TWI382076B - 低應力導電性黏著劑 - Google Patents

低應力導電性黏著劑 Download PDF

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Publication number
TWI382076B
TWI382076B TW095107344A TW95107344A TWI382076B TW I382076 B TWI382076 B TW I382076B TW 095107344 A TW095107344 A TW 095107344A TW 95107344 A TW95107344 A TW 95107344A TW I382076 B TWI382076 B TW I382076B
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Taiwan
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composition
conductive
weight
group
present
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TW095107344A
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English (en)
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TW200704743A (en
Inventor
Chih Min Cheng
Andrew Collins
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Henkel Ag & Co Kgaa
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
    • A01C1/02—Germinating apparatus; Determining germination capacity of seeds or the like
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00—Soilless cultivation, e.g. hydroponics
    • A01G31/02—Special apparatus therefor
    • A01G31/06—Hydroponic culture on racks or in stacked containers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
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    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
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    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Description

低應力導電性黏著劑
本發明關於適用於作為微電子裝置或半導體封裝體中之導電性材料之組成物，俾提供電性安定的互連線。
導電性組合物係用於製造及組裝半導體封裝體和微電子裝置中之許多目的。舉例來說，導電性黏著劑係用以黏著積體電路晶片於基板(模片貼附黏著劑)或黏著電路組件於印刷線路板(表面裝配導電性黏著劑)。
遍及供焊接元件於基板之電子工業所用之領先技術係使用金屬焊料合金，即含有63重量%錫和37重量%鉛之所謂的共熔焊料。其係於膏狀物或焊料預成型物形式加熱至超過其熔點(183℃)以使焊料膏熔化及形成接點而施於電路板。另外，電路板通過焊料的熔波以形成接點，俾將電元件黏著於電路板。於每一例中，使用助熔材料以從金屬表面去除表面氧化作用，並且使熔化的焊料牢固地黏著於表面以及形成具有極佳耐衝擊性之可靠的焊點。雖然焊料技術已存在幾十年，但其具有若干缺點。於合金中之鉛是不符合環保的。已提出許多環境法規以加重負擔、限制或禁止於電子焊料中使用鉛。其次，高製程溫度需要使用更昂貴的熱安定性基板，並且無法配合電子工業中變得更普遍之撓性基板。另一缺點為於回焊程序(為昂貴且無效率的程序)之後從助熔材料清潔殘餘物之額外步驟。
因無鉛、低處理溫度及簡化的組裝方法(不需焊料助溶劑及接續的助熔劑清潔步驟)之緣故，導電性黏著劑提供若干優於習知焊料組件之優點。導電性黏著劑之所需性質為長的室溫工作壽命、相當低的硬化溫度及相當短的硬化時間、良好的絲網印刷用流變性、當硬化時之充足的攜帶電流之導電性、當硬化時可接受的對基板黏附性、高溫下安定的電阻性及長期濕度以及良好的衝擊強度。導電性黏著劑特別適用於欲供許多微波應用(需要黏著FR4或陶瓷電路板於具有鋁或銅核芯之金屬基板)之大面積組件。於此等應用中，導電性黏著劑提供電完整性、黏著性一致性以及改良的散熱性，俾確保與管理需求之順應性、使損失減至最少、使高頻率數位信號失真減至最少以及對於接地平面之低阻抗。
有兩種常用的導電性黏著劑、薄膜及膏狀物。薄膜黏著劑係用作低溫程序之焊料代替物，並且於電路板與金屬襯墊之間產生一致的接地路徑。因黏著線厚度一致性、低流動性值及可用作經細的模切部件之緣故，薄膜導電性黏著劑對於大面積組件而言是較佳的。薄膜黏著劑係由最終組裝者於具有預切割為所欲的PCB尺度之B階段條件下接收。載體基板(通常為MYLAR)係自薄膜去除，將薄膜置於欲黏著的基板之間，並且於升高的溫度和壓力條件下使封裝體黏著在一起。再者，由於薄膜黏著劑具有比膏狀物黏著劑遠更高的黏度，當薄膜貯存於室溫下一段延長的期間時，填料之沉降作用不是被關心的事。
一種圍繞薄膜黏著劑的問題為其撓性。具有高強度之薄膜黏著劑通常為具有有限撓性之高模量黏著劑。因電路板與金屬散熱器於硬化後之熱膨脹係數之極大差異之故，此等具有高模量和高交聯密度之薄膜產生高應力條件。高應力的結果係為最終組件中之高度的翹曲變形。提供低應力之薄膜黏著劑通常具有較低模量以及較低黏附強度。因此，市售的撓性薄膜具有比非撓性薄膜更低的黏附強度。
膏狀物導電性黏著劑亦可用以使大面積黏著在一起，尤其是倘若將黏著劑絲網印刷於基板上時。絲網印刷使得高體積製造以及限制廢料成為可能。膏狀物導電性黏著劑亦可為可B階段的，故可依照類似薄膜之方式預施敷於元件上、貯存以及接著加熱以供最終黏著之用。必須監測膏狀物黏著劑的流變性，俾確保黏著劑正確沉積於電路板上。同樣地，必須監測膏狀物的流變性，俾防止B階段或硬化期間滲出或落下。
因此，提供可賦予低應力和高黏附性之導電性薄膜和膏狀物黏著劑，以形成用於半導體封裝應用之安定性組件，將是有利的。有利的是，相較於高強度薄膜黏著劑，此黏著劑將具有較優的對一般撓性薄膜黏著劑之黏附性以及較優的應力減少率。
 發明概述
本發明為一種低應力等向性的導電性薄膜或膏狀物黏著劑，其包含a)一或多種官能性丙烯酸系共聚物；b)環氧樹脂；以及c)導電性填料。亦可使用其他成分，例如黏附促進劑、硬化劑及導電性增強劑。本發明之導電性薄膜黏 著劑提供比習知的撓性薄膜黏著劑更高的黏附強度以及比現存的高黏附強度導電性薄膜更低的黏著元件間應力。
發明詳述
本發明之導電性黏著劑包含a)一或多種官能性丙烯酸系共聚物或三元聚合物；b)環氧樹脂；以及c)導電性填料。於較佳具體例中，亦可含有一或多種黏附促進劑、硬化劑及導電性增強劑。於指出官能性丙烯酸系共聚物之情形下，應瞭解官能性丙烯酸系亦包含三元聚合物。
本發明之官能性丙烯酸系共聚物可溶於塗料溶劑中，因而使得低應力、高強度薄膜形成或膏狀物黏著劑成為可能。較佳的丙烯酸系共聚物為飽和聚合物，因而比典型的橡膠增強樹脂(例如羧基封端的丁二烯腈橡膠)更耐氧化、老化及退化。共聚物之組成物較佳為丙烯酸丁酯-乙基丙烯腈或丙烯酸丁酯-共-乙基丙烯腈或丙烯酸乙酯-丙烯腈，俾提供高分子量聚合反應。共聚物較佳具有羥基、羧酸、異氰酸酯或環氧基官能度，俾改良溶劑和環氧基相容性。共聚物的分子量是高的，並且較佳為在約200,000至約900,000之範圍內。共聚物的玻璃轉變溫度(Tg)相對於室溫是低的，並且較佳係於約30℃至約-40℃之範圍內。雖然可利用許多官能性丙烯酸系共聚物，但較佳的官能性丙烯酸系共聚物微市售自日本大阪之Nagase ChemteX Corporation之TEISAN RESIN SG80H。
用於本發明之較佳的環氧樹脂包含雙酚A和雙酚F之單官能及多官能縮水甘油基醚、脂族及芳族環氧化物、飽和或不飽和環氧化物或環脂族環氧樹脂或其組合。最佳的環氧樹脂為雙酚A型樹脂。此等樹脂通常係經由一莫耳雙酚A樹脂與二莫耳表氯醇之反應而製得。另一較佳類型的環氧樹脂為環氧基酚樹脂。環氧基酚樹脂通常經由酚系樹脂與表氯醇之反應而製得。二環戊二烯－酚環氧樹脂、萘樹脂、環氧基官能的丁二烯丙烯腈共聚物、環氧基官能的聚二甲基矽氧烷、環氧基官能的共聚物以及其混合物係為其他類型之可使用的環氧樹脂。市售的雙酚F型樹脂係以品名8230E市售自CVC Specialty Chemicals，Maple Shade，New Jersey以及以品名RSL1739市售自ResolutionPerformance Products Ltd.。雙酚A型環氧樹脂係以EPON 828市售自Resolution Performance Product，並且雙酚A與雙酚F之摻合物係以品名ZX－1059市售自Nippon Chemical Company。
導電性材料可包含導電性填料。例示的導電性材料為銀、銅、金、鈀、鉑、碳黑、碳纖維、石墨、鋁、氧化銦錫、塗銀銅、塗銀鋁、鉍、錫、鉍－錫合金、塗金屬的玻璃球、塗銀纖維、塗銀球、摻銻的氧化錫、碳奈米管、導電性奈米填料、導電性氧化物及其混合物。
視情況，必要時可添加適合的流動添加劑、黏附促進劑、導電性添加劑、硬化劑以及流變性修飾劑。視情況選用的流動添加劑包含矽酮聚合物、丙烯酸乙酯/丙烯酸2－乙基己酯共聚物、酮肟的酸式磷酸酯之烷醯基銨鹽或其混合物。適合的黏附促進劑包括不同形式的矽烷。適合的流變性修飾劑包含熱塑性樹脂，並且較佳為聚乙烯基乙縮酫。適合的導電性添加劑包含酸酐、戊二酸、檸檬酸、磷酸以及其他酸觸媒。適合的硬化劑包含(但不限於)路易士酸、酸酐、胺類、咪唑、二氰基二醯胺及其混合物。
本發明之本具體例之等向性導電性黏著劑含有至多約4至19重量%官能性丙烯酸系共聚物、約60至95重量%導電性填料、約1至10重量%環氧樹脂、約0至10重量%硬化劑、約0至5重量%導電性添加劑以及約0至5重量%黏附促進劑、流動添加劑、流變性修飾劑或其他添加劑(合計為100重量%)。較佳為，官能性丙烯酸系共聚物之存在量係在約12至18重量%範圍內，導電性填料之存在量係在約70至90重量%範圍內，環氧樹脂之存在量係在約2至8重量%範圍內，硬化劑之存在量係在約0.1至3重量%範圍內，導電性添加劑之存在量係在約0.01至1重量%範圍內，以及其他添加劑之存在量係在約0至約5重量%範圍內。
本發明可經由以下實施例進一步說明。根據本發明之官能性丙烯酸系共聚物係以表1中之成分調配之。
1 RSL-1462 DGEGA環氧樹脂，市售自Resolution Performance Products。
連同市售的高黏附強度環氧樹脂及低應力環氧樹脂之效能，一起測試表1之調配物A的效能。所測試之高黏附強度環氧樹脂(比較例A)為CF3350(市售自Emerson & Cuming)，並且所測試之低應力環氧樹脂(比較例B)為8450WL(市售自Al Technologies)。此等試驗的結果係顯示於表2中。
如表2中所示，相較於實施例B，含有官能性丙烯酸系共聚物之試樣產生較優的強度以及較優的黏著線完整性。於組件暴露於回焊程序溫度之後，黏附強度之保留於表2中是明顯的。強度保留是必要的，因為此等黏著劑可用以黏著未佔滿的基板。以元件佔滿電路板係以焊接法進行，因而黏附強度之保留對於黏著線完整性而言是重要的。比較例B於暴露於回焊溫度期間表現不佳。明顯的是黏附強度的降低以及暴露後之黏著線完整性的變化。相較於比較例A，測試用調配物亦產生明顯的曲率(應力)降低。可獲致應力降低，而不會於暴露於回焊程序之後喪失黏著完整性。
熟悉本技藝之人士當可明白，本發明可施以許多修飾及變化，然皆不脫本發明之精神及範圍。此中所述之特殊具體例僅透過實施例提供，並且本發明僅受限於如附申請專利範圍以及相當於此等申請專利範圍之完整範圍。

Claims (10)

  1. 一種用於微電子裝置之組成物，其包含：(a)官能性丙烯酸系共聚物或三元共聚物，其中該官能性丙烯酸系共聚物或三元共聚物具有羥基、羧酸、異氰酸酯或環氧基官能度，及Tg於30℃至-40℃之範圍，及其存在量為自4至19重量%；(b)環氧樹脂，其存在量為自1至8重量%；(c)導電性填料，其存在量為自60至95重量%；(d)固化劑，其使該組成物熱固化；及(e)導電性添加劑，其存在量為0.01至1重量%。
  2. 如申請專利範圍第1項之組成物，進一步包含一或多種固化劑，其存在量為0.1至3重量%。
  3. 如申請專利範圍第1項之組成物，其中該官能性丙烯酸系共聚物或三元共聚物具有分子量係於約200,000至約900,000範圍內。
  4. 如申請專利範圍第1項之組成物，其中該導電性填料係選自由銀、銅、金、鈀、鉑、碳黑、碳纖維、石墨、鋁、氧化銦錫、塗銀銅、塗銀鋁、鉍、錫、鉍-錫合金、塗金屬的玻璃球、塗銀纖維、塗銀球、摻銻的氧化錫、碳奈米管、導電性奈米填料、導電性氧化物及其混合物所組成之群。
  5. 如申請專利範圍第1項之組成物，其中該環氧樹脂係選自由雙酚A和雙酚F之單官能及多官能縮水甘油基醚、脂族及芳族環氧化物、飽和及不飽和環氧化物、環脂族環氧樹脂及其混合物所組成之群。
  6. 如申請專利範圍第1項之組成物，其中該導電添加劑選自由流動添加劑、黏附促進劑及流變性修飾劑所組成之群。
  7. 如申請專利範圍第1項之組成物，其中該組成物係為低應力薄膜導電性黏著劑。
  8. 如申請專利範圍第1項之組成物，其中該組成物係為可經B階段作用。
  9. 一種黏著電子元件之方法，其係使用如申請專利範圍第1項之組成物。
  10. 一種提供用於黏著電子元件之撓性薄膜或膏狀物的方法，其係使用如申請專利範圍第1項之組成物。
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KR101325083B1 (ko) 2013-11-06
JP4875386B2 (ja) 2012-02-15
ATE465497T1 (de) 2010-05-15
EP1701361A1 (en) 2006-09-13
CN1831073A (zh) 2006-09-13
US7326369B2 (en) 2008-02-05
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US20060197066A1 (en) 2006-09-07
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