臺灣博碩士論文加值系統

本研究針對構裝製程中使用的鎳基材，探討基材與無鉛銲錫材料間溶解行為。此外並利用自行配製之介金屬相-Ni3Sn4相，研究其與液態銲錫間發生的界面反應及溶解機制。
在反應溫度240、270、300℃下，鎳基材在不同銲錫的溶解速率快慢依序為Sn>Sn-3.0Ag-0.5Cu>Sn-0.7Cu>Sn-58Bi> Sn-9Zn，基材溶解行為隨反應時間與溫度的上升呈現線性增加的關係，並藉由銲料與鎳基材生成之介金屬相形態及晶粒間溝槽多寡解釋各種無鉛銲料對鎳基材溶解速率，並藉由計算相圖得出銲料中鎳之平衡濃度，利用Dybkov’s Equation比較溶解速率，得出240℃下溶解速率為Sn>Sn-3.0Ag-0.5Cu>Sn-58Bi>Sn-0.7Cu>Sn-9Zn、270℃以及300℃下溶解速率為Sn>Sn-3.0Ag-0.5Cu>Sn-0.7Cu>Sn-58Bi> Sn-9Zn，與240℃下實際實驗Sn>Sn-3.0Ag-0.5Cu>Sn-0.7Cu>Sn-58Bi> Sn-9Zn不符，考慮界面反應所生成之介金屬相，Sn-0.7Cu銲料較Sn-58Bi銲料界面多生成一(Cu,Ni)6Sn5相，且Sn-58Bi銲料僅生成薄層的Ni3Sn4相，因此實際不論溫度高低其溶解速率皆為Sn-0.7Cu>Sn-58Bi。研究Sn-9Zn銲料與鎳基材反應，於界面處生成較厚且緻密之Ni5(Zn,Sn)21相，因而能抑制鎳基材之溶解。
介金屬相-Ni3Sn4相基材與不同銲錫反應的溶解速率快慢依序240℃下為Sn>Sn-3.0Ag-0.5Cu>Sn-0.7Cu>Sn-58Bi，300℃下則為Sn-0.7Cu>Sn>Sn-3.0Ag-0.5Cu> Sn-58Bi。Sn、Sn-58Bi銲料與Ni3Sn4相基材反應僅為Ni3Sn4相基材溶解進入銲料之中；Sn-3.0Ag-0.5Cu銲料與Ni3Sn4相基材反應，240℃下有(Cu,Ni)6Sn5層狀剝離發生，並於銲料中析出(Ni,Cu)3Sn4相，300℃下則僅基材溶解進入銲料之中；Sn-0.7Cu銲料與Ni3Sn4相基材反應，240℃下由基材原始界面向下生成一(Cu,Ni)6Sn5相，300℃下則可觀察到(Cu,Ni)6Sn5層狀剝離現象；Sn-9Zn銲料與Ni3Sn4相基材反應，反應於基材原始界面向下生成Ni5(Zn,Sn)21介金屬相並於其下再生成Ni3(Sn,Zn)4介金屬相。

This research is about dissolution behavior and interfacial reaction in liquid Lead-free solders of Ni substrate and intermetallic compound Ni3Sn4 ¬substrate which formulate by ourselves.
Dissolution rate of Ni substrate in liquid lead-free solder: Sn > Sn-3.0Ag-0.5Cu > Sn-0.7Cu > Sn-58Bi > Sn-9Zn. Dissolution behavior in Ni substrate increase with reaction times and temperature. This research explain dissolution rate by Dybkov’s equation, morphology of intermetallic compounds and grain boundary size. Use Sn-Ni-Cu calculation phase diagram to determine solubility equilibrium of Ni substrate in solders, then substitute it into Dybkov’s equation to compare dissolution rate. By PANDAT calculation and Dybkov’s equation, dissolution rate are Sn > Sn-3.0Ag-0.5Cu > Sn-58Bi > Sn-0.7Cu > Sn-9Zn at 240℃, Sn > Sn-3.0Ag-0.5Cu > Sn-0.7Cu > Sn-58Bi > Sn-9Zn at 270, 300℃. But in real experiment Sn-0.7Cu > Sn-58Bi at 240℃, explain it with the kind of intermetallic compound. Sn-58Bi solders only form Ni3Sn4, but Sn-0.7Cu solder form both (Ni,Cu)3Sn4 and (Cu,Ni)6Sn5 intermetallic compound. When Sn-9Zn solder reaction with Ni substrate it form thick and fine Ni5(Zn,Sn)21 which can restrain Ni substrate dissolution.
Dissolution rate of intermetallic compound-Ni3Sn4 substrate in liquid lead-free solders: Sn > Sn-3.0Ag-0.5Cu > Sn-0.7Cu > Sn-58Bi at 240℃, Sn-0.7Cu > Sn > Sn-3.0Ag-0.5Cu > Sn-58Bi at 300℃. In Sn and Sn-58Bi solders only Ni3Sn4 substrate dissolute into solders. In Sn-3.0Ag-0.5Cu solders it form (Cu,Ni)6Sn5 spalling layer and separate (Ni,Cu)3Sn4 at 240℃. And at 300℃ only Ni3Sn4 substrate dissolute into Sn-3.0Ag-0.5Cu solder. In Sn-0.7Cu solders it form (Cu,Ni)6Sn5 layer at 240℃. And at 300℃ it form (Cu,Ni)6Sn5 spalling layer at interface. Sn-9Zn solders reaction with Ni3Sn4 substrate form Ni5(Zn,Sn)21 at interface, then Zn atom diffuse downward into Ni3Sn4 substrate to form Ni3(Sn,Zn)4.

摘要……………………………………………………………………………...I
目錄……………………………………………………………………………...IV
圖目錄…………………………………………………………………………...VI
表目錄…………………………………………………………………………...VIII
第一章 前言…………………………………………………………………….1
第二章 文獻回顧……………………………………………………………….6
2-1 綠色環保與無鉛銲料…………………………………………………... 6
2-2 界面反應………………………………………………………………... 11
2-2-1 錫/鎳界面反應………………………………………………………. 12
2-2-2 錫-3.0 wt%銀-0.5 wt%銅/鎳界面反應……………………………… 13
2-2-3錫-0.7 wt%銅/鎳界面反應…………………………………………… 14
2-2-4 錫-58 wt%鉍/鎳界面反應………………………………................... 14
2-2-5 錫-9 wt%鋅/鎳界面反應……………………………………………. 15
2-3 溶解動力學……………………………………………………………... 16
2-3-1 鎳基材於液態銲錫中的溶解現象文獻回顧……………………….. 20
2-3-2 介金屬相於液態銲錫中的溶解現象文獻回顧…………………….. 24
第三章 實驗方法………………………………………………………………. 26
3-1 液態無鉛銲錫合金與純鎳、純介金屬相-Ni3Sn4相反應實驗………… 26
3-1-1 無鉛銲錫合金……………………………………………………….. 26
3-1-2 鎳棒狀基材備製…………………………………………………….. 26
3-1-3 無鉛銲錫合金與鎳棒基材液固反應實驗………………………….. 27
3-1-4 介金屬相-Ni3Sn4相備製與分析……………………………………. 27
3-1-5 介金屬相-Ni3Sn4相濺鍍鉬(Mo)膜…………………………………. 28
3-1-6 無鉛銲錫合金與介金屬相-Ni3Sn4相液固反應……………………. 29
3-2 實驗試樣分析…………………………………………………………... 30
3-2-1 金相處理…………………………………………………………….. 30
3-2-2 試樣分析…………………………………………………………….. 30
第四章 結果與討論……………………………………………………………. 35
4-1 鎳基材於不同銲錫中界面反應………………………………………... 35
4-1-1 鎳基材於純錫銲錫中界面反應與溶解現象……………………….. 35
4-1-2 鎳基材於錫-3.0 wt%銀-0.5 wt%銅銲錫中界面反應與溶解現象…. 39
4-1-3 鎳基材於錫-0.7 wt%銅銲錫中界面反應與溶解現象……………... 43
4-1-4 鎳基材於錫-58 wt%鉍銲錫中界面反應與溶解現象……………… 48
4-1-5 鎳基材於錫-9 wt%鋅銲錫中界面反應與溶解現象……………….. 51
4-1-6 鎳基材與不同銲錫反應溶解數據………………………………….. 55
4-1-7 鎳基材溶解機制討論……………………………………………….. 59
4-2 Ni3Sn4相基材於不同銲錫中溶解現象…………………………………. 72
4-2-1 Ni3Sn4相組成分析…………………………………………………… 72
4-2-2 Ni3Sn4相基材與純錫反應界面形態………………………………… 74
4-2-3 Ni3Sn4相基材與純錫反應溶解現象………………………………… 77
4-2-4 Ni3Sn4相基材與錫-3.0 wt%銀-0.5 wt%銅銲錫反應界面形態…….. 79
4-2-5 Ni3Sn4相基材與錫-3.0 wt%銀-0.5 wt%銅銲錫反應溶解現象…….. 81
4-2-6 Ni3Sn4相基材與錫-0.7 wt%銅銲錫反應界面形態............................. 86
4-2-7 Ni3Sn4相基材與錫-0.7 wt%銅銲錫反應溶解現象…………………. 87
4-2-8 Ni3Sn4相基材與錫-58鉍銲錫反應界面形態..................................... 94
4-2-9 Ni3Sn4相基材與錫-58鉍銲錫反應溶解現象..................................... 94
4-2-10 Ni3Sn4相基材與錫-9鋅銲錫反應界面形態..................................... 98
4-2-11 Ni3Sn4相基材與錫-9鋅銲錫反應溶解現象..................................... 99
4-2-12 Ni3Sn4基材與各銲錫合金溶解行為討論......................................... 100
第五章 結論……………………………………………………………………. 108
第六章 參考文獻………………………………………………………………. 110

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