臺灣博碩士論文加值系統

在電子構裝產業中軟銲製程是一種經常被應用的技術，在這些製程中，鉛錫合金由於其優異的各種性質，成為最常被使用的銲錫原料。然而因為鉛對人體具有毒性，禁用含鉛產品的呼聲越來越高，無鉛銲錫的研發與使用也成為一種趨勢。而在軟銲反應中，銲錫與母材會在界面產生反應並生成一些介金屬化合物，這些介金屬化合物對接點的性質有重要影響。因此，本研究即以純銦、In49Sn及In10Ag等銦基無鉛銲錫對電子工業常用之金厚膜與銀基板進行軟銲反應，探討其界面生成介金屬之種類與型態、界面介金屬之成長動力學及銲錫與基板間之潤濕行為，並藉此評估這些銲錫系統的實用性與其在實際製程上將面對之問題。
研究的結果顯示，在In/Au與In49Sn的軟銲反應系統中，金厚膜與銲錫界面均會生成以AuIn2相為主之介金屬化合物，但生長機構則互不相同：在In/Au系統中為擴散控制反應，其成長活化能為39kJ/mol，但在In49Sn/Au系統則是界面控制反應，其成長活化能為51kJ/mol。隨著反應時間或溫度的增加，Au/AuIn2界面上會依序再生長出AuIn及Au7In3（g￠）相，當g￠相生成時，界面將產生剝裂現象而影響銲錫接點性質。此外，軟銲過程中溶入銲錫液中的基材金原子會在冷卻過程中以游離島嶼狀之AuIn2相型式析出在銲錫基地內。在In49Sn銲錫系統中，銲錫基地之介金屬以AuIn2相而非AuSn4相析出，可能是其可以避免金脆化現象之主要原因。
在In10Ag/Ag之軟銲反應系統中，在銲錫與銀基板之界面會生成扇貝狀或樹枝狀的Ag2In介金屬化合物，其外圍包覆一層0.5至1mm之AgIn2殼層。此界面Ag2In相之成長為一擴散控制反應，其活化能約為45kJ/mol。除了界面介金屬之成長外，軟銲過程中溶入銲錫之銀原子與In10Ag銲錫內原有之銀原子在冷卻過程中亦會以Ag2In相為主之圓球狀或樹枝狀游離介金屬塊析出在銲錫基地內。這些界面與銲錫基地內之介金屬在試片於常溫下置放時會繼續發生固態反應，使先前生成之Ag2In相為其外圍之AgIn2相消耗而逐漸取代。經進一步以Ag2In/In擴散偶研究結果發現，在Ag2In/In之固態反應中，界面會生成AgIn2相，其成長為擴散控制，活化能約為41kJ/mol，近似於薄膜反應時之AgIn2相成長活化能。
在銲錫對基材之潤濕性方面，In/Au與In10Ag/Ag系統之銲錫錠接觸角q變化可分為三個階段，其中第二階段是一q保持不變之高原期，其生成機構可以界面介金屬之成長與液滴前端帶狀區之生成來解釋，並可經由液滴前端之微觀觀察圖加以證實。相對於上述兩系統，In49Sn/Au之接觸角變化雖亦可區分為三個階段，但其第二階段僅是q下降斜率較為平緩，並無高原期之情形發生，經進一步比較In/Au與Sn/Au系統之q變化結果，推測此種斜率變緩之現象乃是由於In49Sn成份中銦與錫成份分別對金厚膜作用而產生之結果。

Soldering has been widely used on electronics assemblies and PbSn alloys are very popular solder alloys due to their superior properties as good soldering properties, fatigue resistance, adequate thermal and mechanical properties and low cost. However, growing concerns about environmental pollution and lead toxicity have increased the regulations and legislation on lead usage. The development of lead-free solders has been prompted and intensified for the past years. In soldering, the reaction between solder and substrate will result in intermetallic compound growth on the interface, which is crucial to the quality of solder joint. The morphology and growth kinetics of intermetallic compound formed during the soldering reaction of lead-free In/Au, In49Sn/Au and In10Ag/Ag systems and solid-state diffusion couple of Ag2In/In have been investigated in this study. Also, the wettability of these solder systems are determined by contact angle measurements in sessile drop method.
The results show that AuIn2 phase, in the shape of wavy layer, grows as a major phase at the reaction interface in both In/Au and In49Sn/Au reactions. The growth of AuIn2 layer in In/Au reaction is a diffusion-controlled process with an activation energy 39kJ/mol, while the AuIn2 growth in In49Sn/Au reaction is interfacial reaction controlled with an activation energy 51kJ/mol. As reaction time and temperature increase, two minor phases AuIn and Au7In3 phases grow at the Au/AuIn2 interface. The growth of Au7In3 phase induces cracks at the interface and impairs the mechanical integrity of the solder joint. Accompanying the interfacial intermetallic compound growth, the Au atoms dissolving into solder in soldering reaction precipitate as a cluster of AuIn2 islands in the solder matrix during cooling.
In the In10Ag/Ag reaction, a continuous layer of scallop-shaped or dendrite-shaped Ag2In compounds enveloped in thin AgIn2 shells appears at the In10Ag/Ag interface. The growth of the Ag2In phase is diffusion-controlled and the activation energy is 45kJ/mol. The Ag atoms precipitate as a cluster of spherical or dendrite-shaped Ag2In islands in the interior of solder matrix. Solid-state reaction happens on both interfacial and precipitated intermetallic compounds when the soldered specimens are stored at room temperature that the AgIn2 shells grow and consume the former Ag2In phases. The study of Ag2In/In diffusion couple shows that the growth of AgIn2 phase is diffusion-controlled and the activation energy is 41kJ/mol which is similar to the AgIn2 growth energy in thin film In/Ag reaction.
The sessile drop method is used to evaluate the wettability of the former soldering reactions. The result shows that there are three stages on the contact angle variation of In/Au and In10Ag/Ag reactions. The contact angles decline rapidly when the solders begin melting, the first stage, and then the curves remain as a plateau, the second stage, for a period of time before they finally collapse to a very low value which is considered as the last stage. A mechanism involving the interfacial intermetallic compound growth and precursor halo formation has been propounded for this wetting behavior. This mechanism is confirmed through SEM observation of the cross-sections of specimens after wetting test. The contact angle variation in In49Sn/Au reaction includes three stages too. However, the curves in the second stage is not a plateau but a gradual descent. Through comparison with In/Au and Sn/Au reactions, it was brought to light that the contact angle variation in In49Sn/Au reaction is resulted from the effects of In/Au and Sn/Au reactions.

封面
誌謝
中文摘要
英文摘要
目錄
圖目錄
表目錄
壹、前言
貳、文獻回顧
２.１　電子構裝與其發展
２.２　無鉛銲錫的發展
２.３　銲錫反應動力學
２.４　銲錫潤濕性的評估與量測
２.５　界面反應相關文獻回顧
參、實驗方法
３.１　實驗材料與設備
３.２　金厚膜軟銲反應系統
３.３　銀基版軟銲反應系統
肆、結果與討論
４.１　金厚膜軟銲反應系統
４.２　銀基版軟銲反應系統
伍、結論
陸、參考文獻
附錄

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