永續發展是人類最重要的議題之一，對環境友善的材料與能夠再生的能源皆是永續議題中重要之課題。太陽能電池是主要的一種再生能源型式，Cu-In-Se(CIS)與其為基材之合金是太陽能電池中重要的光吸收層(light absorption layer)材料，與太陽能電池的效率息息相關。又太陽能電池中存在著許多電路接點，因此需要銲料合金進行連接。對環境友善的無鉛銲料近年來亦受到很大之關注，Sn-Ag-(In)-Zn合金即是具應用潛力之無鉛銲料。本研究以對環境友善與能源永續發展的太陽能電池為對象，針對其中的Cu-In-Se光吸收層合金與Sn-Ag-(In)-Zn無鉛銲料進行基礎的相圖探討。
相圖是基礎的材料知識，對材料的開發、製程的選擇與產品可靠度評估皆十分重要。然而過去文獻中關於Sn-Ag-Zn、Sn-Ag-In-Zn與Cu-In-Se的相圖資料十分缺乏。因此本研究探討建構Sn-Ag-Zn、Sn-Ag-In-Zn與Cu-In-Se之液相線投影圖(liquidus projection)。液相線投影圖是一種將三維液相曲面投影至平面之相平衡圖，包含了固化首要析出相及含液相之相變化溫度等資料。本研究藉由金相觀察、組成分析以及結構鑑定決定固化首要析出相相區，並以熱分析訂定各個反應點溫度以及固化路徑。本研究依據這些實驗數據以及文獻中相關之二元與三元子系統相圖，建構Sn-Ag-Zn、Sn-Ag-In-Zn與Cu-In-Se系統之液相線投影圖。
在Sn-Ag-Zn三元(ternary)系統的液相線投影圖中，共有八個固化首要析出相(primary solidification phase): ε2-AgZn3、γ-Ag5Zn8、β-AgZn、ζ-Ag4Sn、Ag、ε1-Ag3Sn、β-Sn與Zn相區。在此三元系統中存在著八個三元的不變反應(invariant reaction)，其中含有一個class Ⅰ、六個class Ⅱ及一個class Ⅲ反應。在Sn-Ag-In-Zn四元(quaternary)系統，本研究測定了在95.0、90.0與85.0 wt.% Sn的四元液相線投影圖之等值剖面圖(isoplethal section)。在此四元系統中含有九個固化首要析出相: ε1-Ag3Sn、ζ-Ag4Sn、β-AgZn、γ-Ag5Zn8、ε2-AgZn3、Zn、β-Sn、InSn4以及ζ相區。
在Cu-In-Se三元系統的液相線投影圖中，共有十六個固化首要析出相: β1-Cu2Se、Cu、β2-Cu4In、γ-Cu7In3、η-Cu2In、Cu11In9、In、In4Se3、InSe、In6Se7、In2Se3、Se、CuSe2、CuSe、α-CuInSe2以及δ-CuInSe2相區。除端點相與二元相之外，還包括α-CuInSe2以及δ-CuInSe2兩個三元相之相區。在此三元系統中存在著十九個含液相之反應，其中含有四個class Ⅰ、八個class Ⅱ與七個未知型式反應;以及兩個固相間反應同時被測定出。因Se汽化問題，故富Se端的樣品不易製備，部分反應點溫度無法訂定。

Environmental-friendly materials and renewable energies are important topics among the critical sustainability issues. Solar energy is a major kind of renewable energies. Cu-In-Se (CIS) and its-based alloys are prevalent absorption layer materials in the solar cells and are essential to the cells' conversion efficiencies. Furthermore, there are many solder joints in solar cells. In terms of environmental friendliness, lead-free solders should be used. Sn-Ag-(In)-Zn alloys are promising lead-free solders. Understanding of the Cu-In-Se solar cell materials and Sn-Ag-(In)-Zn lead-free solders is important for the developments of environmental-friendly solar cells.
Phase diagrams are basic knowledge of materials. They are important tools for material developments, process selections and evaluations of product reliabilities. However, there are limited literatures of phase diagrams related to the Sn-Ag-Zn, Sn-Ag-In-Zn and Cu-In-Se systems. This study thus determines the liquidus projections of the Sn-Ag-Zn, Sn-Ag-In-Zn and Cu-In-Se systems. Liquidus projection is a projection diagram of the liquidus surfaces of space phase diagrams into a basal plane. It usually contains the information of primary solidification phases, the temperature descending directions of univariant lines and the temperatures of invariant reactions.
Sn-Ag-Zn, Sn-Ag-In-Zn and Cu-In-Se alloys were prepared from pure constituent elements. They were melted, mixed homogeneously together, and then quenched. The as-cast samples were metallographically examined. The primary solidification phases were determined based on the as-cast microstructures, compositional analysis and X-ray diffraction analysis. The temperatures of the invariant reactions were determined by using differential thermal analyzer. The liquidus projections of Sn-Ag-Zn, Sn-Ag-In-Zn and Cu-In-Se systems were constructed based on these experimental results and available phase diagrams of their binary constituent systems.
The liquidus projection of Sn-Ag-Zn and the isoplethal sections of the Sn-Ag-In-Zn liquidus projection are determined. There are eight primary solidification phases in the ternary Sn-Ag-Zn liquidus projection: ε2-AgZn3, γ-Ag5Zn8, β-AgZn, ζ-Ag4Sn, Ag, ε1-Ag3Sn, β-Sn and Zn phase. There are eight invariant reactions in this ternary system, including one class Ⅰ, six class Ⅱ and one class Ⅲ reactions. There are nine primary solidification phases at the 95.0, 90.0 and 85.0 wt.% Sn isoplethal sections of the quaternary Sn-Ag-In-Zn liquidus projection: ε1-Ag3Sn, ζ-Ag4Sn, β-AgZn, γ-Ag5Zn8, ε2-AgZn3, Zn, β-Sn, InSn4 and ζ phases.
There are 16 primary solidification phases in the ternary Cu-In-Se liquidus projection: β1-Cu2Se, Cu, β2-Cu4In, γ-Cu7In3, η-Cu2In, Cu11In9, In, In4Se3, InSe, In6Se7, In2Se3, Se, CuSe2, CuSe, α-CuInSe2 and δ-CuInSe2 phases. There are 19 ternary invariant reactions in this Cu-In-Se liquidus projection which are all involved with liquid phase. These invariant reactions include four class I, eight class Ⅱ and seven unknown types. In addition, there are two invariant reactions at the solid state are also been determined. Experimental difficulties of Se sublimation were encountered at the Se-rich corner, and it was the main reason for these undetermined types of the invariant reactions.

圖目錄 VIII
表目錄 XIII
一、前言 1
1-1.無鉛銲料與太陽能電池 1
1-2.Sn-Ag-(In)-Zn無鉛銲料 4
1-3.Cu-In-Se太陽能電池材料 8
二、文獻回顧 12
2-1.Sn-Ag-In-Zn系統 12
2-1-1.二元Sn-Ag相平衡 12
2-1-2.二元Sn-In相平衡 14
2-1-3.二元Sn-Zn相平衡 16
2-1-4.二元Ag-In相平衡 18
2-1-5.二元Ag-Zn相平衡 20
2-1-6.二元In-Zn相平衡 22
2-2.Cu-In-Se系統 24
2-2-1.二元Cu-In相平衡 24
2-2-2.二元Cu-Se相平衡 26
2-2-3.二元In-Se相平衡 29
2-2-4.三元Cu-In-Se等值剖面圖 31
2-2-4-1.In2Se3-Cu2Se等值剖面圖 31
2-2-4-2.In2Se3-Cu40Se60等值剖面圖 34
2-2-4-3.20 at.% Se等值剖面圖 35
2-2-4-4.40 at.% Se等值剖面圖 36
2-2-4-5.50 at.% Se等值剖面圖 37
2-2-4-6.80 at.% Se等值剖面圖 38
2-2-4-7.10 at.% Cu等值剖面圖 39
2-2-4-8.CuInSe2-Cu70In30等值剖面圖 40
2-2-4-9.CuInSe2-Cu50In50等值剖面圖 41
2-2-4-10.Se-CuInSe2等值剖面圖 42
2-3.三元Sn-Ag-Zn及四元Sn-Ag-In-Zn液相線投影圖 43
2-3-1.三元Sn-Ag-In液相線投影圖 44
2-3-2.三元Sn-In-Zn液相線投影圖 47
2-3-3.三元Sn-Ag-Zn液相線投影圖 50
2-3-4.三元Ag-In-Zn液相線投影圖 51
2-4.三元Cu-In-Se液相線投影圖 52
三、研究方法 54
3-1.三元Sn-Ag-Zn及四元Sn-Ag-In-Zn系統 54
3-1-1.合金配製 54
3-1-2.樣品熱分析 54
3-1-3.樣品金相及結構分析 55
3-2.三元Cu-In-Se系統 56
3-2-1.合金配製 56
3-2-2.樣品熱分析 56
3-2-3.樣品金相及結構分析 56
3-3.單方向凝固 57
3-3-1.合金配製 57
3-3-2.填充合金與單方向凝固 57
3-3-3.樣品分析 57
四、結果與討論 58
4-1.三元Sn-Ag-Zn液相線投影圖 58
4-1-1.ε2-AgZn3相區 62
4-1-2.γ-Ag5Zn8相區 69
4-1-3.β-AgZn相區 73
4-1-4.ζ-Ag4Sn相區 76
4-1-5.Ag相區 79
4-1-6.ε1-Ag3Sn相區 81
4-1-7.β-Sn相區 85
4-1-8.三元Sn-Ag-Zn系統熱分析 88
4-1-9.三元Sn-Ag-Zn液相線投影圖總結 96
4-2.四元Sn-Ag-In-Zn液相線投影圖 100
4-2-1.四元Sn-Ag-In-Zn液相線投影圖富Sn端85.0 wt.% Sn橫截面 103
4-2-2.四元Sn-Ag-In-Zn液相線投影圖富Sn端90.0 wt.% Sn橫截面 108
4-2-3.四元Sn-Ag-In-Zn液相線投影圖富Sn端95.0 wt.% Sn橫截面 108
4-2-4.四元Sn-Ag-In-Zn液相線投影圖總結 109
4-3.三元Cu-In-Se液相線投影圖 111
4-3-1.β1-Cu2Se相區 115
4-3-2.Cu相區 120
4-3-3.β2-Cu4In相區 122
4-3-4.γ-Cu7In3相區 124
4-3-5.η-Cu2In相區 127
4-3-6.Cu11In9相區 135
4-3-7.In4Se3相區 138
4-3-8.InSe相區 141
4-3-9.α-CuInSe2相區 144
4-3-10.δ-CuInSe2相區 153
4-3-11.三元Cu-In-Se系統熱分析 157
4-3-12.三元Cu-In-Se液相線投影圖總結 168
五、結論 173
六、參考文獻 175

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