder layer or a tin layer is formed at the front end of the copper post. In the case of "gold bumps", a solder layer or a tin layer is formed on the substrate electrode side to form a metal bonding connection method. Further, in the flip chip connection method, since thermal stress due to a difference in thermal expansion coefficient between the semiconductor wafer and the substrate is concentrated on the connection portion and the connection portion is broken, it is necessary to disperse the thermal stress and improve connection reliability. Resin-5- 201235395 Seals the gap between the semiconductor wafer and the substrate. In general, a resin sealing method is used in which a semiconductor wafer is connected to a substrate by using solder or the like, and a liquid sealing resin is injected into the space by capillary action. When the wafer is bonded to the substrate, the metal oxide is easily removed by reduction and removal of the surface oxide film such as solder, and a flux made of rosin or an organic acid or the like is used. Here, if the flux residue remains, when the liquid resin is injected, bubbles called pores are generated, or wiring corrosion occurs due to the acid component, and the connection reliability is lowered. Therefore, it is necessary to carry out the step of washing the residue. However, in recent years, as the gap between the connection gaps is narrowed, the gap between the semiconductor wafer and the substrate is narrowed, so that it is difficult to clean the flux residue. Further, it takes a long time to inject a liquid resin into a narrow space between the semiconductor wafer and the substrate, and there is a problem that productivity is lowered. In order to solve the problem of such a liquid sealing resin, it has been proposed to supply a sealing resin to a substrate by using a sealing resin having a property (flux activity) for reducing and removing an oxide film on a surface of a solder or the like, and then connecting the semiconductor wafer to the substrate. At the same time, a method of connecting the semiconductor wafer and the gap between the substrates by a resin seal and omitting the cleaning of the flux residue is referred to as a first supply method (for example, refer to Patent Documents 1 to 5). [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2005-239. The thermal expansion coefficient and the prepared material may be sandwiched between the protrusion and the substrate electrode to cause a connection failure called trapping, which causes poor conduction, and the protrusion or the substrate is used as a starting point for the protrusion or the substrate. Cracks are generated in the electrodes, which reduces the reliability of the connection. An object of the present invention is to provide a film-like resin composition for semiconductor sealing and filling, which can sufficiently suppress the occurrence of dents and obtain a semiconductor device having good conductivity and connection reliability, when used as a sealing resin for a first supply method, and A semiconductor device using the same and a method of manufacturing the same. [Means for Solving the Problems] The present invention provides a film-like resin composition for semiconductor sealing and filling, which is provided with a first layer composed of a first resin composition containing a thermosetting resin and a coating material, and The mass ratio of the second layer formed of the second resin composition of the flux to the second resin composition in the total amount of the second resin composition is larger than the first resin composition The mass ratio of the dip in the first resin composition of the total amount is smaller. According to the present invention, it is possible to prevent the material from being sandwiched between the protrusion and the substrate electrode, and a good connection portion can be formed. That is, according to the semiconductor-sealed 201235395 packaged film-form resin composition of the present invention, the generation of the depression can be sufficiently suppressed, and a conductor having good conductivity and a conductor can be obtained. Further, according to the semiconductor sealing package of the present invention, the heated additive when the semiconductor wafer and the substrate are bonded is cured, and the first resin composition after curing is filled with the connection portion of the electrode. According to this, the formation of a connection failure such as a hot portion and a crack due to a difference in thermal expansion coefficient between the cold body wafer and the substrate after the completion of the connection can be sufficiently improved by the film-like resin assembly according to the semiconductor sealing compound. Semiconductor device. The second resin composition of the present invention further contains thermoplasticity. The second layer composed of the film-like resin composition of the semiconductor sealing compound has a low surface adhesion. In the semiconductor manufacturing method, the semiconductor layer obtained by singulating the semiconductor wafer to which the semiconductive film-like resin composition is singulated into a half layer is attached to the surface of the second layer, and the present invention provides a method of manufacturing a semiconductor device. A semi-conductive method of forming a substrate having a plurality of electrode-facing surfaces of a plurality of protrusions, wherein the film-forming resin composition of the present invention is used as described above The second layer phase is disposed on the substrate side, and the semi-film-like resin composition of the connection reliability attached to the base supply method presses the first resin group to form a strong protrusion and the substrate, and the semiconductor stress concentration is concentrated. Connected to suppression. That is, the composition can be obtained as a resin composition, preferably a resin. The second resin is used for the purpose of preventing the effect when the thin conductor wafer is filled with a body seal, which will be described later. a first step of sealing the electrode surface of the first layer of the conductor layer -8-201235395 with a conductor wafer and a semiconductor wafer of a specific device, and the substrate and the substrate of the first step The semiconductor wafer is disposed such that the electrode surface and the protrusion forming surface are opposed to each other via the semiconductor sealing and filling film-like resin composition, and are heated and pressed to protrude the electrode of the substrate and the semiconductor wafer. The second step of electrically connecting the material; and the surface of at least one of the electrode and the protrusion connected in the second step is tin or solder. By disposing the film-like resin composition of the present invention on the surface of the substrate, the protrusion of the semiconductor wafer and the electrode of the substrate are brought into contact with the second layer having a small mass ratio of the material, thereby suppressing the sandwiching of the material. At the same time, the oxide film at the tip end of the protrusion is removed by the flux in the second layer to facilitate metal bonding with the substrate electrode. According to still another aspect of the invention, there is provided a method of manufacturing a semiconductor device comprising: a semiconductor wafer having a protrusion forming surface on which a plurality of protrusions are formed; and a semiconductor device having a substrate having a plurality of electrodes; The semiconductor resin composition of the present invention is filled with a film-like resin composition, and the first layer is attached to the semiconductor wafer side so that the first layer is disposed on the semiconductor wafer side, and a plurality of protrusions are formed. a first step of forming the protrusion forming surface of the semiconductor wafer on the protrusion forming surface, and singulating the semiconductor wafer by the first step to obtain a film-like resin composition for sealing the semiconductor sealing film The second step of the semiconductor wafer and the semiconductor wafer and the substrate obtained in the second step are disposed such that the protrusion forming surface and the electrode surface are interposed between the semiconductor sealing and filling film-like resin composition. Oppose each other and heat and press to make the -9-201235395 protrusion of the aforementioned semiconductor wafer The third step of the electrode is electrically connected to the substrate; and in that the electrodes and the protrusions of the third step of connecting at least one among the surface, the presence of tin or solder. By disposing the film-like resin composition of the present invention on the surface of the semiconductor wafer, the protrusion of the semiconductor wafer and the electrode of the substrate are brought into contact with the second layer having a small mass ratio of the material, thereby suppressing the pinching of the material. At the same time, the oxide film at the tip end of the protrusion is removed by the flux in the second layer to facilitate metal bonding with the substrate electrode. According to the method for producing a semiconductor device of the present invention, since the film-like resin composition for semiconductor sealing rinsing of the present invention is used, it is possible to sufficiently suppress the occurrence of dents, and it is possible to manufacture a semiconductor device having excellent conductivity and connection reliability. The present invention further provides a semiconductor device manufactured by the method of manufacturing a semiconductor device of the present invention described above. Since the semiconductor device is sealed and filled with the film-like resin composition for semiconductor sealing and filling of the present invention, it is possible to suppress the occurrence of connection failure or cracking due to the occurrence of the depression, and to have good conductivity and connection reliability. According to the present invention, it is possible to provide a film-like resin composition for semiconductor sealing and filling of a semiconductor device having excellent conductivity and connection reliability when the sealing resin used as the first supply method is used. And a semiconductor device using the same and a method of manufacturing the same. [Embodiment] -10- 201235395 A preferred embodiment of the present invention will be described below. The film-like resin composition for semiconductor sealing and filling of the present embodiment is a second layer composed of a first layer composed of a first resin composition containing a coating material and a second resin composition containing a flux. The mass ratio of the dip in the second resin composition to the total amount of the second resin composition is smaller than the mass ratio of the dip in the first resin composition relative to the total amount of the first resin composition. . Here, the second resin composition may or may not contain a dip. In other words, the "mass ratio of the dip in the second resin composition to the total amount of the second resin composition" may be 〇% by mass. According to the film-like resin composition for semiconductor sealing rinsing of the present embodiment, the occurrence of depressions in the first supply mode can be sufficiently suppressed. For this reason, a semiconductor device having good conductivity and connection reliability can be obtained by using the film-like resin composition for semiconductor sealing of the present embodiment. (First layer) The first layer is a layer composed of a first resin composition containing a dip. As for the dip, the inorganic dip is better used. When the inorganic resin material is used, since the thermal expansion coefficient of the first resin composition (or a cured product thereof) is lower, the connection reliability of the semiconductor device sealed and filled with the semiconductor resin sealing film-filled resin composition is improved. As the inorganic pigment, it is exemplified by glass, sulphur dioxide (Silica), oxidized crystal (alumina), oxidized chin (titania), magnesia (magnesia), carbon black, mica, barium sulfate and the like. These can be used alone or in combination -11 - 201235395 or higher. Further, as the inorganic material, two or more kinds of metal compounds may be used (not those in which two or more kinds of metal oxides are simply mixed, and the oxides are chemically bonded to each other to be inseparable). a composite oxide of at least two elements selected from titanium, aluminum, boron and magnesium. More specifically, for example, a composite oxide of silica sand and titanium oxide, a composite oxide composed of alumina, and a compound composed of boron oxide and aluminum oxide, which is composed of cerium oxide, aluminum oxide, and magnesium oxide. Wait. These composite oxides may be used singly or in combination of two or more kinds thereof in combination with the above-mentioned inorganic materials. Further, in the present embodiment, for the purpose of suppressing the pores, it is also possible to use a combination of the porous inorganic cerium and the organic cerium as a dip. The organic cerium is exemplified by, for example, an acrylic resin, a polydecene diene rubber, a polyester, a polyamine. A resin component such as a carboxylic acid ester, a polyvinyl butyral acid ester, a polymethyl methacrylate, an acrylic rubber, a polyphenylene styrene, an SBR or a polyfluorene-modified resin is preferably used as the organic material. The organic fine particle fine particles having an organic fine particle having a molecular weight of 1,000,000 or more or having a three-dimensional crosslinked structure have high dispersibility to the resin composition. Further, the adhesiveness of the film-form resin composition and the stress relaxation after curing are contained. Here, the polymer chain of the resin having the "three-dimensional crosslinked structure" as the surface microparticles has a three-dimensional mesh structure. The resin of this structure is made of, for example, a composite oxygen having a plurality of reaction points, but a metal. This kind of non-combination group is listed as a composite oxide oxide of ruthenium and oxidized, and is also moderately tempered, ruthenium resin, butyl, polypropylene, and NBR I. The resin. The organic fine particles and the properties are more preferably formed, and the compound is obtained by treating a crosslinking agent having two or more functional groups bonded to the reaction point with -12 to 201235395. It is preferred that the organic fine particles having a resin having a molecular weight of 1,000,000 or more and the organic fine particles having a three-dimensional crosslinked structure have low solubility in any solvent. The above effects can be obtained more remarkably by the organic fine particles having a low solubility in a solvent. Further, from the viewpoint of obtaining the above effects more remarkably, the organic fine particles are preferably an alkyl (meth)acrylate-polyoxyalkylene copolymer, a polyfluorene-(meth)acrylic acid copolymer or the like. Organic microparticles composed of a composite. As the organic tanning material, an organic microparticle having a core-shell type configuration and a composition different from that in the shell layer can be used. Specifically, the core-shell type organic fine particles are particles obtained by grafting an acrylic resin with a polyfluorene-acrylic rubber as a core, and grafting an acrylic resin or a styrene resin with a butadiene rubber as a core. When organic fine particles having a resin having a molecular weight of 100,000 or more or organic fine particles having a three-dimensional crosslinked structure are used as the organic fine material, since the solubility in an organic solvent is low, it is easy to be directly contained in the state of maintaining the particle shape. In a film-like resin composition. According to this, the organic fine particles can be dispersed into an island shape in the film-like resin composition, and the strength of the film-form resin composition after curing can be further enhanced. The shape of the dip material is not particularly limited, and is exemplified by a broken shape, a needle shape, a scale shape, a spherical shape, and the like. Among these, the shape of the dip is preferably spherical. Since the spherical material has good dispersibility in the resin composition, it is possible to prevent the niobium from being concentrated on a specific portion of the resin composition and to easily sandwich between the protrusion and the substrate electrode, thereby obtaining a semiconductor having excellent connection reliability. Device. Further, when the material -13-201235395 is spherical, the viscosity control of the resin composition tends to be easy. Further, the spherical shape here does not necessarily have to be a true ball, and may be a slightly spherical shape. The size of the coating material may be smaller than the gap between the semiconductor wafer and the substrate when the flip chip is connected. The average particle diameter of the dipstick can increase the enthalpy density and make the viscosity control of the resin composition easy, and is preferably 1 Ομηη or less, more preferably 5 μmη or less, and still more preferably 3 μηι or less. Further, the lower limit of the average particle diameter of the dip material is not particularly limited, and for example, an average particle diameter of 0 can be used. 01 μηι or more. Further, in order to obtain more remarkable effects (good conductivity and connection reliability) in the film-like resin composition for semiconductor sealing and filling of the present embodiment, the average particle diameter of the material can be set to 0. 05~0·9μιη, can also be 0. 1~0. 8μηι. Further, the average particle diameter herein is obtained by using a particle size distribution measuring device using a laser light diffraction method with a median diameter. The diameter of the middle cymbal indicates that the cumulative ratio in the particle size distribution of the number basis is 50% of the particle diameter (D50). The mass ratio of the dip in the first resin composition to the total amount of the first resin composition is preferably 20 in terms of lowering the thermal expansion coefficient of the first resin composition (or a cured product thereof). In the case of further increasing the mechanical strength of the first resin composition (or a cured product thereof), it is more preferably 30% by mass or more, and the first resin composition (or a cured product thereof) is further reduced. From the viewpoint of water absorption, it is more preferably 40% by mass or more. The upper limit of the mass ratio of the dip in the first resin composition of the total amount of the first resin composition is not particularly limited, and may be, for example, 70 mass to 14 to 2012,35,395 395 % by weight, or 60 mass. When the amount is more than 70% by mass, the first resin composition becomes brittle and the workability tends to be lowered. When the organic material is used in combination with the inorganic material, the mass ratio of the organic material is preferably from 1 to 10% by mass based on the first resin composition. When the amount is 1% by mass or more, the effect of suppressing the pores or the stress relaxation effect by the organic material can be remarkably obtained. When the amount is 1% by mass or less, the viscosity of the resin composition is suppressed, and the surface of the film-like resin composition can be reduced. The unevenness suppresses the occurrence of voids and further improves the adhesion. The first resin composition preferably contains a thermosetting resin. Thereby, the first resin composition is cured under heat and pressure when the semiconductor wafer and the substrate are joined, and the cured first resin composition can reinforce the connection portion between the protrusion and the substrate electrode. Therefore, during the cooling process after the completion of the connection, the thermal stress caused by the difference in thermal expansion coefficient between the semiconductor wafer and the substrate is sufficiently suppressed from being concentrated on the connection portion to cause connection failure such as cracking. In other words, by providing the first resin composition with a thermosetting resin, the connection reliability of the obtained semiconductor device is further improved. The thermosetting resin is exemplified by a phenol resin, a cyanate resin, a benzocyclobutene resin, an acrylate resin, a methacrylate resin, an epoxy resin or the like. The first resin composition preferably contains an epoxy resin as a thermosetting resin because it is excellent in heat resistance and excellent in workability. For example, an epoxy resin having two or more functional groups (an epoxy resin having two or more epoxy groups in the molecule) is used as the epoxy resin. The epoxy resin can be used, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type epoxy-15 - 201235395 Resin, biphenyl type epoxy resin, hydroquinone type epoxy resin, epoxy resin containing diphenyl sulfide skeleton, phenol aralkyl type polyfunctional epoxy resin, polyfunctional epoxy resin containing naphthalene skeleton a polyfunctional epoxy resin containing a dicyclopentadiene skeleton, a polyfunctional epoxy resin containing a triphenylmethane skeleton, an aminophenol type epoxy resin, a diaminodiphenylmethane type epoxy resin, Other various polyfunctional epoxy resins and the like. In these epoxy resins, the low viscosity of the resin composition can be easily achieved, the water absorption of the resin composition (or a cured product thereof) can be lowered, and the dimensional change can be made more difficult. Further improvement of the resin composition (or a cured product thereof) From the viewpoint of heat resistance and the like, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyfunctional epoxy resin containing a naphthalene skeleton, and a polyfunctional group containing dicyclopentadiene are preferably used. An epoxy resin, a polyfunctional epoxy resin containing a triphenylmethane skeleton, or the like. As for the properties of the epoxy resin, it is liquid or solid at 25 t. Further, these epoxy resins may be used singly or in combination of two or more. The first resin composition may further contain a curing agent. The hardener can be appropriately selected depending on the type of the thermosetting resin. For example, when the first resin composition contains an epoxy resin as a thermosetting resin, imidazoles, acid anhydrides, amines, phenols, hydrazines, polythiols, Lewis acid-amine complexes, or the like can be used. hardener. Among these curing agents, imidazoles, acid anhydrides, and amines are preferably used because of the low viscosity of the resin composition, excellent storage stability, and improved heat resistance of the cured product of the resin composition. Classes, phenols. Further, it is preferable to use a polyurethane material, a polyester polymer material or the like and to use a microencapsulated product as a curing agent, since the usable time can be extended. The above imidazoles are exemplified by 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl 2-methylimidazole, benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, trimellitate, 1-cyanoethyl-2-benzene Pyrimidine gun trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-3-triazine, 2,4-diamino- 6-[2,-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole -(1,)]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1,)]-ethyl-s-trimeric isocyanide Acid addition product, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-3-trimeric isocyanate adduct, 2-phenylimidazole III Polyisocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like. Further, a compound obtained by adding an epoxy resin to the imidazoles may also be used. For the imidazoles, for example, 2ΜΖ, Cl 1Ζ, 2ΡΖ′ 2Ε4ΜΖ, 2Ρ4ΜΖ, 1Β2ΜΖ, 1Β2ΡΖ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2ΜΖ-Α, C11Z-A, 2Ε4ΜΖ-Α, 2Ρ4ΜΗΖ, 2ΡΗΖ, 2ΜΑ-ΟΚ, 2ΡΖ-ΟΚ (all manufactured by Shikoku Chemical Industry Co., Ltd., product name). Further, the above-mentioned imidazoles may be used singly or in combination of two or more. The amount of the imidazole to be added to the first resin composition is preferably from 0 to 100 parts by mass based on the total amount of the epoxy resin in the first resin composition. 1~1Q parts by mass, more preferably 0. 5 to 10 parts by mass, more preferably 1 to 10 parts by mass. -17- 201235395 The amount of deployment is ο.  When the amount of the epoxy resin is sufficiently increased, the above-described effects can be exhibited more reliably (the connection reliability is more excellent, etc.). Further, the amount of the preparation is 10 parts by mass or less, and the storage stability is improved. As the above acid anhydride, for example, maleic anhydride, succinic anhydride, deca-succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetracarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrobenzene can be used. Methylenetetrahydrophthalic anhydride, methyl bridge-methylenetetrahydrophthalic acid humic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid dimerized azelaic acid dianhydride , alkyl styrene-maleic anhydride copolymer, 3,4-yl-6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, propyl-4 -Methyl-bicyclic [2. 2. 2] oct-5-ene-2,3-dicarboxylic anhydride, ethylene terephthalate, glycerol trimellitic anhydride, etc. In these, the resin composition (or a cured product thereof) is heat-resistant and moisture-resistant. From the viewpoint of improving the properties, it is preferred to use methyltetrahydrobenzene dianhydride, methyl hexahydrophthalic anhydride, bridge-methylenetetrahydrophthalic acid bridge-methylenetetrahydrobenzene Formic acid, 3,4-dimethyl-6-(2-methyl-alkenyl)-4-cyclohexene-1,2-dicarboxylic anhydride, 1-isopropyl-4-methyl-[2. 2·2] oct-5-ene·2,3-dicarboxylic anhydride, ethylene glycol trimellitate triol phthalic anhydride ester, and the like. These may be used alone or in combination. The amount of the acid anhydride in the first resin composition is preferably such that the number of epoxy groups in the epoxy resin in the first fat composition is adjusted to the first one. The number of carboxyl groups produced by the anhydride in the resin composition is n2 rows, with better diene hydrogenbenzene, bridge acid, anhydride, dimethyl 1-isool bis- and formic acid, A. 1 - C Double Ring, C Above 1 Tree Available from -18- 201235395 (N1/N2) becomes 〇·5~1. 5 the amount of allocation. The above ratio (N1/N2) is preferably 0. 7~1. 2. The ratio (Ν, /Ν:!) is less than 0. At 5 o'clock, the carboxyl group is excessive and remains in the cured product of the resin composition. The moisture resistance of the cured product of the resin composition may be lowered. In other words, when the ratio (Ν! /Ν2) is 0.5 or more, the moisture resistance of the cured product of the resin composition is further improved. Also, the ratio (Ni/lSh) is 1. When it is 5 or less, the curing of the epoxy resin is sufficiently performed, and the above effects are more reliably exhibited (the connection reliability is more excellent, etc.). The above amines are exemplified by compounds having at least one or more primary or secondary amino groups in the molecule. As for the amines, aromatic amines are preferably used from the viewpoint of excellent storage stability and improved heat resistance of the cured product of the resin composition. The aromatic amines are exemplified by, for example, diaminodiphenylmethane, diaminodiphenylphosphonium, diaminodiphenyl sulfide, m-xylenediamine, 3,3'-diethyl-4, 4'-Diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene , 4,4'-diaminodiphenyl sulfide, 2,2-bis-[4-(4-aminophenoxy)phenyl]-hexafluoropropane, 2,2-bis(4-amine Phenyl phenyl)-hexafluoropropane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene, diethyltoluenediamine, dimethyltoluenediamine, Aniline, alkylated aniline, N-alkylated aniline, and the like. These may be used singly or in combination of two or more. The amount of the diamine in the first resin composition is preferably such that the number of epoxy groups of the epoxy resin in the first resin composition is N, and the amine compound blended in the first resin composition. The ratio of the number of active hydrogens on the amine group N3 (ISh/lSh) becomes 0. 5~1. 5 the amount of allocation. The above ratio (Ν, /Ν3) is more 201235395, which is 0. 7~1. 2. When the ratio (Ν, /Α) is less than 〇·5, excessive amounts remain in the cured product of the resin composition, and the moisture resistance of the cured product may be lowered. That is, the ratio (Ni/Nh) is 1. (in the case of the above, the moisture resistance of the cured product of the resin composition is 1. When it is 5 or less, the epoxy resin is more effective in achieving the above effects (the connection reliability is more excellent than the above phenols, and a bisphenol resin, a phenol naphthol novolak resin, an allylated phenol novolac, a formazan varnish can be used. Resin, phenol aralkyl resin, methylate, triphenylmethane type polyfunctional phenol resin, dialdehyde varnish resin, xylene modified naphthol furfural varnish, phenol resin, etc. These may be used alone. Or the amount of the phenol in the first resin composition is higher than that of the epoxy resin in the epoxy resin in the composition, and the phenolic property of the phenol in the first resin composition (Ni) /N*) becomes 0. 5~1. 5 the amount of allocation. The above i is 0. 7~1. 2. Ratio (NWN4) is less than 0. At 5 o'clock, the resin composition may remain in the cured product of the resin composition, and the moisture resistance of the resin group may be lowered. That is, the moisture resistance of the cured product of the (N i /N4 ) oxime composition becomes more Ni/NO. When it is 5 or less, the hardening of the epoxy resin exhibits the above-described effects (excellent reliability of connection, etc.), and the active hydrogen on the two amine groups of the acid anhydrides, amines, and phenols has a resin composition of N]/ N3) is 0. 5 to become better. And, hardening is sufficiently performed. Novolac resin, resin, bisphenol resin phenol naphthol formaldehyde polycondensed toluene modified phenolic phenol resin, a mixture of two or more kinds of multiple exemplified, so that the ratio of the first resin N i to the number of S bases N4 : 匕 (NWN4) is better than the excess of the hydroxyl group and the hardened substance of the residue.  When 5 or more, the tree is good. In addition, when the ratio is more than 〇, it is better -20- 201235395 so that the ratio [Νι/ ( Ν Ν + Ν 3 + Ν 4 )] becomes 0. 5~1. 5 way to match the way to become 2 ways. When an acid anhydride, an amine, or a phenol is used as a curing agent, a hardening accelerator may be used. For example, the above imidazoles can be used together with hard acid ass, amines, and phenols. Also, as for the hardening, the use of tertiary amines; 1,8-diazabicyclo (5. 4. 0) eleven carbon fire 1,5-diazabicyclo ring (4. 3. 0) cyclic amines such as terpene-5: tetraphenylborate of tertiary cyclic amine; triarylphosphine such as trialkylphosphinophenylphosphine such as tributylphosphine; tetrabutyltriphenylbenzene a scaly salt such as a borate or tetratetraphenyl borate. The amount of the hardening accelerator is appropriately set depending on the test time or storage stability. The first resin composition may also contain a thermoplastic resin. The film formability is improved by a plastic resin. The thermoplastic resin is exemplified by a phenoxy resin, a polyamidimide polyamine resin, a polycarbodiimide resin, an acrylic resin, a poly, a polyethylene resin, a polyether oxime resin, a polyether oxime imide resin, a polyacid. Ester imide resin, polyethylene acetal resin, polyethylene condensate, urethane resin, acrylic rubber, and the like. Among these, it is excellent in film formability, and is preferably a phenoxy resin, a polyimide resin, a bismuth imide resin, or a polyurethane phthalimide resin, more preferably a lipid or a polyimide resin. The weight average molecular weight of the thermoplastic resin is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more. When the weight is 5,000 or more, the film formation property can be sufficiently improved, and the amount of the accelerator can be sufficiently improved. i-7 or an amine or a class: triphenyl scale gel containing a thermal resin, an ester resin amine Base formaldehyde resin heat resistance, polycarbon phenoxy tree or more, uniform molecular effect. -21 - 201235395 The weight average molecular weight here is measured by GPC (gel permeation chromatography) in terms of polystyrene. Further, the thermoplastic resins may be used singly or as a mixture or copolymer of two or more. When the first resin composition contains a thermoplastic resin, the content thereof is preferably from 1 to 50% by mass, more preferably from 1 to 40% by mass, even more preferably from 5 to 10% by mass based on the total mass of the first resin composition. 30% by mass. When the content is more than 50% by mass, the heat resistance of the cured product of the resin composition may be lowered. In the first resin composition, an additive such as a decane coupling agent, a titanium coupling agent, an antioxidant, a leveling agent or an ion-trapping agent may be blended as a component other than the above. These additives may be used singly or in combination of two or more. The amount of the additive to be added may be adjusted to exhibit the effect of each additive. Further, the first resin composition may contain a flux described later. (Second layer) The second layer is a layer composed of a second resin composition containing a flux. In the second resin composition, in order to reduce the surface oxide film of the metal such as solder, the metal bond is used to form a good connection degree, and the flux is prepared as a necessary component. Further, the mass ratio of the dip in the second resin composition to the total amount of the second resin composition is smaller than the mass ratio of the dip in the first resin composition relative to the total amount of the first resin composition. . With this configuration, the occurrence of the depression in the first supply mode is sufficiently suppressed. Further, the second resin composition may or may not contain a dip. The second resin composition may contain the same components as the first resin composition, and the amount of each component may be the same as that of the first resin composition, in addition to the smaller mass ratio of the raw material. The best match is the same. The mass ratio of the dip in the second resin composition with respect to the total amount of the second resin composition is preferably from 〇% by mass to less than 20% by mass, more preferably from 0 to 15% by mass, still more preferably 0. ~10% by mass. By reducing the content of the dip material, the light transmittance of the second resin composition and the second layer is improved. According to this, in the method of manufacturing a semiconductor device to be described later, when the semiconductor wafer is bonded to the semiconductor wafer, the tip end portion of the protrusion can be recognized through the second layer, and the position at the time of dicing or the position of the substrate can be obtained. The effect of quasi-easy change. Further, in order to make the identification of the tip end portion of the protrusion possible, the light transmittance of the second layer is preferably 10% or more, more preferably 20% or more, and still more preferably 40% or more for the visible light of 550 nm. Further, the light transmittance may be 95% or less for the visible light of 5 50 nm, or may be 90% or less. The second resin composition preferably contains a thermoplastic resin. When the second resin composition contains a thermoplastic resin, the surface adhesion force of the second layer tends to be low. Therefore, for example, in the method for producing a semiconductor to be described later, the effect of preventing the cutting layer which is formed when the semiconductor wafer to which the semiconductor resin composition for sealing the semiconductor sealing film is attached is formed into a semiconductor wafer is adhered to the surface of the second layer can be exhibited. . The content of the thermoplastic resin in the second resin composition is preferably from 5 to 99, based on the total amount of the second resin composition, from the viewpoint of obtaining the effect more remarkably. 9% by mass, more preferably 10 to 95% by mass. In the same manner, the total content of the thermoplastic resin and the flux in the second resin composition is preferably 5% by mass or more based on the total amount of the second resin composition of -23 to 201235395. More preferably 1% by mass or more. The second resin composition may be made only of a thermoplastic resin and a flux. The blending amount of the flux in the second resin composition is preferably 0 based on the total amount of the second dendrimer.  1 to 10% by mass, more preferably 0. from the viewpoint of further light permeability. 5 to 7 mass% is more preferably 1 to 5 mass% from the viewpoint of further improving the stability. When the amount of the compound is 5% by weight or more, the oxide film is removed by the flux, so that the connection reliability is further improved. Further, when the flux is excessively present, the insulating property of the resin composition is lowered. However, by reducing the amount of the insulating agent to a mass ratio of not more than 5% by mass, a resin composition having an insulating property is obtained. As the flux, it is preferred to use at least one compound selected from the group consisting of alcohols, phenols and carbonic acids in terms of excellent dispersibility in the resin composition. The above alcohols are exemplified by having two or more alcoholic hydroxy compounds in the molecule. As the alcohol, 1,3-dioxane-5,5-dimethanol, pentanediol, 2,5-furan dimethanol, diethylene glycol, tetraethylene glycol 'pentacohol, hexaethylene glycol can be used. 1,2,3-hexanetriol, 1,2,4-butanetriol, hydrazine, 2,6-ol, 3-methylpentane-1,3,5-triol, glycerol, three Hydroxymethylethane hydroxymethylpropane' erythritol, pentaerythritol, ribitol, sorbose 2,4-diethyl-1,5-pentanediol, propylene glycol monomethyl ether, propylene glycol monoether, 1,3 - Butanediol, 2-ethyl-1,3-hexanediol, Ν-butyldiethanol oxime-ethyldiethanolamine, diethanolamine, triethanolamine, hydrazine, Ν-double (2_,, the composition of the lipid group to improve the high storage quality effect will have the U 10 excellent view of the basis of 1,5-ethylenedihexatriol, triol, ethylamine, hydroxy-24 - 201235395 B Isopropanolamine, bis(2-hydroxymethyl)imidophosphonium (hydroxymethyl)methane, N,N,N',N'-fluorene (2-hydroxyethyl)ethylenediamine, 1, 1', Γ', Γ"-(ethylidene dinitro) hydrazine (2-propanol), etc. Among the alcohols, compounds having a tertiary nitrogen atom, such as hydrazine-butyldiethanolamine, hydrazine- Ethyldiethanolamine, triethanolamine, ν, Ν-bis(2-hydroxyethyl)isopropanolamine, bis(2-hydroxymethyl)imidophosphonium (hydroxymethyl)methane, hydrazine, hydrazine, hydrazine , Ν'-肆(2-hydroxyethyl)ethylenediamine, 1,1 ',1",1 (extended ethyldinitro)anthracene (2-propanol), etc., compared with other compounds, 'shows good Flux activity is preferred. Although the detailed description of the activity of the flux is not clear, it is presumed that the reduction energy of the oxide film of the alcoholic hydroxyl group and the electron supply property of the unpaired electrons derived from the tertiary nitrogen atom are derived. A combination of the effects. Further, these alcohols may be used singly or in combination of two or more. The above phenols are exemplified by a compound having two or more phenolic hydroxyl groups in the molecule. The phenols are listed as catechol, meta-xylenol, hydroquinone, bisphenol, dipyridyl, hydrazine, benzotriazine, methylidene bisphenol (also known as " Bisphenol F"), fork isopropyl bisphenol (also known as "bisphenol A"), fork ethyl bisphenol (also known as "bisphenol AD"), 1,1,1-tris (4-hydroxyl) Phenyl)ethane, trihydroxybenzophenone, trihydroxyacetophenone, poly-p-vinylphenol, and the like. Further, a compound having two or more phenolic hydroxyl groups in the molecule may be a polycondensate of a compound A having a phenolic hydroxyl group in the molecule and a compound B which is polycondensable with the compound A. The compound B herein is exemplified by divinylbenzene; aldehydes; aromatic compounds having two or more halomethyl groups, alkoxymethyl groups -25 to 201235395 or hydroxymethyl groups in the molecule. Further, these phenols may be used alone or in combination of two or more. The above compound A is exemplified by, for example, phenol, alkylphenol, naphthol, catechol, meta-xylenol, hydroquinone, bisphenol, dihydroxynaphthalene, hydroxy, pyrogallol, forked methyl bisphenol (also known as "bisphenol F"), bisphenol (also known as "bisphenol A"), fork ethyl bisphenol (also known as phenol AD), hydrazine (4-hydroxyphenyl) ethane, trihydroxy ketone, Trihydroxyacetophenone, poly-p-vinylphenol, and the like. The above aldehydes are exemplified by formaldehyde (formalin which is an aqueous solution thereof), aldehyde, trioxane, hexamethylenetetramine and the like. As the aromatic compound having two or more halomethyl groups and alkoxymethylmethyl groups in the molecule, for example, 1,2-bis(chloroform, 1,3-bis(chloromethyl)benzene, 1, 4-bis(chloromethyl)benzene, 1,2,oxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 1,4-bismethylmethylbenzene, 1,2- Bis(hydroxymethyl)benzene, 1,3-bis(hydroxy)benzene, 1,4-bis(hydroxymethyl)benzene, bis(chloromethyl)biphenylmethoxymethyl)biphenyl, and the like. That is, the above polycondensate is exemplified by a phenol novolak resin such as phenol and formaldehyde, a cresol lacquer resin of a polycondensate of cresol and formaldehyde, a naphthol novolac phenol of a polycondensation of naphthol and formaldehyde. Phenol aralkyl with polycondensation of 1,4-bis(methoxymethyl)benzene, polycondensate of bisphenol A with formaldehyde, polyphenol and divinylbenzene, cresol and naphthol and formaldehyde Polycondensate, etc., may also be used for the modification of the warp rubber or by introducing an aminotriazine skeleton into the molecular skeleton or by using cresol alone or isopropyl hydrazine as "bisbiphenyl, polymethyl or Hydroxy) benzene bis (methyl methoxymethyl, bis (condensate novolak resin, base resin condensate condensate dicyclopenta-26- 201235395 diene skeleton). In addition, as for the flux, An allylated phenol novolak resin, diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol or the like is used as the liquid state by allylation of the phenols The compound may be used alone or in combination of two or more. The above carboxylic acid may be fat. Any of a carboxylic acid and an aromatic carboxylic acid is preferably a solid at 25 ° C. The aliphatic carboxylic acid is exemplified by, for example, malonic acid, methylmalonic acid, dimethylmalonic acid, and ethyl group. Malonic acid, allyl malonic acid, 2,2'-thiodiacetic acid, 3,3'-thiodipropionic acid, 2,2'-(ethylidene disulfide) diacetic acid, 3, 3'-Dithiodipropionic acid, 2-ethyl-2-hydroxybutyric acid, dithiodiglycolic acid, diglycolic acid, acetylene dicarboxylic acid, maleic acid, malic acid, 2·isopropyl apple Acid' tartaric acid, itaconic acid, 1,3-acetone dicarboxylic acid, glycerol tricarboxylic acid, muconic acid, β-argonic acid, morphic acid, methyl acid, dimethyl Succinic acid, glutaric acid, α-ketoglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylpentane Acid, 2,2-bis(hydroxymethyl)propionic acid, citric acid, adipic acid, 3-tert-butyladipate, pimelic acid, phenyl oxalic acid, phenylacetic acid, nitrophenylacetic acid, Phenoxyacetic acid, nitrophenoxyacetic acid, phenylthioacetic acid, hydroxyphenylacetic acid, dihydroxyphenyl Acid, mandelic acid, hydroxymandelic acid, dihydroxymandelic acid, 1,2,3,4-butanetetracarboxylic acid, suberic acid, 4,4'-dithiodibutyric acid, cinnamic acid, nitrocin Acid, hydroxy cinnamic acid, dihydroxy cinnamic acid, coumaric acid, phenylpyruvate 'hydroxyphenylpyruvate, caffeic acid, homophthalic acid, tolyl acetic acid, phenoxypropionic acid, hydroxyphenylpropionic acid, Benzyloxy-27- 201235395 acetic acid, phenyl lactic acid, tropic acid, 3-(phenylsulfonyl)propionic acid, 3,3-tetramethyleneglutaric acid, 5-oxoindole Diacid, sebacic acid, phenyl succinic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, benzylmalonic acid, bismuth Acid, dodecanedioic acid, undecanedioic acid, diphenylacetic acid, diphenyl glycolic acid, dicyclohexyl acetic acid, tetradecanedioic acid, 2,2-diphenylpropionic acid, 3,3- Diphenylpropionic acid, 4,4-bis(4-phenylphenyl)pentanoic acid, pimaric acid, palustric acid, isopimaric acid, abietic acid Acid ), dehydroabietic acid, new rosin acid, mal Acid (Agathic acid) and the like. The aromatic carboxylic acid is exemplified by, for example, benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5- Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3. 4. 5-trihydroxybenzoic acid, 1,2,3·benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1. 3. 5-Benzenetricarboxylic acid, 2-[bis(4-hydroxyphenyl)methyl]benzoic acid, 1-naphthoic acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthalene Formic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2.naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy -2-naphthoic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2-phenoxybenzoic acid, biphenyl-4-carboxylic acid, biphenyl-2-carboxylic acid, 2_ Benzoyl benzoic acid and the like. Among these carboxylic acids, succinic acid, malic acid, itaconic acid, 2,2-bis(hydroxymethyl)propionic acid, adipic acid, and 3 are preferably used from the viewpoint of excellent storage stability and easy availability. , 3'-thiodipropionic acid, dithiodipropyl-28- 201235395 acid, 1,2,3,4-butane tetracarboxylic acid, suberic acid, azelaic acid, phenylsuccinic acid, twelve Alkanoic acid, diphenylacetic acid, diphenyl glycolic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, abietic acid, 2,5-dihydroxybenzoic acid, 3,4,5-trihydroxyl Benzoic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2-[bis(4-hydroxyphenyl)methyl]benzoic acid, and the like. Further, these carboxylic acids may be used singly or in combination of two or more. The flux may be liquid or solid at room temperature (e.g., 25 ° C). However, when the second resin composition contains an epoxy resin, it is preferred to use a flux which is solid at room temperature. Since the phenolic hydroxyl group present in the phenol or the carboxyl group present in the carboxylic acid reacts with the epoxy resin, when the liquid flux is used to uniformly dissolve the epoxy resin and the flux, the storage stability is lowered. After that. The second resin composition may contain conductive particles such as metal particles. However, from the viewpoint of obtaining excellent connection reliability by bonding the protrusions to the metal of the substrate electrode, the content of the conductive particles is the total of the second resin composition. The amount is preferably from 0 to 10% by mass, more preferably from 0 to 5% by mass, even more preferably from 5% by mass (i.e., no conductive particles are contained). (Thin-film resin composition for semiconductor sealing and filling) The film-like resin composition for semiconductor sealing and filling of the present embodiment can be used, for example, by mixing a component of the first layer with a planetary kneader or a bead kneader in each organic solvent. The composition of the second layer is formed, a paint is prepared, and the paint is applied onto the resin film substrate to which the release treatment is applied using a knife coater or a roll coater, and then the organic solvent is removed by drying, respectively. Manufactured as a film-like resin composition of the first layer and a film-like resin composition which is a second layer, and is produced by laminating these using a laminator. Further, the paint containing the component constituting the first layer and the component constituting the second layer may be applied to the resin film substrate subjected to the release treatment and dried, and then coated again. A paint containing another ingredient is dried and manufactured. The above organic solvent is exemplified by ethyl acetate, methyl ethyl ketone, cyclohexanone, N-methylpyrrolidone or the like. Further, the resin film substrate is exemplified by polyethylene terephthalate, polyurethane, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyolefin, or the like. In the film-like resin composition for semiconductor sealing filling of the present embodiment, the thickness of the second layer is preferably smaller than the thickness of the first layer. The film-like resin composition for semiconductor sealing is small in thermal expansion coefficient, and the connection reliability can be further improved. The thickness of the second layer is preferably 0 of the thickness of the first layer. 8 times or less, more preferably 0. 7 times or less. The lower limit of the thickness of the second layer is not particularly limited and may be the thickness of the first layer. 〇 5 times or more, or 0 of the thickness of the first layer. More than 1 time. The thickness of the film-like resin composition for semiconductor sealing can be appropriately set in accordance with the amount of resin required to fill the gap between the semiconductor wafer and the substrate. For example, the thickness of the film-like resin composition for semiconductor sealing is preferably 0. 5~1. 5 times, better 0. 6~1. 3 times, better for you. 7~1. 2 times. The thickness is 0. When it is 5 times or more, the occurrence of voids due to unfilling of the resin can be sufficiently suppressed, and the connection reliability is further improved. Also, the thickness exceeds 1. At 5 times, when the connection is made, the excess resin composition is extruded from the wafer connection region, and there is a resin composition. 30-201235395 The object adheres to the unnecessary portion. When the semiconductor sealing film is filled with a film-like structure, the manufacturing method of the preparation step A described later can be carried out as a thickness of 5 to 25 μm and a thickness of the second layer of 5 to 15 μm. According to the semiconductor sealing and filling thinner, it is possible to further prevent the thickness of the first layer and the second layer having a higher conductivity and connection reliability from being obtained by the manufacturer having the preparation step 在 in the above range. 1~0. 8 μπι, the above effects in the manufacturing method can be more significantly obtained. Further, in the first layer and the range, the semiconductor sealing film is filled with a film-like connecting protrusion having a height of 40 μm. Further, in the case where the semiconductor sealing film is filled with a film having a preparation step described later, the thickness is 20 to 90 μm (more preferably 30 to 80 μm) 1 to 2 0 μη (more preferably 5 to 15 μm). According to the film-like resin composition, it is possible to further prevent the occurrence of the depression in the method and obtain a semiconductor device having more excellent conductivity. Further, at the time of the first layer and the second layer, the average particle diameter of the tantalum is made 0. When the thickness of the above-mentioned and second layer in the manufacturing method of the preparation step is within the above range, the semiconductive resin composition is suitable for the height of the connection protrusion to be a fat composition, and is used, for example, as the first 1 to 20 μm of the layer (more preferably a film-like resin composition, a depression in the method occurs, a semiconductor device. Further, the thickness of the second layer of the preparation step is made by applying the thickness of the second layer to the upper resin composition) The resin composition can be used, for example, as the first layer, and the thickness of the second layer can be more effectively obtained in the semiconductor sealing/filling preparation step B, and the thickness of the connection reliability is within the above range of 8 μm. The first layer sealing film is filled with a film of about 70 μm. -31 - 201235395 The film-forming resin composition for semiconductor sealing and filling has a gelation time of preferably 3 to 30 seconds, more preferably 3 to 20 seconds at 250 ° C. Further, it is preferably 3 to 15 seconds. When the gelation time is in the above range, the productivity is excellent and the connection reliability is more excellent. Further, the so-called gelation time of 25 ° C means that the semiconductor is sealed. The film-like resin composition is placed on a hot plate set at 2 to 50 ° C, and stirred with a spoon or the like until it is impossible to stir. The film-like resin composition for semiconductor sealing and filling can be attached to a semiconductor cut into a specific size. The wafer, the semiconductor wafer, the substrate, and the like are supplied. (Manufacturing method of the semiconductor device) The method of manufacturing the semiconductor device of the present embodiment includes a substrate on which an electrode is prepared, a semiconductor wafer on which a protrusion is formed, and a substrate or a semiconductor wafer. a semiconductor sealing step of preparing a film-like resin composition, and a connecting step of electrically connecting the electrode of the substrate to the protrusion of the semiconductor wafer. Here, solder is present on at least one surface of the electrode of the substrate and the protrusion of the semiconductor wafer Therefore, as a method described in Patent Document 5, as a recess between the protrusion and the substrate electrode, if the tip of the protrusion is exposed from the resin composition, the exposed solder or tin forms an oxide film and causes The connection is defective. On the other hand, the semiconductor device according to the embodiment Manufacturing method, since the engaging projection system and the substrate electrodes of the first bit. In the second layer, it is possible to prevent connection failure due to the oxide film of solder or tin, and to sufficiently suppress the depression. Moreover, since at least one of the electrodes of the substrate and the protrusion of the semiconductor wafer has solder or tin on the surface of the semiconductor chip, the electrical connection between the electrode of the substrate and the protrusion of the semiconductor wafer is usually completed by metal bonding of solder or tin. . That is, the solder or tin is melted by heating at the time of connection, and the electrode of the substrate and the protrusion of the semiconductor wafer are bonded by solder or tin. Excellent electrical conductivity and connection reliability are obtained by performing the metal bonding. As for the semiconductor wafer, a semiconductor wafer in which a plurality of protrusions are formed on a plurality of electrodes can be used. The material of the semiconductor wafer is not particularly limited, and an elemental semiconductor such as ruthenium or iridium may be used; various semiconductors such as a compound semiconductor such as gallium arsenide or indium phosphide; and the protrusion formed on the semiconductor wafer is exemplified by, for example, a copper protrusion or a gold protrusion. The material, the solder bump, the protrusion of the structure of the solder or the tin layer formed on the front end of the copper post, and the like. Solder can use Sn-37Pb (melting point 183 ° C). However, considering the impact on the environment, it is better to use Sn-3. 5Ag (melting point 221 ° C), Sn-2. 5Ag- 0. 5Cu-lBi (melting point 214 ° C), Sn-0. 7Cu (melting point 227 ° C), Sn-3Ag-0. Lead-free solder such as 5Cu (melting point 217 ° C) and Sn-92 Zn (melting point 198 ° C). Further, from the viewpoint of fine connection, it is preferably a protrusion having a structure in which a solder or a tin layer is formed on the tip end of the copper post. The substrate has an electrode face provided with a plurality of electrodes. As the substrate, a general circuit substrate can be used, and a semiconductor wafer having no protrusion can be used. The circuit substrate can be formed by removing the surface of the insulating substrate such as glass epoxy resin, polyimide, polyester or ceramic. A wiring pattern having an electrode formed by an unnecessary portion of a metal layer such as copper; a wiring pattern including an electrode formed by plating copper on the surface of the insulating substrate-33-201235395; and printing of a conductive substance on the surface of the insulating substrate The wiring pattern type including the electrode is formed. At least one surface treatment layer selected from the group consisting of a gold layer, a solder layer, a tin layer, and a rustproof film layer is preferably formed on the surface of the electrode of the substrate. The metal and tin layers can be formed by electroless plating or electrolytic plating. Further, the solder layer may be formed by electroplating, or may be formed by printing and coating a solder paste and heating and melting, or by disposing fine solder particles on a wiring pattern and heating and melting the same. The anti-rust film layer is also referred to as pre-welding, and the substrate is immersed in a dedicated chemical solution to remove an oxide film on the surface of the wiring pattern formed of copper or the like, and is formed by organic components formed on the surface. It is set up with anti-rust film. Such a rustproof film layer is preferable because it can ensure good wettability to solder or tin and is easy to correspond to fine connection. In order to perform the metal bonding described above, when the protrusion of the semiconductor wafer is such that a copper protrusion, a gold protrusion or the like does not have a solder or tin protrusion on the surface, an electrode having a solder layer or a tin layer formed on the surface is selected as an electrode of the substrate. . Further, when solder or tin is not present on the surface of the electrode of the substrate, the protrusion of the semiconductor wafer is a solder protrusion, a protrusion of a structure in which a solder or a tin layer is formed at the front end of the copper post, or the like. The preparation step is, for example, a preparation step A for preparing a substrate, a semiconductor resin packaged film-like resin composition and a semiconductor wafer attached to the substrate, and a semiconductor wafer for mounting a semiconductor wafer and attached to the semiconductor wafer. The preparation step B of the film-like resin composition and the substrate. -34-201235395 (Preparation step A) In the preparation step A, the semiconductor sealing composition is attached to the electrode surface of the substrate so that the second layer is disposed on the substrate side, and the electrode surface of the substrate is applied. A method of attaching a film-like resin composition for semiconductor sealing and filling is exemplified by a method using a hot roll laminator or a vacuum laminator. (Preparation step B) The preparation step is performed on the protrusion forming surface of the semiconductor wafer having the protrusion forming surface on which the plurality of protrusions are formed, so that the first layer is disposed on the semiconductor wafer side with respect to the second layer In the method of attaching a film-like resin composition for semiconductor sealing and filling, and singulating the semiconductor wafer subjected to the first step, a semiconductor wafer to which a film-like resin composition for semiconductor sealing is attached is obtained Granulation step. In the preparation step B, since a plurality of semiconductor wafers to which a film-like resin composition for semiconductor sealing is attached can be produced at one time, the productivity is excellent. A method of attaching a semiconductor sealing film to a film-forming resin composition on a projection forming surface of a semiconductor wafer is exemplified by a method using a hot roll laminator or a vacuum laminator. When the mass ratio of the coating material in the second resin composition as the total amount of the second resin composition as described above is small (for example, less than 20% by mass), the second layer is excellent in light transmittance. The front end of the -35-201235395 can be highlighted through the second layer. Therefore, in the singulation step or the joining step described later, the front end of the projection can be aligned as a reference to improve workability. The singulation of the semiconductor wafer can be performed by, for example, doctor blade dicing, laser dicing, stealth dicing, or the like. In this case, the semiconductor wafer may be fixed to the dicing device that attaches the dicing tape to the surface of the semiconductor wafer opposite to the protrusion forming surface, or may be fixed to the dicing tape attached to the semiconductor. The semiconductor sealing on the wafer is filled with a dicing device on the film-like resin composition. In the preparation step B, the semiconductor sealing compound can be attached to the semiconductor wafer having a predetermined thickness by a back-grinding process by attaching a film-like resin composition. In addition, after attaching the film-like resin composition for semiconductor sealing to the semiconductor wafer before the back honing process, the back honing tape may be attached to the semiconductor sealing enamel film-like resin composition. The protrusion forming surface and the opposite side surface are subjected to back honing processing and thinning to a specific thickness. Further, in the preparation step B, the semiconductor wafer before the back honing processing may be applied, and the trench is formed by a dicing device along the dicing line, and then the semiconductor sealing film is attached with the film-like resin composition. On the protrusion forming surface. In this case, the back honing tape can be bonded to the semiconductor sealing rinsing film-like resin composition, and the groove can be exposed by back honing from the surface opposite to the surface on which the protrusion is formed, so that the semiconductor crystal is exposed. The wafer is singulated while being thinned. The connecting step electrically connects the electrodes of the substrate to the protrusions of the semiconductor wafer. The connecting step can be carried out, for example, by arranging the semiconductor wafer and the substrate in a direction opposite to the melting point of the solder or tin at a temperature higher than the melting point of the solder or tin. Thereby, the surface oxide film of the solder or tin can be removed by the flux contained in the second layer (or the second layer and the first layer) while simultaneously melting the solder or tin to make the protrusion and the substrate of the semiconductor wafer The electrode is metal bonded. Here, the film-like resin composition for semiconductor sealing is disposed so that the first layer is on the side of the semiconductor film and the second layer is on the side of the substrate. Therefore, the semiconductor device having good conductivity and connection reliability can be manufactured by sufficiently suppressing the occurrence of pits. The heating and pressing time is preferably 0. 1~2 0 seconds, better 0. 1~1 5 seconds, and better for 〇 · 1~1 leap seconds. By heating and pressing time is 0. For more than 1 second, the resin composition can be sufficiently excluded from the protrusion and the electrode, and the surface oxide film of the solder or tin can be uniformly removed, so that the connection reliability is further improved. Moreover, when the connection time exceeds 20 seconds, there is a drop in productivity. The connecting step may include a first heating step of heating and pressurizing at a temperature above the activation temperature of the flux contained in the second layer, below the melting point of the solder or tin, and heating and pressurizing at a temperature above the melting point of the solder or tin. A second heating step of bonding the protrusions of the semiconductor wafer to the electrode metal of the substrate. The first heating step is to remove the low-viscosity resin composition from the protrusion and the substrate electrode by heating while removing the surface oxide film of the solder or tin by the flux. The solder or tin after the first heating step is prevented from being reoxidized by being coated with the resin composition. Further, in the first heating step, the low molecular weight component in the resin composition is volatilized or polymerized. According to the first heating step, since the resin composition is sufficiently excluded from the protrusion and the substrate electrode, the generation of the depression can be further suppressed. Further, in the first heating step, since the low molecular weight component in the resin composition is volatilized or highly molecularized, volatilization of the low molecular weight component and generation of pores can be suppressed under the high temperature joining condition of the second heating step. The heating time of the first heating step is usually preferably 0. 1 to 20 seconds, preferably 0. 5 to 1 5 seconds, and better yet 1. 0~1 5 seconds. The heating time is 〇.  When the thickness is more than 1 second, the surface oxide film of the solder or tin can be uniformly removed, and the resin between the protrusion and the substrate electrode can be sufficiently removed, so that the connection reliability tends to be further improved. Further, when the heating time exceeds 20 seconds, the productivity is lowered. However, in the first heating step, if the semiconductor resin composition is gelatinized by the film-like resin composition, the flow of the molten solder or tin is blocked by the gelled resin composition in the second heating step, and it is impossible to Give full play to the wettability. Accordingly, the heating time is preferably set as appropriate depending on the gelation time of the film-like resin composition for the semiconductor sealing compound to be used. The second heating step melts the solder or tin and bonds the protrusions to the substrate electrode metal. Therefore, the heating temperature is set above the melting point of the solder or tin. In the first heating step, since the removal of the surface oxide film of the solder or tin and the removal of the resin between the protrusion and the substrate electrode are completed, in the second heating step, the solder or the tin may be accelerated to be melted, and in the protrusion And the surface of the substrate electrode exhibits good wettability. The heating time of the second heating step is usually preferably 0. 1 to 20 seconds, preferably 0. 5~15 seconds' is better for 1. 〇~15 seconds. By allowing the heating time to be 〇·1 second or more, the solder or tin can sufficiently wet the surface of the protrusion and the substrate electrode -38 - 201235395, so that the connection failure can be further suppressed. Moreover, when the heating time exceeds 20 seconds, the productivity is lowered. However, in the second heating step, the joint portion of the metal joint is reinforced by gelatinizing the semiconductor sealing compound with the film-like resin composition. Therefore, it is expected that the thermal stress caused by the difference in thermal expansion coefficient between the semiconductor wafer and the substrate during the cooling process after the completion of the connection can be suppressed from being concentrated on the connection portion to cause connection failure such as cracks. Therefore, the heating time in the second heating step is appropriately set in accordance with the gelation time in which the film-like resin composition for the semiconductor sealing compound is sufficiently gelatinized. The first heating step and the second heating step may be continuously performed by a single connecting device, but the working time is prolonged due to the temperature rise and cooling of the connecting device, and the productivity is lowered. On the other hand, the first heating step and the second heating step can be separated and separately performed by different connecting means, and the working temperature of the connecting device can be kept constant, and high productivity can be realized. Further, since the connection device having the temperature rising or cooling mechanism (pulse heating mechanism) is not used, and the connection device having the mechanism (fixed heating mechanism) capable of heating to a constant temperature is used, the apparatus can be simplified. In addition, the positional alignment of the semiconductor wafer and the substrate may be performed before the first heating step, at a temperature lower than the activation temperature of the flux and higher than the temperature at which the semiconductor sealing composition is filled with the film-like resin composition to exhibit adhesiveness. A temporary fixing step of temporarily fixing the semiconductor wafer and the substrate is performed. By providing the temporary fixing step, the first heating step and the second heating step can be performed once for the plurality of semiconductor wafers and the substrate, and high production can be achieved -39-201235395. Further, in order to further improve the connection reliability, after the semiconductor wafer and the substrate are connected, heat treatment may be performed in a heating oven or the like to further cure the film-like resin composition for semiconductor sealing and filling. Hereinafter, a semiconductor device manufactured by the manufacturing method of the present embodiment will be described. Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. The semiconductor device 10 includes a circuit board 7 , a semiconductor wafer 5 , and a sealing resin 6 disposed between the circuit board 7 and the semiconductor wafer 5 . The sealing resin 6 is composed of a cured product of a film-like resin composition for semiconductor sealing and filling of the present embodiment, and seals a gap between the circuit board 7 and the semiconductor wafer 5. The circuit board 7 includes a substrate such as an interposer, and a wiring 4 provided on one surface of the substrate. The wiring 4 of the circuit board and the semiconductor wafer 5 are electrically connected by the protrusions 3. Further, the circuit board 7 has electrode pads 2 and solder balls 1 provided on the electrode pads 2 on the surface opposite to the surface on which the wirings 4 are provided, so as to be connectable to other circuit members. The semiconductor device of the present invention is exemplified by a semiconductor wafer mounted on a substrate called an interposer as shown in Fig. 1, and sealed by a resin. Specifically, it is listed as CSP (Chip Size Package) or BGA (Ball Grid Array). Further, the other semiconductor device of the present invention is a CoC (a wafer mounted on a wafer) having a structure in which another semiconductor wafer is mounted on a semiconductor wafer, and a 3D package having a structure in which a plurality of semiconductor wafers are three-dimensionally laminated by a tantalum penetration electrode. . Further, the method of manufacturing a semiconductor device using the film-like resin composition for semiconductor sealing and filling of the present embodiment is not limited to the above-described manufacturing method, and for example, a protrusion in which the first layer is adjacent to the semiconductor wafer may be used. When a film-like resin composition for semiconductor sealing is supplied to form a surface, two of them are combined, and the protrusions are connected to each other to manufacture a semiconductor device. The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments. [Examples] Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited to the examples. (Examples 1 to 10, Comparative Examples 1 to 6)

以成爲表1〜3所示之構成之方式，以加熱至50°C之輥 層合機貼合以下述所示方法製作之薄膜狀樹脂組成物A〜K ，製造實施例1〜1〇及比較例1〜6之半導體密封塡充用薄 膜狀組成物。 (薄膜狀樹脂組成物A) 將苯氧樹脂「PKCP80」 （Inchem Corporation 製造， 製品名）45g、多官能基環氧樹脂「EP1032H60」（日本環 氧樹脂股份有限公司製造，製品名）3 0g、液狀酸酐「 YH3 07」（日本環氧樹脂股份有限公司製造，製品名） 20g、二氧化矽塡料「SE20 5 0」（Admatechs股份有限公 -41 - 201235395 司製造’製品名，平均粒徑〇·4〜0.6μπι) 100g、己二酸（ Sigma-Aldrich製造）3g、硬化促進劑「TPP-K」（北興化 學工業股份有限公司製造，製品名）lg分散於甲基乙基酮 溶劑中並溶解製作漆料。使用刮刀塗布器將該漆料塗佈於 隔離薄膜（PET薄膜）上後；在7〇 °C之烘箱中乾燥1〇分 鐘，藉此製作特定厚度之薄膜狀樹脂組成物A。 (薄膜狀樹脂組成物B) 除未調配己二酸以外，餘與薄膜狀樹脂組成物A同樣 ，製作特定厚度之薄膜狀樹脂組成物B。 (薄膜狀樹脂組成物C) 除使二氧化矽塡料「SE2050」 （Admatechs股份有限 公司製造，製品名，平均粒徑0.4〜0.6μπι )之調配量設爲 1 〇g以外，餘以與薄膜狀樹脂組成物Α同樣，製作特定厚 度之薄膜狀樹脂組成物C。 (薄膜狀樹脂組成物D) 除未調配二氧化矽塡料以外，餘與薄膜狀樹脂組成物 A同樣，製作特定厚度之薄膜狀樹脂組成物D。 (薄膜狀樹脂組成物E) 將苯氧樹脂「PKCP80」（Inchem Corporation 製造’ 製品名）50g、己二酸（Sigma-Aldrich製造）3g分散於甲 -42- 201235395 基乙基酮溶劑中並溶解製作漆料，且使用刮刀塗布器將該 漆料塗佈於隔離薄膜（PET薄膜）上後，在70 °C之供箱中 乾燥10分鐘，製作特定厚度之薄膜狀樹脂組成物E。 (薄膜狀樹脂組成物F) 除未調配二氧化矽塡料及己二酸以外，餘與薄膜狀樹 脂組成物A同樣，製作特定厚度之薄膜狀樹脂組成物F。 (薄膜狀樹脂組成物G) 將苯氧樹脂「PKCP80」 （Inchem Corporation 製造， 製品名）50g、二氧化砂塡料「SE2050」 （Admatechs股 份有限公司製造，製品名，平均粒徑0.4〜0.6μηι) 50g分 散於甲基乙基酮溶劑中並溶解製作漆料，使用刮刀塗布器 將該漆料塗佈於隔離薄膜（PET薄膜）上後，在70°C之烘 箱中乾燥10分鐘，製作特定厚度之薄膜狀樹脂組成物G (薄膜狀樹脂組成物Η) 將苯氧樹脂「ΖΧ 1 3 56-2」（東京化成股份有限公司製 造，製品名）30g、多官能基環氧樹脂「ΕΡ 1032Η60」（日 本環氧樹脂股份有限公司製造，製品名）45g、雙酚F型 液狀環氧樹脂「YL983U」（日本環氧樹脂股份有限公司 製造，製品名）l〇g、柔軟性環氧樹脂「YL7175_ 1 000」（ 日本環氧樹脂股份有限公司製造，製品名）5g ' 2,4-二胺- -43- 201235395 6-[2’-甲基咪唑基-(1，）]-乙基-s-三聚異氰酸加成物「 2MA-OK」（四國化成工業股份有限公司製造’製品名） 2g、二氧化矽塡料「SE2050」（Admatechs股份有限公司 製造，製品名，平均粒徑0.4〜0.6μπι) 75g、蕊殻型有機塡 料「EXL-2655」 （ROHM&HASS股份有限公司製造，製品 名）l〇g'己二酸（Sigma-Aldrich製造）2g分散於甲基乙 基酮溶劑中並溶解製作漆料，使用刮刀塗布器將該漆料塗 佈於隔離薄膜（PET薄膜）上後，在70°C之烘箱中乾燥10 分鐘，製作特定厚度之薄膜狀樹脂組成物Η。 (薄膜狀樹脂組成物I ) 除未調配己二酸以外，餘與薄膜狀樹脂組成物Η同樣 ，製作特定厚度之薄膜狀樹脂組成物I。 (薄膜狀樹脂組成物J ) 除未調配二氧化矽塡料及有機塡料以外，餘與薄膜狀 樹脂組成物Η同樣’製作特定厚度之薄膜狀樹脂組成物j (薄膜狀樹脂組成物Κ) 除未調配二氧化矽塡料、有機塡料及己二酸以外，餘 與薄膜狀樹脂組成物Η同樣’製作特定厚度之薄膜狀樹脂 組成物Κ。 -44 - 201235395 (光逶過性之測定） 以下述方法測定薄膜狀樹脂組成物A〜K之光透過性 (光透過率之測定方法） 準備使薄膜狀樹脂組成物A~K分別以厚度成爲2 5 μιη 之方式形成於隔離膜上而成者及隔離膜單體，且分別切成 30mmx3〇mm之尺寸後，將形成於隔離膜上之薄膜狀熱硬 化性樹脂組成物設置於日立高科技股份有限公司製造之分 光光度計U-3 3 10之樣品安裝部，將隔離膜單體設置於參 考安裝部，在400〜800nm之波長區域中，以掃描速度 3 00nm/分鐘測定光透過率，讀取5 5 5nm下之光透過率。 [表1] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 第1層 樹脂組成物 A A A B B B 厚度(#m) 20 20 20 20 20 20 光透過率(％) 3 3 3 3 3 3 第2層 樹脂組成物 C D E C D E 厚度(//m) 10 10 10 10 10 10 光透過率(%) 51 85 80 51 85 80 -45- 201235395 [表2] 實施例7 實施例8 實施例9 實施例10 比較例1 比較例2 第1層 樹脂組成物 B Θ Η I Β A 厚度(Am) 60 60 20 20 20 30 光透過率(％) 3 3 7 7 3 3 第2層 樹脂組成物 D E J J F — 厚度(#m) 10 10 1 0 10 10 一 光透過率(％) 80 80 85 85 96 - [表3] 比較例3 比較例4 比較例5 比較例6 第1層 樹脂組成物 G A Η Η 厚度(#m) 20 70 20 30 光透過率(％) 5 3 7 7 第2層 樹脂組成物 E 一 Κ — 厚度(//m) 1 0 一 10 一 光透過率(％) 80 — 95 一 (半導體晶片與基板之連接） 使用實施例1~10及比較例1〜6之半導體密封塡充用 薄膜狀樹脂組成物’以下述連接方法1或連接方法2進行 半導體晶片與基板之連接’製造半導體裝置。針對製造之 半導體裝置，進行下述之導電檢查、孔隙評價、連接狀態 評價。結果示於表4及5。 (連接方法1 ) 準備曰立超LSI系統製造「JTEG PHASE11_80」（尺 -46- 201235395 寸7.3mm><7.3mm，厚度〇.55mm，突出物間距80μιη’突出 物數3 2 8 (外周配置），突出物高度40μιη，商品名）作爲 形成有具有銅柱及設置於該銅柱前端之無鉛銲料層（Sn-3.5Ag ’熔點221°C )之突出物之半導體晶片。另外，準備 表面上具有經預助焊處理形成防銹皮膜之銅配線突出物之 玻璃環氧樹脂基板作爲基板。 將半導體密封塡充用薄膜狀樹脂組成物切成9mm X 9mm，於基板上之搭載半導體晶片之區域上，以80°C/ 0.5MPa/5秒之條件，以使第2層鄰接於基板表面之方式貼 附後，玻璃隔離薄膜。 將貼附有半導體密封塡充用薄膜狀樹脂組成物之基板 吸附固定於覆晶固晶機FCB3 (Panasonic Factory Solution 製造，製品名）之設定成4(TC之檯上，與半導體晶片位置 對準後，以荷重25N、壓頭溫度l〇〇°C進行壓著5秒作爲 暫時固定步驟（到達90°C )，將半導體晶片暫時固定於基 板上。接著，將覆晶固晶機之壓頭溫度設定成290°C，以 荷重25N進行壓著10秒（到達250°C )。 (連接方法2 ) 準備 WALTS股份有限公司製造之「WALTS-TEG FC200JY」（晶圓厚度725 μπι，晶圓尺寸8英吋，突出物 高度80μιη，突出物間距200μηι (外圍配置），每1晶片 之尺寸爲lOmmxlOmm，每1晶片之突出物數爲2116)作 爲形成有無鉛銲錫（Sn-3.0Ag-0.5Cu，熔點221°C )之半 -47- 201235395 導體晶圓。 於該半導體晶圓上，以使第1層鄰接於該半導體晶圓 之突出物形成面之方式，以加熱至80°C之熱輥層合機貼合 半導體.密封塡充用薄膜狀樹脂組成物。接著，將切晶膠帶 貼合於半導體晶圓之與突出物形成面相反之面，將半導體 晶圓固定於晶圓環上。剝離半導體密封塡充用薄膜狀樹脂 組成物之隔離薄膜後，使用切刀切晶裝置，單粒化成 lOmmx 10mm之半導體晶片，且將半導體密封塡充用薄膜 狀樹脂組成物貼附於突出物形成面上，製作半導體晶片。 接著，準備 WALTS股份有限公司製造之「WALTS-KIT 01A200P-10」作爲具有經Ni/快速Au鍍敷處理之Cu 配片圖型之基板。將該基盤配置於覆晶固晶機FCB3 ( Panasonic Factory Solution 製造，製品名）之設定成 40°C 之檯上，與貼附有半導體密封塡充用薄膜狀樹脂組成物之 半導體晶片位置對準後，以荷重25N、壓頭溫度100°C進 行壓著5秒作爲暫時固定步驟（到達90°C )，將半導體晶 片暫時固定於基板上。接著，將覆晶固晶機之壓頭溫度設 定成220°C，以荷重20N進行壓著10秒（到達190°C )後 ，以保持壓頭高度之狀態，使壓頭溫度上升至290°C，再 進行壓著10秒（到達25 0°C )。 (導通檢査） 將可確認菊花鏈（daisy chain )連接者記爲A，無法 確認者記爲B。 -48- 201235395 (孔隙評價） 以超音波探傷裝置（曰立建置機造「Fine SAT」）觀 察所製造之半導體裝置，孔隙所占面積相對於晶片面積爲 1%以下者記爲A，超過1 %者記爲B。 (連接狀態評價） 以剖面硏磨使製造之半導體裝置之連接部露出，以光 學顯微鏡觀察。連接部未發現凹陷，焊錫充分潤濕配線者 記爲A。且，於連接部見到凹陷者，或焊錫未充分潤濕配 線者記爲B。 [表4]The film-like resin compositions A to K produced by the following method were bonded to a roll laminator heated to 50 ° C in the manner shown in Tables 1 to 3, and Production Examples 1 to 1 and The film-like composition for semiconductor sealing rinsing of Comparative Examples 1 to 6 was used. (film-like resin composition A) 45 g of a phenoxy resin "PKCP80" (manufactured by Inchem Corporation), and a polyfunctional epoxy resin "EP1032H60" (manufactured by Nippon Epoxy Resin Co., Ltd., product name) 30 g, Liquid acid anhydride "YH3 07" (manufactured by Nippon Epoxy Resin Co., Ltd., product name) 20g, cerium oxide material "SE20 5 0" (Admatechs Co., Ltd. -41 - 201235395 Division's name, average particle size 〇·4~0.6μπι) 100g, adipic acid (manufactured by Sigma-Aldrich) 3g, hardening accelerator "TPP-K" (manufactured by Kitai Chemical Industry Co., Ltd., product name) lg dispersed in methyl ethyl ketone solvent And dissolve the paint. This paint was applied onto a release film (PET film) using a knife coater; and dried in an oven at 7 ° C for 1 Torr to prepare a film-like resin composition A having a specific thickness. (film-like resin composition B) A film-like resin composition B having a specific thickness was produced in the same manner as the film-form resin composition A except that adipic acid was not prepared. (film-like resin composition C), except that the amount of the cerium oxide material "SE2050" (manufactured by Admatech Co., Ltd., product name, average particle diameter: 0.4 to 0.6 μm) is set to 1 〇g, Similarly, a film-like resin composition C having a specific thickness was produced in the same manner. (film-like resin composition D) A film-like resin composition D having a specific thickness was produced in the same manner as the film-form resin composition A except that the cerium oxide material was not prepared. (film-like resin composition E) 50 g of phenoxy resin "PKCP80" (product name manufactured by Inchem Corporation) and 3 g of adipic acid (manufactured by Sigma-Aldrich) were dispersed in a solvent of methyl-42-201235395 ethyl ketone and dissolved. A paint was prepared, and the paint was applied onto a release film (PET film) using a knife coater, and then dried in a case at 70 ° C for 10 minutes to prepare a film-like resin composition E having a specific thickness. (film-like resin composition F) A film-like resin composition F having a specific thickness was produced in the same manner as in the film-like resin composition A except that the cerium oxide material and the adipic acid were not prepared. (film-like resin composition G) 50 g of a phenoxy resin "PKCP80" (manufactured by Inchem Corporation, product name), and a sand dioxide coating "SE2050" (manufactured by Admatech Co., Ltd., product name, average particle diameter 0.4 to 0.6 μηι 50 g was dispersed in a solvent of methyl ethyl ketone and dissolved to prepare a lacquer, which was applied onto a release film (PET film) using a knife coater, and then dried in an oven at 70 ° C for 10 minutes to prepare a specific Thick film-like resin composition G (film-like resin composition Η) phenoxy resin "ΖΧ 1 3 56-2" (manufactured by Tokyo Chemical Industry Co., Ltd., product name) 30 g, polyfunctional epoxy resin "ΕΡ 1032Η60 (made by Japan Epoxy Resin Co., Ltd., product name) 45g, bisphenol F type liquid epoxy resin "YL983U" (manufactured by Nippon Epoxy Resin Co., Ltd., product name) l〇g, soft epoxy resin "YL7175_ 1 000" (manufactured by Nippon Epoxy Resin Co., Ltd., product name) 5g ' 2,4-Diamine - 43- 201235395 6-[2'-Methylimidazolyl-(1,)]-ethyl -s-trimeric isocyanate adduct "2MA-OK" (Shikoku Chemical Industry Co., Ltd. manufactures 'product name) 2g, cerium oxide material "SE2050" (manufactured by Admatechs Co., Ltd., product name, average particle size 0.4~0.6μπι) 75g, core-shell type organic mash" EXL-2655" (manufactured by ROHM & HASS Co., Ltd.) 1 g of adipic acid (manufactured by Sigma-Aldrich) was dispersed in a solvent of methyl ethyl ketone and dissolved to prepare a paint, which was processed using a knife coater. After the paint was applied onto a release film (PET film), it was dried in an oven at 70 ° C for 10 minutes to prepare a film-like resin composition of a specific thickness. (Film-form Resin Composition I) A film-like resin composition I having a specific thickness was produced in the same manner as the film-form resin composition 除 except that adipic acid was not prepared. (film-like resin composition J) The film-like resin composition j (film-like resin composition Κ) of a specific thickness is produced in the same manner as the film-like resin composition 除 except that the cerium oxide material and the organic cerium material are not prepared. The film-like resin composition of a specific thickness was produced in the same manner as the film-form resin composition 未 except that the cerium oxide material, the organic cerium material, and the adipic acid were not prepared. -44 - 201235395 (Measurement of the optical properties) The light transmittance of the film-like resin compositions A to K was measured by the following method (measurement method of light transmittance). The film-like resin compositions A to K were each made thick. 2 5 μηη is formed on the separator and formed into a separator, and is cut into a size of 30 mm x 3 〇 mm, and the film-like thermosetting resin composition formed on the separator is placed on Hitachi High-Tech. The sample mounting portion of the spectrophotometer U-3 3 10 manufactured by the company, the separator is provided in the reference mounting portion, and the light transmittance is measured at a scanning speed of 300 nm/min in a wavelength region of 400 to 800 nm. The light transmittance at 555 nm was read. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 First layer resin composition AAABBB Thickness (#m) 20 20 20 20 20 20 Light transmittance (%) 3 3 3 3 3 3 second layer resin composition CDECDE thickness (//m) 10 10 10 10 10 10 light transmittance (%) 51 85 80 51 85 80 -45- 201235395 [Table 2] Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 First layer resin composition B Θ Η I Β A Thickness (Am) 60 60 20 20 20 30 Light transmittance (%) 3 3 7 7 3 3 Second layer resin composition DEJJF —Thickness (#m) 10 10 1 0 10 10 Light transmittance (%) 80 80 85 85 96 - [Table 3] Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 First layer resin composition GA Η Η Thickness (#m) 20 70 20 30 Light transmittance (%) 5 3 7 7 Second layer resin composition E Κ — Thickness (//m) 1 0 - 10 - Light transmittance (%) 80 - 95 (Connection of Semiconductor Wafer to Substrate) Using the film-like resin composition for semiconductor sealing and filling of Examples 1 to 10 and Comparative Examples 1 to 6 'Semiconductor crystal by the following connection method 1 or connection method 2 And the connection substrate 'for manufacturing a semiconductor device. For the manufactured semiconductor device, the following conductivity inspection, pore evaluation, and connection state evaluation were performed. The results are shown in Tables 4 and 5. (Connection method 1) Prepare "JTEG PHASE11_80" manufactured by 超立超LSI system (foot-46-201235395 inch 7.3mm><7.3mm, thickness 〇.55mm, protrusion pitch 80μιη' protrusion number 3 2 8 (outer circumference configuration) The protrusion height 40 μm, trade name) is a semiconductor wafer formed with a copper pillar and a protrusion of a lead-free solder layer (Sn-3.5Ag 'melting point 221 ° C) provided at the tip end of the copper pillar. Further, a glass epoxy substrate having a copper wiring protrusion on the surface of which a pre-weld treatment is formed to form a rust-preventing film is prepared as a substrate. The semiconductor resin composition for film sealing is cut into 9 mm X 9 mm, and the second layer is adjacent to the surface of the substrate at a temperature of 80 ° C / 0.5 MPa / 5 sec on the substrate on which the semiconductor wafer is mounted. After attaching the film, the glass isolating film. The substrate to which the film-like resin composition for semiconductor sealing is attached is adsorbed and fixed to the flip chip bonding machine FCB3 (manufactured by Panasonic Factory Solution, product name), and set to 4 (TC stage, after alignment with the semiconductor wafer) The semiconductor wafer is temporarily fixed on the substrate by pressing at a load of 25 N and a head temperature of 10 ° C for 5 seconds as a temporary fixing step (to reach 90 ° C). Next, the head temperature of the flip chip bonding machine is performed. Set to 290 ° C and press at a load of 25 N for 10 seconds (to 250 ° C). (Connection method 2) Prepare "WALTS-TEG FC200JY" manufactured by WALTS Co., Ltd. (wafer thickness 725 μm, wafer size 8 In English, the height of the protrusion is 80 μm, the pitch of the protrusion is 200 μm (peripheral configuration), the size of each wafer is 10 mm×10 mm, and the number of protrusions per wafer is 2116) as the lead-free solder (Sn-3.0Ag-0.5Cu, melting point). 221 ° C) half -47 - 201235395 conductor wafer. On the semiconductor wafer, the first layer is adjacent to the protrusion formation surface of the semiconductor wafer, and heated to 80 ° C hot roll layer Machine-fitted semiconductor. Seal The film-like resin composition is used for the filling. Next, the dicing tape is bonded to the surface of the semiconductor wafer opposite to the surface on which the protrusion is formed, and the semiconductor wafer is fixed on the wafer ring. The semiconductor sealing film is peeled off and formed of a film-like resin. After the separator is used as a separator, a semiconductor wafer of 10 mm x 10 mm is singulated by a cutter dicing apparatus, and a semiconductor resin film is attached to the protrusion forming surface by a semiconductor resin squeezing film to form a semiconductor wafer. Next, preparation of WALTS "WALTS-KIT 01A200P-10" manufactured by the company was used as a substrate with a Cu pattern of Ni/rapust Au plating. The substrate was placed in a flip chip bonder FCB3 (Manufactured by Panasonic Factory Solution) The position is set to 40 ° C, and the semiconductor wafer to which the film-like resin composition for semiconductor sealing is attached is aligned, and then pressed for 5 seconds at a load of 25 N and a head temperature of 100 ° C. Fixing step (reaching 90 ° C), temporarily fixing the semiconductor wafer on the substrate. Then, setting the indenter temperature of the flip chip bonding machine to 220 ° C, with a load of 20 N After pressing for 10 seconds (to 190 ° C), the head temperature was raised to 290 ° C while maintaining the height of the head, and then pressed for 10 seconds (to reach 25 ° C). (Conduction check) It can be confirmed that the daisy chain connector is marked as A, and the unidentified person is marked as B. -48- 201235395 (Pore evaluation) Observed by the ultrasonic flaw detector (Fine SAT) In the semiconductor device, the area occupied by the voids is 1% or less with respect to the wafer area, and the number is more than 1%. (Connection state evaluation) The connection portion of the manufactured semiconductor device was exposed by section honing, and observed by a light microscope. No depression was found in the joint, and the solder was sufficiently wetted by the welder as A. Also, a person who sees a depression at the joint portion or a solder that does not sufficiently wet the line is denoted as B. [Table 4]

實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 連接方法 1 1 1 1 1 1 導通檢査 A A A A A A 孔隙評價 A A A A A A 連接狀態 A A A A A AExample 1 Example 2 Example 3 Example 4 Example 5 Example 6 Connection method 1 1 1 1 1 1 Conduction inspection A A A A A A Pore evaluation A A A A A A Connection state A A A A A A

[表5][table 5]

實施例7 實施例8 實施例9 實施例10 比較例1 比較例2 連接方法 2 2 1 1 1 導通檢查 A A A A 巳 A 孔隙評價 A A A A A A 連接狀態 A A A A B B -49- 201235395Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Connection method 2 2 1 1 1 Conduction inspection A A A A 巳 A Pore evaluation A A A A A A Connection state A A A B B -49- 201235395

[表6] 比較例3 比較例4 比較例5 比較例6 連接方法 1 2 1 1 導通檢査 B 一 B A 孔隙評價 B 一 A A 連接狀態 B 一 B B 使用實施例1~6、9及10之半導體密封塡充用薄膜狀 樹脂組成物時，可實現良好的孔隙狀況與良好的連接部， 獲得導電性及連接信賴性優異之半導體裝置。 圖2爲顯示以超音波探傷裝置觀察實施例2之半導體 裝置之孔隙狀況之觀察圖像。又，圖3爲顯示實施例3之 半導體裝置之連接部之剖面觀察照片。且，圖4爲顯示實 施例6之半導體裝置之連接部之剖面觀察照片。圖3及圖 4中，半導體晶片12之銅柱13與基板11之電極15係以 焊料14金屬接合。另外，基板11與半導體晶片12之空 隙係以半導體密封塡充用薄膜狀樹脂組成物的硬化物之密 封樹脂1 6予以密封塡充。 另一方面，使用比較例1及5之薄膜狀樹脂組成物時 ，焊料未充分潤濕配線（基板電極），無法形成良好的連 接部。圖5爲顯示比較例1之半導體裝置之連接部之剖面 觀察照片。圖5中，半導體晶片12之銅柱13與基板11 之電極1 5之間出現凹陷1 7。且，焊料1 4未潤濕基板1 1 之電極15，而無法進行充分金屬接合。 又，比較例2及6在連接部中發生凹陷。圖6爲顯示 -50- 201235395 比較例2之半導體裝置之連接部之剖面觀察照片。圖6中 ，半導體晶片12之銅柱13與基板11之電極15之間出現 凹陷1 7。 圖7顯示以超音波探傷裝置觀察比較例3之半導體裝 置之孔隙狀況之觀察圖像。比較例3由圖7與圖2之比較 可了解，出現許多孔隙（圖7之1 8 )。 進行連接方法2時，使用實施例7及8之半導體密封 塡充用薄膜狀樹脂組成物時，儘管突出物前端未穿出樹脂 組成物而爲未露出之狀態，仍可充分辨識突出物之前端。 因此，可容易地進行半導體晶片與基板之位置對準。圖8 爲顯示以掃描電子顯微鏡觀察貼附實施例8之半導體密封 塡充用薄膜狀樹脂組成物之半導體晶圓之突出物形成面之 觀察照片。又，圖9爲顯示以覆晶固晶機之照相機觀察貼 附實施例8之半導體密封塡充用薄膜狀樹脂組成物之半導 體晶圓之突出物形成面之觀察照片。 又，如表4所示，使用實施例7及8之半導體密封塡 充用薄膜狀樹脂組成物時，實現良好之孔隙狀況及良好之 連接部，獲得導電性及連接信賴性優異之半導體裝置。圖 10爲顯示實施例8之半導體裝置之連接部之剖面觀察照片 。圖10中，半導體晶片22之焊料突出物23與基板21之 電極25係藉由焊料之熔融而金屬接合。因此，利用半導 體密封塡充用薄膜狀樹脂組成物之硬化物的密封樹脂26 密封塡充基板21與半導體晶片22之空隙。 另一方面，使用比較例4之薄膜狀樹脂組成物時，於 -51 - 201235395 突出物前端未穿出樹脂組成物爲未露出之狀態，並無法辨 識突出物之前端，故無法對準位置。因此，無法製造半導 體裝置。圖11爲顯示以覆晶固晶機之照相機觀察貼附比 較例4之薄膜狀樹脂組成物之半導體晶圓之突出物形成面 之觀察照片。 【圖式簡單說明】 圖1爲顯示本發明之半導體裝置之一實施形態之示意 剖面圖》 圖2爲以超音波探傷裝置觀察實施例3之半導體裝置 之孔隙狀況之觀察圖像。 圖3爲實施例3之半導體裝置之連接部之剖面觀察照 片。 圖4爲實施例6之半導體裝置之連接部之剖面觀察照 片。 圖5爲比較例1之半導體裝置之連接部之剖面觀察照 片。 圖6爲比較例2之半導體裝置之連接部之剖面觀察照 片。 圖7爲以超音波探傷裝置觀察比較例3之半導體裝置 之孔隙狀況之觀察圖像。 圖8爲以掃描電子顯微鏡觀察貼附實施例8之半導體 密封塡充用薄膜狀樹脂組成物之半導體晶圓之突出物形成 面之觀察照片。 -52- 201235395 圖9爲覆晶固晶之以照相機觀察貼附實施例8之半導 體密封塡充用薄膜狀樹脂組成物之半導體晶圓之突出物形 成面之觀察照片。 圖10爲實施例8之半導體裝置之連接部之剖面觀察 照片。 圖1 1爲覆晶固晶之以照相機觀察貼附比較例4之薄 膜狀樹脂組成物之半導體晶圓之突出物形成面之觀察照片 【主要元件符號說明】 1 :焊料球 2 :電極焊墊 3 :焊料突出物 4 :配線 5 :半導體晶片 6 :密封樹脂 7 :電路基板 10 :半導體裝置 11 :基板 1 2 :半導體晶片 1 3 :銅柱 1 4 :焊料 15 :基板電極 1 6 :密封樹脂 -53- 201235395 1 7 :凹陷 1 8 :孔洞 21 :基板 22 :半導體晶片 2 3 :焊料突出物 25 :基板電極 2 6 :密封樹脂 -54[Table 6] Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Connection Method 1 2 1 1 Conduction Inspection B-BA Pore Evaluation B-AA Connection State B-BB Semiconductor Seals of Examples 1 to 6, 9 and 10 were used. When a film-like resin composition is used for charging, a favorable pore state and a good connection portion can be realized, and a semiconductor device excellent in conductivity and connection reliability can be obtained. Fig. 2 is a view showing an observation of the state of the pores of the semiconductor device of the second embodiment observed by the ultrasonic flaw detector. Further, Fig. 3 is a cross-sectional observation photograph showing the connection portion of the semiconductor device of the third embodiment. Further, Fig. 4 is a cross-sectional observation photograph showing a connecting portion of the semiconductor device of the sixth embodiment. In Figs. 3 and 4, the copper pillars 13 of the semiconductor wafer 12 and the electrodes 15 of the substrate 11 are metal-bonded by solder 14. Further, the gap between the substrate 11 and the semiconductor wafer 12 is sealed and filled with a sealing resin 16 which is a semiconductor seal and a cured product of a film-like resin composition. On the other hand, when the film-like resin compositions of Comparative Examples 1 and 5 were used, the solder did not sufficiently wet the wiring (substrate electrode), and a good connection portion could not be formed. Fig. 5 is a cross-sectional observation photograph showing a connection portion of the semiconductor device of Comparative Example 1. In FIG. 5, a recess 17 appears between the copper post 13 of the semiconductor wafer 12 and the electrode 15 of the substrate 11. Further, the solder 14 does not wet the electrode 15 of the substrate 1 1 and cannot be sufficiently metal bonded. Further, Comparative Examples 2 and 6 were recessed in the joint portion. Fig. 6 is a cross-sectional observation photograph showing the connection portion of the semiconductor device of Comparative Example 2 of -50 to 201235395. In Fig. 6, a recess 17 appears between the copper post 13 of the semiconductor wafer 12 and the electrode 15 of the substrate 11. Fig. 7 is a view showing an observation image of the state of the pores of the semiconductor device of Comparative Example 3 observed by an ultrasonic flaw detector. Comparative Example 3 From the comparison of Fig. 7 and Fig. 2, it is understood that many pores appear (18 of Fig. 7). When the connection method 2 is carried out, when the film-like resin composition for semiconductor sealing of Examples 7 and 8 is used, the front end of the protrusion can be sufficiently recognized even if the tip end of the protrusion is not exposed to the resin composition and is not exposed. Therefore, the positional alignment of the semiconductor wafer and the substrate can be easily performed. Fig. 8 is a photograph showing the observation of the protrusion forming surface of the semiconductor wafer to which the film-like resin composition for semiconductor sealing of Example 8 was attached by a scanning electron microscope. Further, Fig. 9 is a photograph showing a projection forming surface of a semiconductor wafer to which a film-like resin composition for semiconductor sealing and filling of Example 8 is attached by a camera of a flip chip bonding machine. Further, as shown in Table 4, when the film-like resin composition for semiconductor sealing of Examples 7 and 8 was used, a favorable pore state and a good connection portion were obtained, and a semiconductor device excellent in conductivity and connection reliability was obtained. Fig. 10 is a cross-sectional observation photograph showing the connection portion of the semiconductor device of the eighth embodiment. In Fig. 10, the solder bumps 23 of the semiconductor wafer 22 and the electrodes 25 of the substrate 21 are metal-bonded by melting of solder. Therefore, the sealing resin 26 filled with the cured product of the film-like resin composition by the semiconductor sealing means seals the gap between the filling substrate 21 and the semiconductor wafer 22. On the other hand, when the film-form resin composition of Comparative Example 4 was used, the resin composition was not exposed at the tip end of -51 - 201235395, and the front end of the protrusion was not recognized, so that the position could not be aligned. Therefore, it is impossible to manufacture a semiconductor device. Fig. 11 is a photograph showing a projection forming surface of a semiconductor wafer to which a film-like resin composition of Comparative Example 4 is attached by a camera of a flip chip crystallizer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. Fig. 2 is an observation image showing a state of pores of a semiconductor device of a third embodiment observed by an ultrasonic flaw detector. Fig. 3 is a cross-sectional view showing a connecting portion of the semiconductor device of the third embodiment. Fig. 4 is a cross-sectional view showing a connecting portion of the semiconductor device of the sixth embodiment. Fig. 5 is a cross-sectional observation photograph of the connection portion of the semiconductor device of Comparative Example 1. Fig. 6 is a cross-sectional observation photograph of the connection portion of the semiconductor device of Comparative Example 2. Fig. 7 is an observation image of the state of the pores of the semiconductor device of Comparative Example 3 observed by the ultrasonic flaw detector. Fig. 8 is a photograph showing a projection forming surface of a semiconductor wafer to which a film-like resin composition for semiconductor sealing and filling of Example 8 is attached by a scanning electron microscope. -52-201235395 Fig. 9 is a photograph of a projection of a projection of a semiconductor wafer in which a film-like resin composition for a semiconductor sealing and attaching film of the eighth embodiment is attached by a camera. Fig. 10 is a cross-sectional view showing the connection portion of the semiconductor device of the eighth embodiment. Fig. 11 is a photograph of a projection forming surface of a semiconductor wafer to which a film-like resin composition of Comparative Example 4 is attached by a camera, and a photoreceptor of the semiconductor wafer of the comparative example 4 is attached. [Main component symbol description] 1 : Solder ball 2 : Electrode pad 3 : solder bump 4 : wiring 5 : semiconductor wafer 6 : sealing resin 7 : circuit substrate 10 : semiconductor device 11 : substrate 1 2 : semiconductor wafer 1 3 : copper pillar 1 4 : solder 15 : substrate electrode 1 6 : sealing resin -53- 201235395 1 7 : recessed 1 8 : hole 21 : substrate 22 : semiconductor wafer 2 3 : solder bump 25 : substrate electrode 2 6 : sealing resin - 54

Claims (1)

201235395 七、申請專利範圍： 1. 一種半導體密封塡充用薄膜狀樹脂 備：由含有熱硬化性樹脂及塡料之第1榻 的第1層、與含有助焊劑之第2樹脂組员 層，且 相對於前述第2樹脂組成物總量之前 物中的塡料之質量比率，比相對於前述第 量之前述第1樹脂組成物中的塡料之質量 2. 如申請專利範圍第1項之半導體密 樹脂組成物，其中前述第2樹脂組成物進 性樹脂。 3. —種半導體裝置之製造方法，其係 複數個突出物之突出物形成面之半導體晶 複數個電極之電極面的基板之半導體裝置 特徵在於具備： 將如申請專利範圍第1或2項之半導 膜狀樹脂組成物，以使前述第2層相對於 於前述基板側的方式，貼附於前述基板之 第1步驟、與 將經前述第1步驟之前述基板與前述 置成爲使前述電極面與前述突出物形成面 體密封塡充用薄膜狀樹脂組成物而互相對 加壓以使前述基板之電極與前述半導體晶 接的第2步驟；且 組成物，其係具 f脂組成物所構成 艺物所構成的第2 述第2樹脂組成 1樹脂組成物總 比率更小。 封塡充用薄膜狀 一步含有熱可塑 具備具有形成有 片、與具有設有 之製造方法，其 體密封塡充用薄 前述第1層配置 前述電極面上的 半導體晶片、配 介隔著前述半導 向，且進行加熱 片之突出物電連 -55- 201235395 在於前述第2步驟連接之前述電極及前述突出物當中 至少一者的表面，存在有錫或焊料。 4. 一種半導體裝置之製造方法，其係具備具有形成有 複數個突出物之突出物形成面的半導體晶片、與具有設有 複數個電極之電極面的基板之半導體裝置之製造方法，其 特徵在於具備： 將如申請專利範圍第1或2項之半導體密封塡充用薄 膜狀樹脂組成物，以使前述第1層相對於前述第2層配置 於前述半導體晶圓側的方式貼附於具有形成有複數個突出 物之突出物形成面之半導體晶圓的該突出物形成面上的第 1步驟、 將經前述第 1步驟之前述半導體晶圓單粒化 (singulation)，得到貼附有前述半導體密封塡充用薄膜狀 樹脂組成物之半導體晶片的第2步驟、與 將於前述第2步驟得到之前述半導體晶片與前述基板 ，配置成爲使前述突出物形成面與前述電極面介隔著前述 半導體密封塡充用薄膜狀樹脂組成物而互相對向，且進行 加熱加壓以使前述半導體晶片之突出物與前述基板之電極 電連接的第3步驟；且 在於前述第3步驟連接之前述電極及前述突出物當中 至少一者的表面，存在有錫或焊料。 5. —種半導體裝置’其係藉由如申請專利範圍第3或4 項之半導體裝置之製造方法來製造。 -56-201235395 VII. Patent Application Range: 1. A film-like resin for semiconductor sealing and filling: a first layer of a first couch containing a thermosetting resin and a coating material, and a second resin component layer containing a flux, and The mass ratio of the tantalum in the previous amount to the total amount of the second resin composition is greater than the mass of the tantalum in the first resin composition relative to the first amount. 2. The semiconductor of claim 1 A dense resin composition in which the second resin composition is a resin. 3. A method of manufacturing a semiconductor device, characterized in that the semiconductor device of the substrate of the plurality of electrode surfaces of the plurality of protrusions of the protrusion forming surface of the plurality of protrusions is characterized in that: the object of claim 1 or 2 a semiconductive film-like resin composition in which the second layer is attached to the substrate so that the second layer is attached to the substrate, and the substrate subjected to the first step is placed on the electrode a second step of pressurizing the surface of the protrusion with the film-like resin composition and pressurizing the electrode of the substrate to be in contact with the semiconductor; and the composition comprising a fat composition The second resin composition 1 composed of the art object has a smaller total resin composition ratio. The sealing film-filled one-step film-containing thermoplastic material has a manufacturing method including a sheet formed thereon, and the semiconductor wafer is disposed on the electrode surface in the first layer, and the half-guide is interposed therebetween. Further, the protrusion of the heater chip is electrically connected - 55 - 201235395. The surface of at least one of the electrode and the protrusion connected in the second step is tin or solder. A method of manufacturing a semiconductor device, comprising: a semiconductor wafer having a protrusion forming surface on which a plurality of protrusions are formed; and a semiconductor device having a substrate having a plurality of electrodes; The semiconductor sealing composition of the first or second aspect of the invention is filled with a film-like resin composition, and the first layer is attached to the semiconductor wafer side so as to be formed on the semiconductor layer side. a first step of forming the protrusion formation surface of the semiconductor wafer of the protrusion formation surface of the plurality of protrusions, and singulation of the semiconductor wafer by the first step to obtain the semiconductor seal The second step of filling the semiconductor wafer using the film-like resin composition, and the semiconductor wafer obtained in the second step and the substrate are disposed such that the protrusion forming surface and the electrode surface are interposed between the semiconductor sealing layer Filling with the film-like resin composition to face each other, and performing heat and pressure to make the protrusion of the semiconductor wafer The third step of electrically connecting to the electrodes of the substrate; and the surface of at least one of the electrodes and the protrusions connected in the third step is tin or solder. A semiconductor device is manufactured by a method of manufacturing a semiconductor device as claimed in claim 3 or 4. -56-
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JP5344097B2 (en) 2013-11-20
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CN103249559B (en) 2015-08-05
CN103249559A (en) 2013-08-14

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