TW201615854A - 用於焊料層次的低溫高可靠度合金 - Google Patents

用於焊料層次的低溫高可靠度合金 Download PDF

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Publication number
TW201615854A
TW201615854A TW104123598A TW104123598A TW201615854A TW 201615854 A TW201615854 A TW 201615854A TW 104123598 A TW104123598 A TW 104123598A TW 104123598 A TW104123598 A TW 104123598A TW 201615854 A TW201615854 A TW 201615854A
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Taiwan
Prior art keywords
weight
alloy
indium
silver
copper
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TW104123598A
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English (en)
Inventor
喬杜里普里沙
迪阿維拉里巴斯摩卡那
木克吉蘇塔巴
沙卡蘇利
潘德賀蘭吉特
巴特卡爾拉維卓亞
西恩寶瓦
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阿爾發金屬公司
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Publication of TW201615854A publication Critical patent/TW201615854A/zh

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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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/002—Soldering by means of induction heating
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/005—Soldering by means of radiant energy
    • B23K1/0056—Soldering by means of radiant energy soldering by means of beams, e.g. lasers, E.B.
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/08—Soldering by means of dipping in molten solder
    • B23K1/085—Wave soldering
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B23K35/0227—Rods, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B23K35/0233—Sheets, foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B23K35/0233—Sheets, foils
    • B23K35/0238—Sheets, foils layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • 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
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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
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
    • B23K2101/40—Semiconductor devices
    • 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
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Abstract

一無鉛無銻焊料合金，包含： (a)1至4重量%的銀 (b)0.5至6重量%的鉍 (c)3.55至15重量%的銦 (d)3重量%或更少的銅 (e)可選的一種或更多種以下的元素 0至1重量%的鎳 0至1重量%的鈦 0至1重量%的錳 0至1重量%的稀土元素，例如鈰 0至1重量%的鉻 0至1重量%的鍺 0至1重量%的鎵 0至1重量%的鈷 0至1重量%的鐵 0至1重量%的鋁 0至1重量%的磷 0至1重量%的金 0至1重量%的碲 0至1重量%的硒 0至1重量%的鈣 0至1重量%的釩 0至1重量%的鉬 0至1重量%的鉑 0至1重量%的鎂 (f)其餘的錫，連同任何無法避免的雜質。

Description

用於焊料層次的低溫高可靠度合金
本發明大體而言係關於冶金的領域及合金，尤其本發明係關於無鉛且無銻的焊料合金。該合金尤其(但非排他地)適用於電子焊接應用，例如波焊、表面安裝技術、熱風整平和球柵陣列、平面柵格陣列、底部終結封裝、LED及晶片級封裝。
波焊(或流焊)是一種廣泛使用的大量焊接電子組件的方法。波焊可被用於例如通孔電路板，其中該板經過熔融焊料波，熔融焊料波拍打該板的底部，以潤濕待接合的金屬表面。另一種焊接技術涉及將焊膏印刷在印刷電路板的焊接墊上，隨後放置並使整個組件通過回流爐。在回流製程期間，焊料熔化並潤濕板上的焊接表面以及元件。另一種焊接製程涉及將印刷線路板浸沒於熔融焊料中，以使用可焊保護層塗佈銅終端。這個製程被稱為熱風整平。球柵陣列接點或晶片級封裝通常是使用焊料球在兩個基板之間組裝。這些接點的陣列被用於將晶片安裝在電路板上。
隨著無鉛焊接材料的使用變得普遍(無論是由於環保指令或來自終端使用者的壓力)，這種材料的應用 範圍亦日益普及。高Ag焊料合金(例如SnAg3.0Cu0.5)具有優異機械性能和良好熱可靠度的益處。然而，這種合金的熔點為約217-221℃。這個較高的熔點要求約240-250℃的回流溫度，在某些情況下此舉可能會損壞印刷電路板(PCB)和電子元件。
需要有熔點比傳統的高銀合金更低、但具有類似或更有利的機械和熱性能的無鉛焊料合金。
本發明旨在解決至少一些與先前技術相關的問題或提供商業上可接受的替代品。
因此，在第一態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)1至4重量%的銀
(b)0.5至6重量%的鉍
(c)3.55至15重量%的銦
(d)3重量%或更少的銅
(e)可選的一種或更多種以下的元素
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鎵
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的磷
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(f)其餘的錫，連同任何無法避免的雜質。
現在將進一步描述本發明。在以下段落中更詳細地界定本發明的不同態樣。可以將如此界定的每種態樣與任一或多個其他態樣結合，除非有明確相反的指示。特別是，可以將任何被指示為較佳或有利的特徵與任一或多個其他被指示為較佳或有利的特徵結合。
本文中使用的術語「焊料合金」包括熔點在90至400℃範圍中的可熔金屬合金。
本文所述的合金表現出改良的高溫可靠度，並且能夠承受通常至少125℃的操作溫度。
該合金具有相對低的熔點，更具體為低液相溫度，典型為215℃或更低的液相溫度，更典型為低於210 ℃，甚至更典型為低於205℃。這使得該合金能夠被用於低溫回流製程，例如在210至230℃的回流製程。這種低溫回流製程與傳統回流製程相比造成焊接元件損傷之可能性較低。
該合金可以被有利地用於在單個板上採用多回流製程的焊接方法。例如，在第一回流製程中，可以使用標準合金(例如SnAg3.0Cu0.5)將所有可以容忍較高回流溫度的電子元件焊接到板上。在第二回流製程中，可以使用本發明的合金處理溫度敏感元件。
該合金可以表現出改良的機械性能和機械可靠度。該等機械性能、機械可靠度及熱可靠度可以與傳統的高銀焊料合金(例如SnAg3.0Cu0.5)類似或更有利。
該合金可以表現出改良的熱衝擊性能。例如，該合金安全度過超過2000個循環的IPC-9701熱循環測試，該循環係從-40℃至125℃，且在各溫度的停留時間為10分鐘。
該合金是無鉛和無銻的，意思是沒有蓄意添加鉛或銻。因此，鉛和銻的含量為零或在不超過附帶雜質的水平。
該合金組成物包含1至4重量%的銀。該合金較佳包含1.2至3.8重量%的銀，更佳包含2.5至3.5重量%的銀，甚至更佳包含2.75至3.76重量%的銀，還甚至更佳包含2.75至3.75重量%的銀。以指定量存在的銀可 用於通過金屬間化合物的形成來改良機械性能，例如強度。另外，銀的存在可以作用來改良潤濕和擴散。
該合金組成物包含0.5至6重量%的鉍。該合金較佳包含1.5至5.5重量%的鉍，更佳包含2至5重量%的鉍，甚至更佳包含2.5至5重量%的鉍，還甚至更佳包含2.5至4.5重量%的鉍。以指定量存在的鉍可用於通過固溶體強化來改良機械性能。鉍也可以作用來改良抗潛變性。鉍也可以改良潤濕和擴散。
該合金組成物包含3.55至15重量%的銦。該合金較佳包含3.6至12重量%的銦，更佳包含3.65至12重量%的銦，甚至更佳包含3.7至11重量%的銦，還甚至更佳包含4至10.5重量%的銦，還甚至更佳包含4.50至10重量%的銦。該合金較佳可以包含3.7至10重量%的銦。或者，該合金較佳包含3.6至8重量%的銦，更佳包含3.65至7重量%的銦，甚至更佳包含3.7至6.7重量%的銦，還甚至更佳包含4至6.5重量%的銦。銦的存在可以作用來通過固溶體強化改良機械性能。以所列舉量存在的銦連同其他合金元素還可用於降低該合金的液相溫度。在替代的態樣中，該合金可以包含高達25重量%的銦。
該合金組成物包含3重量%或更少的銅，例如0.1至3重量%的銅。該合金較佳包含0.01至3重量%的銅，更佳包含0.1至1重量%的銅，甚至更佳包含0.4至0.8重量%的銅，還甚至更佳包含0.4至0.75重量%的 銅。以指定量存在的銅可用於通過金屬間化合物的形成來改良機械性能，例如強度。此外，銅的存在減少銅的溶解，而且還可以提高抗潛變性。
該合金組成物可選地包含0至1重量%的鎳，例如從0.01至1重量%的鎳。假使鎳存在時，則該合金較佳包含0.01至1重量%的鎳，更佳包含0.03至0.6重量%的鎳，甚至更佳包含0.05至0.5重量%的鎳，還甚至更佳包含0.08至0.25重量%的鎳。以指定量存在的鎳可用於通過與錫形成金屬間化合物來改良機械性能，從而可以導致析出強化。鎳也可以藉由減少在基板/焊料界面的IMC增長來提高耐掉落衝擊性。
該合金組成物可選地包含0至1重量%、例如0.005至1重量%的鈦。假使鈦存在，則該合金較佳包含0.005至0.5重量%的鈦，更佳包含0.007至0.1重量%的鈦，甚至更佳包含0.008至0.06重量%的鈦，而且最佳包含0.01至0.05重量%的鈦。以指定量存在的鈦可用於改良強度和界面反應。鈦還可以藉由控制在基板/焊料界面的銅擴散來改良掉落衝擊性能。
該合金組成物可選地包含0至1重量%的錳，例如從0.005至1重量%的錳。假使錳存在，則該合金較佳包含0.005至0.5重量%的錳，更佳包含0.007至0.1重量%的錳，甚至更佳包含0.008至0.06重量%的錳，而且最佳包含0.01至0.05重量%的錳。以指定量存在的錳 可用於改良強度和界面反應。錳也可以改良掉落衝擊性能。
該合金組成物可選地包含0至1重量%的鈷，例如從0.01至1重量%的鈷。假使鈷存在，則該合金較佳包含0.01至0.6重量%的鈷，更佳包含0.02至0.5重量%的鈷，甚至更佳包含0.03至0.4重量%的鈷，而且最佳包含0.04至0.3重量%的鈷。鈷還可以減緩IMC在基板/焊料界面形成的速率，並提高耐掉落衝擊性。
該合金還可以可選地含有0.005至1重量%的鋁、0.005至1重量%的鈣、0.005至1重量%的鍺、0.005至1重量%的鎂、0.005至1重量%的磷、0.005至1重量%的釩中之一者或更多者。這樣的元素可以用來作為去氧化劑。這些種元素的存在可以改良合金的可潤濕性。
該合金還可以可選地含有0.005至1重量%的金、0.005至1重量%的鉻、0.005至1重量%的鐵、0.005至1重量%的鉬、0.005至1重量的鉑%、0.005至1重量%的碲、0.005至1重量%的硒中之一者或更多者。這樣的元素可以用來作為去氧化劑。這些種元素可用以改良強度和界面反應。
該合金可以可選地含有0.005至1重量%的稀土元素。稀土元素可以作用來改良散佈和可潤濕性。已發現鈰在這方面特別有效。
本文中使用的術語稀土元素係指選自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及Lu的一種或更多種元素。
該合金通常將包含至少74重量%的錫，更典型包含至少80重量%的錫，還更典型包含至少85重量%的錫。
在一個實施例中，提供了一種合金，該合金包含2至4重量%的銀、1至6重量%的鉍、0.1至1.5重量%的銅、3.65至4.5重量%的銦、0.05至0.25重量%的鎳，其餘為錫。這種合金可以表現出特別有利的低液相溫度連同有利的熱和機械性能的組合。例如，該合金通常可以表現出210℃或更低的液相溫度連同大於或等於100MPa的極限拉伸強度。
在進一步的實施例中，提供了一種合金，該合金包含3至4.5重量%的銀、3至4.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、0.05至0.25重量%的鎳。這種合金具有209.2℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.5重量%的銀、4重量%的鉍、0.7重量%的銅、3.7重量%的銦、0.2重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、4至5.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有208.1℃的液相溫度。在這個實施 例的一個具體實例中，該合金包含約3重量%的銀、5重量%的鉍、0.7重量%的銅、3.75重量%的銦、0.1重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含1至2重量%的銀、4至5.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有215℃的液相溫度。在這個實施例的一個具體實施例中，該合金包含約1.5重量%的銀、5重量%的鉍、0.7重量%的銅、3.75重量%的銦、0.16重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、1至2重量%的鉍、3至4.5%的銦、及0.1至1.5重量%的銅。這種合金具有213℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、0.9重量%的鉍、0.5重量%的銅、3.6重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、1至2重量%的鉍、4至5.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有210.5℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、1重量%的鉍、0.5重量%的銅、4.6重量%的銦、0.11重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、3.5至5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有210.2℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、0.5重量%的銅、4重量%的銦、0.2重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、4至5.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有207.9℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、2.9重量%的鉍、0.5重量%的銅、4.75重量%的銦、0.11重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀，2.5至4重量%的鉍，5至6.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。這種合金具有206.50℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、0.5重量%的銅、6wt%的銦、0.1重量%的鎳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、5至6.5%的銦、0.1至1.5重量%的銅、0.05至0.25重量% 的鎳、及0.001至0.05重量%的錳。這種合金具有207.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、0.5重量%的銅、6重量%的銦、0.15重量%的鎳、0.022重量%的錳，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、10至13%的銦、0.1至1.5重量%的銅、及0.001至0.01重量%的Ge。這種合金具有196℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、0.6重量%的銅、12重量%的銦、0.005重量%的鍺，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含1.5至3重量%的銀、2.5至4重量%的鉍、9至11%的銦、0.1至1.5重量%的銅、及0.001至0.05重量%的Co。這種合金具有202℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約2重量%的銀、3重量%的鉍、0.7重量%的銅、10重量%的銦、0.03重量%的鈷，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含3至4重量%的銀、4至5重量%的鉍、3至4%的銦、0.1至1.0重量%的銅。這種合金具有208℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.6 重量%的銀、4重量%的鉍、0.4重量%的銅、4重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含3至4重量%的銀、2至3重量%的鉍、6至7重量%的銦、0.1至1重量%的銅。這種合金具有208℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.6重量%的銀、3重量%的鉍、6重量%的銦、0.4重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含3至4重量%的銀、2至4重量%的鉍、7至8重量%的銦、0.1至1重量%的銅。這種合金具有201℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.5重量%的銀、4重量%的鉍、8重量%的銦、0.4重量%的銅，其餘為錫連同無法避免的雜質。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至0.7重量%的銅、0.05至0.25重量%的鎳、及0.005至0.05重量%的錳。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、7至9%的銦、0.3至0.8重量%的銅、及0.005至 0.05重量%的鈦。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、9至11%的銦、0.3至0.8重量%的銅、及0.005至0.05重量%的錳。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、11至13%的銦、及0.3至0.8重量%的銅。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至0.8重量%的銅、0.05至0.4重量%的鎳、0.005至0.05重量%的錳、及0.01至0.15重量%的磷。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在特別較佳的進一步實施例中，提供了一種合金，該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至7重量%的銅、0.05至0.25重量%的鎳、及0.001至0.03重量%的鍺。該合金可以表現出特別有利的低熔點、優異機械性能、及優異熱循環特性的組合。
在進一步的態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)10重量%或更少的銀
(b)10重量%或更少的鉍
(c)多於0.5重量%的鎵
(d)12重量%或更少的銦
(e)可選的一種或更多種以下的元素
2重量%或更少的銅
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的磷
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(g)其餘的錫，連同任何無法避免的雜質。
這種合金具有低的液相溫度和有利的熱和機械性能。
本發明第一態樣的較佳銀、鉍、銅、及可選元素含量也適用於此態樣。
該合金可以包含1至10重量%的銀及/或0.5至10重量%的鉍及/或0.5至3重量%的鎵及/或3.55至12重量%的銦。
該合金包含多於0.5重量%的鎵，例如0.5至2.5重量%的鎵。該合金較佳包含0.7至2.1重量%的鎵，更佳包含0.8至2.05重量%的鎵。列舉範圍中的鎵可用於降低該合金的液相溫度。該合金可以包含10重量%或更少的銦，例如2至3.5重量%的銦、或2.5至5.5重量%的銦、或2.5至10重量%的銦、或3.5至10重量%的銦。在替代的態樣中，該合金可以包含3重量%或更少的銅。
在一個實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、3.5至4.5重量%的鉍、2至3.5%的銦、0.1至1.5重量%的銅、0.05至0.25重量%的鎳、及1至2重量%的鎵。這種合金具有206.9℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、4重量%的鉍、0.7重量%的銅、2.94重量%的銦、 0.2重量%的鎳、1.14重量%的鎵，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、1至3重量%的鉍、2.5至5.5%的銦、0.1至1.5重量%的銅、及0.5至2重量%的Ga。這種合金具有207.2℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、1重量%的鉍、0.6重量%的銅、5重量%的銦、1.55重量%的鎵，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、1至4重量%的鉍、2.5至10%的銦、及0.5至3重量%的Ga。這種合金具有199.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、7.76重量%的銦、2.03重量%的鎵，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含1.5至4重量%的銀、1至4重量%的鉍、3.5至10%的銦、0.5至3重量%的Ga、及0.005至0.1重量%的錳。這種合金具有203℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約2重量%的銀、3重量%的鉍、8重量%的銦、1重量%的鎵、0.01重量%的錳，其餘為錫連同無法避免的雜質。
在進一步的態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)10重量%或更少的銀
(b)10重量%或更少的鉍
(c)3重量%或更少的銅
(d)10重量%或更少的銦
(e)多於0.5重量%的鎵
(f)可選的一種或更多種以下的元素
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的磷
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(g)其餘的錫，連同任何無法避免的雜質。
第一態樣的較佳元素含量也適用於此態樣。
在進一步的態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)10重量%或更少的銀
(b)10重量%或更少的鉍
(c)25重量%或更少的銦
(d)可選的一種或更多種以下的元素
0至3重量%的Cu
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的磷
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(e)其餘的錫，連同任何無法避免的雜質。
這種合金具有低的液相溫度和有利的熱和機械性能。
本發明第一態樣的較佳銀、鉍、銦含量也適用於此態樣。
該合金可以包含1至10重量%的銀及/或0.5至10重量%的鉍及/或3.55至25重量%的銦。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2至4重量%的鉍、16至21重量%的銦。這種合金具有191.9℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、20重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2至4重量%的鉍、22至25重量%的銦。這種合金具有183℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、25重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2至4.5重量%的鉍、22至25重量%的銦。這種合金具有181.6℃的液相溫度。在這個 實施例的一個具體實例中，該合金包含約3重量%的銀、4重量%的鉍、25重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含2.5至4重量%的銀、0.5至2重量%的鉍、12至15重量%的銦。這種合金具有201.1℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、1重量%的鉍、13重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含2.5至4重量%的銀、2至4重量%的鉍、12至15重量%的銦。這種合金具有198.9℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、14重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含3.5至6重量%的銀、2至4重量%的鉍、10至14重量%的銦。這種合金具有203.2℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約5重量%的銀、3重量%的鉍、12重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、7至10重量%的鉍、12至16重量%的銦。這種合金具有189.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、 10重量%的鉍、15重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含2.5至4重量%的銀、7至10重量%的鉍、7至10重量%的銦、及0.1至1重量%的銅。這種合金具有195.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、10重量%的鉍、10重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、3至6重量%的鉍、15至20重量%的銦。這種合金具有189.9℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、1重量%的鉍、20重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、1至4重量%的鉍、10至15重量%的銦、1至2.5重量%的鎵，其餘為錫連同無法避免的雜質。這種合金具有189.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、15重量%的銦、2.0重量%的鎵，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2至6重量%的鉍、10至15重量%的銦、0至2重量%的銅，其餘為錫連同無法避免的雜 質。這種合金具有192.7℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、5重量%的鉍、15重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含3至4重量%的銀、8至10重量%的鉍、0.5至1.5重量%的銦。這種合金具有207℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.6重量%的銀、8重量%的鉍、1.5重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含3至4重量%的銀、5至8重量%的鉍、2至3重量%的銦。這種合金具有207℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.6重量%的銀、8重量%的鉍、2重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例，提供了一種合金，該合金包含3.5至5重量%的銀、7至9重量%的鉍、6至7重量%的銦。這種合金具有200℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3.5重量%的銀、7.6重量%的鉍、6重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含3至4重量%的銀、8至10重量%的鉍、5至6重量%的銦。這種合金具有199℃的液相溫度。在這個實施例的 一個具體實例中，該合金包含約3.5重量%的銀、10重量%的鉍、5.6重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含0.5至2重量%的銀、10至12重量%的鉍、6至7重量%的銦。這種合金具有203℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約1重量%的銀、10重量%的鉍、6重量%的銦，其餘為錫連同無法避免的雜質。
在進一步的態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)10重量%或更少的銀
(b)30重量%或更少的銦
(c)3重量%或更少的銅
(d)可選的一種或更多種以下的元素：
0至3重量%的鉍
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的磷
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(e)其餘的錫，連同任何無法避免的雜質。
第一態樣的較佳元素含量也適用於此態樣。
該合金可以包含1至10重量%的銀及/或3.55至30重量%的銦及/或0.1至3重量%的銅。
在一個實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、22至25重量%的銦、及0.1至1重量%的銅。這種合金具有183.5℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、25重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、16至21重量%的銦、0.1至1重量%的銅。這種合金具有190.6℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、20重量%的銦、0.6重量%的銅，其餘為錫連同無法避免的雜質。
在進一步的態樣中，本發明提供一種無鉛無銻焊料合金，包含：
(a)10重量%或更少的銀
(b)10重量%或更少的鉍
(b)8重量%或更少的銦
(c)3重量%或更少的銅
(d)1重量%或更少的磷
(d)可選的一種或更多種以下的元素：
0至1重量%的鎳
0至1重量%的鈦
0至1重量%的錳
0至1重量%的稀土元素，例如鈰
0至1重量%的鉻
0至1重量%的鍺
0至1重量%的鈷
0至1重量%的鐵
0至1重量%的鋁
0至1重量%的金
0至1重量%的碲
0至1重量%的硒
0至1重量%的鈣
0至1重量%的釩
0至1重量%的鉬
0至1重量%的鉑
0至1重量%的鎂
(e)其餘的錫，連同任何無法避免的雜質。
第一態樣的較佳元素含量也適用於此態樣。
該合金可以包含1至10重量%的銀及/或0.5至10重量%的鉍及/或3.55至8重量%的銦及/或0.1至3重量%的銅及/或0.01至1重量%或更少的磷。
在一個實施例中，提供了一種合金，該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、5至8重量%的銦、0.1至1重量%的銅、0.05至0.3重量%的鎳、0.001至0.05重量%的錳、0.001至0.1重量%的磷。這種合金具有183.5℃的液相溫度。在這個實施例的一個具體實例中，該合金包含約3重量%的銀、3重量%的鉍、0.6重量%的銅、6重量%的銦、0.19重量%的鎳、0.02重量%的錳、0.08重量%的磷，其餘為錫連同無法避免的雜質。
本文所述的合金基本上可以由列舉的元素所組成。因此，可以理解的是，除了那些指定的元素之外，其他非指定的元素也可以存在於該組成物中，前提是該組成物的基本特性不會因非指定元素的存在而受到實質影響。
該合金可以處於例如棒、條、固體或助焊劑芯線、箔或帶、或粉末或膏料(粉末加助焊劑摻合物)、或焊球的形式，用於球柵陣列接點或晶片級封裝、或其他預成形焊件，有或沒有助焊劑芯或助焊劑塗層。
在進一步的態樣中，本發明提供一種焊接點，該焊接點包含本文所述的合金。
在進一步的態樣中，本發明提供一種形成焊接點的方法，包含以下步驟：(i)提供兩個或更多個待接合工件；(ii)提供本文所述的焊料合金；及(iii)在該等待接合工件附近加熱該焊料合金。
在進一步的態樣中，本發明提供本文所述的合金組成物在焊接方法中的用途，該焊接方法例如波焊、表面安裝技術(SMT)焊接、晶粒黏附焊接、熱界面焊接、手焊、雷射和RF感應焊接、焊接到太陽能電池模組、2級LED封裝板的焊接、及重工焊接。
現在將藉由這些合金的少數非限制性實例及該等實例之性能總結的方式來進一步描述本發明，並參照以下圖式，其中：第1圖圖示先前技術的合金及依據本發明的合金之維氏硬度(Hv-1)值。
第2圖圖示現有技術的合金及依據本發明的合金之極限拉伸強度(UTS)。
第3圖圖示現有技術的合金及依據本發明的合金之屈服強度(YS)。
第4圖圖示熱循環測試的結果。
參照第1圖，合金的硬度在25-30Hv之間變化，除了合金E為35Hv。也就是說，與SnAg3.0Cu0.5相比，合金硬度增加的範圍從67至100%。合金E的硬度比SnAg3.0Cu0.5的硬度大133%。
將極限拉伸強度(UTS)和屈服強度(YS)分別圖示於第2圖和第3圖(參見ASTM E8/E8M-09的張力量測測試方法)。UTS在合金F增加至少53%，而且在合金M增加多達137%。YS在合金D增加至少41%，而且在合金M增加多達104%。
現在將參照以下的非限制性實例進一步描述本發明。
實例1-合金A
合金A包含3.5重量%的銀、4重量%的鉍、0.7重量%的銅、3.7重量%的銦、0.2重量%的鎳，其餘為錫連同無法避免的雜質。合金A具有分別為196.4℃和209.2℃的固相和液相溫度、及31的維氏硬度(Hv-1)。用於比較的目的，習用的合金SnAg3.0Cu0.5具有217.3至223.5℃的熔點範圍；及15的維氏硬度(Hv-0.5)。
實例2-合金B
合金B包含約3重量%的銀、5重量%的鉍、0.7重量%的銅、3.75重量%的銦、0.1重量%的鎳，其餘為錫連同無法避免的雜質。合金B具有197.4和208.1℃的熔點範圍；及30的維氏硬度(Hv-1)。
實例3-合金C
合金C包含1.5重量%的銀、5重量%的鉍、0.7重量%的銅、3.75重量%的銦、0.16重量%的鎳，其餘為錫連同無法避免的雜質。合金C具有191至215℃的熔點範圍；及29的維氏硬度(Hv-1)。
實例4-合金D
合金D包含1.02重量%的銀、3.67重量%的鉍、0.68重量%的銅、3.5重量%的銦、0.12重量%的鎳、0.9重量%的鎵，其餘為錫連同無法避免的雜質。合金D具有190.6至212.9℃的熔點範圍；及27的維氏硬度(Hv-1)。
實例5-合金E
合金E包含3重量%的銀、4重量%的鉍、0.7重量%的銅、2.94重量%的銦、0.2重量%的鎳、1.14重量%的鎵，其餘為錫連同無法避免的雜質。合金E具有196.7至206.9℃的熔點範圍；及36的維氏硬度(Hv-1)。較多的鎵存在導致此合金與合金D相比有較高的硬度。
實例6-合金F
合金F包含3重量%的銀、0.9重量%的鉍、0.5重量%的銅、3.6重量%的銦，其餘為錫連同無法避免的雜質。合金F具有206.2至213℃的熔點範圍；及24的維氏硬度(Hv-1)。在這種情況下，較少的鉍(固溶體硬化)及不存在鎳(沉澱硬化)導致該合金的硬度較低。
實例7-合金H
合金H包含3重量%的銀、1重量%的鉍、0.5重量%的銅、4.6重量%的銦、0.11重量%的鎳，其餘為錫連同無法避免的雜質。合金H具有204至210.5℃的熔點範圍。
實例8-合金K
合金K包含3重量%的銀、3重量%的鉍、0.5重量%的銅、4重量%的銦、0.2重量%的鎳，其餘為錫連同無法避免的雜質。合金K具有196.4至210.2℃的熔點範圍。
實例9-合金L
合金L包含3重量%的銀、2.9重量%的鉍、0.5重量%的銅、4.75重量%的銦、0.11重量%的鎳，其餘為錫連同無法避免的雜質。合金L具有196.6至207.9℃的熔點範圍。
實例10-合金M
合金M包含3重量%的銀、3重量%的鉍、0.5重量%的銅、6重量%的銦、0.1重量%的鎳，其餘為錫連同無法避免的雜質。合金M具有196.1至206.5℃的熔點範圍。
實例11-合金N
合金N包含3重量%的銀、3重量%的鉍、0.5重量%的銅、6重量%的銦、0.15重量%的鎳、0.022重 量%的錳，其餘為錫連同無法避免的雜質。合金N具有195.3至207.6℃的熔點範圍。
實例12-合金P
合金P包含3重量%的銀、3重量%的鉍、0.5重量%的銅、6重量%的銦、0.2重量%的鎳、0.02重量%的鈦，其餘為錫連同無法避免的雜質。合金P具有196.7至206.8℃的熔點範圍。
實例13-合金Q
合金Q包含3重量%的銀、3重量%的鉍、0.5重量%的銅、6重量%的銦、0.2重量%的鎳、0.04重量%的鈰，其餘為錫連同無法避免的雜質。合金Q具有198.8至207.2℃的熔點範圍。
實例14-合金R
合金R包含3重量%的銀、1重量%的鉍、0.6重量%的銅、8重量%的銦，其餘為錫連同無法避免的雜質。合金R具有196.5至205.8℃的熔點範圍。
實例15-合金S
合金S包含3重量%的銀、1重量%的鉍、0.6重量%的銅、1.55重量%的鎵、5重量%的銦，其餘為錫連同無法避免的雜質。合金S具有198.3至207.2℃的熔點範圍。
實例16-合金T
合金T包含3.8重量%的銀、3重量%的鉍、0.6重量%的銅、8重量%的銦、0.2重量%的鎳，其餘為錫連 同無法避免的雜質。合金T具有190.5至203.5℃的熔點範圍。
實例17-合金U
合金U包含3重量%的銀、3重量%的鉍、0.6重量%的銅、8重量%的銦、0.02重量%的鈦，其餘為錫連同無法避免的雜質。合金U具有191.9至203.2℃的熔點範圍。
實例18-合金V
合金V包含3重量%的銀、3重量%的鉍、0.6重量%的銅、10重量%的銦、0.02重量%的錳，其餘為錫連同無法避免的雜質。合金V具有186.8至199.5℃的熔點範圍。
實例19-合金W
合金W包含3.8重量%的銀、3重量%的鉍、2重量%的鎵、8重量%的銦，其餘為錫連同無法避免的雜質。合金W具有176.8至199.6℃的熔點範圍。
實例20-合金X
合金X包含3重量%的銀、3重量%的鉍、12重量%的銦、0.6重量%的銅，其餘為錫連同無法避免的雜質。合金X具有179至196℃的熔點範圍。
實例21-合金Y
合金Y包含2重量%的銀、3重量%的鉍、10重量%的銦、0.7重量%的銅，其餘為錫連同無法避免的雜質。合金Y具有178至202℃的熔點範圍。
實例22-合金Z
合金Z包含2重量%的銀、3重量%的鉍、8重量%的銦、1重量%的鎵，其餘為錫連同無法避免的雜質。合金Y具有175至203℃的熔點範圍。
實例23-合金A1
合金A1包含3重量%的銀、3重量%的鉍、20重量%的銦，其餘為錫連同無法避免的雜質。合金A1具有132.5至191.9℃的熔點範圍。
實例24-合金A2
合金A2包含3重量%的銀、3重量%的鉍、25重量%的銦，其餘為錫連同無法避免的雜質。合金A2具有120.9至183℃的熔點範圍。
實例25-合金A3
合金A3包含3重量%的銀、4重量%的鉍、25重量%的銦，其餘為錫連同無法避免的雜質。合金A3具有113.7至181.6℃的熔點範圍。
實例26-合金A4
合金A4包含3重量%的銀、1重量%的鉍、13重量%的銦，其餘為錫連同無法避免的雜質。合金A4具有170至201.1℃的熔點範圍。
實例27-合金A5
合金A5包含3重量%的銀、3重量%的鉍、14重量%的銦，其餘為錫連同無法避免的雜質。合金A5具有152.9至198.9℃的熔點範圍。
實例28-合金A6
合金A6包含5重量%的銀、3重量%的鉍、12重量%的銦，其餘為錫連同無法避免的雜質。合金A6具有157至203.2℃的熔點範圍。
實例29-合金A7
合金A7包含3重量%的銀、10重量%的鉍、10重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。合金A7具有144.9至195.6℃的熔點範圍。
實例30-合金A8
合金A8包含3重量%的銀、10重量%的鉍、15重量%的銦，其餘為錫連同無法避免的雜質。合金A8具有123至189.6℃的熔點範圍。
實例31-合金A9
合金A9包含3重量%的銀、10重量%的鉍、15重量%的銦，其餘為錫連同無法避免的雜質。合金A9具有138.5至189.9℃的熔點範圍。
實例32-合金A10
合金A10包含3重量%的銀、3重量%的鉍、2重量%的鎵、15重量%的銦，其餘為錫連同無法避免的雜質。合金A10具有128.4至189.6℃的熔點範圍。
實例33-合金A11
合金A11包含3重量%的銀、5重量%的鉍、15重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。合金A11具有132.8至192.7℃的熔點範圍。
實例34-合金A12
合金A12包含3重量%的銀、25重量%的銦、0.5重量%的銅，其餘為錫連同無法避免的雜質。合金A12具有139.7至183.5℃的熔點範圍。
實例35-合金A13
合金A13包含3重量%的銀、20重量%的銦、0.6重量%的銅，其餘為錫連同無法避免的雜質。合金A13具有144.6至190.6℃的熔點範圍。
實例36-合金B1
合金B1包含3.6重量%的銀、4重量%的鉍、4重量%的銦、0.4重量%的銅、0.01%的錳，其餘為錫連同無法避免的雜質。合金B1具有186至208℃的熔點範圍。
實例37-合金B2
合金B2包含3.6重量%的銀、3重量%的鉍、6重量%的銦、0.4重量%的銅、0.03重量%的鈷，其餘為錫連同無法避免的雜質。合金B2具有187至208℃的熔點範圍。
實例38-合金B3
合金B3包含3.5重量%的銀、4重量%的鉍、8重量%的銦、0.4重量%的銅、0.01重量%的錳，其餘為錫連同無法避免的雜質。合金B3具有182至201℃的熔點範圍。
實例39-合金B4
合金B4包含3.6重量%的銀、8重量%的鉍、1.5重量%的銦、0.4重量%的銅、0.03重量%的鈷，其餘為錫連同無法避免的雜質。合金B4具有187至207℃的熔點範圍。
實例40-合金B5
合金B5包含3.6重量%的銀、8重量%的鉍、2重量%的銦、0.4重量%的銅、0.01重量%的錳，其餘為錫連同無法避免的雜質。合金B5具有184至207℃的熔點範圍。
實例41-合金B6
合金B6包含3.5重量%的銀、7.6重量%的鉍、6重量%的銦、0.4重量%的銅、0.01重量%的錳，其餘為錫連同無法避免的雜質。合金B6具有176至200℃的熔點範圍。
實例42-合金B7
合金B7包含3.3重量%的銀、10重量%的鉍、5.6重量%的銦、0.4重量%的銅、0.03重量%的鈷，其餘為錫連同無法避免的雜質。合金B6具有174至199℃的熔點範圍。
實例43-合金B8
合金B8包含1重量%的銀、10重量%的鉍、6重量%的銦、0.125重量%的銅、0.03重量%的鈷，其餘為錫連同無法避免的雜質。合金B6具有176至203℃的熔點範圍。
實例44-合金B9
合金B9包含3重量%的銀、3重量%的鉍、6重量%的銦、0.6重量%的銅、0.19重量%的鎳、0.02重量%的錳、0.08重量%的磷，其餘為錫連同無法避免的雜質。合金B6具有190.6至207.1℃的熔點範圍。
實例45-合金B10
合金B10包含2.9重量%的銀、3重量%的鉍、6重量%的銦、0.5重量%的銅、0.12重量%的鎳、0.008重量%的鍺，其餘為錫連同無法避免的雜質。合金B6具有189.9至207.1℃的熔點範圍。
表1顯示習用的SnAg3.0Cu0.5合金及合金A-W和A1至A13的固相和液相溫度。所有合金的熔化溫度都比習用的SnAg3.0Cu0.5合金低得多。
第4圖圖示熱循環對晶片電阻器CR1206之剪切強度的影響。在熱循環過程中，與合金N和M分別損失18和25%的剪切強度相比，習用的SnAg3.0Cu0.5合金損失了68%的剪切強度。將熱循環測試的結果顯示於表2。
前面的實施方式已經藉由解釋和說明的方式來提供，而且並無意圖限制所附申請專利範圍的範圍。在本文說明的當前較佳實施例中的許多變化對於所屬技術領域中具有通常知識者而言將是顯而易見的，而且仍在所附申請專利範圍及其均等物的範圍內。

Claims (37)

  1. 一種無鉛無銻焊料合金，包含：(a)1至4重量%的銀(b)0.5至6重量%的鉍(c)3.55至15重量%的銦(d)3重量%或更少的銅(e)可選的一種或更多種以下的元素0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻0至1重量%的鍺0至1重量%的鎵0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的磷0至1重量%的金0至1重量%的碲0至1重量%的硒0至1重量%的鈣 0至1重量%的釩0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(f)其餘的錫，連同任何無法避免的雜質。
  2. 如請求項1所述之焊料合金，其中該合金包含1.2至3.8重量%的銀，較佳包含2.5至3.5重量%的銀，更佳包含2.75至3.75重量%的銀。
  3. 如請求項1或2所述之焊料合金，其中該合金包含1.5至5.5重量%的鉍，較佳包含2至5重量%的鉍，更佳包含2.5至4.5重量%的鉍。
  4. 如請求項1所述之焊料合金，其中該合金包含3.6至12重量%的銦，較佳包含3.65至12重量%的銦，更佳包含3.7至10重量%的銦，甚至更佳包含4至10重量%的銦。
  5. 如請求項1所述之焊料合金，其中該合金包含0.01至3重量%的銅，較佳包含0.1至1重量%的銅，更佳包含0.4至0.8重量%的銅。
  6. 如請求項1所述之焊料合金，其中該合金包含0.01至1重量%的鎳，較佳包含0.03至0.6重量%的鎳，更佳包含0.05至0.5重量%的鎳，甚至更佳包含0.08至0.25重量%的鎳。
  7. 如請求項1所述之焊料合金，其中該合金包含2至4重量%的銀、1至6重量%的鉍、及3.65至7重量%的銦。
  8. 如請求項1所述之焊料合金，其中該合金包含3至4.5重量%的銀、3至4.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  9. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、4至5.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  10. 如請求項1所述之焊料合金，其中該合金包含1至2重量%的銀、4至5.5重量%的鉍、3至4.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  11. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、1至2重量%的鉍、3至4.5%的銦、及0.1至1.5重量%的銅。
  12. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、1至2重量%的鉍、4至5.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  13. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、3.5至5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  14. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、4至5.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  15. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、5至6.5%的銦、0.1至1.5重量%的銅、及0.05至0.25重量%的鎳。
  16. 如請求項1所述之焊料合金，其中該合金包含2.5至4重量%的銀、2.5至4重量%的鉍、5至6.5%的銦、0.1至1.5重量%的銅、0.05至0.25重量%的鎳、及0.001至0.05重量%的錳。
  17. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至0.7重量%的銅、0.05至0.25重量%的鎳、及0.005至0.05重量%的錳。
  18. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、 7至9%的銦、0.3至0.8重量%的銅、及0.005至0.05重量%的鈦。
  19. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、9至11%的銦、0.3至0.8重量%的銅、及0.005至0.05重量%的錳。
  20. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、11至13%的銦、及0.3至0.8重量%的銅。
  21. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至0.8重量%的銅、0.05至0.4重量%的鎳、0.005至0.05重量%的錳、及0.01至0.15重量%的磷。
  22. 如請求項1所述之焊料合金，其中該合金包含2.5至3.5重量%的銀、2.5至3.5重量%的鉍、5.5至6.5%的銦、0.3至7重量%的銅、0.05至0.25重量%的鎳、及0.001至0.03重量%的鍺。
  23. 一種無鉛無銻焊料合金，包含：(a)10重量%或更少的銀(b)10重量%或更少的鉍(c)多於0.5重量%的鎵 (d)12重量%或更少的銦(e)可選的一種或更多種以下的元素2重量%或更少的銅0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻0至1重量%的鍺0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的磷0至1重量%的金0至1重量%的碲0至1重量%的硒0至1重量%的鈣0至1重量%的釩0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(g)其餘的錫，連同任何無法避免的雜質。
  24. 如請求項23所述之合金，包含1至10重量%的銀、0.5至10重量%的鉍、0.5至3重量%的鎵、及3.55至12重量%的銦。
  25. 一種無鉛無銻焊料合金，包含：(a)10重量%或更少的銀(b)10重量%或更少的鉍(c)3重量%或更少的銅(d)10重量%或更少的銦(e)多於0.5重量%的鎵(f)可選的一種或更多種以下的元素0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻0至1重量%的鍺0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的磷0至1重量%的金0至1重量%的碲 0至1重量%的硒0至1重量%的鈣0至1重量%的釩0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(g)其餘的錫，連同任何無法避免的雜質。
  26. 如請求項25所述之合金，其中該合金包含2.5至4重量%的銀、3.5至4.5重量%的鉍、2至3.5%的銦、0.1至1.5重量%的銅、0.05至0.25重量%的鎳、及0.1至2.5重量%的Ga。
  27. 一種無鉛無銻焊料合金，包含：(a)10重量%或更少的銀(b)10重量%或更少的鉍(c)25重量%或更少的銦(d)可選的一種或更多種以下的元素0至3重量%的Cu 0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻 0至1重量%的鍺0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的磷0至1重量%的金0至1重量%的碲0至1重量%的硒0至1重量%的鈣0至1重量%的釩0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(e)其餘的錫，連同任何無法避免的雜質。
  28. 如請求項27所述之合金，包含1至10重量%的銀、0.5至10重量%的鉍、及3.55至25重量%的銦。
  29. 一種無鉛無銻焊料合金，包含：(a)10重量%或更少的銀(b)30重量%或更少的銦(c)3重量%或更少的銅(d)可選的一種或更多種以下的元素： 0至3重量%的鉍0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻0至1重量%的鍺0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的磷0至1重量%的金0至1重量%的碲0至1重量%的硒0至1重量%的鈣0至1重量%的釩0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(e)其餘的錫，連同任何無法避免的雜質。
  30. 如請求項29所述之合金，包含1至10重量%的銀、3.55至30重量%的銦、及0.1至3重量 %的銅。
  31. 一種無鉛無銻焊料合金，包含：(a)10重量%或更少的銀(b)10重量%或更少的鉍(b)8重量%或更少的銦(c)3重量%或更少的銅(d)1重量%或更少的磷(d)可選的一種或更多種以下的元素：0至1重量%的鎳0至1重量%的鈦0至1重量%的錳0至1重量%的稀土元素，例如鈰0至1重量%的鉻0至1重量%的鍺0至1重量%的鈷0至1重量%的鐵0至1重量%的鋁0至1重量%的金0至1重量%的碲0至1重量%的硒0至1重量%的鈣0至1重量%的釩 0至1重量%的鉬0至1重量%的鉑0至1重量%的鎂(e)其餘的錫，連同任何無法避免的雜質。
  32. 如請求項31所述之合金，包含1至10重量%的銀、0.5至10重量%的鉍、3.55至8重量%的銦、0.1至3重量%的銅、及0.01至1重量%的磷。
  33. 如請求項1、2及4至32中任一項所述之焊料合金，其中該合金具有215℃或更低、較佳低於210.5℃、更佳低於210℃、甚至更佳為200至208℃的一液相溫度。
  34. 如請求項1、2及4至32中任一項所述之焊料合金，該焊料合金處於棒、條、固體或助焊劑芯線、箔或帶、或粉末或膏料(粉末加助焊劑摻合物)、或焊球的形式，用於球柵陣列接點或晶片級封裝、或其他預成形焊件，有或沒有一助焊劑芯或一助焊劑塗層。
  35. 一種焊接點，包含一如請求項1至34中任一項所界定之合金。
  36. 一種形成一焊接點的方法，包含以下步驟：(i)提供兩個或更多個待接合工件；(ii)提供如請求項1至34中任一項所界定的焊料 合金；及(iii)在該等待接合工件附近加熱該焊料合金。
  37. 如請求項1至34中任一項所界定的合金組成物在一焊接方法中的用途，該焊接方法例如波焊、表面安裝技術(SMT)焊接、晶粒黏附焊接、熱界面焊接、手焊、雷射和RF感應焊接、焊接到一太陽能電池模組、2級LED封裝板的焊接、及重工焊接。
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TWI756575B (zh) * 2018-10-24 2022-03-01 美商阿爾發金屬化工公司 用於聚合物基材、印刷電路板、及其他接合應用之低溫焊接溶液
TWI773022B (zh) * 2018-10-24 2022-08-01 美商阿爾發金屬化工公司 用於聚合物基材、印刷電路板、及其他接合應用之低溫焊接溶液
TWI816282B (zh) * 2018-10-24 2023-09-21 美商阿爾發金屬化工公司 用於聚合物基材、印刷電路板、及其他接合應用之低溫焊接溶液
TWI771903B (zh) * 2020-02-14 2022-07-21 日商千住金屬工業股份有限公司 無鉛且無銻之焊料合金、焊球、及焊料接頭
TWI784761B (zh) * 2020-02-14 2022-11-21 日商千住金屬工業股份有限公司 無鉛且無銻之焊料合金、焊球、及焊料接頭

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EP3172349A2 (en) 2017-05-31
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