現今世界對能源的需求日益增加，綠色能源之議題因此受到世人重視，而熱電材料屬於綠色能源的一環。熱電材料具直接將熱能轉換成電能之性質，能夠作為廢熱回收之裝置。在眾多熱電材料中，Zn4Sb3是具有前景的中溫型之熱電材料之一，結構為六角菱面體，具有較低的晶格熱傳導係數(κL)，根據文獻內容，Zn4Sb3於溫度670K具有最高zT值1.3。本研究根據該系統之相圖資訊配製熱電合金，相圖為材料之基礎資料，表示合金於不同因素下具有不同之相，而目前尚未具有完善之Cu-Sb-Zn三元系統相圖資訊，故本實驗將致力完成Cu-Sb-Zn三元系統相圖。本實驗之研究目標包括(1)以實驗方式建構Cu-Sb-Zn三元系統液相線投影圖、(2)以實驗方式建構Cu-Sb-Zn三元系統350oC之等溫橫截面圖、(3)製備二元系統之熱電材料，探討Zn含量對Zn4Sb3熱電性質之影響、(4)製備三元系統之熱電材料，探討不同量之Cu摻雜對Zn4Sb3合金之熱電性質的影響性。
根據研究結果，於Cu-Sb-Zn系統液相線投影圖由實驗分析，存在十個首要析出相區，而三元系統相圖之邊界由二元子系統相圖建構，於Cu-Sb-Zn系統350oC之等溫橫截面圖，Zn4Sb3二元合金可穩定存在於350oC，固溶範圍為0.1-2.4at%Cu與57.1-57.8at%Zn，可確定三個單相區、九個兩相區、八個三相區。熱電性質量測部分，探討二次相對Zn4Sb3之影響，二元合金中，Zn4.06Sb2.94合金於657K時zT值可達0.9，而Cu摻雜Zn4Sb3之合金中，(Zn4Sb3)0.93Cu0.07具最好熱電性質，於658K時zT值達到0.8。

Energy shortage has become one the most critical issues, and therefore the development of thermoelectric (TE) materials, which allows the direct conversion between waste heat and electricity, has attracted growing attentions. Among all types of thermoelectric materials, the hexagonal rhombohedric β-Zn4Sb3, which is constituted by cost-effective, earth-abundant and non-toxic elements, features with intrinsically low lattice thermal conductivity, owing to the disordering of Zn-interstitials, and has been viewed as a promising mid-temperature TE material. Phase diagram provides fundamental yet essential information, and therefore the 350˚C isothermal section and liquidus projection of ternary Cu-Sb-Zn system are constructed in this study. Various ternary alloys are thermally-equilibrated at 350oC for 45 days to clarify the phase relations, with an emphasis upon the homogeneity rang of Zn4Sb3 phase at elevated temperature. As for the liquidus projection, the ternary alloys are either air-cooled or water-quenched, to investigate the solidification behaviors of ternary Cu-Sb-Zn system.
Apart from the phase diagram determinations, the selective p-type Zn4-xSb3 alloys with varying Zn/Sb ratios were grown by Bridgman method, and their thermoelectric properties were measured. Alloy Zn4.06Sb2.94 featured with nano-sized Zn inclusion reaches a peak value of zT~0.9 at 657K, showing 112% enhancement compared with that of the stoichiometric Zn4Sb3 (zT~0.8). In addition, the Cu-doped Zn4-xSb3 alloys are prepared, and the maximum zT of 0.8 is obtained in (Zn4Sb3)0.93Cu0.07 at 659 K, presumably attributed to the existence of secondary Cu5Zn8 that improves the electrical conductivity.

致謝 ................................................................................................................................................. i
摘要 ................................................................................................................................................ ii
Abstract ........................................................................................................................................ iii
目錄 ............................................................................................................................................... iv
圖目錄 ....................................................................................................................................... viii
表目錄 ..................................................................................................................................... xviii
一、前言 ...................................................................................................................................... 1
二、文獻回顧 ............................................................................................................................ 6
2.1熱電元件 ....................................................................................................... 6
2.2 β-Zn4Sb3熱電材料 ....................................................................................... 8
2.3 相圖 ............................................................................................................ 11
2.4 Cu-Sb二元子系統 ..................................................................................... 13
2.5 Sb-Zn二元子系統 ...................................................................................... 15
2.6 Cu-Zn二元子系統 ..................................................................................... 17
三、實驗方法 ......................................................................................................................... 21
v
3.1 Cu-Sb-Zn三元系統之350oC等溫橫截面圖............................................ 21
3.2 Cu-Sb-Zn三元系統液相線投影圖 ............................................................ 23
3.3 Cu-Sb-Zn三元系統之熱電性質量測........................................................ 24
四、結果與討論 .................................................................................................................... 27
4.1 Cu-Sb-Zn三元系統之350oC等溫橫截面圖............................................ 27
4.1.1 Zn4Sb3-CuZn5-Zn三相區 ........................................................................ 35
4.1.2 CuZn5-Zn4Sb3兩相區 .............................................................................. 39
4.1.3 Cu5Zn8-CuZn5-Zn4Sb3三相區 ................................................................. 46
4.1.4 Cu5Zn8-Zn4Sb3兩相區 ............................................................................. 50
4.1.5 Cu5Zn8-ZnSb兩相區 ............................................................................... 52
4.1.6 Cu5Zn8-ZnSb-Cu5Sb2Zn3三相區 ............................................................. 58
4.1.7 Cu5Zn8-Cu5Sb2Zn3兩相區 ....................................................................... 67
4.1.8 Cu5Sb8-CuZn-Cu5Sb2Zn3三相區 ............................................................ 70
4.1.9 Cu5Sb2Zn3 單相區 .................................................................................. 73
4.1.10 ZnSb-Cu5Sb2Zn3兩相區 ........................................................................ 75
4.1.11 Cu3SbZn單相區 .................................................................................... 77
4.1.12 CuZn-Cu3SbZn兩相區 ......................................................................... 79
vi
4.1.13 Cu5Sb2Zn3-Cu3SbZn-ZnSb三相區 ....................................................... 81
4.1.14 Cu-Cu3SbZn兩相區 .............................................................................. 83
4.1.15 Cu-Cu2Sb兩相區 .................................................................................. 85
4.1.16 Cu2Sb-Cu-Cu3SbZn 三相區 ................................................................. 90
4.1.17 Cu2Sb-Cu3SbZn兩相區 ........................................................................ 92
4.1.18 Cu2Sb-ZnSb-Cu3SbZn三相區 .............................................................. 95
4.1.19 Cu2Sb單相區 ...................................................................................... 100
4.1.20 Cu2Sb-Sb-ZnSb三相區 ....................................................................... 102
4.1.21 Cu-Sb-Zn三元系統之350oC等溫橫截面圖結果 ............................ 108
4.2 Cu-Sb-Zn三元系統液相線投影圖 .......................................................... 110
4.2.1 CuZn5首要析出相區............................................................................. 114
4.2.2 Zn3Sb2首要析出相區 首要析出相區 ............................................................................ 125
4.2.3 Zn4Sb3首要析出相區 首要析出相區 ............................................................................ 128
4.2.4 Cu5Zn8首要析出相區 首要析出相區 ........................................................................... 131
4.2.5 CuZn首要析出相區 首要析出相區 首要析出相區 ............................................................................. 139
4.2.6 Cu5Sb2Zn3首要析出相區 首要析出相區 ...................................................................... 142
4.2.7 Cu首要析出相區 首要析出相區 首要析出相區 .................................................................................. 151
4.2.8 ZnSb首要析出相區 首要析出相區 首要析出相區 .............................................................................. 155
vii
4.2.9 Cu2Sb首要析出相區 首要析出相區 首要析出相區 首要析出相區 ............................................................................ 160
4.2.10 Sb首要析出相區 首要析出相區 首要析出相區 ................................................................................ 170
4.2.10 Cu-Sb-Zn三元系統液相線投影圖結果............................................. 175
4.3 Cu-Sb-Zn 三元系統之熱電性質 ............................................................. 176
4.3.1 Zn-Sb二元合金之熱電性質 ................................................................. 179
4.3.2 (Zn4Sb3)1-xCux之熱電性質.................................................................... 189
4.3.4 Zn4-x Sb3Cux之熱電性質....................................................................... 199
五、總結 ................................................................................................................................. 210
六、參考文獻 ....................................................................................................................... 214

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