臺灣博碩士論文加值系統

本研究以相平衡實驗的量測，與CALPHAD方法的計算，測定了銀-錫-銅與銀-錫-金三元系統的等溫橫截面圖。利用所建立的三元系統熱力學模型，計算各組成元素的穩定性圖。以反應偶的實驗方法，研究銀-錫/銅與銀-錫/金之界面反應。由反應偶的實驗結果，配合等溫橫截面圖與穩定性圖，分析界面生成相與相成長之動力學。銀-錫合金是最具潛力的無鉛銲料之一，銅與金則是目前電子工業中最常使用的的基材材料。本研究所得之銀-錫-銅與銀-錫-金三元系統的相平衡知識、與銀-錫/銅與銀-錫/金之界面反應資料，對銀-錫合金作為無鉛銲料之應用與發展將具有重要的參考價值。
銀-錫-銅系統的240與450℃相平衡實驗結果顯示，銀-錫-銅系統並沒有三元化合物的生成。在上述二個溫度所存在的平衡相，皆為銀-銅、銀-錫與錫-銅二元系統的平衡相。雖然h1-(Cu6Sn5)與d1-(Cu4Sn)相，分別僅存在240與450℃。但銀-錫-銅系統於此二個溫度下，皆分別有五個三相區、十一個雙相區與七個穩定相。e1-(Cu3Sn)與多數的相，均有縛線的連接，顯示e1相是頗為穩定的相。利用文獻已建立的銀-銅、銀-錫與錫-銅二元系統之熱力學模型，參考此研究的三元相平衡實驗結果，建立了銀-錫-銅之三元系統熱力學模型，並據以計算銀-錫-銅在240與450℃下的等溫橫截面圖、與銅、錫元素的穩定性圖。
銀-錫/銅的界面反應實驗，包括了液相/固相反應的240與450℃的Sn-3.5 wt. %Ag/Cu與450℃的Sn-25 wt. %Ag/Cu反應偶實驗，以及450℃下的Sn-74 wt. %Ag/Cu與Sn-84 wt. %Ag/Cu固相/固相反應偶實驗。在240與450℃的液相/固相反應偶中，其反應路徑分別為L/h1/e1/Cu與L/e1/d1/Cu。與液相相接的界面皆呈波浪的不規則形態，其與固態基材相接的介金屬相界面則頗為平整，所生成的介金屬相則成層狀的結構。Sn-74 wt. %Ag與Sn-84 wt. %Ag分別在e2-(Ag3Sn)與z1-(Ag4Sn)二相的組成範圍內，450℃的e2/Cu與z1/Cu的界面形態則成較複雜的指狀交錯，而且有明顯的孔洞與裂縫。介金屬相的成長，主要是由錫原子的擴散所控制。其厚度皆隨反應溫度升高與反應時間延長而增加。
銀-錫/金的反應偶實驗，皆為固相/固相的反應。合金為Sn-3.5 wt. %Ag與Sn-25 wt. %Ag二種，反應溫度分別為200、180、150與120℃。雖然合金與反應溫不同，但是這些反應偶的界面生成相皆為d2-(AuSn)、e3-(AuSn2)與h2-(AuSn4)。依據文獻中已建立的銀-金、銀-錫與金-錫二元系統之熱力學模型，參考文獻中相平衡資料，如無三元化合物、Ag與Au、z1與z2生成連續固體溶液等，建立了銀-錫-金之三元系統熱力學模型。並據以計算銀-錫-金在200與150℃下的等溫橫截面圖，與金、錫元素在200℃下的穩定性圖。

Sn-Ag alloys are the most promising lead-free solders. Cu and Au are popular substrate materials. Experimental and CALPHAD methods have been carried out to investigate the phase equilibria of the Ag-Sn-Cu ternary system. Various Ag-Sn-Cu alloys were prepared to determine the isothermal sections of the Ag-Sn-Cu ternary system at 240 and 450℃. The results indicate that the e1 phase is a very stable phase in the Ag-Sn-Cu ternary system. Based on literature data, phase diagrams of three binary systems, Ag-Cu, Ag-Sn, Cu-Sn, Au-Sn, and Ag-Au, have been calculated by using CALPHAD methods. According to these binary thermodynamic models, the ternary thermodynamic models of the Ag-Sn-Cu and Ag-Au-Sn systems have been established. Owing to these ternary thermodynamic model, isothermal sections of the Ag-Sn-Cu system and stability diagrams about Cu and Sn elements at 240 and 450℃, and the Ag-Au-Sn system at 200 and 150 ℃ can been calculated. The stability diagrams of Au and Sn elements at 200 ℃ also can be calculated. The calculated results are reasonable and accepted when compared to experimental results. The e1 phase has the lowest value of Gibbs formation energy; this can explain why e1 phase is a very stable phase in the Ag-Sn-Cu ternary system. Several Ag-Sn alloys reacting with Cu or Au substrates have been examined by using reaction couples. The thickness of the reaction layers increased with higher temperature and longer reaction time. Their growth rates in all the couples followed the parabolic law. Based on the interfacial morphology in the reaction couples, the phase formation relationship and the concept of Kirkendall effect, it is concluded the Sn is the fastest diffusion species in these couples.

摘要………………………………………………………………………I
目錄……………………………………………………………………IV
表目錄…………………………………………………………………III
圖目錄…………………………………………………………………VII
一、前言…………………………………………………………………1
二、文獻回顧……………………………………………………………9
2-1：相平衡…………………………………………………………9
2-1-1：相平衡圖……………………………………………………9
2-1-2：熱力學與相圖………………………………………………12
2-1-3：穩定性圖……………………………………………………15
2-1-4：銀-錫-銅的相平衡…………………………………………17
2-1-5：銀-錫-金的相平衡…………………………………………22
2-2：界面反應……………………………………………………………25
2-2-1：熱力學之驅動力與區域平衡…………………………………26
2-2-2：動力學之因素，成核與成長…………………………………27
2-2-3：反應路徑與界面形態…………………………………………29
2-2-4：銀-錫/銅的界面反應…………………………………………36
2-2-5：銀-錫/金的界面反應…………………………………………38
三、研究方法………………………………………………………………39
3-1：相平衡的實驗方法…………………………………………………39
3-1-1：合金配置………………………………………………………39
3-1-1：合金分析………………………………………………………40
3-2：界面反應的實驗方法………………………………………………41
3-2-1： 合金配製與反應偶製作………………………………………41
3-2-2：樣品金相處理與分析……………………………………………43
3-3：熱力學模型建立與相圖計算…………………………………………44
3-3-1：二元平衡相圖(T-X圖)…………………………………………44
3-3-2：三元平衡相圖(等溫截面相圖)…………………………………46
3-3-3：穩定性圖…………………………………………………………48
四、結果與討論……………………………………………………………49
4-1：相平衡實驗……………………………………………………………49
4-1-1：銀-錫-銅三元系統在240℃下的相平衡………………………49
4-1-2：銀-錫-銅三元系統在450℃下的相平衡………………………62
4-2：銀-錫-銅三元系統的相圖計算與穩定性圖…………………………75
4-2-1：銀-錫、銀-錫、與銅-錫二元系統的計算……………………75
4-2-2：銀-錫-銅三元系統的計算……………………………………83
4-2-3：銀-錫-銅三元系統的穩定性圖………………………………88
4-3：銀-錫/銅界面反應……………………………………………………97
4-3-1：銀-錫/銅反應偶的固相/液相界面反應………………………97
4-3-2：銀-錫/銅反應偶的固相/固相界面反應………………………101
4-3-3：銀-錫/銅反應偶的動力學與反應路徑………………………106
4-3-4：銀-錫/銅反應偶的反應路徑與穩定性圖的關係……………112
4-4：銀-錫/金反應偶的界面反應………………………………………117
4-4-1：錫-3.5wt%銀/金反應偶的固相/固相界面反應……………117
4-4-2：錫-25wt%銀/金反應偶的固相/固相界面反應………………121
4-4-3：銀-錫/金反應偶的動力學……………………………………124
4-5：銀-錫-金三元系統的相圖計算與穩定性圖………………………129
4-5-1：金-錫、銀-金、與銀-錫二元系統的計算…………………129
4-5-2：銀-錫-金三元系統的計算……………………………………139
4-5-3：銀-錫-金三元系統的穩定性圖與銀-錫/金反應偶的反應路徑與
穩定性圖的關係……………………………………………146
五、結論…………………………………………………………………151
5-1： 銀-錫-銅三元系統的相平衡…………………………………151
5-2：銀-錫/銅的界面反應……………………………………………152
5-3：銀-錫/金的界面反應……………………………………………153
5-4： 銀-錫-銅三元系統的相平衡……………………………………153
5-5： 穩定性圖與反應路徑……………………………………………154
六、參考文獻………………………………………………………………155
附錄…………………………………………………………………………163

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