TW201038699A - Resin paste for die bonding, process for producing semiconductor device using the resin paste, and semiconductor device - Google Patents
Resin paste for die bonding, process for producing semiconductor device using the resin paste, and semiconductor device Download PDFInfo
- Publication number
- TW201038699A TW201038699A TW099107287A TW99107287A TW201038699A TW 201038699 A TW201038699 A TW 201038699A TW 099107287 A TW099107287 A TW 099107287A TW 99107287 A TW99107287 A TW 99107287A TW 201038699 A TW201038699 A TW 201038699A
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- Prior art keywords
- wafer
- resin paste
- resin
- semiconductor device
- bonding
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- 229920005989 resin Polymers 0.000 title claims abstract description 142
- 239000011347 resin Substances 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000004065 semiconductor Substances 0.000 title claims description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 15
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 54
- 238000004519 manufacturing process Methods 0.000 claims description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims 1
- 238000005538 encapsulation Methods 0.000 claims 1
- 239000004519 grease Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 229910000679 solder Inorganic materials 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 140
- 239000000463 material Substances 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
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- 230000000052 comparative effect Effects 0.000 description 11
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- 239000003960 organic solvent Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
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- 230000007547 defect Effects 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
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- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 238000004448 titration Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
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- 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
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- H01L24/74—Apparatus for manufacturing arrangements for connecting or disconnecting semiconductor or solid-state bodies
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Description
201038699 六、發明說明: 【發明所屬之技術領域】 本發明係有關作爲1C、LSI等之半導體晶片( 有時稱爲晶片)與導線框架或絕緣性支持基板等( 爲基板)之支持構件之接合材料所用之晶片接合用 使用其之半導體裝置的製造方法以及半導體裝置等 D 【先前技術】 作爲IC、LSI等之半導體元件與導線框架或絕 ί寸基板寺之支持構件之接合材料,亦即晶片接合材 以往已知有Au - S i共晶合金、焊錫、銀膏等。然厅 S i共晶合金由於耐熱性及耐濕性高,彈性率大, 用在大型晶片時有容易破裂之傾向。又,Au-Si共 亦有高價之缺點。另一方面,焊錫雖然便宜但耐熱 其彈性率與Au-Si合金一樣高,而難以使用於大型 〇 相對於此,銀膏(例如參考專利文獻1 )爲便 濕性高,相較於Au-Si共晶合金及焊錫彈性率較低 具有可使用於在350°C熱壓著型晶片接合之耐熱性 ,現在在上述晶片接合材料中亦已廣泛使用銀膏。 對應於隨著1C或LSI之高積集化之進展,伴隨於 大型化之狀況’銀膏難以在晶片全面上廣範圍地塗 法稱爲有效率。 另一方面’可對應於晶片大型化之晶片接合材 有使用特定的聚醯亞胺樹脂之接著薄膜,以及於特 以下亦 以下稱 樹脂、 緣性支 料,自 ΐ ' Au-故於使 晶合金 性差, 晶片。 宜 '耐 ,進而 。因此 然而, 此晶片 佈,無 料已知 定聚酶 -5- 201038699 亞胺樹脂中添加導電性塡料或無機塡料之晶片接合用接著 薄膜等之薄膜狀晶片接合材料(參考專利文獻2〜4)。 先前技術文獻 專利文獻 專利文獻1·特開2002-179769號公報 專利文獻2:特開平〇7_228697號公報 專利文獻3 :特開平〇 6 _丨4 5 6 3 9號公報 專利文獻4:特開平〇6_264035號公報 【發明內容】 [發明欲解決的問題] 接著薄膜型之晶片接合材料可容易地在支持基板上形 成晶片接合層。尤其,如專利文獻2〜4所揭示之接著薄膜 ’可較好地對於42合金框架(鐵-鎳合金)等支持基板使 用’進而具有良好的熱時晶片剪切強度之優點。然而,作 爲晶片接合材料之接著薄膜有效率地貼合於支持基板時, 有必要用以預先將接著薄膜切出或衝壓成晶片大小,接著 貼附於支持基板之貼附裝置。又,衝壓出接著薄膜並以一 次貼附複數個晶片量之方法,有容易產生接著薄膜浪費之 傾向。再者,支持基板的大部分由於係在基板內部形成有 內配線層,故貼附接著薄膜之表面大多爲凹凸,而有接著 薄膜貼附時產生空隙,易使半導體裝置的信賴性降低之傾 向。 -6 - 201038699 又,近幾年來,BOC ( Board On Chip )型半導體裝置 備受囑目,並已使用有機基板等之絕緣性支持基板。於使 用上述絕緣性支持基板之半導體裝置之製造步驟,考慮到 絕緣性支持基板之耐熱性等,有必要在例如20CTC以下之 較低溫度搭載半導體元件。然而,如專利文獻2~4所揭示 之接著薄膜有低溫接著性差的傾向,大多有在比較低溫( 2 00°C以下)難以貼附晶片之情況。因此,於BOC型半導 〇 體裝置的製造中,低溫接著性優異之晶片接合用樹脂膏備 受關注。 使用晶片接合用樹脂膏貼附晶片的方法,一般爲例如 使塗佈在基板上之晶片接合用樹脂膏經B階段化後,於此 時使晶片加熱壓著而暫時接著,爲使晶片與基板完全固定 而在1 8(TC進行1小時左右之後硬化。通常,若省略晶片 接合用樹脂膏之後硬化,則晶片與基板等之接著性變得不 充分,而在金屬線接合步驟中,有發生晶片震動之缺陷的 〇 可能性。又,於封裝步驟中,若晶片與基板等之接著性不 充分,則自晶片側面流下封裝材而有使晶片剝離之情況。 然而,最近,由縮短半導體封裝之組裝時間之觀點而 言,要求有即使省略後硬化,於金屬線接合及封裝步驟中 亦不會產生缺陷之晶片接合用樹脂膏。因此,於省略後硬 化步驟而使用晶片接合用樹脂膏之貼附方法中,B階段化 狀態之晶片接合用樹脂膏之層,有必要具備與晶片之良好 接著性。又,亦期望不因B階段化之溫度範圍而對影響與 晶片之接著性,亦即在廣的溫度範圍具有良好接著強度之 201038699 晶片接合用樹脂膏。又,於晶片貼附時,於B階段化狀態 之晶片接合用樹脂膏之層與晶片間有產生空隙(以下稱爲 孔隙)之情況,亦期望孔隙得以減低。孔隙大時,於焊錫 回焊步驟中於晶片接合材料容易產生龜裂,而有使半導體 裝置之信賴性降低之可能性。 又,於封裝步驟後,有焊錫回焊步驟,此時之最高溫 度爲2 50 °C〜260 °C ’故對晶片接合用樹脂膏亦要求有在 250°C〜260°C之加熱時晶片剪切強度優異。 本發明係鑒於此等情況而完成者,目的在於提供一種 在B階段化中,在廣溫度範圍內與晶片之接著強度優異同 時亦可降低與晶片間之孔隙,且即使在焊錫回焊步驟中亦 具有加熱時之充分晶片剪切強度之晶片接合用樹脂膏。又 ,本發明目的在於提供一種使用上述晶片接合用樹脂膏之 半導體裝置之製造方法。進而,本發明之目的在於提供一 種使用上述晶片接合用樹脂膏之信賴性優異之半導體裝置 [用以解決問題之手段] 爲達成上述問題,本發明採用以下構成。亦即,本發 明之一實施形態,係有關一種晶片接合用樹脂膏,其包含 使具有羧基之丁二烯之聚合物(al)及具有環氧基之化合 物(a2 )反應獲得之聚合物(A )、熱硬化性樹脂(B ) 及塡料(C )。 本發明之另一實施形態,係有關一種半導體裝置之製 -8 - 201038699 造方法’其係使用上述晶片接合用樹脂膏之半導體裝置之 製造方法,其包含(1)在基板上塗佈上述晶片接合用樹 脂膏之步驟,(2 )使前述樹脂膏乾燥並使樹脂膏b階段 化之步驟’ (3 )於經B階段化之前述樹脂膏上搭載半導 體晶片之步驟。 本發明之另一實施形態,係有關一種半導體裝置,其 係由有關使用上述晶片接合用樹脂膏之半導體裝置之製造 〇 方法製得者’該方法包含(1)在基板上塗佈上述晶片接 合用樹脂膏之步驟,(2)使前述樹脂膏乾燥並使樹脂膏 B階段化之步驟’ (3 )於經B階段化之前述樹脂膏上搭 載半導體晶片之步驟。 本發明之另一實施形態,係有關一種半導體裝置之製 造方法,其包含(1)於基板上塗佈上述晶片接合用樹脂 膏之步驟,(2)於塗佈之樹脂膏上搭載半導體晶片之步 驟’(3 )利用封裝劑封裝前述半導體晶片之步驟。 〇 進而本發明之另一實施形態’係有關一種由半導體裝 置之製造方法所得之半導體裝置,該製造方法包含(1) 於基板上塗佈上述晶片接合用樹脂膏之步驟,(2 )於塗 佈之樹脂膏上搭載半導體晶片之步驟,(3 )利用封裝劑 封裝前述半導體晶片之步驟。 本說明書之揭示係有關日本專利申請特願2009-07053 1號(2009年3月23日申請)中所含之主題,該等 申請說明書以全文參照之方式倂入本文供參考。 201038699 [發明效果] 依據本發明之一實施形態,可提供在B階段化中,在 廣溫度範圍內具有與晶片之良好接著強度同時亦可降低與 晶片間之孔隙,且即使在焊錫回焊步驟中加熱時亦具有充 分的晶片剪切強度之晶片接合用樹脂膏。又,依據本發明 之一實施形態,即使省略晶片貼附後之後硬化,於金屬線 接合及封裝步驟中亦不會產生缺陷,故可縮短製造步驟。 依據本發明之一實施形態之晶片接合用樹脂膏,由於 其低溫接著性優異,故可適當作爲晶片接合材而使用於有 機基板等之絕緣性支持基板。又,依據本發明之一實施形 態’藉由使用上述本發明之晶片接合用樹脂膏,可提供作 業丨生優異之半導體裝置之製造方法。再者,依據本發明之 一實施形態,藉由使用上述本發明之晶片接合用樹脂膏, 可提供信賴性優異之半導體裝置。 【實施方式】 以下’依據情況參考圖式對本發明之較佳實施形態加 以詳細說明。又,圖式中,相同或相當部份賦予相同符號 ’並省略重複說明。又,本發明中,所謂「B階段化」意 指晶片接合用樹脂膏塗佈後經熱處理使溶劑(D )揮發, 使經塗佈之晶片接合用樹脂膏成乾燥狀態,且於該狀態晶 片接合用樹脂膏未完全硬化。所謂完全硬化係定義爲以 DSC (不差掃描卡 g十’ Differential scaning calorimetry) 之測定中’在8 0〜1 8 0 °C (升溫速度:1 〇。<: /分鐘)之範圍 -10- 201038699 無吸熱峰之狀態,後文有時亦稱爲「後硬化」。 以下,對本發明更詳細加以說明。 本發明之晶片接合用樹脂膏(以下有時亦僅稱爲「樹 脂膏」)包含使具有羧基之丁二烯之聚合物(al)與具有 環氧基之化合物(a2)反應而得之聚合物(A)、熱硬化 性樹脂(B )以及塡料(C )。 〇 [具有羧基之丁二烯之聚合物(al )] 作爲具有羧基之丁二烯之聚合物(以下有時簡稱爲成 分(al)),只要是具有丁二烯構造及羧基則並未特別限 制。例如,可爲由丁二烯衍生之丁二烯構造與具有羧基之 化合物之共聚物。又,亦可爲以丁二烯與丙烯腈等之其他 聚合性化合物之共聚物作爲主鏈,於其末端之至少一端具 有羧基者。由印刷性、接著強度及作業性之觀點觀之,成 分(al)之數平均分子量較好爲 500~1 0000,更好爲 〇 100〇〜7000。本發明中,前述成分(al)更好爲以下述通 式(1)表示之具有羧基之丁二烯-丙烯腈共聚物。 [化1] HOOC- -fCH2-CH=CH-CH2)^(CH2-CH-}
-COOH (l)
CN
[通式(1)中,x/y爲95/5〜50/50,η爲5〜50之整數]。 以上述通式(1 )表示之化合物亦可以市售品獲得。 以前述通式(1)表示之具有羧基之丁二烯-丙烯腈共 聚物例如可以 Hycar CTBN-2009xl62、CTBN-1300x31、 -11 - 201038699 CTBN-l 3 00 x 8 ' CTBN- 1 3 00x 1 3 ' CTBNX- 1 3 00 x 9 (均爲宇 部興產股份有限公司製)之市售品獲得。又本發明中之較 佳成分(a 1)之例,舉例有爲具有羧基之低分子量液狀聚 丁二烯的NISSO-PB-C-2000 (日本曹達股份有限公司製, 商品名)(日本曹達(股)製,商品名)等。 該等可單獨使用或組合兩種以上使用。 [具有環氧基之化合物(a2 )] 作爲具有環氧基之化合物(以下有時簡稱爲(a2 )成 分)並無特別限制,但可舉例爲例如乙二醇二縮水甘油醚 、二乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、二丙二 醇二縮水甘油醚、甘油三縮水甘油醚等之縮水甘油醚型環 氧化合物;二聚酸等之以多元羧酸與其酸酐作爲原料之縮 水甘油酯型環氧化合物;以脂肪族胺作爲原料之縮水甘油 基胺型環氧化合物等之脂肪族環氧化合物;由氫醌、甲基 氫醌、二甲基氫醌、三甲基氫醌、間苯二酚、甲基間苯二 酚、兒茶酚、甲基兒茶酚、二酚、四甲基二酚、二羥基萘 、二羥基甲基萘、二羥基二甲基萘、雙(4-羥基苯基)酮 、雙(4-羥基-3,5_二甲基苯基)酮、雙(4_羥基-3,5-二氯 苯基)酮、雙(4-羥基苯基)颯、雙(4-羥基-3,5-二甲基 苯基)楓、雙(4_羥基-3,5-二氯苯基)颯、雙(4-羥基苯 基)六氟丙烷、雙(4-羥基-3,5-二甲基苯基)六氟丙烷、 雙(4-羥基-3,5-二氯苯基)六氟丙烷、雙(4-羥基苯基) 二甲基矽烷、雙([羥基-3,5_二甲基苯基)二甲基矽烷、 12- 201038699 雙(4-羥基-3,5-二氯苯基)二甲基矽烷、雙(4-羥基苯基 )甲烷、雙(4 -羥基_3,5_二氯苯基)甲烷、雙(4_羥基_ 3,5 -二溴苯基)甲烷、2,2 -雙(4 -羥基苯基)丙烷、2,2 -雙 (4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二 氯苯基)丙烷、2,2 -雙(4_羥基_3_甲基苯基)丙烷' 2,2_ 雙(4 -羥基-3-氯苯基)丙烷、雙-羥基苯基)醚、雙( 4 -羥基-3,5 -二甲基苯基)醚、雙(4_羥基-3, 5 -二氯苯基) 〇 醚、9,9·雙(4_羥基苯基)蕗、9,9-雙(4-羥基-3-甲基苯 基)莽、9,9·雙(4-羥基-3_氯苯基)蒹、9,9·雙(4-羥基_ 3-溴苯基)莽、9,9 -雙(4 -羥基-3-氟苯基)莽、9,9 -雙( 4_羥基-3-甲氧基苯基)莽、9,9_雙(4_羥基-3,5_二甲基苯 基)荛、9,9-雙(4-羥基_3,5_二氯苯基)葬、9,9-雙(4-經基-3,5 -二溴苯基)蒔等之1種以上與環氧鹵丙烷縮合所 得之二縮水甘油基化合物等之具有芳香環之環氧化合物等 之1分子內具有2個環氧基之化合物。 〇 又’亦可使用酚之縮水甘油醚型之環氧樹脂。作爲此 等樹脂,舉例有雙酚A、雙酚AD、雙酚S、雙酚F或鹵 化雙酚A與環氧氯丙烷之縮合物、酚類酚醛樹脂之縮水 甘油醚、甲酚酚醛樹脂之縮水甘油醚、雙酚A酚醛樹脂 之縮水甘油醚等。該等可單獨或組合兩種以上使用。該等 環氧化合物中’由樹脂強度之觀點而言,最好爲以下述通 式(2)表示之環氧化合物。 201038699 [化2]
;R1及R2各獨立爲氫原子、碳數1〜6之烷基或鹵素原子 ;m及η各獨立表不1〜4之整數;又,η爲2以上時,複 數個存在之R1可爲相同亦可相異’《^爲2以上時,複數 個存在之R2可爲相同亦可相異]。 該等具有環氧基之化合物可單獨或組合兩種以上使用 [聚合物(A )] 聚合物(A)係由成分(al)及成分(a2)反應獲得 。此時之配合比,相對於成分(a 1 )之1羧酸當量,成分 (a2 )之環氧當量,若考慮接著強度則爲0.01以上,若 考慮因逸出氣體產生而引起剝離困難則較好爲1 〇以下, 更好爲〇,1〜2,最好爲0.25〜1。 聚合物(A)之黏度,可藉由合成時之反應溫度及反 應溫度而調整,藉提高反應溫度或增長反應時間,成爲黏 度變高之傾向。聚合物(A)之較佳黏度,由可提高接著 強度之觀點而言,爲150 Pa. s以上,更好爲300〜900 Pa -14- 201038699 .S ’最好爲500〜700 Pa . s。尤其以較佳之材料比,使具 有羧基之丁二烯之均聚物或共聚物與具有環氧基之化合物 反應,進而黏度設爲300 pa. s以上時,就可更提高成爲 樹脂膏時之接著強度之觀點而言爲較佳,爲900 Pa. s以 下時成爲樹脂膏時之作業性變良好。 聚合物(A)之重量平均分子量較好爲5000以上, 更好爲15000〜70000,最好爲17000〜40000。重量平均分 0 子量若爲5000以上,則接著強度更優異,若小於70000 ,則成爲樹脂膏時之作業性可更提高。 又,重量平均分子量(Mw)及數平均分子量(Μη) 可藉由凝膠滲透層析儀(GPC )測定(使用標準聚苯乙烯 由校正線換算)。 又,聚合物(A )之酸價較好爲1 〇〜25 mg KOH/g,更 好爲 15〜23 mg KOH/g。 酸價若爲10〜25 mg KOH/g,則成爲樹脂膏時之作業 〇 性可更提高。 上述聚合物(A)之酸價可由以下方法測定。首先, 精秤約1 g之聚合物(A )之樹脂溶液後,於該樹脂溶液 中添加丙酮3 0 g,使樹脂溶液均一溶解。接著,於該溶液 中適量添加作爲指示劑之酚酞,使用0.1N之KOH水溶液 進行滴定。接著,由滴定結果以下式(3)算出酸價。 A= 1〇xVfx56. 1 / (W p x I ).....(3) -15- 201038699 又’式(3)中’ a表示酸價(mg KOH/g) ,Vf表示 酣献之滴定量(mL) ’ Wp表示聚合物(A )之樹脂溶液 重量(g ) ’ 1表示聚合物(A )之樹脂溶液之不揮發份比 例(質量% )。 (A )成分之含有率,就基板與晶片間之應力緩和性 以及接著強度之觀點而言,於(A)成分及(B)成分之 總量中,較好爲5〇〜9ξ)重量%,更好爲75~97重量%,最 好爲80~95重量%。 [熱硬化性樹脂(B )] 作爲熱硬化性樹脂(B ),並無特別限定,舉例有例 如環氧樹脂、酚樹脂、1分子中具有至少2個熱硬化性醯 亞胺基之醯亞胺化合物等。該等可單獨使用1種或組合2 種以上使用。 前述環氧樹脂爲分子內至少具有2個環氧基者,由加 熱時晶片剪切強度之觀點觀之,較好爲酚之縮水甘油醚型 之環氧樹脂。作爲該等樹脂,舉例有雙酚A、雙酚AD、 雙酚S、雙酚F或鹵化雙酚A與環氧氯丙烷之縮合物,酚 型酚醛樹脂之縮水甘油醚、甲酚酚醛樹脂之縮水甘油醚、 雙酚A酚醛樹脂之縮水甘油醚等。該等可單獨使用1種 或組合2種以上使用。 使用環氧樹脂時之含有量’由加熱時晶片剪切強度之 觀點觀之,對於聚合物(A) 100重量份較好爲1〜100質 量份’更好爲2〜50質量份’最好爲3〜20質量份。 -16- 201038699 前述酣樹脂爲分子中具有至少兩個酣性經基者,舉例 爲例如酚型酚醛樹脂、甲酚酚醛樹脂、雙酚A型酣醒樹 月旨 '聚-對-乙烯基酚、酚醇酸樹脂等。該等可單獨使用1 種或組合2種以上使用。 使用前述酚樹脂時之含有量,若考慮加熱時晶片剪切 強度以及半導體封裝信賴性,則相對於聚合物(A ) 1 0 0 重量份’較好爲0·5~100質量份,更好爲uo質量份, 最好爲2~20質量份。 就可提高半導體封裝信賴性之觀點而言,較好倂用環 氧樹脂與酚樹脂。 至於前述1分子中具有至少2個熱硬化性醯亞胺基之 醯亞胺化合物,舉例有例如鄰-雙馬來醯亞胺苯、間-雙馬 來醯亞胺苯 '對-雙馬來酿亞胺苯、1,4_雙(對-馬來酸亞 胺對-異丙基苯基)苯、1,4 -雙(間-馬來醯亞胺對—異丙基 苯基)苯等。該等可單獨使用1種或組合2種以上使用。 〇 再者’亦較好使用以下述式(I)〜(III)表示之醯亞 胺化合物等。 -17- 201038699 [化3]
[式中,X,或 Y 表示 0、CH2、CF2' S〇2、s、CO、c( CH3) 2 或 C ( CF3) 2 ; Rl、Κ·2、R3、R4、R5、R6、R7 及 各獨立表示氫、低級院基、低級院氧基、氟、氣或溴 ;D表示具有乙烯性不飽和雙鍵之二羧酸殘基;m’表示 0〜4之整數]。 使用醯亞胺化合物時之含有量’若考慮樹脂膏之保存 安定性,則相對於聚合物(A ) 1 00重量份’更好爲小於 1 0 0重量份。 作爲式(I )之醯亞胺化合物’舉例有例如4,4 -雙馬 來醯亞胺二苯基醚、4,4 -雙馬來醯亞胺二苯基甲烷、4,4-雙馬來醯亞胺_3,3,_二甲基-二苯基甲院、4,4·雙馬來醯亞 胺二苯基碾、4,4·雙馬來醯亞胺二苯基亞颯、4,4-雙馬來 醯亞胺二苯基酮、2,2’ -雙(4 -馬來醯亞胺苯基)丙烷、 4,4 -雙馬來醯亞胺二苯基氟甲烷、丨,1,1,3, 3,3·六氟-2,2 -雙 -18- 201038699 (4-馬來醯亞胺苯基)丙烷等。 作爲式(II )之醯亞胺化合物舉例有例如雙[4- ( 馬 來醯亞胺苯氧基)苯基]醚、雙[4_( 4-馬來醯亞胺苯氧基 )苯基]甲烷、雙[4-(4-馬來醯亞胺苯氧基)苯基]氟甲烷 、雙[4- (4-馬來醯亞胺苯氧基)苯基]颯、雙[4_ (3-馬來 醯亞胺苯氧基)苯基]颯、雙[4- ( 4-馬來醯亞胺苯氧基) 苯基]硫醚、雙[4- (4 -馬來醯亞胺苯氧基)苯基]酮、2,2-0 雙[4- (4-馬來醯亞胺苯氧基)苯基]丙烷、1,1,1,3,3,3·六 氟-2,2-雙[4- (4-馬來醯亞胺苯氧基)苯基]丙烷等。 爲促進該等醯亞胺化合物之硬化’亦可使用自由基聚 合劑。作爲自由基聚合劑’舉例有乙醯基環己基磺基過氧 化物、異丁醯過氧化物、苯甲醯基過氧化物、辛醯基過氧 化物、乙醯基過氧化物、二異丙苯基過氧化物、異丙苹過 氧化氫、偶氮雙異丁腈等。使用自由基聚合劑時之含有量 ,相對於醯亞胺化合物1 〇 〇重量份,較好爲0 _01 ~1.0重 Q 量%。 (B)成分的熱硬化性樹脂之含有量’於B階段化在 較高溫進行時,由在隨後之晶片加熱壓著時提高晶片接合 層之濡濕展開之觀點而言,相對於上述成分(A ) 1 00質 量份,較好爲1〜100質量份,更好爲3~30質量份’最好 爲5〜20質量份。 [塡料(C )] 作爲塡料(C ),舉例有例如銀粉、金粉、銅粉等之 -19- 201038699 導電性塡料;氧化砂、氧化鋁、氧化 陶瓷等之無機物質塡料等,但不限定 單獨使用1種或可組合2種以上使用 塡料(C)中,銀粉 '金粉、銅 提闻晶片接合材料之導電性、傳熱性 。又,氧化矽、氧化鋁、氧化鈦、玻 之無機物質塡料可提高晶片接合材料 濕率及觸變性。 該等中’由半導體封裝之信賴性 最好爲氧化砂。 塡料(C ),若考慮半導體封裝 均粒徑爲 Ο.ΟΟΙμπι〜ΙΟμτη,更好爲 0.0 1 〜1 μτη。 作爲提高半導體裝置之電性信賴 添加無機離子交換體。作爲無機離子 化物於熱水中進行萃取時,可有效判 所萃取出之離子例如Na+、K+、C1—、 子之作用者。作爲該等離子交換體其 出之沸石、沸石類、酸性白土、白雲 然礦物;人工合成之合成沸石等。 該等導電性塡料或無機物質塡料 而使用。在不損及物性之範圍內,亦 料之1種以上及無機物質塡料之1種 塡料(c )之含有量,相對於上; 鈦、玻璃、氧化鐵、 於上述之例。該等可 〇 粉等之導電性塡料可 以及樹脂膏之觸變性 璃、氧化鐵、陶瓷等 之低熱膨脹性、低吸 之觀點而言,大致上 信賴性,則較好爲平 0.005μηι〜5μιη,最好 丨性之塡料(C )亦可 交換體,於樹脂膏硬 定具有捕捉水溶液中 F·、RCOO·、Βγ·等離 例舉例有例如天然產 石、水滑石類等之天 亦可各混合2種以上 可混合使用導電性塡 以上。 並聚合物(A ) 1 0 〇質 -20- 201038699 量份,若考慮樹脂膏之觸變指數(1 .5以上), 1重量份以上,若考慮接著強度、硬化物之彈性 接合材料之應力緩和能以及半導體裝置之安裝信 較好爲100質量份以下。更好爲2〜50質量份 3〜3 〇質量份。又,於b階段化在較低溫進行時 制隨後之晶片加熱壓著時之晶片接合層之濡濕展 而言’較好爲1 0質量份以上。 〇 塡料(c )之混合、混練係適宜地組合一般 、擂潰機、三輥混合機、球磨機等之分散機。 [溶劑(D )] 本發明之樹脂膏亦可含有溶劑(D )。溶齊! 好自可均一混練或分散塡料之有機溶劑中加以選 到印刷時防止有機溶劑之揮發發散以及B階段化 性’較好選擇沸點(大氣壓)爲1 00。(:以上且小 〇 之有機溶劑。 作爲該等有機溶劑,舉例有N -甲基-2 - Π比略 乙二醇二甲醚(亦稱爲二甘醇二甲醚)、三乙二 (亦稱爲三甘醇二甲醚)、二乙二醇二乙醚、2-基乙氧基)乙醇、丁內酯、異佛爾酮、卡必 醇乙酸酯、1,3-二甲基-2-咪唑啶酮、乙酸2- (2-氧基)乙酯、乙基溶纖劑、乙基溶纖劑乙酸酯、 劑、二噁烷、環己酮、苯甲醚 '以石油蒸餾物爲 劑等。該等可單獨使用1種或可組合2種以上使 則較好爲 率、晶片 賴性,則 *最好爲 ,由可抑 開之觀點 之攪拌機 1 ( D )較 擇。考慮 時之乾燥 於 2 5 0 〇C 啶酮、二 醇二甲醚 • ( 2-甲氧 醇、卡必 丁氧基乙 丁基溶纖 主體之溶 用。 -21 - 201038699 該等溶劑中,由吸水性低之觀點而言’最好爲卡必醇 乙酸酯。 使用溶劑(D )時之含有量’由印刷性之觀點而言’ 相對於聚合物(A) 100質量份,較好爲5~2〇〇質量份’ 更好爲10〜100質量份,最好爲30~80質量份。 又’樹脂膏於不使用溶劑(D )時’可省略B階段化 之步驟。未使用溶劑(D)時,由印刷性之觀點觀之’熱 硬化性樹脂(B )較好於常溫下爲液狀。 [硬化促進劑(E)] 本發明之樹脂膏較好含有硬化促進劑(E )。硬化促 進劑(E )可促進熱硬化性樹脂(B )之硬化。尤其使用 環氧樹脂作爲熱硬化性樹脂(B )時特別有效° 作爲硬化促進劑(E ),舉例有例如咪哩類、二氰基 二醯胺衍生物、二羧酸二醯肼、三苯膦、四苯基錢四苯基 硼酸鹽、2 -乙基-4-甲基咪唑四苯基硼酸酯、丨,8·二氮雜雙 環(5,4,0) Η——碳烯-7 -四苯基硼酸酯等。該等可單獨使 用1種或可組合2種以上使用。 使用硬化促進劑(Ε )時之含有量’相對於熱硬化性 樹脂(Β ) 1 0 0質量份,較好爲0.0 1質量份’若考慮樹脂 膏之保存安定性則較好爲20質量份以下。更好爲0·1〜10 重量份,最好爲0.5〜5重量份。 [其他成分] -22 - 201038699 進而於本發明之樹脂膏中’依據需要可添加消泡劑、 破泡劑、抑泡劑、矽烷系偶合劑、鈦系偶合劑、非離子系 界面活性劑、氟系界面活性劑、聚矽氧系可塑劑等之各種 添加劑。 上述各成分可使用例如高速分散機等混練機,以葉片 1 Orpra混合.攪拌1 〇分鐘,獲得樹脂膏。 樹脂膏硬化後(於1 8 0 °C下1小時,以厚度1 〇 〇 μ m硬 0 化時)之彈性率,亦即樹脂膏硬化物之彈性率,若考慮基 板與晶片不易偏離以及組裝作業,較好爲1 MP a以上,若 考慮基板與晶片間之應力緩和性及半導體封裝之耐溫度循 環性,較好爲300MPa以下。 上述彈性率爲以動態黏彈性測定裝置測定乾燥硬化後 之樹脂膏硬化物之儲存彈性率E ’時成爲2 5 °C之値。所謂 「乾燥硬化後」意指使樹脂成分完全硬化後者,例如,塗 佈樹脂膏且經B階段化後以乾燥機等在1 80°C加熱1小時 〇 再者,樹脂膏之固體成分濃度較好爲20〜95重量%, 更好爲40〜90重量%以上,最好爲60〜80重量%。上述固 體成分若爲20重量%以上,基於樹脂膏乾燥後之體積減 少之形狀變化抑制之觀點而§爲較佳’若爲95重量%以 下,則可提高樹脂膏之流動性與印刷作業性。 樹脂膏之觸變性指數較好爲1.5〜10.0,更好爲 2.0〜7.0,最好爲3.0〜5.0。樹脂膏之觸變性指數爲1.5以 上時’就抑制以印刷法供給•塗佈樹脂膏塌邊等之發生, -23- 201038699 且良好地保有印刷形狀之觀點而言爲較佳。再者,若該觸 變指數爲1 0 · 0以下,就抑制以印刷法供給.塗佈樹脂膏 時之「碎片」或留白等之發生之觀點而言爲較佳。 樹月曰霄之黏度(25C )較好爲5〜1000 Pa· s,更好爲 20~5 00 Pa · s,最好爲50〜200 pa · s。樹脂膏之黏度爲 5〜1 000 Pa · s時’就印刷性之觀點而言爲較佳。樹脂膏之 黏度較好依據印刷法之種類適當調整,例如,如絲網網版 等之在遮罩開口部張開網目時’考慮網目部份之透過性, 較好在5〜100 Pa . s之範圍,刻花模版等時較好調整爲 20~500 Pa · s之範圍。又,於B階段化之晶片接合層中 見到多數殘存之孔隙時,較好調整成1 5 〇 P a · s以下之黏 度。 上述黏度係使用E型旋轉黏度計,在251,以轉數 0.5rpm測定時之値。觸變指數定義爲以e型旋轉黏度計 ’在2 5 °C以轉數0.5 r p m測定時之値,與以轉數5 r p m測 定時之値之比(觸變指數=(於0.5rpm之黏度)/(於 5rpm之黏度))。 [半導體裝置(半導體封裝)之製造] 以下針對半導體裝置之製造方法加以說明。 圖1爲顯示半導體裝置之製造步驟之一例之示意圖。 首先,將本發明之樹脂膏印刷於被印刷體上。作爲被 印刷體列舉爲42合金導線框架或銅導線框架等導線框架 :或聚醯亞胺樹脂、環氧樹脂、聚醯亞胺系樹脂等之塑膠 -24- 201038699 膜;進而爲於玻璃不織布等之基材中含浸·硬化聚醯亞胺 樹脂、環氧樹脂、聚醯亞胺系樹脂等之塑膠而成者;或者 氧化鋁等之陶瓷製等之絕緣性支撐基板。印刷方法列舉爲 例如網版印刷法。具體而言亦可如圖1 ( a )所示,使用 刮板1 03 ’透過金屬遮罩1 02,於基板1 01上塗佈本發明 之樹脂膏104而成。 接著,使塗佈之樹脂膏經熱處理使溶劑乾燥(B階段 ¢) 化),獲得B階段化之晶片接合層(圖1(b))。據此 ,獲得形成有B階段化狀態之樹脂膏之層(以下稱爲晶片 接合層)之支撐基板。B階段化之溫度較好爲1 〇 〇〜2 0 0 °C ’更好爲12〇〜180°C。B階段化之時間,就作業效率之觀 點而言’較好爲1 20分鐘以下,使用溶劑(D )時就提高 揮發率之觀點而言,較好爲5分鐘以上。又,B階段化之 條件就防止晶片接合層龜裂之觀點而言,較好使自室溫之 升溫及朝室溫之降溫步驟在10分鐘以上緩緩加熱、降溫
G 接著,於形成該晶片接合層之支撐基板上貼附I c、 LSI等半導體元件(晶片)’並加熱將晶片壓著在支撐基 板上。如圖1(c)所示,亦可在載置於熱源106上之晶 片1 〇 7上貼附基板之晶片接合層側。加熱溫度在使用有機 基板等時’就有機基板之耐熱性觀點而言較好爲20(TC以 下,就接著強度之觀點而言較好爲100〜200。〇。 接著,於使晶片接合層後硬化之步驟,獲得硬化狀態 之晶片接合層1 08,將晶片搭載於支撐基板上(圖d ) -25- 201038699 )。晶片接合層之後硬化,在無安裝組裝步驟的問題時亦 可與封裝材之後硬化步驟時一起進行。此處所謂安裝組裝 步驟的問題係指晶片與基板等之固定不充分時,在金屬線 接合步驟之際,晶片振動而於金屬線接合產生缺陷,或者 由於封裝步驟之際晶片在基板上之固定不足,因封裝材自 晶片側面流動而造成晶片剝離。 接著,亦可以金屬線1 09將基板與晶片電性連接(圖 1 ( e ) ) ° 接著,亦可將搭載晶片之基板配置於模具內,利用擠 出機1 1 1將封裝材1 1 2塡充於模具1 1 0內並進行封裝(圖 1 ( f) ) ° 本發明之半導體裝置之製造方法亦可包含以上各步驟 ’本發明之半導體裝置可利用包含以上各步驟之製造方法 製造。 圖2爲顯示本發明之半導體裝置之一實施形態的 BOC型半導體裝置之構造之示意剖面圖。B0C型半導體 裝置100具有下述構造:在中央部設有窗之基板2之一面 上,透過晶片接合層4搭載半導體元件6,在基板2之與 半導體元件搭載面相反之面上形成配線圖型8、絕緣層χ 〇 及焊錫球1 2,藉由金屬線1 4連接半導體元件2之端子部 (未圖示)與配線圖型8,且進一步藉由樹脂等封裝材16 至少封裝其連接部。本發明之樹脂膏在加熱1C、LSI等半 導體元件(晶片)並貼附之步驟中,由於可於100〜200。(: 接合,故特別適用於使用有機基板之BOC型半導體裝置 -26- 201038699 之製造。然而,本發明之樹脂膏並不限於BOC型半導體 裝置之製造,亦可適當地使用於具有其他構成之半導體裝 置(例如’圖3所示之導線框架型半導體裝置)之製造中 〇 圖3之導線框架型半導體裝置中,矽晶片201係利用 樹脂膏202固定於導線框架203上,矽晶片上之A1焊墊 204與導線框架上之Ag鍍層2〇5係藉由金線206予以電 0 性連接。 藉由封裝樹脂2 07對該等進行封裝時,對突出至外部 之導線框架之端部施加外部鍍層2 0 8。 上述樹脂膏雖含有溶劑,但使用於半導體裝置之製造 方法之際,由於乾燥步驟中藉由B階段化溶劑大部分已揮 發,故於晶片接合層中之孔隙少,可組裝具有良好安裝信 賴性之半導體裝置。 另一方面,利用印刷法塗佈樹脂膏之後,只要對半導 〇 體封裝之信賴性不產生影響,則亦可不經B階段化而貼附 半導體元件(晶片),隨後,加熱,將晶片接合於支撐基 板上。進而亦可省略封裝劑之硬化步驟。再者亦可省略B 階段化與封裝劑之硬化步驟二者。 因此,另一本發明之半導體裝置之製造方法爲包含在 基板上塗佈特定量之上述樹脂膏,於樹脂膏上搭載晶片, 使樹脂膏中之樹脂硬化之各步驟,另一本發明之半導體裝 置係利用包含以上各步驟之製造方法製造者。 -27- 201038699 實施例 以下,藉由實施例更具體說明本發明。 (合成例1 ) 秤取100重量份之作爲成分(al)之CTBNX- 1300X9 (宇部興產股份有限公司製造,含有羧基之丙烯腈聚丁二 烯共聚物之商品名,丙烯腈含量約爲1 7重量% )及1 0重 量份之作爲成分(a2 )之EXA-83 0CRP ( DIC股份有限公 司製造’通式(2)中X爲-CHz-'R1及R2爲氫原子,η 及m爲4之雙酚F型環氧化合物),並添加於燒瓶中。 在145°C下邊加熱該等(羧酸當量:環氧當量=1: 1)邊 攪拌1小時,獲得作爲聚合物(A )之樹脂A。黏度爲 450 Pa· s。重量平均分子量(Mw)爲25000。 (合成例2 ) 除將攪拌時間自1小時變更爲3 0分鐘以外,餘如合 成例1般,獲得樹脂B。黏度爲l88Pa . s。重量平均分子 量(Mw )爲 1 70〇〇。 (合成例3 ) 除將攪拌時間自1小時變更爲1小時4 5分鐘以外’ 餘如合成例1般,獲得樹脂C。黏度爲962 Pa· s。重量 平均分子量(Mw)爲37000。 -28- 201038699 (合成例4 ) 除將成分(a2)之EXA-830CRP之量自ι〇重量份變 更爲2 · 5重量份以外,餘如實施例1般,獲得樹脂〇 (羧 酸當量:環氧當量=1: 0.25)。黏度爲212 Pa· s。重量 平均分子量(Mw)爲1 8700 ° (合成例5) Ο 除將成分(a2)之EXA-83 0CRP之量自10重量份變 更爲1 〇〇重量份以外,餘如實施例1般,獲得樹脂E (羧 酸當量:環氧當量=1: 1〇)。黏度爲472 Pa· s。重量平 均分子量(Mw )爲23 500。 (合成例6 ) 除將成分(a2)自10重量份之EXA-830CRP變更爲 10重量份之R171〇(雙酚AD型’三井化學股份有限公司 〇 製造)以外,餘如實施例1般’獲得樹脂F (羧酸當量: 環氧當量=1: 1)。黏度爲412 Pa. S。重量平均分子量( Mw)爲 25000。 黏度之測定方法如下。 以東機產業股份有限公司製造之E型黏度劑,使用直 徑19.4mm,3 °角錐,測定於 25 °C之樹脂膏之黏度( 0.5 rpm )。 分子量之測定方法係使用GPC,以下列條件測定。 機種:日立 L6000 -29- 201038699
檢測器··日立 L-3 300 RI
數據處理機:ATT
管柱:Gelpack GL-R440+ Gelpack GL-R450+ Gelpack GL-R400M 管柱尺寸:10.7mm<i)x300mm
溶劑:T H F 試料濃度:120mg/5ml 注入量:200μ1 壓力:3 4kgf/cm2 流量:2.05ml/min (實施例1 ) 秤取80重量份之作爲聚合物(A )(基底樹脂)之 樹脂A,且將其倒入混練機中。於其中加入以40重量份 之溶劑(D )的卡必醇乙酸酯(C A )溶解4.7重量份之作 爲熱硬化樹脂(B )之環氧樹脂(商品名:YDCN-700-7, 東都化成股份有限公司製造)及3 · 3重量份之酚樹脂(商 品名:TrisP-PA-MF,本洲化學工業股份有限公司製造) 而成之溶液(熱硬化性樹脂之固體成分濃度約爲40重量 % ),及0.12重量份之硬化促進劑(商品名:TPPK,東 京化成工業股份有限公司製造),並經混合。接著,添加 I 5重量份之作爲塡料(C )之氧化矽微粉末(商品名: Aerosil#50,日本AEROSIL股份有限公司製造),接著添 加1 1.4重量份之卡必醇以酸酯(CA ) ’且攪拌•混練1 -30- 201038699 小時,獲得樹脂膏。實施例1獲得之樹脂膏之固體成分濃 度、黏度及觸變係數示於表2。 (實施例2〜7、比較例1 ) 除如表1所示替換基底樹脂、硬化促進劑、塡料之種 類及含量以外,餘如實施例1般獲得樹脂膏。實施例2~7 及比較例1中獲得之樹脂膏之固體成分濃度、黏度及觸變 0 係數示於表2。 [接著強度] 以1 0 0 μ m厚度將實施例1〜7及比較例1之樹脂膏印 刷於42合金導線框架上。接著,將B階段化溫度設定成 1 3 5 °C進行B階段化。B階段化之條件爲以熱風乾燥機自 40 °C於30分鐘內升溫至135 °C,在135 °C乾燥30分鐘後 ,於3 0分鐘內自1 3 5 °C降溫至4 0 °C ’藉此形成B階段化 Q 狀態之塗膜(晶片接合層)。隨後’在14(TC之熱盤上施 力口 5kg之荷重,將5x5mm之矽晶片(厚度0.5mm)壓著 於晶片接合層上1秒鐘。使用自動接著力試驗機(商品名 ·- serie-4000,Dage公司製造)測定其在180C之剪切斷 裂強度(kgf/晶片)。 又,在將B階段化之設定溫度變更成l4〇°C、Id 、1 5 0 °C、1 5 5 °c、1 6 0 °c、1 6 5 °C 及 1 7 0 °C 之條件,分別對 實施例1〜7及比較例1之樹脂膏測定於1 80 t:之剪切斷裂 強度(kgf/晶片)。結果示於表3。 -31 - 201038699 [孔隙] 以3mmxl〇mm、厚度ΙΟΟμηι將實施例1~7及比較例1 之樹脂膏印刷於42合金導線框架上。接著,將Β階段化 溫度設定成1 3 5 t進行Β階段化。Β階段化之條件爲以熱 風乾燥機於3 0分鐘內自4 0 °C升溫至1 3 5 °C,在1 3 5 °C乾 燥30分鐘後,於30分鐘內自135°C降溫至40°C,藉此形 成B階段化狀態之塗膜(晶片接合層)。隨後,在140°C 之熱盤上施加5kg之荷重,將透明玻璃板壓著於晶片接合 層上1秒鐘。使之在18〇°C、4MPa下90秒之條件加熱壓 著,且以下列基準目視評價孔隙。 又,在將B階段化之設定溫度變更成140°C、145°C 、1 5 0 °C、1 5 5 °C、1 6 0 °C、1 6 5 °C 及 1 7 0 °C 之條件下,亦分 別對實施例1〜7及比較例1之樹脂膏,以目視同樣地評價 孔隙。結果示於表3。 A :對於晶片接合層與玻璃基板之接著面積,孔隙之 面積小於5 % B :對於晶片接合層與玻璃基板之接著面積,孔隙之 面積爲5%以上 [B階段化溫度裕度] 於接著強度爲O.IMPa以上,且孔隙之評價成爲[A]之 B階段化溫度範圍設爲B階段化之溫度裕度。結果示於表 3。B階段化溫度裕度較大意指較佳。 -32- 201038699 通常,若接著強度爲o.l MPa以上,則即使是省略後 硬化之步驟以後之組裝步驟,亦即金屬線接合及封裝亦係 可能。 [2 5 0 °C之加熱時晶片剪切強度] 以1 0 0μιη厚度於42合金導線框架上印刷樹脂膏,以 熱風乾燥機於30分鐘內自40°C升溫至160°C,在160°C 0 乾燥30分鐘後’於30分鐘內自I60t:降溫至40°C,藉此 乾燥,形成B階段化狀態之塗膜(晶片接合層)。隨後, 在14(TC之熱盤上施加5kg之荷重,將5x 5mm之矽晶片 (厚度0.5mm )壓著於晶片接合層上1秒鐘。接著,以 1 8 0°C之熱風乾燥機加熱60分鐘,進行後硬化。使用自動 接著力試驗機(商品名:serie-4000,Dage公司製造)測 定其在250°C之剪切斷裂強度(kgf/晶片),設爲25〇°C 下之加熱時晶片剪切強度。 〇 結果示於表3。 [耐回焊性評價] 使用印刷機與金屬遮罩(遮罩形狀9.〇χ4.〇χ12〇μπιχ2 處),將實施例1〜7及比較例1之樹脂膏分別印刷於塗佈 有焊錫光阻劑(商品名:AUS-3 08,太陽油墨製造(股) 公司製造)之有機基板上。接著,對分別印刷有實施例 1〜7及比較例1之樹脂膏之各有機基板,藉由熱風乾燥機 在3 0分鐘內自40°C升溫至Β階段化溫度裕度之最下限激 -33- 201038699 度(例如,實施例1之樹脂膏爲155 °c ),且在B階段化 溫度裕度之最下限溫度保持30分鐘,隨後在30分鐘內降 溫至40°C藉此進行乾燥,形成B階段化狀態之塗膜(晶 片接合層)。接著,使用曰立製作所製造之晶片安裝機( CM-110),在140°C之熱盤上施加6kg之荷重,將貼附熱 氧化膜之矽晶片(8.8mmx8.8mmx280umt)壓著在晶片接 合層上1秒鐘,製作成評價用封裝基板。所得各評價用封 裝基板,使用轉移成形機(藤和精機製造之轉移壓印機) 進行封裝(封裝劑;商品名:CEL-9240HF-SI (日立化成 工業(股)製造),封裝條件;模具溫度:1 80°C,壓力 :6.9MPa,成形時間:90秒)。隨後,在17 5 °C之熱風乾 燥機鐘加熱硬化封裝材 5 小時,獲得 10.lmmxl2_2mmxl.0mmt 之評價用 BOC 封裝。 所得評價用BOC封裝分別以85°C /85%RH/168小時, 及85%/60%RH/168小時之條件吸濕處理後,於使評價用 BOC封裝之最高表面溫度達到260°C之方式所設定之IR 回焊爐(TAMURA製造)中來回通過3次。接著,使用 超音波偵測影像裝置 (SAT : Scanning Automatic Tomograph,日立製作所製造HYE-FOCUS),對該評價用 B OC封裝以目視確認晶片接合層之剝離或氣泡之有無, 且以下列基準評價耐回焊性。結果示於表3。 等級 1 ;在 8 5 °C / 8 5 % R Η /1 6 8 小時及 8 5 °C / 6 0 % R Η / 1 6 8 小時之任一條件下均無晶片接合層之剝離或氣泡。 等級2 ;在8 5 °C / 6 0 % R Η /1 6 8小時之條件下,雖無晶 -34 - 201038699 片接合層之剝離或氣泡,但在8 5 °C /8 5 %RH/ 1 6 8小時之條 件下有晶片接合層之剝離或氣泡。 等級1意味著耐回焊性優於等級2。 〇
裊 -35- 201038699 【1谳: 比較例1 g 寸· m cn I 0.12 1 yn i 50.6 實施例7 m rn 0.12 » yn 50.3 實施例6 寸 m ΓΟ 0.12 1 r 52.5 丨實施例5 g 寸· m ro* ^ 0.12 1 i 51.2 丨實施例4 卜 寸 rn ^ 0.12 1 iTi 「 54.9 實施例3 § ^J· m m' 0.12 1 [ 50.8 實施例2 卜 m 1 0.12 in 53.2 實施例1 g 卜 — m 0.12 1 [ 51.4 材料 25000 17000 37000 18700 23500 25000 15000 YDCN-700-7 TrisP-PA TPPK 2P4MHZ AEROSIL 50 < u Mw 樹脂A 樹脂B 樹脂c 樹脂D 樹脂E 樹脂F CTBN-1003x9 1 基底樹脂 環氧樹脂 酚樹脂 1 硬化促進劑 塡料 匿 锲 成分 (A) 代替(A) /"N ω N' /-~s u (D) -36- 201038699
Τ—Μ § 卜 鎰 七 卜 辑 67.21 CN 00 CO IH m m 66.26 s r- cn u in (N 〇〇 in 辑 VO 觀 實施例4 65.26 $ 寸 c〇 m 〇 % 辑 U CN Os 00 >T) 辑 … v〇 {H » 嶙 辑 vd v〇 Γ〇 到 t 成份濃度 (%) 度 '25°c ) 额 am 4V» ΰΐπ πχ» *S w 親 m 画 cd On 避 W- -37 201038699 表1中,各種記號意指下述。 YDCN-700-7:東都化成股份有限公司, 環氧樹脂(環氧當量:1 97-207g/eq)
TrisP-PA :本州化學工業股份有限公司, 雙(4_羥基苯基)乙基]-α,α-二甲基苄基]苯酚 ΤΡΡΚ :東京化成工業股份有限公司,四 基硼酸鹽 2Ρ4ΜΗΖ :四國化成工業股份有限公司, 甲基-5 -羥基甲基咪唑) AEROSIL#50 :日本AEROSIL股份有限么 之微粉末,平均粒徑〇.〇3μη〇 CA :卡必醇乙酸酯 甲酚酚醛型 (4-[4-[l,i- ) 本基鱗四苯 (2-苯基-4-司(氧化矽 -38- 201038699
OD 【ε«】 比較例1 0.01 c 0.01 < 0.01 < 0.01 < 0.03 < 0.08 < 0.25 < 0.31 < i 165 〜170°C 1 ,4.10 銮 她 實施例7 1 0,01 < 0.01 < 0.03 < 0.05 < 0.26 < 0.34 < 0.37 < 0.41 < 155~170〇C 5.30 栅 實施例6 0.01 < 0.01 < 0.01 < 0.04 < 1 1 0.25 < 0.37 < 1- 0.35 < 0.38 < 155-170°C 5.20 銮 她 實施例5 0.01 < 1 0.01 < 0.01 < 0.03 < 0.20 < ! 0.29 < ! 0.33 < ! 0.38 < 155-170°C 1 4.40 1 她 實施例4 0.01 < 0.01 1 < 0.03 < 0.06 < 0.26 < 0.33 < 0.38 < 0.35 < 155-170°C 4.80 她 實施例3 | 0.01 < 0.01 < 0.01 < 0.03 < 0.17 < 0.30 < 0.33 < 0.38 < 155-170°C 5.10 她 實施例2 0.10 < 0.18 < 0.24 < I 0.31 < 1 0.27 < I 0.35 1 0.31 1 1 135-155〇C 5.30 銮 她 U 1 1 1 1 0.02 < 0.04 < 0.24 < 0.32 < 0.35 < 0.40 < | 155〜170°c | 5.40 等級1 評價項目 接著強度 (MPa) 孔隙 接著強度 (MPa) 孔隙 接著強度 (MPa) 孔隙 接著強度 (MPa) 孔隙 接著強度 (MPa) m 接著強度 (MPa) 孔隙 接著強度 (MPa) 丨接著強度 (MPa) 趣 4¾ il 伽 〇υ (N i狂 H「一 回 135〇C 140°C 145。。 150°C 155°C 160°C 165〇C 170°C 1 i 1 B階段化 溫度 CQ mg 盤 ii【-】 -39- 201038699 本發明之晶片接合用樹脂膏,於B階段化中,在廣的 溫度範圍與晶片之接著強度優異,同時晶片間之孔隙亦得 以減少,且即使於焊錫回焊步驟中加熱時之晶片剪切強度 及耐回焊性亦優異。 依據本發明,可提供一種可藉由印刷法容易地對於有 必要在較低溫度貼附半導體晶片之基板進行供給及塗佈之 晶片接合用樹脂膏。 應注意除已述及者以外,在不脫離本發明之新穎且有 利之特徵之範圍內,亦可對上述實施形態進行各種修正及 變更。因此’該等所有修正及變更均欲包含於隨附之申請 專利範圍內。 【圖式簡單說明】 圖1係顯示本發明之半導體裝置之製造步驟之一例的 圖。 圖2爲本發明之半導體裝置之一例的BOC之剖面圖 〇 圖3爲本發明之半導體裝置之一例的導線框架型半導 體裝置之一實施例的剖面圖。 【主要元件符號說明】 2 :基板 4 :晶片接合層 6 :半導體晶片 -40- 201038699 8 :配線圖型 1 〇 :絕緣層 1 2 :焊錫球 1 4 ·金屬線 1 6 :封裝材 100 :半導體裝置 1 〇 1 :基板 0 1 02 :金屬遮罩 103 :刮板 104 :晶片接合用樹脂膏 1 05 :晶片接合層(B階段化狀態) 1 〇 6 :熱源 1 〇 7 :晶片 1 08 :晶片接合層(完全硬化狀態) 1 〇 9 :金屬線 〇 110 :模具 1 1 1 :擠出機 1 1 2 :封裝材 2 0 1 :矽晶片 202 :晶片接合用樹脂膏 203 :導線框架 204 : A1 墊 205 : Ag鍍層 2 0 6 :金線 -41 - 201038699 2 0 7 :封裝樹脂 2 0 8 :外部鍍層 -42
Claims (1)
- 201038699 七、申請專利範圍: 1. 一種晶片接合用樹脂膏,其特徵 丁二烯之聚合物(al)與具有環氧基 而獲得之聚合物(A )、熱硬化性樹 〇 2.如申請專利範圍第1項之晶片 一步包含溶劑(D )。 0 3 ·如申請專利範圍第1項之晶片 一步包含硬化促進劑(E )。 4. 如申請專利範圍第1項之晶片 使前述具有羧基之丁二烯之聚合物( 化合物(a2 )反應而獲得之聚合物( 量爲 15,000〜70,000 。 5. —種半導體裝置之製造方法, 在基板上塗佈申請專利範圍第1至3 〇 合用樹脂膏之步驟,(2 )使前述樹月1 ,(3 )於經B階段化之前述樹脂膏 步驟。 6. —種半導體裝置,其特徵係利 項之半導體裝置之製造方法獲得。 7. —種半導體裝置之製造方法, 於基板上塗佈申請專利範圍第1至3 合用樹脂膏之步驟,(2)於前述樹 片之步驟,(3 )利用封裝劑封裝前 爲包含使具有羧基之 之化合物(a2 )反應 脂(B )及塡料(C ) •接合用樹脂膏,其進 接合用樹脂膏,其進 接合用樹脂膏,其中 al)與具有環氧基之 A)之重量平均分子 其特徵係包含(1 ) 項中任一項之晶片接 旨膏B階段化之步驟 上搭載半導體晶片之 用申請專利範圍第5 其特徵係包含(1 ) 項中任一項之晶片接 脂膏上搭載半導體晶 述半導體晶片之步驟 -43- 201038699 8 . —種半導體裝置,其特徵係利用申請專利範圍第7 項之半導體裝置之製造方法獲得。 -44 -
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TWI689016B (zh) * | 2016-08-22 | 2020-03-21 | 日商千住金屬工業股份有限公司 | 金屬燒結接合體、及晶片接合方法 |
TWI830901B (zh) * | 2019-04-25 | 2024-02-01 | 日商力森諾科股份有限公司 | 半導體裝置的製造方法 |
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US9704820B1 (en) * | 2016-02-26 | 2017-07-11 | Taiwan Semiconductor Manufacturing Company Ltd. | Semiconductor manufacturing method and associated semiconductor manufacturing system |
US10590232B2 (en) * | 2016-06-02 | 2020-03-17 | Hitachi Chemical Company, Ltd. | Resin composition and method of producing laminate |
CN107541168A (zh) * | 2017-07-31 | 2018-01-05 | 常州聚盛节能工程有限公司 | 一种建筑结构胶及其制备方法 |
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TWI689016B (zh) * | 2016-08-22 | 2020-03-21 | 日商千住金屬工業股份有限公司 | 金屬燒結接合體、及晶片接合方法 |
US11024598B2 (en) | 2016-08-22 | 2021-06-01 | Senju Metal Industry Co., Ltd. | Metallic sintered bonding body and die bonding method |
TWI830901B (zh) * | 2019-04-25 | 2024-02-01 | 日商力森諾科股份有限公司 | 半導體裝置的製造方法 |
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