TWI478178B - 用於連接電子組件至基板之糊狀物及方法 - Google Patents

用於連接電子組件至基板之糊狀物及方法 Download PDF

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Publication number
TWI478178B
TWI478178B TW101132412A TW101132412A TWI478178B TW I478178 B TWI478178 B TW I478178B TW 101132412 A TW101132412 A TW 101132412A TW 101132412 A TW101132412 A TW 101132412A TW I478178 B TWI478178 B TW I478178B
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Taiwan
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paste
substrate
activator
weight
electronic component
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TW101132412A
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English (en)
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TW201320106A (zh
Inventor
Wolfgang Schmitt
Albert Heilmann
Jens Nachreiner
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Heraeus Materials Tech Gmbh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
    • B23K35/3618—Carboxylic acids or salts
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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    • B23K35/3006—Ag as the principal constituent
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Description

用於連接電子組件至基板之糊狀物及方法
本發明係關於一種用於連接電子組件至基板之糊狀物及連接電子組件至基板之方法。
在電力電子學之領域中，將電子組件緊固於基板上為一特殊難題。
在終端裝置操作期間所產生之機械應力需要電子組件與基板之間的連接具有足夠強度以使得該電子組件不會與該基板分離。因此，通常使用含鉛焊料糊狀物，該連接技術在焊接製程中產生就強度而言顯示高可靠性之連接層。由於鉛有毒性及相關健康危害，因此正尋找該等含鉛焊料糊狀物之適合替代物。目前討論的是，作為鉛焊料之替代物，無鉛焊料糊狀物非常適合於在電子組件與基板之間產生具有高強度之連接層。然而，該等焊料具有略高於操作時電子組件所曝露之溫度的低熔點。因此，該等連接層之強度可靠性在電子組件操作期間顯著下降。
電子組件與基板之間的連接強度之高可靠性可使用多種連接劑及連接方法來實現。然而，此等情況通常需要高製程溫度及高製程壓力，其導致待連接之零件受損並在大批量生產中產生高不良率。
此為旨在降低該等連接方法所需之製程溫度及製程壓力的潛在原因。因此在一些應用中使用黏著劑連接該等零件。經由使用黏著劑，可在一些情況下獲得連接電子組件 與基板之高強度連接層。然而，黏著技術之缺點為由此產生的電子組件與基板之間的接觸點之熱導率及電導率通常不足。
為滿足關於連接點之可靠性、熱導率及電導率的要求，已有一段時間提出經由燒結連接電子組件與基板(參見例如DE 10 2007 046 901 A1)。燒結技術為以穩定方式連接組件之極簡單方法。使用該等燒結方法，經常相當成功地連接電子組件至基板，其限制條件為其各包含含有貴金屬之接觸區。然而，通常需要經由至少一個非貴金屬接觸區連接電子組件與基板。使用習知燒結方法，經由該等非貴金屬接觸區產生穩定連接通常為不可行的。
此外，更早地已提出使用基於粒徑不超過100 nm之奈米粒子的糊狀物連接電子組件與基板。然而，奈米粒子之處理與健康危害相關且因此通常因職業安全性而加以避免。
因此，本發明之一個目標為提供一種糊狀物，其經由接觸區使得至少一個電子組件連接至至少一個基板，其中該等接觸區中之至少一者含有非貴金屬。較佳地，該糊狀物應用於在電子組件與基板之間形成連接，該連接確保在操作時電子組件所曝露之溫度下具有高可靠性。此外，該糊狀物較佳亦應克服自先前技術已知之其他缺點。
本發明之一目標亦為提供一種經由接觸區連接至少一個電子組件至至少一個基板之方法，其中該等接觸區中之至少一者含有非貴金屬。
該等目標係藉由獨立項之標的物來達成。
因此，本發明提供一種糊狀物，其含有(a)金屬粒子、(b)至少一種在分子中帶有至少兩個羧酸單元之活化劑及(c)分散介質。
此外，本發明提供一種經由接觸區連接至少一個電子組件至至少一個基板之方法，其中該等接觸區中之至少一者含有非貴金屬，該方法包含以下步驟：(i)提供具有第一接觸區之基板及具有第二接觸區之電子組件，其中該等接觸區中之至少一者含有非貴金屬；(ii)提供糊狀物，其含有(a)金屬粒子；(b)至少一種在分子中帶有至少兩個羧酸單元之活化劑；及(c)分散介質；(iii)產生結構，其中該基板之該第一接觸區經由該糊狀物接觸該電子組件之該第二接觸區；及(iv)燒結該結構，同時產生至少包含經由經燒結之糊狀物互相連接之基板及電子組件的模組。
本發明係基於絕對驚人之洞見：藉助於糊狀物、經由燒結使得迄今不可能之經由至少一個包含非貴金屬之接觸區連接電子組件至基板成為可能，其限制條件為該糊狀物含有在分子中帶有至少兩個羧酸單元之活化劑。
根據本發明，提供一種糊狀物。
術語糊狀物之定義無限制。然而，糊狀物較佳理解為意 謂可經由常見塗覆技術塗覆之任何分散液，例如印刷技術(例如網版印刷或模板印刷)、分散技術、噴霧技術、針腳轉印或浸漬，且具有足夠高的黏度及內聚力以容許隨後步驟對所塗覆之糊狀物進行加工。
本發明之糊狀物含有(a)金屬粒子。
金屬粒子較佳理解為意謂含有金屬之粒子。
根據一較佳實施例，該金屬係選自由銅、銀、鎳及鋁組成之群。根據一尤其較佳實施例，金屬為銀。
金屬可以純金屬形式存在於金屬粒子中，例如具有至少99重量%之純度、至少99.9重量%之純度、至少99.99重量%之純度或至少99.999重量%之純度。另一方面，金屬粒子亦可含有多種金屬。亦可行的是金屬粒子含有由多種金屬組成之合金或金屬間相。
根據一較佳實施例，金屬粒子包含選自由銀、銅、鎳及鋁組成之群的元素作為其主要組份。在本發明之範疇內，主要組份理解為意謂存在於所關注之金屬粒子中之分率比存在於該金屬粒子中之任何其他元素大的元素。
根據一尤其較佳實施例，金屬粒子為銀粒子、銅粒子、鎳粒子或鋁粒子。適當時，該等粒子之表面可經部分或完全氧化。
根據一尤其較佳實施例，金屬粒子為銀粒子。
該等金屬粒子之形狀無限制。較佳地，金屬粒子採用薄片形狀、橢球形或圓形。亦可行的是金屬粒子為多種形狀之混合物。
根據一尤其較佳實施例，金屬粒子採用薄片形狀。在該實施例中，以金屬粒子之總重量計，薄片之分率為至少70重量%，更佳為至少80重量%，甚至更佳為至少90重量%，且尤其較佳為至少99重量%。
根據另一較佳實施例，金屬粒子之長度比大於1.0，更佳長度比大於1.2，甚至更佳長度比大於1.5，且尤其較佳長度比大於2.0。較佳地，金屬粒子之長度比不大於20，更佳長度比不大於15，且甚至更佳長度比不大於10。在本上下文中，長度比應理解為意謂延伸穿過金屬粒子之橫截面之最寬處的距離(a)與沿垂直於距離(a)之直線延伸穿過該橫截面之最寬處的距離(b)之比率。在此情況下，橫截面為穿過金屬粒子且具有最大表面積之截面。若金屬粒子具有例如矩形橫截面，則長度比為橫截面之長度與寬度的比率。舉例而言，具有2 μm長度及1 μm寬度之矩形橫截面之金屬粒子的長度比為2。
根據另一較佳實施例，長度比大於1.0之金屬粒子的分率、更佳長度比大於1.2之金屬粒子的分率及甚至更佳長度比大於1.5之金屬粒子的分率為至少70重量%，更佳為至少80重量%，且甚至更佳為至少90重量%，各以金屬粒子之總重量計。
存在於糊狀物中之金屬粒子可具有不同粒徑分佈。
根據一較佳實施例，金屬粒子之平均粒徑(d50值)為至少500 nm，更佳為至少650 nm，且甚至更佳為至少1 μm。平均粒徑(d50值)較佳不大於20 μm，更佳不大於15 μm， 且甚至更佳不大於10 μm。因此，平均粒徑(d50值)較佳在500 nm至20 μm之範圍內，更佳在650 nm至15 μm之範圍內，且甚至更佳在1至10 μm之範圍內。較佳地，平均粒徑(d50值)理解為意謂50體積%之金屬粒子未達到且50體積%之金屬粒子超過的粒徑。
根據另一較佳實施例，金屬粒子之粒徑d10(d10值)為至少150 nm，更佳為至少200 nm，且甚至更佳為至少250 nm。粒徑d10(d10值)較佳不大於5 μm，更佳不大於4 μm，且甚至更佳不大於3 μm。因此，粒徑d10(d10值)較佳在150 nm至5 μm之範圍內，更佳在200 nm至4 μm之範圍內，且甚至更佳在250 nm至3 μm之範圍內。較佳地，粒徑d10(d10值)理解為意謂10體積%之金屬粒子未達到且90體積%之金屬粒子超過的粒徑。
根據另一較佳實施例，金屬粒子之粒徑d90(d90值)為至少1.75 μm，更佳為至少2 μm，且甚至更佳為至少2.25 μm。粒徑d90(d90值)較佳不大於100 μm，更佳不大於50 μm，且甚至更佳不大於25 μm。因此，粒徑d90(d90值)較佳在1.75 μm至100 μm之範圍內，更佳在2 μm至50 μm之範圍內，且甚至更佳在2.25 μm至25 μm之範圍內。較佳地，粒徑d90(d90值)理解為意謂90體積%之金屬粒子未達到且10體積%之金屬粒子超過的粒徑。
前述粒徑規格適用於根據ISO 13320(2009)經由LALLS(低角度鐳射光散射 (Low Angle Laser Light Scattering ))方法測定粒徑之分析。在本上下文中，較佳地，Mastersizer 2000 (Malvern Instruments Ltd.,Worcestershire,United Kingdom)用作量測儀器。該量測及該分析係在適合條件下進行(例如：標準物：折射率為0.14、吸光度為3.99之銀；分散介質：折射率為1.36之乙醇；程序：將200 ml乙醇添加至0.5公克粉末中且音波處理所得懸浮液5分鐘，接著將用於量測之該懸浮液的等分試樣轉移至Mastersizer 2000 之Hydro Accessory ；用於分析之光學模型：米氏理論(Mie theory))。
較佳地，根據BET(Brunauer ,Emett ,Teller )量測，金屬粒子之比表面積在1 m2 /g至5 m2 /g之範圍內且更佳在1 m2 /g至4 m2 /g之範圍內。較佳地，此BET量測係根據DIN ISO 9277：2003-05進行。
適當時，金屬粒子亦可以多種分率之金屬粒子的混合物形式存在。該等分率可例如因金屬粒子之組成、形狀或尺寸而不同。
較佳地，以糊狀物之總重量計，金屬粒子之分率為至少50重量%，更佳為至少60重量%，甚至更佳為至少70重量%，且尤其較佳為至少80重量%。較佳地，以糊狀物之總重量計，金屬粒子之分率不大於95重量%，更佳不大於93重量%，且甚至更佳不大於90重量%。因此，以糊狀物之總重量計，金屬粒子之分率[較佳]在50重量%至95重量%之範圍內，更佳在60重量%至93重量%之範圍內，且甚至更佳在70重量%至90重量%之範圍內。
金屬粒子可包含塗層。
在本發明之範疇內，金屬粒子之塗層理解為意謂金屬粒子表面上之牢固黏著層。較佳地，牢固黏著層意謂該層僅在重力作用下不會與金屬粒子分離。
金屬粒子之塗層經常含有至少一種塗佈化合物。
該至少一種塗佈化合物較佳為有機化合物。
較佳地，塗佈化合物係選自由飽和化合物、單不飽和化合物、多不飽和化合物及其混合物組成之群。
較佳地，塗佈化合物係選自由分支鏈化合物、未分支化合物及其混合物組成之群。
較佳地，塗佈化合物具有8-28個、甚至更佳12-24個且尤其較佳12-18個碳原子。
根據一較佳實施例，塗佈化合物係選自由脂肪酸、脂肪酸鹽及脂肪酸酯組成之群。
可想到之脂肪酸鹽較佳為如下鹽：其陰離子組份為去質子化脂肪酸且其陽離子組份係選自由銨離子、單烷基銨離子、二烷基銨離子、三烷基銨離子、鋰離子、鈉離子、鉀離子、銅離子及鋁離子組成之群。
較佳脂肪酸酯係衍生自相應脂肪酸，其中羧酸單元之羥基由烷基，尤其甲基、乙基、丙基或丁基置換。
根據一較佳實施例，至少一種塗佈化合物係選自由以下組成之群：辛酸(caprylic acid/octanoic acid)、癸酸(capric acid/decanoic acid)、月桂酸(十二酸)、肉豆蔻酸(十四酸)、棕櫚酸(十六酸)、硬脂酸(十八酸)、其混合物、以及相應的酯及鹽、及其混合物。
根據一尤其較佳實施例，至少一種塗佈化合物係選自由月桂酸(十二酸)、硬脂酸(十八酸)、硬脂酸鈉、硬脂酸鉀、硬脂酸鋁、硬脂酸銅、棕櫚酸鈉及棕櫚酸鉀組成之群。
經使用之經塗佈之金屬粒子較佳可於市面購得。可經由此領域中常用之技術將相應塗佈化合物塗覆於金屬粒子之表面。
舉例而言，可使塗佈化合物、尤其為上文所提及之硬脂酸酯或棕櫚酸酯在溶劑中成漿並將成漿之塗佈化合物與金屬粒子一起在球磨機中濕磨。濕磨後，將直至彼時才經塗佈化合物塗佈之金屬粒子乾燥，接著移除粉塵。
較佳地，以塗層之總重量計，至少一種選自由脂肪酸、脂肪酸鹽及脂肪酸酯組成之群的塗佈化合物之分率為至少80重量%，更佳為至少90重量%，尤其較佳為至少95重量%，甚至更尤其較佳為至少99重量%，且尤其為100重量%。
根據一較佳實施例，以經塗佈之金屬粒子的總重量計，塗佈化合物之總分率為0.05-3重量%，更佳為0.07-2.5重量%，且甚至更佳為0.1-2.2重量%。
定義為塗佈化合物質量與金屬粒子表面積之比率之塗佈程度較佳為每平方公尺(m2 )金屬粒子表面積0.00005-0.03 g，更佳為0.0001-0.02 g，且甚至更佳為0.0005-0.02 g塗佈化合物。
令人驚訝地發現金屬粒子上具有塗層顯著改良電子組件 與基板之間的連接強度之可靠性。
根據本發明，糊狀物亦含有至少一種活化劑(b)。
該活化劑在分子中帶有至少兩個羧酸單元。相應地，活化劑在分子中亦可帶有大於兩個、大於三個或大於四個羧酸單元。
羧酸單元在分子中之位置不受限制。然而，活化劑之羧酸單元較佳在末端位置飽和。
此外，活化劑之羧酸單元經由不大於五個碳原子、更佳不大於四個碳原子、甚至更佳不大於三個碳原子、尤其較佳不大於兩個碳原子且甚至更尤其不大於一個碳原子互相連接已證明為有利的。此外，較佳的是活化劑之羧酸單元經由至少一個碳原子互相連接。判定活化劑之羧酸單元互相連接所用之碳原子的數目、羧酸單元自身之碳原子數不應包括在根據本發明範疇之計算中。因此，舉例而言，在丙二酸(HOOCCH2 COOH)之情況下，羧酸單元經由一個碳原子互相連接，而在順丁烯二酸(HOOC(CH)2 COOH)之情況下，羧酸單元經由兩個碳原子互相連接。
根據一較佳實施例，活化劑包含至少2個碳原子且更佳為至少3個碳原子。較佳地，活化劑包含不大於18個碳原子，更佳不大於14個碳原子，甚至更佳不大於12個碳原子，尤其較佳不大於10個碳原子，甚至更尤其較佳不大於8個碳原子，且尤其不大於6個碳原子。因此，活化劑較佳包含2-18個碳原子，更佳為2-14個碳原子，甚至更佳為2-12個碳原子，尤其較佳為2-10個碳原子，更尤其較佳為2-8 個碳原子，尤其2-6個碳原子或3-6個碳原子。
活化劑可為飽和或不飽和化合物。
不飽和活化劑在分子中較佳包含至少一個碳碳鍵。此外，順式異構體已證明為尤其有利之活化劑。
活化劑可為分支鏈或未分支化合物。
分支鏈活化劑之側鏈的長度、類型及位置不受任何限制。較佳地，分支鏈活化劑包含至少一個長度為1-8個碳原子之側鏈。通常，該側鏈為適當時可經取代之烷基鏈。
活化劑可為芳族或脂族化合物。然而，活化劑較佳為脂族化合物。
除羧酸單元中存在之氧原子外，本發明之活化劑可帶有其他雜原子。然而，活化劑在羧酸單元中較佳不含有除氧原子以外之雜原子。
較佳地，活化劑之羧酸單元以非質子化形式存在於糊狀物中。因此，選擇適於使羧酸單元不解離之分散介質可為有利的。
在許多情況下已證明活化劑之分解點低於300℃溫度、更佳低於270℃溫度、甚至更佳低於240℃溫度且尤其較佳低於200℃溫度為有利的。在此等情況下，活化劑之分解點較佳在100℃至300℃之範圍內，更佳在110℃至270℃之範圍內，甚至更佳在120℃至240℃之範圍內，且尤其較佳在130℃至200℃之範圍內。
此外，在許多情況下已證明為有利的是活化劑之熔點為至少80℃、更佳為至少90℃且甚至更佳為至少100℃。在此 等情況下，熔點較佳不大於200℃，更佳不大於180℃，且甚至更佳不大於160℃。因此，活化劑之熔點較佳在80℃至200℃之範圍內，更佳在90℃至180℃之範圍內，且甚至更佳在100℃至160℃之範圍內。
活化劑可以非複合形式呈現。另一方面，活化劑亦可以複合形式存在，較佳以包括元素週期系統之副族元素的複合物形式存在。若活化劑以複合形式存在，則其可尤其為複合二羧酸。
根據一較佳實施例，活化劑係選自由以下組成之群：草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、順丁烯二酸(cis-butenedioic acid/maleic acid)、反丁烯二酸(trans-butenedioc acid/fumaric acid)、順-2-戊烯酸、反-2-戊烯酸及二甲基丙二酸。
根據一尤其較佳實施例，活化劑係選自由草酸、丙二酸、順丁烯二酸及二甲基丙二酸組成之群。
根據一甚至更尤其較佳實施例，活化劑係選自由草酸、丙二酸、順丁烯二酸及二甲基丙二酸組成之群。
以糊狀物之總重量計，活化劑之分率較佳為至少0.1重量%，更佳為至少0.3重量%，甚至更佳為至少0.5重量%，尤其較佳為至少1重量%，且甚至更尤其較佳為至少2重量%。較佳地，以糊狀物之總重量計，活化劑之分率不大於30重量%，更佳不大於20重量%，甚至更佳不大於10重量%，尤其較佳不大於7重量%，且甚至更尤其較佳不大於5重量%。相應地，以糊狀物之總重量計，活化劑之分率在 0.1重量%至30重量%之範圍內，更佳在0.3重量%至20重量%之範圍內，甚至更佳在0.5重量%至10重量%之範圍內，尤其較佳在1重量%至7重量%之範圍內，且甚至更尤其較佳在2重量%至5重量%之範圍內。
此外，本發明之糊狀物含有分散介質(c)。
較佳的是金屬粒子(a)可分散於分散介質(c)中。至少一種活化劑(b)亦可分散於分散介質(c)中。然而，亦可行的是活化劑(b)溶解於分散介質(c)中。
分散介質可為此領域中常見之分散介質。
因此，分散介質可含有一或多種溶劑。
在本上下文中，有機化合物例如為可想到之溶劑。
該等有機化合物較佳含有5-50個碳原子，更佳為8-32個碳原子，且甚至更佳為18-32個碳原子。
有機化合物可為分支鏈或未分支化合物。有機化合物亦可為環狀化合物。
有機化合物亦可具脂族或芳族特性。
此外，用作溶劑之有機化合物可為飽和或單不飽和或多不飽和化合物。
有機化合物亦可包含雜原子，尤其為氧原子或氮原子。該等雜原子可為官能基之一部分。可想到之官能基包括例如羧酸基、酯基、酮基、醛基、羥基、胺基、醯胺基、偶氮基、醯亞胺基、氰基或腈基。
因此，可用作溶劑的為例如α-萜品醇((R)-(+)-α-萜品醇、(S)-(-)-α-萜品醇或外消旋物)、β-萜品醇、γ-萜品醇、 δ-萜品醇、前述萜品醇之混合物、N-甲基-2-吡咯啶酮、乙二醇、二甲基乙醯胺、醇類(尤其為包含具有5-9個碳原子之未分支或分支鏈的彼等醇類)、1-己醇、1-辛醇、1-十二醇、1-十三醇、2-十三醇、3-十三醇、4-十三醇、5-十三醇、6-十三醇、異十三醇、二元酯(較佳為戊二酸、己二酸或丁二酸之二甲酯或其混合物)、甘油、二乙二醇、三乙二醇或其混合物。
根據另一較佳實施例，分散介質含有至少一種非質子性溶劑。亦可為有利的是，以在25℃溫度及1.1013巴壓力下為液體之糊狀物之所有組份的總重量計，至少一種非質子性溶劑之分率為至少70重量%，更佳為至少80重量%，甚至更佳為至少90重量%，尤其較佳為至少95重量%，且甚至更尤其較佳為至少99重量%。
非質子性溶劑較佳選自由脂族烴化合物、羧酸酯及醚組成之群。
根據一尤其較佳實施例，分散介質含有至少一種脂族烴化合物。該脂族烴化合物較佳包含5-50個碳原子，更佳為8-32個碳原子，且甚至更佳為18-32個碳原子。
因此，脂族烴化合物亦可為石蠟。
以糊狀物之總重量計，分散介質之分率較佳為至少5重量%，更佳為至少8重量%，且甚至更佳為至少10重量%。以糊狀物之總重量計，分散介質之分率較佳不大於40重量%，更佳不大於30重量%，甚至更佳不大於20重量%，且尤其較佳不大於15重量%。相應地，以糊狀物之總重量 計，分散介質之分率較佳在5重量%至40重量%之範圍內，更佳在8重量%至30重量%之範圍內，且甚至更佳在10重量%至20重量%之範圍內。
適當時，本發明之糊狀物可含有除金屬粒子(a)、至少一種活化劑(b)及分散介質(c)以外之其他物質。
可想到之其他物質為此領域中常見之稀釋劑、增稠劑及穩定劑。
以糊狀物之總重量計，除(a)金屬粒子、(b)至少一種在分子中帶有至少兩個羧酸單元之活化劑及(c)分散介質外之物質的分率較佳不大於20重量%，更佳不大於15重量%，甚至更佳不大於10重量%，尤其較佳不大於5重量%，甚至更尤其較佳不大於3重量%，且尤其不大於1重量%。
本發明之糊狀物可經由此領域中常見之方法製造。
糊狀物可例如經由將金屬粒子(a)、至少一種在分子中帶有兩個羧酸單元之活化劑(b)及分散介質(c)混合來製造。
根據一尤其較佳實施例，糊狀物係以多個步驟製造。
在本上下文中，在第一步驟中濕磨至少一種活化劑(b)。濕磨可在研磨機中進行且用於改良分散介質(c)中活化劑之可分散性。
經濕磨之活化劑(b)可接著與分散介質(c)在第二步驟中合併。通常在此步驟中產生活化劑(b)於分散介質(c)中之均質懸浮液。為產生該均質懸浮液，適當時可用混合器(例如Ultraturax混合器)處理混合物。
最後，來自第二步驟之懸浮液可與金屬粒子(a)在第三步 驟中合併。隨後，適當時對所得混合物進行均質化，例如手動進行。隨後，混合物可反覆通過輥磨機且需要時進一步均質化。接著所得糊狀物可用於所欲用途。
本發明之糊狀物較佳用於連接至少一個電子組件至至少一個基板。
在此製程中，至少一個電子組件較佳緊固於基板上。
該緊固係經由燒結來實現。在本發明之範疇內，燒結理解為意謂經由加熱連接兩個或兩個以上組件而不產生液相。因此，燒結較佳在至少一個電子組件與基板之間產生牢固結合的連接。
如此領域中所共知，電子組件理解為可為電子設備之一部分的物件。根據一較佳實施例，電子組件理解為意謂不可進一步拆卸且可用作電子電路之組件的單一組件。作為單元，適當時，電子組件可由多個組件組成。電子組件可為例如主動組件或被動組件。根據特定實施例，電子組件用於高功率電子儀器中。較佳地，電子組件係選自由以下組成之群：二極體(例如LED(發光二極體 (light emitting diode ))、電晶體(例如IGBT(絕緣閘雙極電晶體 (insulated-gate bipolar transistor )，即具有絕緣閘電極之雙極電晶體)、積體電路、半導體晶片、裸晶片(晶粒 )、電阻器、感測器、電容器、線圈及散熱片。
通常，基板理解為意謂可連接至電子組件之物件。根據一較佳實施例，基板係選自由引線框架 、DCB基板(直接銅結合 基板)及陶瓷基板組成之群。
根據一較佳實施例，以下各對電子組件及基板互相連接：LED/引線框架 、LED/陶瓷基板、晶粒 /引線框架 、晶粒 /陶瓷基板、晶粒 /DCB基板、二極體/引線框架 、二極體/陶瓷基板、二極體/DCB基板、IGBT/引線框架 、IGBT/陶瓷基板、IGBT/DCB基板、積體電路/引線框架 、積體電路/陶瓷基板、積體電路/DCB基板、感測器/引線框架 、感測器/陶瓷基板、散熱片(較佳為銅或鋁散熱片)/DCB、散熱片(較佳為銅或鋁散熱片)/陶瓷基板、散熱片/引線框架 、電容器(較佳為鉭電容器，更佳為敞開狀態下之鉭電容器)/引線框架 。
根據另一較佳實施例，可使多個電子組件連接至基板。此外，較佳可將電子組件配置於基板之相反側。
然而，電子組件與基板皆包含至少一個接觸區。
在本發明之範疇內，接觸區應理解為意謂電子組件中經由本發明之糊狀物接觸基板之區域或基板中經由本發明之糊狀物接觸電子組件之區域。因此，電子組件之接觸區較佳包含一旦基板與其連接則經基板覆蓋之接觸表面。同樣地，基板之接觸區較佳包含一旦電子組件與其連接則經電子組件覆蓋之接觸表面。較佳地，電子組件之接觸區之體積係由電子組件之接觸區的接觸表面(由接觸表面之寬度及長度限定)及50 nm之厚度限定。同樣地，基板之接觸區之體積較佳由基板之接觸區的接觸表面(由接觸表面之寬度及長度限定)及50 nm之厚度限定。電子組件及基板之接觸區的該體積具有一特定重量。該重量可例如藉助於歐傑 光譜學(Auger spectroscopy)經由濺鍍移除接觸區且接著測定所移除區域的重量來測定。
接觸區可為塗覆於電子組件或基板之區域。舉例而言，在許多情況下，將金屬化施用於待連接之電子組件的表面。該金屬化在許多情況下可佔在100 nm至400 nm範圍內的厚度。此類型之金屬化或其區域可代表本發明之接觸區。
另一方面，接觸區亦可為電子組件或基板之整合組件。舉例而言，根據本發明，由銅製成之引線框架 可用作基板。該等引線框架之厚度可在數毫米之範圍內。在此情況下，與該引線框架 之其他區域在物質或結構方面不必不同的該引線框架 之區域可表示本發明之接觸區。
電子組件及基板之接觸區中的至少一者含有至少一種非貴金屬。
根據一較佳實施例，電子組件及基板之至少一個包含非貴金屬之接觸區含有至少一種選自由以下組成之群的元素：(i)銅、鋁、鋅及鎳；(ii)包含至少一種選自銅、鋁、鋅及鎳之元素的合金；及(iii)包含至少一種選自銅、鋁、鋅及鎳之元素的金屬間相。
以包含非貴金屬之接觸區的重量計，至少一種非貴金屬(例如選自由銅、鋁、鋅及鎳組成之群的非貴金屬)之分率較佳為至少5重量%，更佳為至少7重量%，甚至更佳為至少10重量%，尤其較佳為至少15重量%，甚至更尤其較佳為至少50重量%，且尤其至少90重量%。
較佳地，非貴金屬(更佳為選自由銅、鋁、鋅及鎳組成之群的非貴金屬)為接觸區之主要成份。在本發明之範疇內，接觸區之主要成份理解為意謂存在於該接觸區中之分率大於存在於該接觸區中之任何其他元素的元素。
在本發明之範疇內，包含非貴金屬之接觸區亦可包含其他元素，尤其包括貴金屬。
若包含非貴金屬之接觸區含有包含至少一種選自銅、鋁、鋅及鎳之元素的合金，則該合金可為例如基本上由銅、鎳、鋅及常見雜質組成之合金或基本上由錫、金及常見雜質組成之合金。
在本發明之方法的第一步驟中，提供具有第一接觸區之基板及具有第二接觸區之電子組件，其中該等接觸區中之至少一者含有非貴金屬。
因此，基板之接觸區、電子組件之接觸區或基板之接觸區與電子組件之接觸區可含有非貴金屬。
根據定義，基板包含第一接觸區且電子組件包含第二接觸區。此外，適當時，基板或電子組件可包含其他接觸區。舉例而言，若引線框架 用作基板，則該引線框架 通常含有欲連接至眾多電子組件之眾多(相鄰)接觸區以形成次總成。
在本發明之方法的下一步驟中，提供根據上文提供之定義的糊狀物。
因此，該糊狀物含有(a)金屬粒子、(b)至少一種在分子中帶有至少兩個羧酸單元之活化劑及(c)分散介質。
在本發明之方法的另一步驟中產生結構。
該結構至少含有基板、電子組件及糊狀物。在本上下文中，該糊狀物位於基板之第一接觸區與電子組件之第二接觸區之間。因此，基板之第一表面藉助於糊狀物接觸電子組件之第二表面。
該結構可例如藉由將糊狀物塗覆於基板之第一接觸區的接觸表面且藉由第二接觸區之接觸表面將電子組件置於所塗覆之糊狀物上來產生。同樣，該結構亦可例如藉由將糊狀物塗覆於電子組件之第二接觸區的接觸表面且藉由第一接觸區之接觸表面將基板置於所塗覆之糊狀物上來產生。塗覆糊狀物較佳可藉助於此領域中常見之塗覆技術來進行，例如藉助於印刷方法(例如網版印刷或模板印刷)、分散技術、噴霧技術、針腳轉印或浸漬。
基板之第一表面與電子組件之第二表面之間的距離(產生結構後，即基本上依據糊狀物之厚度來測定)較佳在20 μm至200 μm之範圍內，且更佳在50 μm至100 μm之範圍內。
一旦產生結構，即可將其乾燥(若適當)。較佳地，在80℃至200℃之範圍內的溫度下且更佳在100℃至150℃之範圍內的溫度下乾燥該結構。乾燥較佳進行2至20分鐘時間，且更佳為5至10分鐘時間。需要時，乾燥亦可改為或另外在且較佳在以上所提及之條件下進行，同時產生結構，例如在將電子組件置於塗覆於基板之糊狀物上之前或在將基板置於塗覆於電子組件上之糊狀物上之前。
在本發明之方法的另一步驟中，對含有基板、電子組件及糊狀物之結構進行燒結。
燒結後，即將糊狀物中存在之金屬粒子與接觸區之至少一部分一起烘烤。在此製程中通常自糊狀物移除糊狀物中存在之其餘組份，例如適當時經由在經歷化學轉化後將其蒸發。燒結基於擴散製程來進行，其中糊狀物之金屬粒子中存在之元素擴散至接觸區中且接觸區中存在之元素擴散至由糊狀物之金屬粒子形成之介於其間的空間中。由於此製程中之溫度及擴散速率佔主導，因此形成穩定牢固結合之連接。
較佳地，結構之燒結係經由加熱至至少150℃之溫度、更佳為至少175℃之溫度且甚至更佳為至少200℃之溫度來實現。較佳地，結構之燒結係經由加熱至不大於350℃之溫度且甚至更佳為不大於300℃之溫度來實現。因此，較佳將結構加熱至150℃至350℃之範圍內的溫度，更佳為150℃至300℃之範圍內的溫度，甚至較佳為175℃至300℃之範圍內的溫度，且尤其較佳為200℃至300℃之範圍內的溫度。
加熱較佳在不施加任何製程壓力之情況下，亦即在0千巴之製程壓力下進行，但亦可在高製程壓力下進行，例如在1千巴或1千巴以上之製程壓力下進行。
加熱較佳進行1-60分鐘時間，且更佳為2-45分鐘時間。
關於實現加熱之氛圍無限制。然而，加熱較佳在含有氧氣之氛圍中進行。
燒結係在適合於燒結且較佳可設定上述製程參數的此領域常見裝置中進行。
燒結後，獲得模組，其至少含有經由經燒結之糊狀物互相連接的基板及電子組件。
根據一尤其較佳實施例，用於連接至少一個電子組件至至少一個基板之本發明方法係經由接觸區進行，其中該等接觸區中之至少一者含有銅作為非貴金屬。在此情況下使用含有(a)金屬粒子、(b)至少一種選自由丙二酸、順丁烯二酸及草酸組成之群的化合物作為活化劑及(c)分散介質之糊狀物已證明為特別有利。
根據另一尤其較佳實施例，用於連接至少一個電子組件至至少一個基板之本發明方法係經由接觸區進行，其中該等接觸區中之至少一者含有鎳作為非貴金屬。在此情況下使用含有(a)金屬粒子、(b)至少一種選自由二甲基丙二酸及草酸組成之群的化合物作為活化劑及(c)分散介質之糊狀物已證明為特別有利。
本發明在下文中根據實例加以說明，該等實例不限制本發明之範疇。
 實例：
本發明之糊狀物1-3及參考糊狀物1-3根據下表1之組成如下製備：
在六種不同樣品(對於糊狀物1-3及參考糊狀物1-3而言)中，首先在咖啡磨中精細濕磨相應活化劑，接著添加至分散介質中。使用Ultraturax混合器使該等混合物產生均質懸浮液。接著將該等均質懸浮液添加至銀粉中。首先使用刮勺將所得混合物手動均質化，接著通過輥磨機三次並再次均質化以獲得糊狀物1-3及參考糊狀物1-3。
使用糊狀物1-3及參考糊狀物1-3連接引線框架 至半導體晶片。
將由銅或鎳製成之引線框架 及經銀金屬化之半導體晶片用於此目的。
在六種樣品中將糊狀物1-3及參考糊狀物1-3塗覆於相應引線框架 。接著將半導體晶片置於所塗覆之糊狀物上。引 線框架 之相反表面與半導體晶片之間的距離為80 μm。在150℃溫度下將由此獲得之結構預乾燥5分鐘。隨後，在250℃溫度下在無壓力下燒結由此獲得之結構。
燒結製程後，進行分析以評估半導體晶片與引線框架 之間連接之存在以及該連接之可靠性。
此分析之結果總結於表2中。
該等測試顯示，僅使用本發明之糊狀物1-3便形成穩定連接，但使用參考糊狀物1-3時則未形成穩定連接。

Claims (10)

  1. 一種糊狀物，其含有(a)金屬粒子；(b)至少一種在分子中帶有至少兩個羧酸單元之活化劑；及(c)分散介質。
  2. 如請求項1之糊狀物，其中該等金屬粒子為銀粒子。
  3. 如請求項1或2之糊狀物，其中該活化劑之分解點在100℃至300℃之範圍內。
  4. 如請求項1或2之糊狀物，其中該活化劑係選自由二羧酸及複合二羧酸組成之群。
  5. 如請求項1或2之糊狀物，其中該活化劑係選自由丙二酸、順丁烯二酸、二甲基丙二酸及草酸組成之群。
  6. 如請求項1或2之糊狀物，其中該分散介質含有脂族烴化合物。
  7. 一種經由接觸區連接至少一電子組件至至少一基板之方法，其中該等接觸區中之至少一者含有非貴金屬，該方法包含以下步驟：(i)提供具有第一接觸區之基板及具有第二接觸區之電子組件，其中該等接觸區中之至少一者含有非貴金屬；(ii)提供糊狀物，其含有(a)金屬粒子；(b)至少一種活化劑，其分子中帶有至少兩個羧酸 單元；及(c)分散介質；(iii)產生一結構，其中該基板之該第一接觸區經由該糊狀物接觸該電子組件之該第二接觸區；及(iv)燒結該結構，同時產生一模組，該模組至少包含經由該經燒結之糊狀物互相連接之該基板及該電子組件。
  8. 如請求項7之方法，其特徵在於該等接觸區中之至少一者為該電子組件或該基板之整合組件。
  9. 如請求項7或8之方法，其中該非貴金屬為銅且該活化劑係選自由丙二酸、順丁烯二酸及草酸組成之群。
  10. 如請求項7或8之方法，其中該非貴金屬為鎳且該活化劑係選自由二甲基丙二酸及草酸組成之群。
TW101132412A 2011-09-20 2012-09-05 用於連接電子組件至基板之糊狀物及方法 TWI478178B (zh)

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EP2572814B1 (de) 2016-03-30
EP2572814A1 (de) 2013-03-27
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