TW201642281A - 於半導體晶粒附著應用之具有高金屬負載之燒結糊 - Google Patents

於半導體晶粒附著應用之具有高金屬負載之燒結糊 Download PDF

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TW201642281A
TW201642281A TW105113321A TW105113321A TW201642281A TW 201642281 A TW201642281 A TW 201642281A TW 105113321 A TW105113321 A TW 105113321A TW 105113321 A TW105113321 A TW 105113321A TW 201642281 A TW201642281 A TW 201642281A
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metal
composition
particles
lmp
temperature
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TW105113321A
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TWI708264B (zh
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凱瑟琳Ａ 席爾樂
尤速克 巴伯
麥可Ｃ 馬修斯
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歐爾麥特電路有限公司
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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
    • B23K35/02—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
    • 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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual 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
    • 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
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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
    • B23K35/0244—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
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    • 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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    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • 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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    • B23K35/262—Sn as the principal constituent
    • 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
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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
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    • B23K35/3006—Ag 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
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    • B23K35/3013—Au as the principal constituent
    • 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
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    • B23K35/302—Cu 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
    • 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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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3026—Mn 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
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    • 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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    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni 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
    • 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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    • B23K35/3046—Co 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
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    • B23K35/3053—Fe as the principal constituent
    • 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
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    • 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
    • B23K35/3613—Polymers, e.g. resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49503—Lead-frames or other flat leads characterised by the die pad
    • H01L23/49513—Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
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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
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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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本發明提供一種在熱反應後具有大於60%金屬體積之半導體晶粒附著組合物，其具有：(a)80至99wt%之金屬顆粒混合物，該金屬顆粒混合物包含30至70wt%之無鉛低熔點(LMP)顆粒組合物及25至70wt%之高熔點(HMP)顆粒組合物，該無鉛低熔點(LMP)顆粒組合物包含在溫度T1以下熔化的至少一種LMP金屬Y，該高熔點(HMP)顆粒組合物包含與該至少一種LMP金屬Y在處理溫度T1下反應之至少一種金屬元素M，其中M之wt%與Y之wt%的比率為至少1.0；(b)0至30wt%之金屬粉末添加劑A；及(c)具有揮發性部分及不超過50wt%之非揮發性部分之助熔媒劑。

Description

於半導體晶粒附著應用之具有高金屬負載之燒結糊
本發明係關於金屬組合物、其製備方法及其用途。更具體而言，本發明係關於金屬組合物、其製備方法及其將半導體晶粒附著至封裝元件的用途。
在電子器件之生產中，將半導體晶粒裝配到基板上以產生一平台，用於將晶粒信號輸入與輸出功能與將與其通信之其他器件互連。通常，使用安置於晶粒之非功能側與基板之間的特別設計的焊料及/或聚合物黏著劑來實現此裝配。
在半導體晶粒之某些子集(通常用於功率管理或照明應用)中，將附著於基板之晶粒之側面金屬化以促進操作中半導體晶粒與基板之間的良好熱轉移，以及在一些情況下亦促進電氣互連。製造用於功率應用之矽基半導體晶粒通常以此方式金屬化以便達成與晶粒之背側之電及熱連接。隨著器件操作溫度增加，額外材料(諸如，碳化矽及氮化鎵)以類似方式製備以改良在高溫環境中的器件效能。
對於待自晶粒耗散之熱量相對較低的應用，金屬顆粒填充的聚合黏著劑係用於將半導體晶粒黏附至封裝元件之最常見種類的材料。在該等黏著劑系統中，熱及(視需要)電傳導基於金屬填充物之體積分數經由各種機制傳播。研究(及工業實踐)已顯示，具有約30%金屬填 充物體積分數之導電黏著劑可達成低電阻率及高熱導率。然而，導電黏著劑對其電性可靠性效能有固有限制，且因此，亦對其在半導體器件中替代軟焊料之能力有限制。由於熱及電傳導效率直接依賴於填充物顆粒相對於聚合物黏著劑含量之比例，故歸因於對可在不損害黏著劑之機械完整性的情況下併入之填充物的量的實際限制，該等黏著劑之傳導率存在上限。
對於需要較高功率耗散之應用，使用焊料或銀基燒結材料以將半導體附著至封裝元件係更常見的。傳統地，鉛基焊料用於功率半導體之晶粒附著，係因為該等焊料將金屬化晶粒及一或多個封裝元件充分濕潤，提供極佳的電及熱傳導率，並具有較高伸長率以減小半導體晶粒與該或該等封裝元件之間的熱膨脹係數(CTE)的差異。在過去十年中，已倡議用無鉛焊料替代鉛基焊料。對於特殊應用，使用金錫基、錫銻基、銦基或鉍基合金，但該等合金通常昂貴且常常具有機械或電效能限制。對於更廣泛基礎的功率晶粒附著應用，已將錫基焊料評定為無Pb溶液。通常地，該等錫基焊料以糊或基於導線之形式塗覆。在熱處理期間，錫合金之單獨顆粒熔化，並與彼此及金屬化表面熔合，以形成整體接合。隨著單獨的顆粒坍縮並固結成單一熔融塊狀物，從該塊狀物中排除揮發性助熔劑媒劑，產生已抽空助熔劑揮發物之空隙空間之大型集中式凹穴。歸因於在彼位置缺乏熱傳導或由電接觸面積縮減引起的器件之電氣效能降低，該等凹穴可在半導體晶粒上產生熱點。儘管該等空隙凹穴係含鉛焊料及無鉛焊料兩者所特有的，但在無鉛焊料中，隨後的熱偏移可引起合金再熔化，此可導致空隙凹穴進一步合併成極大空位。另外，無鉛錫基合金並不展現鉛基焊料之伸長特性，且因此並未有效地減輕半導體晶粒與封裝元件之間的CTE失配。
所提出的滿足功率半導體要求之一類材料被稱為銀燒結糊。銀 燒結糊由銀顆粒(大小通常為奈米或微米)結合載劑構成。在熱處理期間，補充奈米大小之銀顆粒之高表面能以在遠低於銀金屬之熔化溫度的溫度下將銀顆粒燒結在一起。亦可在載劑組合物中使用有機金屬添加劑以提昇燒結效能。在熱處理期間通常需要施加壓力而非典型製造方案來用於半導體附著，以達成充分固結及機械穩固的接合。儘管此類材料提供多種合乎需要的特性，但該等昂貴材料通常並未與由於成本原因愈來愈風行之許多封裝元件表面很好地結合。
因此，業界目前正在搜尋用於將金屬化半導體晶粒附著至封裝元件上之替代類別的材料。新穎材料類別之所需屬性係使用現存沈積及處理基礎結構；高熱導率(>20W/mK)；穩定的電阻、穩固黏著、經由多個熱偏移(包括標準工業可靠性測試)之機械及電可靠性；接合中之低空隙體積及小尺寸空隙；不同的熱膨脹係數(CTE)機械應力管理；以及低成本。
在本發明之態樣之一者中，本發明係關於將金屬化半導體晶粒附著至封裝元件(諸如，夾片、引線框架、基板、插入件及引線)上，以實現穩固的電與熱互連。本發明之組合物為一新穎類別半導體裝配材料，其擁有用於高功率應用之半導體晶粒之互連所需的所有所需屬性並補償先前技術組合物之不足。
本發明之組合物採用與助熔有機媒劑組合之兩種或兩種以上類型之金屬顆粒以產生糊狀物。選擇兩種或兩種以上類型之金屬顆粒以在特定處理溫度下發生不可逆反應，以自金屬化封裝元件上之附著點，經由大量所處理的組合物及終止半導體晶粒之金屬化連接點而形成連續冶金互連網狀物。本發明之助熔媒劑用於遞送呈糊形式的金屬顆粒，促進金屬顆粒之間的反應，及在熱處理期間大量揮發，從而引起與體積分數等於或大於60%之互連金屬的接合。經處理接合中之互 連金屬之高體積分數引起與焊料類似的高、穩定且可靠的電及熱效能。最終接合中之互連金屬之高體積分數亦支配經處理接合之機械特性，從而克服先前技術金屬填充之聚合物組合物之機械降解問題。成分金屬顆粒之成本及處理需求與為當前工業標準之焊料材料類似。
在一個實施例中，本發明之組合物可描述為：a)無鉛金屬顆粒之混合物，其包含：i)包含金屬元素Y之低熔點(LMP)顆粒組合物；及ii)高熔點(HMP)顆粒組合物，其包含與金屬Y在處理溫度T1下反應之金屬M，及b)助熔媒劑，其中該助熔媒劑包含：i)揮發性部分，及ii)不超過50wt%之在T1下變成惰性之非揮發性部分。
10‧‧‧金屬封裝元件
20‧‧‧組合物
30‧‧‧金屬化物
40‧‧‧半導體晶粒
50‧‧‧金屬化物
60‧‧‧金屬化物
70‧‧‧非金屬封裝元件
80‧‧‧HMP金屬
90‧‧‧LMP金屬
100‧‧‧助熔劑媒劑
圖1描繪本發明組合物將一個半導體晶粒連接至兩個封裝元件的例示性用途。
圖2描繪本發明組合物在製備時與在T1下熱處理後之間的轉變。
應理解，前文一般描述及以下詳細描述皆為說明性及解釋性的，且不欲限制所主張之標的物。
本文所用之章節標題係用於組織目的而不應解釋為限制所描述之標的物。本申請案中所引用之所有文件或文件之部分(包括但不限於專利、專利申請案、文章、書籍及論文)在此明確地以引用之方式出於任何目的以其全文併入本文中。在併入文獻中之一或多者及類似材料以與在本申請案中術語之定義矛盾的方式定義術語的情況下，以本申請案為準。
除非提供特定定義，否則本文中所描述之關於材料科學、冶 金、冶金工程、電子以及化學所採用之命名法及其實驗室操作步驟與技術為此項技術中已知之彼等命名法及實驗室操作步驟與技術。標準化學符號與由該等符號所代表之全名可互換使用。因此，例如術語「錫(Tin)」及「Sn」應理解為具有相同含義。標準技術可用於冶金處理、焊接、化學合成、化學分析及調配。
定義
在本申請案中，除非另有具體陳述，否則單數之使用包括複數，字詞「一」意謂「至少一個」，且「或」之使用意謂「及/或」。此外，術語「包括(including)」以及其他形式(諸如「包括(includes)」及「包括(included)」)之使用不具限制性。此外，除非另有具體陳述，否則諸如「要素」或「組分」之術語涵蓋包含一個單位之要素或組分及包含一個以上單位之要素或組分兩者。如本文所使用，除非另有指示，否則連接詞「及」意欲為包括性的且連接詞「或」並不意欲為排他性的。舉例而言，習語「或，可替代地」意欲為排他性的。如本文所使用，術語「及/或」係指前文要素之任何組合，包括使用單一要素。
此外，術語「包括(including)」以及其他形式(諸如「包括(includes)」及「包括(included)」)之使用應理解為「包含」且不具限制性。應理解，如在本說明書及申請專利範圍中所使用，任何字詞之單數形式亦可指其複數，取決於使用其之上下文。
如本文所使用之「約」或「大致」意謂被稱為「約」或「大致」之數字包含所述數字加上或減去該所述數字的1-10%。舉例而言，視情景而定，約50度可意謂45-55度或少至49-51度。
不論其在本文中何時出現，數值範圍(諸如「45-55」)係指各整數在給定範圍中，例如，「45-55%」意謂百分比可為45%、46%等，高達並包括55%。在本文所述之範圍包括十進位值(諸如「1.2%至 10.5%」)之情況下，該範圍係指給定範圍中所指示之最小增量之每一個十進位值，例如，「1.2%至10.5%」意謂百分比可為1.2%、1.3%、1.4%、1.5%等，高達並包括10.5%；而「1.20%至10.50%」意謂百分比可為1.20%、1.21%、1.22%、1.23%等，高達並包括10.50%。
如本文所使用，術語「實質上」係指大範圍或程度。舉例而言，「實質上所有」通常係指至少約90%、常見地至少約95%、通常至少99%及更通常至少約99.9%。
術語「合金」係指含有兩種或兩種以上金屬且視情況含有額外非金屬之混合物，其中合金之元素在熔融時一起熔合或溶解於彼此中。本文中所用之用於合金組合物之標記使用其由前斜線(「/」)隔開之IUPAC符號列出兩種或兩種以上元素。當給出時，元素在合金中之比例由對應於元素在合金中之重量百分比之下標指示。舉例而言，Sn/Bi表示錫(Sn)及鉍(Bi)之合金，其可為該等兩種元素之任何比例。Sn(60)/Bi(40)表示含有60wt%錫及40wt%鉍的錫與鉍的特定合金。在針對一或多種元素在合金中之重量百分比給出範圍的情況下，該範圍指示元素可以所指示範圍內之任何量而存在。舉例而言，Sn(70-90)/Bi(10-30)係指含有70wt%至90wt%之錫及10wt%至30wt%之鉍的合金。因此，由「Sn(70-90)/Bi(10-30))」範圍所涵蓋之合金包括但不限於：Sn(70)/Bi(30)、Sn(71)/Bi(29)、Sn(72)/Bi(28)、Sn(73)/Bi(27)、Sn(74)/Bi(26)、Sn(75)/Bi(25)、Sn(76)/Bi(24)、Sn(77)/Bi(23)、Sn(78)/Bi(22)、Sn(79)/Bi(21)、Sn(80)/Bi(20)、Sn(81)/Bi(19)、Sn(82)/Bi(18)、Sn(83)/Bi(17)、Sn(84)/Bi(16)、Sn(85)/Bi(15)、Sn(86)/Bi(14)、Sn(87)/Bi(13)、Sn(88)/Bi(12)、Sn(89)/Bi(11)及Sn(90)/Bi(10)。此外，Sn(70-90)/Bi(10-30)表示其中元素Sn及Bi之具體比例可在Sn(70)/Bi(30)至Sn(90)/Bi(10)之間變化的合金，包括Sn在70wt%直至90wt%之間變化且Bi相反在30wt%降至10wt%之間變化 的比例。
術語「偽合金」係指包含金屬元素之混合物的顆粒，在該混合物中，金屬元素當處於熔融形態時不溶解於彼此中。「偽合金」顆粒係藉由使元素自非溶液熔融狀態共固化以使得每一顆粒包含經共固化元素之混合物而形成。
如本文所使用之「助熔劑」係指用於促進金屬熔合且特定言之移除金屬氧化物並且防止金屬氧化物形成的物質(通常為酸或鹼)。
如本文所使用之術語「熔化溫度」或「熔點」係指在大氣壓力下固體變成液體時之溫度(點)。
如本文所使用之術語「高熔化溫度金屬」、「高熔點金屬」或「HMP金屬」係指具有等於或高於約400℃之熔化溫度之金屬。HMP金屬包括Cu、Ag、Pd、Au、Al、Ni、Be、Rh、Co、Fe、Mo、W、Mn及Pt。通常，用於本發明之組合物中之HMP金屬為CU、Ag、Pd、Au、Al、Ni或Pt，且最常見地，HMP金屬為CU、Ni或Ag。
如本文所使用之術語「低熔化溫度金屬」、「低熔點金屬」或「LMP金屬」係指具有低於約400℃之熔化溫度之金屬。例示性LMP金屬包括在該等金屬之合金中之Sn、Bi、Zn、Ga、In、Te、Hg、Tl、Sb、Se、Po、Pb、Cd及Po。通常，用於本發明之組合物中之LMP金屬為合金中之Sn、Ga、In或Zn，且最常見地，LMP為合金中之Sn。
術語「固相線」係指給定物質在其以下完全為固體(結晶)之溫度。固相線量化物質開始熔化但並不一定完全熔化時之溫度，亦即，固相線並不一定為熔點。對於此區別，固相線可與「液相線」形成對比，液相線規定晶體與熔融物質可共存時之最大溫度。在液相線溫度以上，材料為均質的且在平衡時為液體。在液相線溫度以下，愈來愈多之晶體可形成。固相線溫度及液相線溫度並不在所有情況下對齊或 重疊。若固相線溫度與液相線溫度之間存在間隙，則將該間隙稱為「凝固範圍」或「成糊狀範圍」，且在該間隙內，物質由固相及液相之混合物組成。
術語「共晶」係指其中組成部分以各成分同時熔化之此類比例存在且熔點為儘可能低的混合物或合金。因此，共晶合金或混合物在單一溫度下固化。在共晶混合物中，固相線溫度與液相線溫度係相同的，亦即，混合物在一個溫度(共晶點)下完全熔化。
術語「非共晶」係指並不擁有共晶性質之混合物或合金。因此，當非共晶合金固化時，其組分在不同溫度下固化，且總組成展現一熔化範圍。
術語「粉末」或「顆粒」或「微粒」係指呈離散形式的經固化金屬成分，其大小通常在1奈米至100微米之範圍內。
術語「差示掃描熱量測定」「(DSC)」係指熱分析方法，其中隨溫度變化量測使樣品與標準品之溫度增加所需的熱量差。DSC用於研究合金顆粒之熔化行為及用金屬與合金調配之TLPS糊的反應特徵(signature)。
術語「燒結」係指其中金屬粉末顆粒之相鄰表面係藉由加熱結合之製程。「液相燒結」係指其中固態粉末顆粒與液相共存之燒結形式。混合物之緻密化及均勻化在金屬擴散至彼此中時發生並形成新合金及/或金屬間化合物質。
在「暫時液相燒結」或「TLPS」中，由於金屬均質化形成固體合金及/或金屬間化合物質之混合物，液相僅存在一段較短時間。液相在周圍固相中具有極高溶解度，因此快速擴散至固體中並最終固化。擴散均質化形成最終組合物而不需要將混合物加熱至HMP金屬之固相線溫度以上。
如本文所使用之「熔化熱」或「熔化焓」係指在不改變物質之 溫度的情況下將物質自固態改變為液態所需的能量。發生此改變之溫度為熔點。因此，熔化熱為「潛熱」，原因係在熔化期間，不可觀測隨溫度變化之熱量引入，並且溫度在處理期間保持不變。
「焊料」為用以將金屬部件接合在一起且具有低於一或多個工件之熔點之可熔金屬合金。焊料具有實質上不隨著重複加熱/冷卻循環變化之特徵熔化行為。焊料可包括共晶或非共晶合金，但對於接合應用而言，共晶合金係較佳的，係因為接點快速固化。歸因於TLPS組合物中存在HMP金屬，TLPS不同於焊料，TLPS組合物與TLPS低熔點溫度合金中之反應性LMP金屬相互作用以形成具有特定化學計量比例且熔化溫度遠高於原始TLPS組合物的結晶金屬間化合物。因此，TLPS組合物通常不會在原始製程溫度下再融化。儘管金屬間化合物可在焊料內及在經接合表面中之焊料與元件(例如，銅襯墊)之間形成，但其僅代表焊接接合之較小比例(<5%)。因此，所施用之焊料可在實質上與原始應用相同的條件下再熔化。
如本文所使用之「回焊」或「回焊焊接」係指用以將一個或幾個電子組件附著至(例如)接觸襯墊或另一基板之製程，其中經附著組件及基板/接觸襯墊之組合件經受足以引起焊料熔化、流動及固化之控制熱量，從而在部件與焊料之間形成永久性機電結合。
術語「延性(ductility)」或「延性的(ductile)」係指固體材料在張應力下變形之能力，此通常表徵為材料被拉伸(例如)成絲之能力。固體材料之類似但可區分的性質為「延展性」，其為在壓縮應力下材料變形之能力且表徵為材料藉由錘擊或滾軋形成薄片之能力。
「熱膨脹係數」或「CTE」係描述物質之熱力學性質之技術術語。CTE使溫度變化與材料之線性尺寸中之變化相關。
如本文所使用之關於TLPS組合物之術語「處理溫度」或「T1」為兩種反應性金屬(例如，Cu及Sn)形成金屬間化合物質之溫度。
術語「金屬間化合物」或「金屬間化合物質」係指固體材料，其由兩種或兩種以上金屬原子以某一比例構成，具有與該固體材料之構成金屬不同之明確結構。
本發明之組合物
本發明組合物係將半導體晶粒附著至封裝元件中之軟焊料及金屬填充聚合物之替代物。本發明組合物之高體積金屬負載及低孔隙度在半導體與金屬封裝元件之間提供優良機械、電及熱互連效能。
在本發明中，將金屬之顆粒與無鉛金屬合金顆粒在助熔媒劑中混合。無鉛金屬合金顆粒內之至少一種元素與金屬顆粒中之金屬反應。隨著溫度升高至無鉛金屬合金顆粒之熔點，無鉛金屬合金顆粒變為熔融的。來自無鉛金屬合金顆粒及接受性金屬顆粒之一或多種反應性元素之擴散及反應持續直至反應物完全耗盡為止，在處理溫度下不再有熔融階段，或藉由冷卻混合物中止反應。在冷卻之後，反應材料中之金屬的體積分數超過總體積之60%，及/或反應材料中之空隙的總體積分數少於10%。反應的本發明組合物之後續溫度偏移即使超過原始熔化溫度，仍不會再生混合物之原始熔化特徵。
本發明組合物克服了焊料晶粒附著材料中之大空隙及再熔化之問題，以及具有相對低的金屬負載百分比的被動負載導電黏著劑組合物之不良熱效能，同時亦提供與常見製造方案的一致性及與風行表面修整之相容性。在本發明組合物中，將金屬顆粒與無鉛焊料糊組合物摻合且用助熔媒劑溶劑稀釋，以使得熱處理之後的淨金屬含量超過60體積百分比。可按一定糊稠度製備本發明組合物，以便於藉由諸如分配及模板印刷之常見工業方法來塗覆。一旦糊經塗覆且半導體及一或多個封裝元件已按所需組態裝配，則組合件經受在控制熱升溫(thermal ramp)及環境下的熱偏移。在此熱處理期間，助熔媒劑中之揮發性部分緩慢蒸發，無鉛金屬合金顆粒熔化，熔融合金中之LMP金 屬Y擴散進入金屬元素M之相鄰表面並且發生反應以形成高熔點合金。剩餘的助熔媒劑及填充顆粒之間的間隙之助熔劑化學品熱固且變成化學惰性的。所得組合物含有至少約60體積%的冶金互連金屬。
本發明組合物優於習知顆粒填充黏著劑，係因為機械強度及熱以及電效能係源自冶金互連路徑之高體積負載，該等冶金互連路徑由無鉛合金顆粒中之LMP金屬(例如，錫)相互擴散至半導體晶粒、一或多個封裝元件及金屬顆粒之可焊接表面中而形成。在習知顆粒填充黏著劑中，體積金屬負載由維持聚合物黏著劑之機械完整性之需要限制。
本發明組合物優於習知含鉛焊料及無鉛焊料，係因為本發明組合物係無鉛的，且在將組件裝配至模組或印刷電路板期間，當曝露於後續焊料回焊剖面時將不會再熔化。
本發明組合物不同於先前技術組合物，係因為本發明組合物已經具體設計以滿足功率半導體晶粒附著之特有挑戰，諸如針對高熱及電效能之極低空隙體積及密集互連金屬的高體積。首先，低空隙百分比為助熔劑媒劑之揮發性部分之控制揮發相對於所定義的熱處理體系之函數。另外，藉由最小化助熔媒劑之非揮發性部分及最佳化無鉛金屬合金顆粒與金屬顆粒之間的比率而達成互連金屬之高體積分數。最後，已選擇本發明組合物中之金屬粉末的粒徑來提供經改良結合控制及晶粒附著應用之易應用性。
在最簡單的術語中，本發明半導體晶粒附著組合物為金屬粉末及助熔媒劑之組合物，該組合物一旦反應即形成含有至少60%體積金屬(合金+金屬粉末)部分及/或少於10%體積分數之空隙的冶金互連網狀物。該組合物包含：a. 80至99重量百分比(wt%)之金屬顆粒混合物，其包含：i. 30至70wt%之無鉛、低熔點(LMP)顆粒組合物，其包含至少 一種LMP金屬Y；及ii. 25至70wt%之高熔點(HMP)顆粒組合物，其包含在處理溫度T1下與至少一種LMP金屬Y發生反應之至少一種金屬元素M，其中，M之wt%與Y之wt%的比率為至少1.0，b. 0至30wt%之金屬粉末添加劑A及c. 助熔媒劑，其中該助熔媒劑包含：i. 揮發性部分，及ii. 不超過50wt%之在T1下變成惰性之非揮發性部分。
在本發明之實踐中，無鉛金屬合金顆粒、金屬粉末及助熔媒劑可混合在一起以形成可印刷或可分配糊。通常，無鉛金屬合金與金屬顆粒之混合物將以組合物之至少約80或至少約85重量百分比且以組合物之至多約90或至多約95或至多約99重量百分比而存在。通常，無鉛金屬合金粉末將以混合物之至少約20或至少約30重量百分比且以混合物之至多約50或至多約70重量百分比而存在。通常，金屬粉末將以混合物之至少約30或至少約40重量百分比且以混合物之至多約70或至多約80重量百分比而存在。通常，助熔媒劑將以組合物之至多約20、或至多約10、或至多約5重量百分比而存在，其中不超過約50、或約25、或約10、或約5重量百分比的助熔媒劑為非揮發性的。通常，組合物中M之重量百分比與Y之重量百分比的比率為至少約1.0、或至少約1.3、或至少約1.5。
本發明組合物可有利地用以將半導體晶片之頂側及/或背側連接至半導體封裝元件(諸如，夾片、引線框架或其他基板)。本發明組合物最有利地用以形成組合件，其中半導體晶片與一或多個封裝元件之頂側及/或背側皆用可焊接表面金屬化，以促進半導體晶片與封裝元件之間的熱轉移及/或電連接。此組態使本發明組合物能夠自半導體晶粒上之金屬化物經由大量接合至封裝元件上之金屬化物形成連續冶 金互連路徑。
本發明組合物可為糊基的或可轉化為薄膜。可對本發明組合物進行網板印刷或模板印刷、分配、噴射、拾取及置放、層壓及其類似處理，以在半導體晶片表面、封裝元件表面上或在半導體晶片及封裝元件可接著附著至之臨時載體上形成經圖案化之沈積物。存在於助熔劑媒劑組合物中之揮發物在b階製程中抑或在溫度至峰值溫度T1之升溫期間釋出。T1等於或大於無鉛金屬合金顆粒之熔化溫度。在焊料回焊中，通常將峰值回焊溫度選擇為超過無鉛金屬合金顆粒之熔化溫度5-50℃，以確保所有顆粒變為熔融的及流體。此峰值溫度亦適合於本發明組合物，但可能需要更長全處理循環時間，以實現低體積百分比空隙所需之揮發性成分之釋出，並形成經相互擴散之冶金結構。
在本發明組合物之熱處理偏移期間，無鉛金屬合金顆粒中之LMP金屬(例如，錫)經歷與組合物中之剩餘金屬顆粒的相互擴散，從而引起熔化溫度極大地超過回焊處理溫度之新合金組合物之不可逆形成。正是此特徵，使得本發明組合物能夠用於在將經封裝組件裝配至電路板時在後續回焊操作期間將半導體晶粒附著至經封裝組件中而無需再熔化。
無鉛金屬合金顆粒亦可含有與金屬顆粒不反應之元素。可用反應性元素合金化之典型元素可包括Bi、Ag、Cu、Sb、Au或其組合。通常，併入該等額外無反應性元素以達到特定處理溫度，改良對諸如銅之較佳金屬表面之潤濕、或操控經熱處理組合物之機械性質。特定合金化元素可能在諸如提供低處理溫度之一態樣中係有利的，但在諸如對特定表面修整之潤濕及黏著之另一態樣中係不利的。特定合金化元素因此對於應用之特定需求為特定的。
在半導體晶粒與封裝元件之間的成品接縫中存在空隙通常對熱效能係不利的，且可產生機械故障之起始點。本發明組合物可以類似 於通常用於焊料之熱剖面之方式或以與導電黏著劑一致之方式加以處理。應選擇所用熱剖面以將經反應組合物中之空隙之總體積限制為低於約10%或低於約5%。應選擇自剖面之峰值溫度至室溫之冷卻速率，以防止由於熱衝擊引起的對半導體晶片之損壞，且該冷卻速率例如小於每秒約6℃，或介於每分鐘約2.17℃與約3.25℃之間。應瞭解，最佳冷卻速率可取決於所採用之處理類型(例如，黏著劑類型處理中之冷卻速率比用於回焊類型處理之冷卻速率慢許多)及具體半導體晶粒與封裝形式因素。
TLPS組合物之熱固性質
本發明之組合物係基於以下觀測：TLPS組合物可在溫度T1下處理以連接電子組件，並且所得經處理連接在隨後加熱至溫度T1及甚至在更高溫度時仍將係穩定的。換言之，一旦經冶金處理，TLPS組合物不會在加熱超過處理溫度時熔化。因此，TLPS組合物表現類似於「熱固物」而非「熱塑性塑料」。
熟習此項技術者將認識到，「熱固物」在施加熱量後將不可逆地「固化」以變為不溶的硬化形態，而「熱塑性塑料」在加熱時熔化、在充分冷卻時固化且可反覆地再熔化及再固化。儘管此術語通常用於描述聚合物黏著劑，但在本文中係用以描述用於連接(例如)電子組件及其他金屬元件之冶金組合物。
習知金屬焊料之特徵可為「熱塑性」。焊料熔化以將金屬部件接合在一起且在冷卻時固化以將彼等部件固持在適當位置；然而在隨後再加熱時，焊料再熔化。相比之下，TLPS組合物表現類似於熱固物。在加熱時，TLPS組合物充分熔化以將金屬部件接合在一起，且在冷卻時固化以將彼等部件固持在適當位置。然而，在熔化製程期間，TLPS組合物經歷不可逆的冶金變化，該等不可逆的冶金變化可被視為「固化」，其結果為在再加熱時，「經固化」或經處理TLPS組 合物將不會熔化。
在本發明之某些實施例中，按將焊料轉化為「熱固」形態之比例將含有低熔點(LMP)無鉛金屬合金之習知焊料糊與反應性金屬顆粒進行組合，該「熱固」形態之焊料在典型焊料回焊循環期間不可逆地「固化」。此「熱固」行為引起之接合在原始回焊溫度下不會再熔化，且因此適合於在相同回焊溫度下二次裝配循環以及適合於高操作溫度應用。
在習知焊料回焊中，通常選擇回焊溫度為超過焊料糊之熔化溫度5-50℃以確保所有顆粒變為熔融的及流體。當使用本發明組合物代替焊料糊以用於電子組件之附著時，可遵循標準焊料回焊實踐。
在本發明之實踐中，選擇高熔點金屬M及至少一種LMP金屬Y，使得暫時液相燒結反應之產物將具有用於所預期應用之屬性的最佳組合。可針對M之選擇考慮之關鍵屬性涵蓋諸如熱穩定電阻、延性、高電及熱傳導率、類似於周圍材料之熱膨脹係數及在具體環境下可能需要之其他特性的特性。
本發明組合物在焊料回焊條件下經歷熱固反應，以形成結晶金屬間化合物與合金產品(亦即，在TLPS反應期間形成之新合金)的混合物，金屬間化合物與合金產品皆具有實質上比初始無鉛金屬合金顆粒熔化溫度高的熔化溫度，並極大地超過回焊處理溫度。在TLPS處理期間形成之合金產品具有實質上不同於LMP與HMP金屬顆粒之原始混合物的組成。此反應係不可逆的且經處理組合物在後續高溫曝露期間不會明顯熔化。正是此特徵使得本發明組合物能夠在後續回焊操作期間用於電子組件之標準回焊附著，而無需再熔化。因此，本發明組合物實現分級焊接操作且使得能夠在不使用鉛、諸如金之昂貴元素或外來合金的情況下在標準工業焊料回焊條件下製造高操作溫度電子組合件。
在焊料回焊期間使用本發明組合物形成之結晶金屬間化合物包含具有固定元素比例及定義粒度之多樣性結構的單位晶胞。結晶金屬間化合物係堅固但脆性的材料。當金屬間化合物在標準焊料糊與組件附著襯墊之間的界面處形成時，大型粒子通常和與襯墊及塊狀焊料之層狀界面一起生長。該等層狀界面易受裂紋之形成及擴展影響。然而，使用本發明組合物，反應性金屬粉末使大量眾多無序小粒子在不同定向上成核。此眾多粒子之生長受到每一個顆粒中之反應性金屬的體積限制。每一個粒子之無規定向防止小粒子合併成幾個大粒子。此眾多無序小粒子促進堅固接合之形成，該堅固接合並不如同幾個大粒子沿層狀界面易受裂紋擴展影響。
通常，本發明組合物在無鉛金屬合金顆粒之熔化溫度下之熔化熱在初始焊料回焊製程期間降低了至少70%。在初始處理期間，TLPS組合物在無鉛金屬合金顆粒之熔化溫度下展現顯著熔化熱峰值。在處理之後，在再加熱至無鉛金屬合金之熔化溫度時，甚至當針對總組成中之比例而標準化時，熔化熱亦實質上減少。
在不改變溫度的情況下將一公克之物質自固態改變至液態所需的能量稱為熔化熱。用於任何材料之熔化熱係特定於該材料的。TLPS組合物內之LMP金屬之熔化熱之表現將取決於LMP金屬在總組成中之比例。在處理後，由於M與Y反應以形成金屬間化合物質引起的任何既定TLPS組合物中之LMP金屬相之耗盡可藉由將未經處理之組合物之樣品之熔化熱與已在T1下處理之一個樣品之熔化熱相比較而測定。由於未經處理之組合物中之LMP金屬之熔化熱可藉由同Y與M之TLPS反應相關聯之劇烈能量釋放掩蓋，使用純LMP金屬之熔化熱通常係有用的，且接著根據組合物中之LMP金屬之重量百分比標準化此值以獲得用於未經處理之TLPS組合物之值。
高熔點金屬
HMP金屬(M)包括但不限於Cu、Ag、Pd、Au、Al、Ni、Be、Rh、Co、Fe、Mo、W、Mn及Pt。通常，用於本發明之組合物中之HMP金屬為Cu、Ag、Pd、Au、Al、Ni或Pt，且最常見地，HMP金屬為Cu、Ni或Ag。包含M之HMP顆粒實質上可為元素M、可為用其他元素合金化之M、可為塗佈至非金屬或其他核心顆粒上之M、或可為用另一元素、無機塗層或有機塗層而塗佈自身之M。為了獲得具有最佳特性之TLPS反應產物而考慮多種HMP金屬之使用。舉例而言，在一些應用中，經處理組合物之機械強度不如電導率重要，或熱導率可比延性重要。由於通常需要以另一性質為代價來最佳化一個特性，故可根據此項技術中熟知之元素之性質來選擇單獨成分以得到預期應用中之最佳效能。具體考慮銀、金、鈀、鎳及鋁以在本發明之組合物及方法中單獨或以各種組合(包括與銅組合)的方式使用。
在本發明中，Cu係用於(M)的較佳元素，但當情況許可時，可考慮其他金屬。為了獲得與具有諸如低CTE或複合模數之最佳特性之無鉛焊料的金屬反應產物，亦考慮結合銅使用額外高熔點金屬。亦具體地考慮Ag、Au、Pd、Ni、Al、Fe、Mn、Mo及W以用作主金屬元素或合金化金屬元素。
低熔點金屬
理想地，為取代由電子工業正使用之現有無鉛焊料回焊處理，本發明之TLPS組合物中所使用之LMP金屬係無鉛焊料糊之製造中之一種常用金屬。例示性LMP焊料糊合金(Y/X)包括但不限於Sn/Ag/Cu、Sn/Cu、Sn/Ag、Sn/Sb、Sn/In、Sn/Bi、Sn/Bi/Ag。儘管使用可商購的合金係有利的，但本發明可用任何合適的合金來實踐。可改變成分之精確比例且本發明涵蓋常規合金。在對於無鉛金屬合金顆粒之表示「Y/X」中，「X」表示與Y形成合金之至少一種金屬。在本發明之一些實施例中，X表示一種、兩種、三種或更多種合金金屬。 舉例而言，在本文中使用Y/X表示其中Y為錫且X為單一金屬之Y的各種合金，例如，銅(Sn/Cu)、銀(Sn/Ag)、銻(Sn/Sb)、銦(Sn/In)及鉍(Sn/Bi)。Y/X亦用於表示Y為錫且X表示兩種金屬之各種合金，諸如銀與銅(Sn/Ag/Cu；例如，SAC)，及銀與鉍(Sn/Bi/Ag)。
LMP無鉛金屬合金中之例示性反應性元素(Y)單獨地或以與(X)成合金的形式包括以下金屬：Sn、Zn、Ga、In。通常，本發明之組合物中之Y為Sn或In，且最常見地，Y為呈Y/X合金形式之Sn。在本發明之某些實施例中，反應性金屬Y為Sn，其以低熔化溫度合金Y/X形式存在，且反應性HMP金屬M為Cu、Ni或Ag。在本發明之一個實施例中，Y/X為SAC(Sn/Ag/Cu)且M為Cu。
金屬添加劑
本發明之態樣係基於對包括金屬添加劑可改良經處理TLPS組合物之性質(諸如延性)的觀測。因此，經由添加劑元素性或合金粉末與主導性金屬M及Y或上述合金粉末Y/X成分之摻合，將有益金屬添加劑(A)併入至TLPS冶金中。作為固有反應性成分或作為藉由用反應性金屬元素塗佈、合金化或偽合金化使得具有反應性的成分，此類金屬添加劑A參與本發明之冶金。添加劑金屬包括Cu、Ag、In、Pd、Au、Ni、Ce及Pt。若用可與M或Y反應之金屬合金化、偽合金化或塗佈，則亦考慮諸如Be、Rh、Co、Fe、Mo、W及Mn之其他金屬作為添加劑。
添加劑金屬顆粒A之主要目的為在處理本發明之TLPS組合物時在由M與Y反應形成之結晶金屬間化合反應產物之基質內提供延性相。為了有效改良整體組合物之延性，添加劑顆粒A必須以冶金方式結合至基質中。若A未結合至基質中，則經由脆性結晶相(例如，金屬間化合物)形成且擴展之裂痕將僅避開延性添加劑顆粒A而非獲得較高延性相之益處。然而，當添加劑顆粒A結合至基質時，由添加劑延性相賦 予之提高的延性調節裂紋擴展並且允許接縫抵抗提高的機械應變。
在本發明之某些實施例中，例如當在二次回焊操作中在TLPS接縫上存在有少量機械負載時，本發明組合物在回焊之後的部分再熔化並非係不利的。在此類應用中，可併入過量元素Y或合金Y/X以提供延性相。亦可藉由在LMP合金Y/X中用Y合金化之元素賦予延性，藉此在由與M反應而耗盡Y時使延性相X係可用的。
當需要併入延性相而非過量元素Y或合金Y/X時，存在至少兩種併入手段。第一種方法係在雙峰式粒徑分佈併入一或多種HMP金屬(亦即，含有HMP金屬之小及大顆粒)。HMP金屬之較小顆粒用作與Y反應之HMP金屬M TLPS試劑，而HMP金屬之較大顆粒太大而不能有效地轉化為金屬間化合物質。因此，充當金屬添加劑A的較大粒徑之HMP金屬僅在顆粒表面上發生反應，同時大多數仍為不反應的延性金屬。兩種大小之HMP金屬顆粒可為相同或不同的HMP金屬。
用於產生延性相之第二種方法係將延性材料併入至本發明組合物中，該延性材料不與Y或M反應，而係用反應性金屬塗佈、合金化或偽合金化以作為金屬添加劑A顆粒。在此替代例中，經塗佈、合金化、或偽合金化之反應性金屬以冶金方式反應成為基質，從而使延性材料為完整的以形成延性相。
亦可採用併入添加劑A之前述方法以控制經處理組合物之其他特性，諸如熱膨脹係數及其類似者。
粒徑、形狀及比率
將高熔點金屬M、金屬Y或合金Y/X、及視情況存在之金屬添加劑A作為顆粒(例如，粉末)引入至組合物中。顆粒可為球形的、不規則的、片狀的、海綿狀的、桿狀的及為熟習此項技術者已知之其他形式。HMP金屬M之顆粒可實質上為元素態的，可用其他元素合金化，可作為塗層沈積至非金屬或其他核心顆粒上、或可用另一元素、無機 塗層或有機塗層而塗佈自身。同樣，LMP金屬Y或包含Y/X之合金可為僅由金屬元素X及反應性LMP金屬元素Y組成之二元合金，或可用其他成分合金化，可作為塗層沈積至非金屬或其他核心顆粒上，或可用另一元素、無機塗層或有機塗層而塗佈自身。
本發明組合物之關鍵特徵在於，粒徑分佈係控制的，使得本發明組合物適合於在半導體晶粒之平坦表面與接合表面之間產生薄、一致結合線。HMP金屬M及LMP金屬Y或合金Y/X之諸如粉末之顆粒通常具有約0.1μm至高達約100μm之間的標稱直徑。金屬粉末更常具有1μm與50μm之間的標稱大小。
在一些實施例中，在TLPS組合物中存在兩種或兩種以上大小之顆粒，包括多種粒徑及顆粒混合物，該等顆粒混合物包括遍及約1nm至約100μm、約10nm至約100μm、約100nm至約75μm、約1μm高達約75μm，及約1μm至約50μm之範圍之顆粒。在一些情況下，通常經由硬篩分達成之對粒徑分佈之嚴格控制可用以使本發明之TLPS組合物適合於諸如分配、噴墨及其類似者之沈積技術。通常，HMP金屬M、LMP金屬Y或合金Y/X及金屬添加劑A之平均粒徑為1至50微米；其最通常在5至20微米之範圍內。
製造高溫焊料/TLPS組合物之方法
本發明亦提供用於藉由以下步驟製備本文中所描述之TLPS組合物之方法：提供至少一種呈微粒形式之HMP金屬M；至少一種呈微粒形式之LMP金屬合金Y/X；視情況存在之呈微粒形式之金屬添加劑A；及助熔媒劑；及按所揭示的基於組合物之總重量之比例組合顆粒與助熔媒劑。
本發明亦提供用於製備本文所揭示之TLPS組合物之方法，其包括以下步驟：1. 提供至少一種呈微粒形式之HMP金屬M、至少一種呈微粒形 式之LMP金屬Y及/或合金Y/X、助熔媒劑及一或多種呈微粒形式之金屬添加劑A；以及2. 按所提及之基於組合物之總重量之比例組合顆粒與助熔媒劑。
涵蓋用於本發明之組合物之合金大體上係可商購的。
顆粒塗層
塗層可存在於分別包含M及Y之第一顆粒及第二顆粒中之一者或兩者上，及/或存在於金屬粉末添加劑A上。考慮使用之塗層包括金屬、無機塗層、有機塗層及有機-金屬塗層。製備具有塗層之顆粒可用於例如將額外金屬元素引入本發明之TLPS組合物中，以便更改經處理金屬基質之性質，保護顆粒免受氧化，防止金屬或金屬氧化物提前與有機成分反應，促進顆粒在基質中之分散，使顆粒維持懸浮，向組合物賦予潤滑性，防止顆粒凝聚及其類似者。塗層之存在及類型之特定選擇取決於針對TLPS組合物所考慮之應用、沈積方法及助熔媒劑之化學反應，以上各者皆在熟習此項技術者之知識內。金屬(諸如，錫及銀)、含磷部分(諸如，自裝配磷酸鹽單層)、飽和及不飽和脂肪酸、無機及有機金屬鹽、金屬醇鹽、三唑及聚苯胺皆加以具體考慮以作為根據本發明之有用塗層之組分。
助熔媒劑
用於本發明組合物之助熔媒劑充當金屬顆粒之載劑，從而用以將混合物固持在一起以易於應用以及使各種顆粒彼此極為接近。助熔媒劑亦用以使金屬試劑可用於反應且如同溶劑在有機反應中的作用一樣用以保護金屬試劑免受環境影響。若干因素(例如，極性、質子性或非質子性、與水混溶性，等等)決定用於有機反應之適當溶劑之選擇。同樣，針對適當屬性選擇本發明之組合物中之助熔媒劑。助熔媒劑之最關鍵屬性為其必須自金屬試劑之表面移除金屬氧化物以使得該等試劑可用於反應。金屬氧化物之移除被稱為「助熔」且可藉由為熟 習此項技術者已知之多種化學物質(包括有機酸及強鹼)實現。
為達成有用的糊稠度同時亦實現具有最大金屬含量之接合，助熔媒劑包含一或多種揮發性組分。揮發性組分可為用作助熔劑之活性物質或可為諸如溶劑之化學惰性材料。在本發明組合物之熱處理期間，揮發性成分在控制升溫及峰值溫度條件下逐漸蒸發，使得在經熱處理的接縫中形成極少空隙空間。
助熔媒劑可包括允許TLPS組合物在處理之前按需要成形之熱塑性聚合物材料，且可含有在處理期間發生反應以在金屬網狀物內形成內置沈積物之聚合物前驅體及/或其他化合物及溶劑。
本發明TLPS組合物之應用
由本發明之TLPS組合物形成之冶金網狀物可用於電、熱及/或機械連接電結構內之元件。本發明提供用於連接多種電子部件之組合物，該等多種電子部件用於可能遭遇高操作溫度之應用，包括但不限於分級焊接、下向鑽眼、鑽油、電氣控制、汽車機艙、智慧型電網分佈及航空應用。
可使用本發明組合物之例示性應用包括將半導體晶粒連接封裝元件，從而在經堆疊晶粒與其類似者之間形成連接。
本發明之組合物可有利地用以將金屬化半導體晶粒連接至引線、電路板、引線框架、夾片、內插物、額外晶粒或其他基板。當由此連接之組合件將經受需要另一焊料回焊之後續裝配操作時，及/或當該組合件將在惡劣的操作環境中使用時，本發明組合物最有利地用以連接半導體晶粒。
可使用各種技術施加上述組合物，該等技術包括但不限於針頭點膠(needle dispensing)、模板印刷、網板印刷、噴墨、層壓、擠塑、鑄造、噴塗或為將熟習此項技術者已知之其他方法(諸如，形成電子組件可接著附著至其之經圖案化沈積物的方法)。一旦施加，則在烘 箱中、在回焊爐中、在熱板上、在壓合機(lamination press)中，或藉由通常用於處理焊料或金屬填充有機黏著劑之其他手段對所述組合物進行熱處理。具體熱處理條件取決於應用以及對金屬系統及任何有機黏合劑成分之選擇。
在沈積之後，金屬半導體晶粒或封裝元件與所沈積之本發明組合物接觸以形成組合件。可接著在烘箱中、在回焊爐中、在熱壓設備中、在熱板上、在壓合機中，或藉由任何其他可用手段(諸如，通常用於處理焊料或所填充的機黏著劑之手段)將本發明之組合物熱處理至溫度T1。熟習此項技術者將意識到，通常用於處理焊料或所填充的有機黏著劑之額外方法將適合於處理本文中所描述之TLPS組合物。具體熱處理條件取決於應用、預期用途、TLPS組合物及任何助熔有機媒劑成分。通常，處理溫度T1在100℃至300℃之範圍內，更常在150℃至280℃之範圍內，及最常在200℃至280℃之範圍內。
圖1描繪本發明組合物將一個半導體晶粒連接至兩個封裝元件之例示性用途。半導體晶粒40在兩個主表面上金屬化(30與50)以提供電與熱互連點。本發明組合物20係安置於金屬封裝元件10與半導體晶粒40上之金屬化物30之間。本發明組合物20亦安置於半導體晶粒上之金屬化物50與非金屬封裝元件70上之金屬化物60之間。在圖1中，在熱處理至T1之前描繪本發明組合物，其中單獨顆粒仍分散於助熔媒劑中。
圖2描繪本發明組合物在製備時與在T1下熱處理後之間的轉變。在每一描繪中，本發明組合物20係安置於金屬封裝元件10與半導體晶粒40表面上之金屬化物30之間。在T1下熱處理之前，HMP金屬80與LMP金屬90之單獨顆粒在助熔劑媒劑100中係顯而易見的。在T1下熱處理之後，該等單獨顆粒已經歷相互擴散以自金屬封裝元件10經由本發明組合物沈積物20且至半導體晶粒40表面上之金屬化物30形成冶金 互連結構。
現將參考以下說明性、非限制性實例進一步描述本發明。儘管已藉助於說明及實例出於清晰性及理解之目的相當詳細地描述前述發明，但將對一般熟習此項技術者顯而易見的是，鑒於本發明之教示，可在不脫離所附申請專利範圍之精神或範疇的情況下對本發明作出某些變化及修改。
實例
現將參考本發明的更具體實施例及為該等實施例提供支援之實驗結果。然而，申請者應注意，以下揭示內容係出於說明之目的且不意欲以任何方式限制所主張之標的物之範疇。
比較實例A至D
藉由使用雙行星混合器於真空下在容器中混合表1中所列出之組分來製備四種比較糊(A至D)。
表2中給出比較實例A至D之特性。描述了在熱處理前後之金屬百分比，且使不同金屬與聚合物成分之密度差標準化以提供處理之後的金屬體積分數。
表2展示低體積金屬負載引起不良電可靠性，其意謂在可靠性測試期間大於10%之導通電阻變化。該等實例中應注意，具有不良可靠性效能之組合物在熱處理之後具有低金屬體積百分比。表1中之實例之組合物具有在經燒結組合物中剩餘之10至11重量百分比的助熔劑媒劑，其產生相對較低的處理後金屬體積百分比。
實例1至4
藉由使用雙行星混合器於真空下在容器中混合表3中所列出之組分來製備本發明之四種組合物。
表4中給出實例1至4之特性。描述了熱處理前後之金屬百分比，且使不同金屬與聚合物成分之密度差標準化以提供處理之後的金屬體積分數。
作為表2中之比較實例之結果，採取新方法以確保燒結後之金屬體積百分比增加。藉由實質上減少助熔有機媒劑之量以及用揮發性溶劑替代該助熔有機媒劑以維持組合物之糊稠度，處理後之金屬之體積百分比充分升高以達成所需效能。出乎意料地，助熔劑在組合物中之比例可減少至遠低於通常在焊料糊中使用之助熔劑的比例，而對金屬元件之間的所需TLPS反應上無不利影響。助熔有機媒劑中之此減少亦引起處理後有機相移至隔離凹穴而非連續相。因此，處理後組合物出乎意料地由經互連金屬網狀物機械主導而非表現為複合物，不同於 先前技術之金屬填充聚合物黏著劑。表4展示在燒結後具有較高金屬體積百分比之糊中之電效能及可靠性效能之結果。
本發明之具有高體積金屬負載及利用無鉛金屬顆粒之混合物之無鉛糊在機械及電可靠性測試中至少表現得與含鉛焊料糊一樣好。如可經由表4中之實例觀測到的，與銀環氧化物黏著劑及產生成功的可靠性結果的先前技術之TLPS組合物相比，本發明組合物達成了高黏著級別與高電導率及熱導率的出乎意料的組合。
10‧‧‧金屬封裝元件
20‧‧‧組合物
30‧‧‧金屬化物
40‧‧‧半導體晶粒
50‧‧‧金屬化物
60‧‧‧金屬化物
70‧‧‧非金屬封裝元件

Claims (23)

  1. 一種在熱反應之後具有大於60%金屬體積之半導體晶粒附著組合物，其包含：a. 80至99重量百分比(wt%)之金屬顆粒混合物，其包含：i. 30至70wt%之無鉛、低熔點(LMP)金屬合金顆粒組合物，其包含至少一種LMP金屬Y；及ii. 25至70wt%之高熔點(HMP)顆粒組合物，其包含與該至少一種LMP金屬Y在處理溫度T1下反應之至少一種金屬元素M，其中，M之wt%與Y之wt%的比率為至少1.0，b. 0至30wt%之金屬粉末添加劑A及c. 助熔媒劑，其中該助熔媒劑包含：i. 揮發性部分，及ii. 不超過50wt%之在T1下變成惰性之非揮發性部分。
  2. 如請求項1之組合物，其中該金屬元素M在T1下經歷與至少一種LMP金屬Y的相互擴散，使得由此相互擴散形成之產物具有超過T1之熔點。
  3. 如請求項1之組合物，其中該LMP顆粒組合物不含有超過痕量可檢測程度之鉍。
  4. 如請求項1之組合物，其中該至少一種M係選自由以下各者組成之群：Cu、Ag、Pd、Au、Al、Ni、Be、Rh、Co、Fe、Mo、W、Mn、Pt及其組合。
  5. 如請求項1之組合物，其中該至少一種M係選自由以下各者組成之群：Cu、Ag、Pd、Au、Al、Ni、Pt及其組合。
  6. 如請求項1之組合物，其中該至少一種M為Cu、Ni、Ag及其組合。
  7. 如請求項1之組合物，其中該至少一種Y係選自由以下各者組成之群：Sn、Zn、Ga、In及其組合。
  8. 如請求項1之組合物，其中該至少一種Y係選自由以下各者組成之群：Sn、In及其組合。
  9. 如請求項1之組合物，其中該至少一種Y為Sn。
  10. 如請求項1之組合物，其中該金屬粉末添加劑A包含Cu、Ag、In、Pd、Au、Ni、Ce、Pt或其組合。
  11. 如請求項1之組合物，其中該金屬添加劑A包含用可與M或Y反應之金屬合金化、偽合金化或塗佈之Be、Rh、Co、Fe、Mo、W、或Mn。
  12. 如請求項1之組合物，其中T1係在100℃至300℃之範圍內。
  13. 如請求項1之組合物，其中T1係在150℃至280℃之範圍內。
  14. 如請求項1之組合物，其中T1係在200℃至280℃之範圍內。
  15. 如請求項1之組合物，其中該等金屬粉末之最大粒徑為50微米。
  16. 如請求項1之組合物，其中該非揮發性部分包含羧酸、酚或其組合。
  17. 如請求項1之組合物，其中該揮發性部分包含無反應性溶劑。
  18. 一種包含如請求項1之組合物之結構，該組合物安置於至少一個主表面上之半導體晶粒承載金屬化物與至少一個主表面上之封裝元件承載金屬化物之間。
  19. 一種包含在峰值溫度T1下處理如請求項19之結構之步驟之方法，其實現自該晶粒承載金屬化物至該封裝元件承載金屬化物之連續冶金互連路徑。
  20. 如請求項19之方法，其中T1係在150℃與280℃之間。
  21. 如請求項19之方法，其中在峰值溫度T1處之持續時間係自15至75分鐘。
  22. 如請求項19之方法，其中達到峰值溫度T1之斜率係在每分鐘2.67℃與4.4℃之間。
  23. 如請求項19之方法，其中自T1返回至室溫之冷卻速率係在每分鐘2.17℃與3.25℃之間。
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