臺灣博碩士論文加值系統

 本研究主要的目的在於應用in-situ方式添加大小約2-3μm Ni顆粒於共晶Sn-3.5Ag無鉛銲錫內，製作成的複合銲錫，並探討Ni的添加量(0.5-5wt%)於熱儲存試驗條件下，評估對銲錫以及銲點之微結構、機械特性之影響。
首先利用光學顯微鏡及附有EDX之掃瞄式電子顯微鏡（SEM）對於無鉛複合銲錫之塊材以及銲點之微結構加以分析。同時也將經過熱儲存的銲點之IMC層微結構及形貌之影響加以深入的分析。
 實驗結果發現添加Ni顆粒可增加銲料之微硬度。當Ni粉末的添加量少於3wt%時其主要微結構為Ag3Sn於β-Sn之邊界周圍上析出，並與β-Sn形成共晶組織。同時有一些少量的Ni3Sn4金屬間化合物於β-Sn基地及周圍析出。而當Ni粉末的添加量超過3wt%以上時，殘留的Ni 及Ni3Sn4會聚集成團且粗大化。同樣的於銲點的微結構，會有(Cu,Ni)6Sn5 IMC 層形成，以及銲料內部則析出(Ni,Cu)3Sn4。而且會因Ni增加而使IMC 層厚度增加，且同樣的(Ni,Cu)3Sn4會聚集成團且粗大化。
拉伸試件係以兩根銅棒以對接方式浸入融熔的銲錫內所形成。實驗結果發現接合強度於as-soldered的條件下，會因為Ni增加而使銲點之接合強度增加。同時也會因為熱儲存時間之增長的作用而使其接合強度降低。拉伸試件的破壞形貌，Sn-Ag-0.5wt%Ni銲點顯示為之延性破壞及脆性破斷的混合形。Ni粉末的添加量超過1wt%以上時，主要為脆性破斷並有(Cu,Ni)6Sn5 IMC 層暴露於破斷面上。
於剪切試驗中Sn-Ag-xNi銲料單剪銲點試件經迴銲以及150℃高溫於不同儲存時間後之剪切強度變化。一般而言，於迴銲條件下，銲點之剪切強度會因為Ni增加而使銲點之剪切強度增加。但經熱儲存及儲存時間增加，銲點剪切強度會降低。而當Ni添加量少於1%時的單剪銲點試件，其破斷面發生於接近IMC層界面的銲錫內部，為延性的拉長型的類似韌窩破斷面。顯示銲錫內部強度比IMC層低。而當Ni添加量超過1%以上時，其破斷面形式由延性轉變為脆性破壞，且破壞部位發生於IMC層。所以Ni的添加能增強銲錫的強度，因此當受到剪切力作用時，就會由強度較差的界面層形成裂縫並由此部位開始破壞，而後延著界面層間或往銲料內部產生破壞。
雖然添加Ni之複合銲錫之銲點經熱儲存後，其IMC層的厚度明顯的成長，主要因素為Ni於Sn內過度的擴散所引起。但是於本研究中發現添加Ni之複合銲錫之銲點比Sn-3.5Ag銲點有顯著的改善其接合強度及剪切強度的效果。

The composite solders were manufactured in the this investigation by in-situ adding 0.5 to 5wt% of 2-3μm sized Ni particles into the Sn-3.5Ag lead-free solder. The principle aim of this study is to investigate how the microstructure, thermal aging as well as mechanical properties of composite solders and joints are affected by in-situ incorporation of Ni particles as reinforcements.
The initial microstructure of as-fabricated composite solders and joints are examined and analyzed using Optical and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX). The effect of thermal aging on the microstructure as well as the morphological changes in the interfacial intermetallic (IMC) layers of the composite solder joints are extensively analyzed.
The experimental results reveal that the addition of Ni particles increases the microhardness of the composite solder. Ni additions of less than 3 wt. % yield a microstructure of β-Sn grains surrounded by a eutectic mixture of Ag3Sn and a Sn-rich matrix. An intermetallic compound of Ni3Sn4 particles is dispersed throughout the eutectic. For 5wt% Ni addition, the remaining Ni particles and the Ni3Sn4 phase are agglomerated. In the case of the copper substrate dipped with a thick layer of composite solder the induced (Ni,Cu)3Sn4 particles coarsen and agglomerate. Additionally, the intermetallic (Cu,Ni)6Sn5 compound layer formed at the solder/Cu interface thickens with increasing Ni content.
Cu/solder/Cu specimens are prepared by dipping two Cu rods into a solder bath to produce a solder joint. The adhesive strength of the joint is found to increase with increasing Ni content in the as-soldered specimens. In general, the strength of the thermally processed specimens reduces as the thermal storage time increases. The Sn-Ag-0.5wt%Ni joints show a mixture of ductile and brittle fracture, whereas the joints containing more than 1wt% of Ni show mainly brittle fracture with solder residue at the exposed (Cu,Ni)6Sn5 IMC layer.
The single lap shear strength, fracture behavior and microstructure evolution after thermal aging at 150℃ were investigated for this Sn-Ag-xwt%Ni /Cu joints. The single lap shear strength of the joints, in general, increase with increasing Ni addition at as-reflowed condition, and decrease by thermal aging for all test specimens. When Ni addition is less than 1wt%, fracture occurred of solder near the IMC layer/solder interface. Elongated ductile dimples reveal on the fracture surface. The strength of the solder matrix is weaker than that of the IMC. When Ni addition is over 1wt%, the fracture observed is transferred from ductile mode to brittle and occurred at IMC interface. The Ni addition raises apparently the strength of the solder matrix and even above that of the interface. Crack propagates along the interface between the IMC layer and the solder matrix or inside the IMC layer.
In spite of excessive microstructure evolution in terms of IMC growth was observed in Ni composite solder joints under thermal aging at 150℃ due to the profuse diffusion of Ni in Sn. Significant findings in this study revealed that Ni composite solder joints significantly improved the adhesive strength and shear strength of Sn-3.5Ag solder joints.

總 目 錄
授權書 I
口試合格證明 II
中文摘要 III
英文摘要 V
誌謝 VII
總目錄 VIII
表目錄 X
圖目錄 XI
一、前言 1
1-1鉛之危害 1
1-2世界各國無鉛產品期程規劃 4
1-3研究動機與目的 8
二、文獻回顧 10
2-1無鉛銲錫合金的開發狀況 10
2-1-1無鉛銲錫合金的性質需求 14
2-1-2無鉛銲錫銲點的性質需求 16
2-2二元無鉛銲錫合金系統 21
2-3三元無鉛銲錫合金系統 28
2-4四元及五元無鉛銲錫合金系統 33
2-5複合銲料系 35
2-6界面IMC層之成長與特性 40
2-6-1 固態Cu與液態銲錫之生長模式 40
2-6-2 Ni-Sn之介面反應 43
2-6-3 界面IMC層生長的影響因素 47
2-7 銲點強度機械測試 52
三、實驗步驟與方法 56
3-1實驗規劃 56
3-2實驗試件製備 58
3-3實驗處理過程及實驗分析所使用的儀器 60
四、結果與討論 63
4-1 Sn-Ag-xNi複合銲料之性質 63
4-1-1添加Ni對微結構之影響 63
4-1-2添加Ni對熔點的影響 71
4-1-3添加Ni對微硬度的影響 73
4-2 Sn-Ag¬-xNi 銲點微結構與性質 76
4-3 IMC層的形貌 94
4-4 IMC 之形成及厚度變化 108
4-5 添加Ni對銲點接合強度的影響 118
4-5-1拉伸試件之銲點破壞形貌 123
4-6銲點剪切強度 131
4-6-1剪切破壞斷面分析 133
五、結論 141
六、參考文獻 144
著作權聲明 155
自述 156

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