TW323371B - - Google Patents

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Publication number
TW323371B
TW323371B TW084112792A TW84112792A TW323371B TW 323371 B TW323371 B TW 323371B TW 084112792 A TW084112792 A TW 084112792A TW 84112792 A TW84112792 A TW 84112792A TW 323371 B TW323371 B TW 323371B
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TW
Taiwan
Prior art keywords
weight
patent application
item
composition according
inorganic binder
Prior art date
Application number
TW084112792A
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English (en)
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Du Pont
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
    • C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
    • C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D5/24—Electrically-conducting paints
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    • 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
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    • C09J9/02—Electrically-conducting adhesives
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
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    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
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    • H05K2203/107—Using laser light

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
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7五、發明説明（1 ) 發明之領域 本發明係關於厚膜導體組合物，特別關於對於所使用之 基底具有改良焊接及黏著力之組合物。 發明之背景 使用厚膜導體於混雜（hybrid)之微電子成份中爲電子領域 中眾所周知者。該材料一般包含貴金屬、貴金屬合金或其 >昆合物之组合粒子及有機粘合劑均分散於有機介質中之分 散液’以形成糊狀產物。該糊料之稠度及流變性係調節以 適'&特定之施用方法’如絲網印刷（screen printing)、刷、 次、擠、喷等。該糊料一般以絲網印刷塗於惰性載體（如 蓉土）以形成圖型層。然後圖型厚膜導體層燃燒，以揮發（ 例如「燒盡」）有機介質及燒結無機粘合劑，典型爲玻璃 或玻璃形成材料，及貴金屬' 貴金屬合金或其混合物之細 分粒子。該糊料之燃燒（firing)溫度一般約6〇〇_9〇〇〇c。 經燃燒之導電層除具有導電性外，該層需牢固地附著於 基底，並需接受焊劑。可焊接性（s〇lderabiUty)爲極需性質 ，因爲需要連接導電圖型與所用電子系統之其他成份，例 如電阻器及電容器網路、電阻器、調整（tdm)電位計、小 片（chip)電阻器、小片電容器、小片載體等。 顧吝需要並期待繼續增加商業上可得之厚膜糊料。高黏 著力及高可焊接性之需要變得愈來愈難同時符合。爲黏著 之目的包含於厚膜導體組合物中之無機粘合劑Z可干擾焊 剤之濕潤性（WeUing)。因此，可提高焊接之黏著力並使褛 體之可焊接性之退化達最小之技術及组合物特別有價値/ * 4 -
本紙張尺度逋用中國國家標f (0¥73規格（公釐） _五、發明説明（2 A7 B7 經濟部中央標準局員工消費合作社印製 因此’本發明係關於—種厚 4腰組合物，包含糊料重量 50至90重量％之金屬導電相 令榊村里重（A) 幻子电相^細分粒子 之無機粘合劑相， Λ, s. 0 夕溆基 士 7 · 0重量 0/0之式[MAxtMb2^: 牝為+x〇8之黏著力促進劑’其中乂選自κ, Na，…爲 Ca，X爲〇]，（A)、（B)及（c)均分散於有機介質中。 細説明 本發明組合物包含導電金屬、合金或其混合物之細分粒 子、無齡合劑及黏純進劑，均分散於介質卜「知分 」乙詞可爲熟習「厚膜」技藝人士所明瞭，意指充分細小 可通過400網目篩（美國標準篩尺寸）之粒子。較佳爲實質上 所有粒子大小在O.Oi-20微米範圍内，最大尺寸較佳不大於 5微米。 導電相 貴金屬、其合金或其混合物之任一者可用作本發明組合 物之導電相。因此，可用貴金屬如Ag、Au、pt&pd，以及 其合金如 Pt/Au、Pd/Ag、pd/Au、pt/Ag、pt/pd/Au& Pt/'Pd/Ag。 組合物中固體含量相對於糊料爲5〇_95重量％，補充5_ 50%有機介質。固體物較佳爲60-90重量％，最佳爲70·85 重量。/〇。組合物中導電金屬含量相對於總固體係在組合物（ 不包括有機介質）之60-99重量％之範圍内。然而，75_98重 量〇/。導電金屬及補充25-5重量％無機粘合劑爲較佳。 無^粘合劑 1-x (請先聞讀背面之注意事項再填寫本頁) • m ---人 .裝------訂-- 5- 本紙張尺度逍$中國國家標準（CNS > A4規格（210χ297公釐y 水---------Γ----------- 發明説明（3 適&之無機枯合劑爲在燒結時用以使金屬結合於陶资基 底之習知材料，如玻璃、某些金屬氧化物及玻璃前驅物。 習知之玻璃料如硼酸鉛、矽酸鉛、硼矽酸鉛、硼酸鎘、硼 妙酸鎘鉛、硼矽酸鋅、硼矽酸鎘鈉、矽酸鉍、硼碎酸祕、 梦酸錯紐及硼矽酸鉛鉍可使用，但上述者並不限制本發明 。通常任何具有高含量氧化鉍之玻璃爲較佳者。該高鉍玻 璃含有至少50重量。/。氧化鉍，較佳至少70%。或者，可使 用玻璃及氧化鉍之混合物以替代鉍酸鹽玻璃。加入氧化錯 作爲另一相亦相當普遍。較佳玻璃示於下表1 ;氧化物成 (請先閱讀背面之注意事項再填寫本黃) i - Is _· -- -I --- ------ I - .....I-*-> I 111 B : i -......I 一aJml !- i -I ^-^ 經濟部中央標準局員工消費合作社印製 份以重 量％表示： 表 】 A B C D E F G H Bi2〇3 75.1 82.7 78.1 94.8 73.3 73.7 PbO 10.9 1.83 43.6 0.7 B2〇3 1.2 1.34 4.8 26.7 Si02 9.3 10.3 37.5 21.7 8.6 5.2 4.7 4.8 CaO 2.4 2.68 9.7 4.0 BaO 0.9 ZnO 27.6 3.9 5.0 CuO 7.6 5.5 CoO 1.8 A1203 1.1 1.22 4.3 5.7 Na20 8.7 Zr〇2 4.0 Ge02 16.5 16.6 -6 - 本紙浪尺度適用中國國家標窣（CNS ) A4規格210X297公釐） Ο 3 A7 Β7 經濟部中央標準局員工消費合作社印製 —五、發明説明（4 ) 玻璃粘合劑係以習知玻璃製造技術製備，由混合所欲比 例之所欲成份（或其前驅物，例如H3b〇3，對於b2〇3)及加 熱混合物以形成熔化物。如此技藝中眾所周知，加熱達高 峰溫度歷一段期間’以使熔化物完全變成液體，而氣體之 釋出停止。在此過程中，高峰溫度係在1100_1500eC範圍 内，一般1200-140(TC。然後熔化物以冷卻淬火，典型爲 倒於冷卻帶上或倒入冷流水中。然後粒子大小之減小可以 研磨（如需要）而完成。 其他過渡金屬氧化物亦可用作無機粘合劑之—部份，如 熟習技藝人士所周知。鋅 '始、銅、鎳、娃及鐵之氧化物 或氧化物前驅物爲普通者。這些添加已知可増進導體焊接 之黏者力。 無機枯合劑亦可含有多達糊料之約4份重量之燒綠石 (pyrochlore)相關之氧化物，具有下通式： (mxm，2_x)m，，2o7-z 式中 Μ係選自Pb、Bi、Cd、Cu、Ir、Ag、Y、具有原子數57_ 71之稀土金屬及其混合物中至少一個； Μ ’係選自p b、B i及其混合物； 係選自 RU、ir、Rh及其混合物；χ=〇-〇·5 ; z = 〇-i。 燒綠石材料詳細説明於1971年6月8日頒發給R】 Bouchard之美國專利3,5S3，93 1，併入本文供參考。繞綠石 材料係用作本發明組合物之黏著力促進劑。釕酸鉍销 CuojBh 5Ru2〇6 75爲較佳。 本紙張尺度逋;fj中國國家標準（οτ丨八4規格（2丨〇'〆297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 ΑΊ Β7 經濟部中央標準局員工消費合作社印製 .Λ、發明説明（5 添力Ρ劑 長石類之結晶材料加入上述組合物中。如本文所定義， 結晶材料係定義爲具規則週期排列之原子及在接受X光時 產生明顯繞射峰者。此情況不同於一般具有不規則排列、 無長期順序（ordering)之原子及擴散X光繞射圖型之玻璃。 添加劑可選自[Mai+]x[Mb2+]i xAl2xSi2+x〇8之組合物範園 ’其中Ma典型可爲鉀（κ)或鈉（Na)，^^典型爲鈣（Ca)，X爲 〇-1。孩材料爲陶瓷工業所知者，另説明於w. D Kinergy， et al., Introduction to Ceramics, Second Ed., John Wiley & S〇nS，NY，1976。相似地，咸信三價離子（Mc)(如鉍）可以 取代二價鈣，以Al/Si電荷補償，例如[Mc3+】x[Mb2+]卜χ
Af2+xSi2-x〇8。 除這些灰長石（anorthite)結構衍生物外，其他Ca_A1_si_〇 相亦存在，例如劈黃長石（gehlenite) Ca2Al2Si〇7。舜黃長 石亦具有廣泛範圍之取代容量，例如[Md]2[Me】[M山07， 其中Md選自Ca、Na，Me選自Mg、A卜Mf選自Si，A卜 此外’結晶結構添加劑屬於長石類，具有廣泛範圍之可 犯取代。例如，若使用鉀長石（微斜長石或正長石） K(AlSi3)〇s取代石灰長石（灰長石）於本發明中，可期待老 化黏著（aged adhesion)之相似利益。相似地，預期鈉長石 Na(AlSi3)〇8可用以取代石灰長石，對於導體黏著有相似之 有利效果。 本發明之較佳組合物含有糊料之〇〇1至3重量％之式 -8 - 木紙張尺度剌㈣时轉 (請先閱讀背面之注意事項再填寫本頁) -裝. 、1Τ A7 B7 〇371 .五、發明説明（6 ) '~~~
CaAl2Si208之結晶灰長石。 I.----------- ^------’訂 (請先鬩讀背面之注意事項再填寫本頁) 灰長石添加劑之存在非可預期地發現可提供較高導體老 化黏著力，而可焊接性極少喪失。在低於〇 〇丨重量％，黏 著利益不可期待；而在高於3重量％，可焊接性之退化預 期不理想。〇.〇5-0.50重量％之範園較佳，而〇·ι_〇·3重量％ 最佳。 有機介質 無機粒子與實質上惰性液體介質（載劑）使用行星式混合 器機械混合，然後於三輥磨機上分散以形成具有適合絲網 印刷之稠度及流變性之糊狀組合物。後者在習知陶资基底 上以習知方式印或「厚膜」。 經濟部中央標準局員工消費合作社印製 任何實質上惰性液體可用作載劑。各種有機溶體，含或 不含增稠劑及/或安定劑及/或其他普通添加劑，可用作載 劑。可使用之有機液體之實例爲脂族醇，該醇之酯例如醋 醋及丙酸醋’紅稀如松油’私品醇（terpjne〇i)等，樹脂 如低醇之聚甲基丙晞酸酯之溶液，及乙基纖維素於溶劑如 松油及乙二醇單醋酸酯之單丁基醚中之溶液。較佳載劑係 基於乙基纖維素樹脂及π -，/?-及，-萜品醇之溶劑混合物 (一般85-92% α -萜品醇，含有8-15%々-及r -萜品醇）。載 劑可令有揮發液體’以促進施於基底後迅速凝結（setting) 〇 分散液中載體對固體之比例可有相當大變化，偯分散液 施用之方式及所用載體之種類而定。一般爲獲得良好之遮 -9- 本紙译尺度適用中國國家蟋率（CNS ) Λ4^格（2!0X297公釐 A7 B7 >、發明説明（7 ) 蓋，分散液含有補充之60-90%固體物及4〇·10%載劑，如上 述。當然’本發明之組合物可以加入不會影響其有利特性 之其他材料而修飾。該調合物係在此技藝之技術内。 糊料方便於三輥磨機上製備。糊料之粘度典型在下列範 圍内，在Brookfield ΗΒΤ粘度計上以低、中及高剪切速率 測量： 剪切速率（秒-1) 粘度（Pa.s) 0.2 100-5000 300-2000 較佳 600-1500 最佳 4 40-400 100-250 較佳 140-200 最佳 40 10-150 25-120 較佳 50-100 最佳 所用載劑之量係以最終調配物所欲之粘度而決定。 £ - I -I - —1^ i 二· 1 (請先閲讀背面之注意事項再填寫本頁) 訂 L· 經濟部中央標準局員工消费合作社印製 調配及施用 在製備本發明之組合物中，粒狀無機固體物與有機介質 混合，以適合裝置（如三輥磨機）分散以形成懸浮液，產生 枯度於剪切速率4秒—1下在約100-200帕斯卡（pascai)·秒範 圍内之组合物。 在下列實例中，調配係以下列方式進行。 糊料之各成份於容器中一起稱重。然後各成份劇烈混合 10 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐)〜 經濟部中央標準局員工消費合作社印製 A7 ___B7 _五、發明説明（8 ) 以形成均勻摻合物；然後摻合物通過分散裝置（如三棍磨 機）以使粒子達到良好分散。使用Hegman規（gauge)以測定 糊料中粒子之分散狀況。此裝置包含一溝槽於一鋼塊中， 其一端深25微米（1 mil)，另一端傾斜達0深度。使用一刀 片沿溝槽之長度拉下糊料。刮痕出沉於溝槽中，若凝結物 之直徑大於溝槽深度。滿意之分散典型產生第四刮點1〇_ 18微米。溝槽之一半未覆蓋充分分散糊料之點典型係在3 至8微米之間。第四刮痕測量>20微米及「一半溝槽」測量 >10微米係表tf不良分散之懸浮液。 然後組合物塗於基底，如蓉土陶瓷，一般以絲網印刷方 法，至濕厚度約30-80微米，較佳35-70微米，最佳40-5〇微 米。本發明組合物可以使用自動印刷機或手動印刷機以習 知方法印於基底，較佳使用自動絲網印刷技術，使用2〇〇 至3 2 5網目碑.。然後印刷圖型在燃燒（firjng)前於低於2〇〇〇c ，約l5〇°C ’乾燥約s-ι5分鐘。使無機粘合劑及金属之細 分粒子燒結之燃燒較佳於充分通氣之帶式運輸機爐中進行 ，溫度情形（profile)爲有機物質在約300-60CTC燒光，然後 約800-1000°C之最大溫度期間持續約5_ i 5分鐘，然後爲經 控制之冷卻循環以防止過度燒結，在中間溫度不欲之化學 反應，或由於冷卻太迅速可能發生之基底破碎。整個燃燒 程序較佳延長約30-60分鐘之期間，以10_25分鐘達燃燒溫 度’在燃燒溫度約1 〇分鐘，及冷卻約1 〇_25分鐘。在—些 情況，總循環時間可使用短至20-30分鐘之習知燃燒及7_14 分鐘之紅外線燃燒。 測試程序 -11 - ;紙張尺度適用中國國家標,（CNS )八4規格（210X297^51 (請先閲讀背面之注意事項再填寫本頁) —裝. 訂 經濟部中央標準局員工消費合作社印製 A7 B7 7五、發明説明（9 ) 可焊接性（solderability):可焊接性測試係如下進行：所 用焊接劑合金爲Sn/36 Pb/2 Ag，維持在22(TC。經燃燒之 部份侵入溫和活性松香助溶劑（flux)如Alpha Metals Inc.， Jersey City, NJ所製造之焊接助溶劑之商品名稱）中，然後 陶瓷小片（chip)之邊緣浸入熔化之焊劑中加熱3秒鐘。然後 小片浸入焊劑中5秒鐘，取出，清洗及檢查。可焊接举係 以厚膜測試圖型上所獲得之焊劑覆蓋百分比（組成）測定。 可焊接値95%或以上一般視爲極佳濕潤（wetting)。 另一方法係使用小焊劑歷片（preform)之展開（spread)。導 體之1公分方塊印刷及燃燒，然後一細條上述助溶劑以一 細刷塗過方塊。直徑約1.4毫米及高0.4毫米之焊劑壓片放 於濕助嫁劑上，部份放入Browne Corporatio.n LR-6型帶式 反流（reflow)單元上以進行焊劑反流。尖峰反流溫度典型 爲220-230C歷10-20秒鐘。或者，若反流單元不可得，基 體可放於熱板上以進行在片之反流。然後測量反流壓片之 直徑，並報告相對於壓片起始直徑之增加百分比，以評估 導體組合物之可濕性（wettability)。較高度濕澗之材料在反 流後具有較大量之壓片展開。直徑增加25%或以上一般視 爲極佳濕调（wetting)。 黏著力（Adhesion):黏著力係使用Instron 1122型拉引 (pull)測試機於90°C剝離（peel)結構中以拉速每分鐘2对測 量。20規（gauge)之預先鍍錫電線（wires)，以焊接浸入 62Sn/36Pb/2Ag焊劑中於220°C 或 63Sn/37Pb焊劑中於 230°C 歷10秒鐘，使用Alpha 61 1助熔劑，接於80 mil X 80 mil墊 。老化（aging)研究在空氣中於Blue M StabU-Therm®爐控制 .12 - 本紙張尺度適用中國國家標準（CNS〉A4規格（210X 297公瘦） (請先閲讀背面之注意事項再填寫本頁) '装. 訂 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（1〇 ) 在150 C或170°C進行。在老化後，於拉電線之前測試部份 在空氣中平衡數小時。在150。〇老化48或更多小時之後， 剝離力至少15牛頓，較佳大於18牛頓，視爲大多數應用必 要者。 經谭接之厚膜導體於陶瓷基底之電線剝離（peel)黏著力 進一步説明於 Ε· I. Du Pont de Nemours and Company之 Bulletin No. A-74672, "Method of Test for Wire Peel
Adhesion of Soldered Thick Film Conductors to Ceramic Substrates” 0 實例 在下列實例中’導體糊料印於1^〇€(：1181：〇6^11^〇96%裝土 基底上，除非另有説明。燃燒之厚度約8至12微米。老化 黏著（Aged adhesion)部份經帶式爐以尖學溫度850°C燃燒5 次，在尖峰溫度1〇分鐘，由100°C至85(TC加熱及冷卻1〇分 鐘。在爐中，總逐室（door-to-door)過渡時間爲約48小時。 可焊接部份以相同情形（p.r〇file)燃燒1次。 實例1-6證明本發明之本質。導體調配物用或不用灰長石 (anorthite)製備，用0.2%灰長石具有顯著增進之老化黏著 力（aged adhesion)，可烊接性極少退化，以焊劑反流 (reflow)直徑測量。該老化黏著力之增加量極難以習知方 式（即加入熟習技藝人士所周知之其他玻璃料或過渡金屬 氧化物黏著促進劑）達成。此外，有利效果係以二種不同 叙酸鹽玻璃料測得，以及以硼矽酸鉛玻璃料加入氧化鉍測 得。 -13- 本紙張從剌巾關緒準（CNS丨'2Ϊ0Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) ‘裝· 訂 S37l 五、發明説明（11
實例號碼Ag Pd 玻璃料類型 玻璃料 Bi203 燒綠石 Cu20 C03O4 灰長石 載劑 4 4 1 0 170 經濟部中央橾準局員工消費合作.社印製 8 1 53. 13.8 C 1.7 20.8 老化 條件 48小 (°C) 老化黏著力 142 [N] 可焊接性 3 4 % [展開增加] 2 _ 3 4 5 53.7 56.8 56.5 56.8 13.8 14.5 14.6 C A A B 1.7 5.5 5.7 5.5 4.0 ··> _ μ 4.0 2.1 2.1 2.1 1气 1.1 1.1 1.1 0.3 0.3 0.3 0.3 0.2 —_ _ 0.2 _ _ _ 20.7 … iy.6 19.5 19.6 170 150 150 150 48小時 ioo小時 100小時 100小時 22.8 16.4 20.6 13.8 31% 36% 3 6% 3 0% 6 56.5 14.5 B 5.7 · _ _2.1 1.1 0.30.2 19.5 150 1 〇〇小時 19.3 恭加灰長石之功效之 性並非於所有樣品上測哥，p實例7至12中探究°可坪接 σ 量’而疋基於實例12中高灰長石樣 品之極佳濕潤性（wetting)(焊劑壓片直徑增加29〇/。），咸信所 有樣品均具有極佳濕潤性。較大量玻璃料使用於實例7-1 2 -14- 本紙張尺窆適用中國國家榡準（CNSTA4规ϋ 210X297公楚) (請先閲讀背面之注意事項再填寫本頁} • Hr*' ttr— Hi —I— Hi --^‘ Is -------- I — 訂一 A7 B7 一五、發明説明（12 中，相對於實例5及6，固而黏著力較大。然而，甚至在蝴 =疋0.02%灰長石含量，灰長石添加之功效仍然明顯，黏 著力増進。預期在低於糊料之〇〇ι %含量，灰長石對於老 化黏著力之有利效果微小。 基_3 ^ Ί-- 背面之項再L )
• l n J— If· JI 訂 經濟部中央棣準局員工难費合作.社印製 老化條件 120小時120小時 (。〇 150 老化黏著力 [N] 120小時120小時120小時120小時 150 150 150 150 25.2 27.7 28.5 28.4 可焊接性 _ --— - 擊 _- [展開增加] 實例1 -1 2均使用氧化姑作爲調配物之一部份。然而， 21.3 150 25.2 29% 本 實例號碼 7 8 9 10 11 Ag 56.1 56.1 56.1 56.1 56.1 Pd 14.4 14.4 14.4 14.4 14.4 破璃科類型 B Β Β Β Β 玻璃科 6.73 6.71 6.68 6.62 6.57 燒綠石 2.10 2.10 2.10 2.10 2.10 Cu〇0 …一 1.05 1.05 1.05 1.05 1.05 C〇,o. . 3 4 0.32 0.32 0.32 0.32 0.32 灰县；f； ^ _ _ _ 載劑 υ 0.02 0.05 U.11 0.16 19.4 19.3 19.3 19.3 19.3 本成張尺度適用 -15- 準（CNS ) Α4規格（21.」χ6Τϋ ) 一五、發明説明（13 I I— I.....I - i I— I J! · 經濟部中央標準局員工消費合作衽印製 ，明不需氧化鈷之存在，如實例13_16證明。先前已揭示 氧化鈷對於老化黏著力具有利效果，但氧化姑在達到增進 黏著力之量會使可焊接性降低。因此，本發明可增進黏著 力，而無氧化鈷有關之可焊接性降低。 表 — — 4 實例號碼 13 14 15 16 Ag 56.5 56.5 56.5 56.5 Pd 14.5 14.5 14.5 14.5 破璃料類型 B B A A 破璃料 6.0 6.0 6.0 6.0 燒綠石 2.0 2.0 2.0 2.0 Cu20 1.0 1.0 1.0 1.0 c〇3〇4 — _ ... 灰長石 — 0.2 _ _ _ 0.2 載劑 19.8 19.8 19.8 19.8 老化條件 120小時120小時120小時120小時 (°C) 150 150 150 150 老化黏著力 14.6 20.8 11.7 15.4 [N] 可焊接性 39% 34% 3 5% 36% [展開增加] 實例1-16均使用 相似之赵含量約14.5 %， -16 本紙張尺度適用中國图家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁} ^ tflai— ml I J nn m nll« -訂-- 9/1。本發明可使用廣泛範圍合金含量，如實例i7_28證 明。例如，0.5%灰長石顯示，對於使用2〇%pd之糊料調配 物，老化黏著力増加大於12 N(實例17及18)。增加丨丨N發 現於0.25%灰長石加入使用7%鉑之銀糊料調配物（實例19及 20)。含16%Pd及4%Pt之三元Ag/Pd/Pt糊料揭示於實例21及 22 ’其中證明1%灰長石獲得近12 n利益。相似地，含 3.5%Pd及l%Pt之二元Ag/Pd/Pt顯示於實例23及；24，其中 0.2%灰長石增加老化黏著力由ΐ6·7至21 _3 N。在實例25及 26中，本發明含〇.4%Pt之低粘合劑Ag/Pt組合物顯示由 0.2%灰長石獲得較少量黏著力之增加。實例27及28顯示含 18%Pt之組合物。 在實例25及26中，灰長石加入pt/Ag糊料中減少黏著力之 利可邊由於低量無機枯合劑存_在於起始組合物中（總糊 料之1%)所造成。因此，實驗顯示灰長石本身實際上不會 導致黏著力增加，需要連同無機粘合劑使用；1〇/〇無機粘合 劑代表灰長石添加具有利效果之實施下限。另一方面，灰 長石可有利地使用於無機粘合劑含量高至1 8%之導體系統 中，如實例2 1及22所示，但含大於約1 8°/〇粘合劑之導體之 經濟部中央橾準局員工消費合作社印製 T焊接性可能降低，如實例21及22中可焊接性値約90_93〇/〇 所證明。 灰長石添加之有利效果已經證明於所謂之玻璃粘合、氧 化物枯合及混合粘合系統中。玻璃粘合系統使用玻璃料作 爲無機粘合劑，如實例i 7及丨8及實例2 1及2 2所示（當然 ’灰長石糊料18及22之存在在技街上不適合稱爲玻璃轴 s系統’但是「玻璃枯合」乙詞係用以描述起始之糊料調 -17 - 本紙張尺度適用中國國家標率（CNS ) A4規松（210X297公—1 ------ A7 五、發明説明（15 配物）。在本發明之實例中，玻璃結合系統均使用單一玻 璃料，但玻璃料之混合物亦可使用，對熟習技蓺 而易知者。實例25及婦明灰長石加入氧化；枯合；； 之利益，而實例1 -1 6顯示灰長石於混合粘合系統中之有利 效果。混合粘合系統亦使用單一玻璃料，但玻璃料之混合 物亦可使用，對熟習技藝人士爲顯而易知者。 灰長石添加之上限定義爲可焊接性之下降太大而不能耐 受之程度。在某個程度，此上限依合金含量而定，因爲高 Pd含量導體需要較高量玻璃料以發生粘合，故可耐受較高 量糊料添加劑’爲熟習技藝人士所周知。0.5%及1.0%之灰 長石含量分別使用於實例18及22中，其起始組合物之可 焊接性接少變化。咸信在所有欲實施系統中灰長石含量大 於約3%會導致可焊接性下降。然而’在可焊接性極少或 無價俊之用途中，或使用其他方式以達到互相連接時，可 使用灰長石含量大於3 〇/〇。 (請先閲讀背面之注意事項再填寫本頁) ‘裝·
、1T 經濟部中央標準局員工消費合作社印製 -18-
7公釐） 3^〇37l A7 B7 Λ、發明説明（is ) 畸窆鹑ii Acra Pd Pt 蚪is-聿绪1¾ 鲜ia-聿 ®.2〇3 pbo 痒铎；ε CUSJ〇 ζη〇 COJJ04 婢¾re) 涞含龄蜥Λ 【Ν1 iP5 —I — loo.o 18.0 23.0 48vaf 4848+-^-150 150 150 7.2 19.3 18.5 99% 99% 99% 2.0 17 100^ 47.0 47056.0 20.0 20.0 i — — 7.0 AAA 15.0 15.0 12.0 (請先閱讀背面之注意事項再填寫本頁) * fn^—· fluLrl 29.6 13.1 24.9 16.7 21.3 9S/D 93% 90% 100% 10〇y〇 S5 --- 10 23.0 180loo.o 48*hBf 48-j»令 48VS令 150 150 s 100.85 48 二 i 150 2.0 20 56.0 7.0 A 12.0 21t.o 16.0 s A 180 22 t.o 160 i A 180 〇 I Ο U) J —一〇一 I · · I * · ^ 〇 (-Λ O U> 23 70.0 3.5 2公 700 3.5 1.0 C 1.5 10 3.5 0.15 0.5 0.2 18.85 48、Ji 150 > 經濟部中央標準局員工消費合作社印製 96。/。 98% 99% 100% 10.4 12·2 16.
2S --- 0.2 ί 0.2 15.3 15.3 207 20.7 48*>尊 48<.Mf 矣v^48,*r3f 170 170 170 170 0.23 0.17 0.23 0.17 0.3 0.3 0.45 0.15 0.45 0.15 0.4 0.4 18.0 C 2.06 -^.9 厶 91 18.0 0 206 4.9公 25 26 27 28 83.3 83.3 540540 本紙乐尺度適用中國國家標準（CNS ) A4規格（2 H)'〆297公釐） 經濟部中央標準局員工消費合作社印製 A7 ___B7 ，五I發明説明（17 ) — '〜〜 本發明不限於銀之導體調配物。Au/Pt/Pd組合物示於實 例29中，證明使用0_2%灰長石有高黏著力及可焊接性。'爲 不使用灰長石於系統中而獲得高老化黏著力，需要相當大 量無機粘合劑’此會使可焊接性降低。所用之焊^爲 63/37 Sn/Pb，在 240°C 之溫度。糊料印於 c〇〇r Ceramics (Golden Colorado) 96% 蓉土 基底上，燃燒 6次 〇 表 6 實例號碼 29 Au 56.5 Pd 2.58 Pt 15.2 玻璃料類型 C 玻璃料 2.2 Bi2〇3 4.6 C〇3〇4 0.35 灰長石 0.20 載劑 19.8 老化條件 3 0 0小時 (C) 150 老化黏著力[N] 蓉土 > 25N 老化黏著力[N] 5704介電體 > 25N 可焊接性 [百分比]礬土 99% 可焊接性 [百分比] 100% 5704介電體 評估幾種其他導體玻璃系統，以測定灰長石於厚膜導體 調配物中之多樣性，如實例30-39中所述。例如，複合之 蝴碎酸鋅（玻璃D)使用於Ag/Pd/Pt導體調配物中，示於實例 -20- 本紙張尺度適用中國國( ^ ; 10X297^ )~一' (請先閱讀背面之注意事項再填寫本頁)
Λ、發明説明（18 ) 30及31中。其中，氧化姑以灰長石取代，具增加之 性能。同時，一系列無鉛玻璃於實例32_39中評估。所 估之特定調配物不具有高老化黏著力，實例32_39中所有 値均低於18 Ν’但0.2%灰長石使黏著力增加31至561^。 較高玻璃料含量，或加入其他過渡金屬氧化物如氧化鈷或 氧化鎳，於這些實例中可使黏著力增加。 實例40-42係用作比較，以證明不定形之錯梦酸芬不可用 以取代本發明中灰長石。Ca-Al-Si玻璃之組成重量〇/0如下 :24.0% CaO，14.6% Al2〇3，61.4% Si02。其中，當 〇.2%
Ca-Al-Si玻璃加入起始組合物中時，未測得老化黏著力發 生變化，與0.2%結晶灰長石加入時相反。（請注意，實例 4〇及42實質上分別爲實例13及14之重製，但使用不同批之 粉末°測試數據之差異可以少許加工變化解釋，如最終糊 料中金屬粒子之凝聚程度，導體之敏密化（densification)程 度，等）。 (請先閲讀背面之注意事項再填寫本頁) ---JU.‘裝------訂----- 經濟部中央標準局貝工消费合作社印製 21 - Μ氏張.尺度適用㈣®家標^ CNS ) A4规格（21GX297公餐） i、發明説明（19 ) A7 B7 表 7 實例號碼 30 31 32 33 34 Ag 47.0 47.0 56.5 56.5 56.5 Pd 16.0 16.0 14.5 14.5 14.5 Pt 1.0 1.0 ••場 玻璃料類型 D D E E F 玻璃料 3.0 3.0 6.0 6.0 6.0 Bi2〇3 9.0 9.0 燒綠石 0.75 0.75 2.0 2,0 2.0 Cu2〇 … — 1.0 1.0 1.0 C03O4 0.25 —— __ 灰長石 -一 0.25 一- 0.2 載劑 23.0 23.0 19.8 19.8 19.8 老化 48小時48小時48小時48小時 48小時 條件 150 150 150 150 ISO (C) 老化黏著力 20 28 12.4 16.2 6.4 [N] 可烊接性 100% 100% 100% 100% 100% 11.8 4.7 [百分比j 35 56.5 14.5 F 6.0 2.0 1.0 0.2 19.8 48小a 150 36 56.5 14.5 G 6.0 2.0 1.0 37 56.5 14.5 G 6.0 2.0 1.0 38 56.5 14.5 Η 6.02.0 1.0 39 56.5 14.5 Η 6.0 2.0 1.0 — 0.2 19.8 19.8 48小時48小時 150 150 … 0.2 19.8 19.8 48小時48小時 150 150 7.8 9.7 62% 15.3 60% (請先閱讀背面之注意事項再填寫本頁) -|~ —II ^ I^1 裝.
-、1T 經濟部中央標準局員工消費合作钍印製 -22 - 本紙張尺度適用中國萏家標準（CNS )八4規格（21〇Χ297公釐） 〇^Z37l A7 B7 ;、發明説明（2〇 )A__ 實例號碼 40 41 42
Ag 56.5 56.5 Pd 14.5 14.5 玻璃料類型 B B 玻璃料 6.0 6.0 燒綠石 2.0 2.0 Cu2〇 1.0 1.0 Ca-Al-Si 玻璃 -— 0.2 灰長石 — — 載劑 19.8 19.8 6 5
4 IX B 6 2 ;ο 9 5 5 ο ο ο 2 8 (請先閲讀背面之注意事項再填寫本頁) 老化條件(uc) 老化黏著力[N] 可焊接性 [百分比] 48小祠48小祠48小時 150 150 150 5.4 5.0 12.6 100% 99% 100% 經濟部中央標準局員工消費合作社印製.
1^1 —In— ml m· I mM i I、一一i»Jnn n^— 1 nn J n ^1^11 —ϋ I -23 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐）

Claims (1)

  1. 1Γ2Τ92號專利申請案 請專利範圍修正本(86年4月） Α8 Β8 C8 D8
    .經濟部中央梂準局員工消f合作社印製 々、申請專利範圍 1. 一種厚膜組合物’包含糊料重量（A) 5〇至9〇重量％之金屬 導電相之細分粒子’（B) 1至18重量％之無機粘合劑相， (c) 〇.〇1至3·〇重量％之式队1+]具2+]1 X Αΐ2』2+χ〇8之黏著 力促進劑’兴中Ma選自κ，Na，Mb爲Ca，X爲0-1，（A)、 (B) 及（C)均分散於有機介質中。 2. —種厚膜組合物，包含糊料重量（A)5〇至9〇重量％之金屬 導電相之細分粒子，（B) 1至18重量％之無機粘合劑相， (C) 0.01 至 3.0重量％之式[d%% xAl2+xSi2 x〇8之黏 著力促進劑’其中三價離子Mc選自Bi，Fe，Mn，Cr，V ，Sc，In，Y，Gd，Eu，Sm，Nd，Pr，Ce，La及 Sb，（A) 、（B)及（C)均分散於有機介質中。 j. 一種厚膜組合物’包含糊料重量（A) 5〇至90重量％之金屬 導電相之細分粒子’（B)【至^重量％之無機粘合劑相’ (c) 〇.〇1至3_〇重量％之式[Md]2[Me][Mf]2〇7t黏著力促進劑 ，其中Md選自Ca，Na，Me選自Mg，Al，Mf選自Si， A1，（A)、（B)及（C)均分散於有機介質中。 4.根據申請專利範圍第1項之组合物，其中黏著力促進劑爲 CaAl2Si2〇8 0 5_根據申請專利範圍第i項之組合物，其中導電相選自Ag ，Ag及Pd，Ag及Pt，或Ag及Pd及Pt，其中pd含量爲〇 至20重量％，Pt含量爲〇至20重量％。 ό.根據申請專利範圍第1項之組合物，其中導電相選自au ，Au及Pd，Au及Pt，或Au及Pd及Pt，其中Pd含量爲0 至20重量％，Pt含量爲〇至20重量％。 本紙張尺度逋用中國國家橾準（CNS > Α4現格（210X297公釐） 11—-----一—裝—— (請先閲讀背面之注意事項再填寫本頁) 訂 Λ 32〇37i 經濟部中央橾準局員工消費合作杜印製 A8 B8 C8 D8六、申請專利範圍 " 7 .根據申請專利範園第1項之組合物，其中無機粘合劑包含 一或多種玻璃。 8 .根據申請專利範圍第1項之组合物，其中無機粘合劑包含 一或多種玻璃，及一或多種氧化物或氧化物前驅物。 9 .根據申請專利範固第丨項之組合物，其中無機粘合劑包含 一或多種氧化物或氧化物前驅物。 10,根據申請專利範圍第8項之組合物，其中破璃係選自鉍酸 鹽玻璃料、矽酸鉛玻璃料、硼矽酸鉛破璃料或其混合物 ，氧化物包括糊料之0至3重量％氧化銅、〇至4重量％燒 綠石（pyrochlore)有關之化合物、〇至1重量。氧化銘、〇至 5重量％氧化鉛及〇至丨2重量％氧化鉍，或其前驅物。 11_根據申請專利範圍第1 〇項之組合物，其中燒綠石有關之 化合物具有式（mxm，2-x)m"2o7-z，其中M係選自Pb、Bi、 Cd、Cu、Ir、Ag、Y、具有原子數57_71之稀土金屬及其 混合物；Μ，係選自Pb、Bi及其混合物；Μ"係選自Ru、卜 、Rh及其混合物；χ=〇·〇.5 ; ζ=0-1。Π.根據申請專利範圍第n項之組合物，其中燒綠石有關之 化合物爲Cu〇 #丨丨5Ru2〇6 75。 (锖先閱讀背面之注意事項再填寫本頁) 裝 訂 -2-
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EP0716430A1 (en) 1996-06-12
CN1129340A (zh) 1996-08-21
DE69515108T2 (de) 2000-09-28
EP0716430B1 (en) 2000-02-16
DE69515108D1 (de) 2000-03-23
KR960025816A (ko) 1996-07-20
US5518663A (en) 1996-05-21
JPH08245239A (ja) 1996-09-24
CN1090369C (zh) 2002-09-04

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