Bi-In-Se-Te四元熱電材料系統相圖｜國立清華大學博碩士論文庫

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研究生：	林奕丞 Lin, Yi-Cheng
論文名稱：	Bi-In-Se-Te四元熱電材料系統相圖 Phase diagrams of thermoelectric Bi-In-Se-Te quaternary system
指導教授：	陳信文 Chen, Sinn-Wen
口試委員:	呂明生王朝弘
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	中文
論文頁數：	83
中文關鍵詞：	相圖、熱電材料、相平衡
外文關鍵詞：	phase diagram, thermoelectric material, phase equalibra
相關次數：	點閱：1 下載：0
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(硒,碲)化鉍基[Bi2(Se,Te)3-based]熱電材料是目前最廣泛商業使用的熱電材料。文獻指出當(硒,碲)化鉍中摻雜銦元素，熱電性質可能可以進一步提升。相圖提供基礎相平衡資料，對了解材料相變化與微結構變化非常重要。本研究探討Bi-In-Se-Te四元系統相圖，以作為(硒,碲)化鉍熱電材料進一步發展的基礎。
Bi-In-Se-Te系統中存在四個三元子系統，Bi-In-Se、Bi-In-Te、Bi-Se-Te與In-Se-Te。在文獻中已有Bi-In-Se和Bi-In-Te的相圖資料，本研究先以實驗探討文獻中所欠缺的In-Se-Te與Bi-Se-Te三元系統的相圖。再將Bi-In-Se、Bi-In-Te、Bi-Se-Te與In-Se-Te等三元系統的相圖，進一步建構Bi-In-Se-Te四元系統的相圖。探討的溫度選定為(硒,碲)化鉍材料所常使用溫度範圍的250oC。
本研究以純元素鉍、銦、碲與硒配製不同組成比例的三元In-Se-Te 與 Bi-Se-Te合金，並以SEM (Scanning Electron Microscopy)、EPMA(Electron Probe Microanalysis)與XRD(X-ray Diffraction)進行相平衡樣品的微結構分析、組成分析與生成相鑑定。依據所得到的三元系統相平衡結果、與其相關的二元系統相圖，進一步推定三元In-Se-Te 與 Bi-Se-Te系統的相圖。
250oC的In-Se-Te 三元系統的穩定相，包括了端點相的液相(銦)、液相(硒)與固相(碲、硒)，二元相的In4Se3、In6Se7、In2Se3、InSe、In4Te3、InTe、In3Te4、In2Te3、In2Te5，以及於本研究所新發現的兩個三元相In4Se7Te9與In4SeTe2。但是上述三元相的組成範圍與邊界，仍須進一步確認。在In-Se-Te 250oC等溫橫截面圖中，共有15個三相區，為In2Se3+(Se,Te)+Liquid(Se)、Te+In2Se3+In6Se7、Te+InSe+In6Se7、Te+InSe+In7Se4Te9、Te+In2Te5+In7Se4Te9、In2Te3+In2Te5+In7Se4Te9、In2Te3+In2Te5+In7Se4Te9、In3Te4+In2Te3+In7Se4Te9、InTe+In3Te4+In7Se4Te9、InTe+InSe+In7Se4Te9、InTe+InSe+In4Te3、In4SeTe2+InSe+In4Te3、In4SeTe2+liquid(In)+In4Te3、In4SeTe2+liquid(In) +In4Se3、與In4SeTe2+InSe+In4Se3。
在250oC 的Bi-Se-Te三元系統，未發現有三元相。穩定相包括端點的固相(鉍)、液相(硒)與固相(碲、硒)。在Bi-Se與Bi-Te二元系統的複雜二元相群，簡化成Bi2Se3與(Bi2)n(Bi2Se3)m 及Bi2Te3與(Bi2)n(Bi2Te3)m。在250oC，(Bi2)n(Bi2Te3)m和(Bi2)n(Bi2Se3)m兩相完全互溶，生成(Bi2)n(Bi2(Se,Te)3)m相。Bi2Se3與Bi2Te3具有相當大的三元溶解度，但並未完全互溶。在250oC 的Bi-Se-Te等溫橫截面圖，含有(Bi2)n(Bi2(Se,Te)3)m+Bi2Te3+Bi2Se3、Bi2Te3+Bi2Se3+(Se,Te)、與Bi2Se3+(Se,Te)+ Liquid等3個三相區。

Bi2(Se,Te)3-based alloys are the most common commercial thermoelectric materials. Literatures results have indicated that their thermoelectric properties could be enhanced with indium doping. Phase diagrams provide phase equilibria information and are fundamentally important for the understanding of phase transformation and microstructural evolution. This study investigates the phase diagrams of Bi-In-Se-Te quaternary system to provide necessary data for further development of Bi2(Se,Te)3-based thermoelectric materials.
There are four constituent ternary systems, Bi-In-Se, Bi-In-Te, Bi-Se-Te and In-Se-Te in the Bi-In-Se-Te quaternary system. The phase diagrams of Bi-In-Se and Bi-In-Te systems are available in the literatures. This study experimentally determines the phase diagrams of In-Se-Te and Bi-Se-Te systems which are lacking in the literatures. The Bi-In-Se-Te quaternary phase diagram is then constructed based on the phase diagrams of their four constituent ternary systems. The temperature examined in this study is 250oC which is in the application temperature range of Bi2(Se,Te)3-based thermoelectrics.
Ternary In-Se-Te and Bi-Se-Te alloys were prepared with pure bismuth, indium, selenium and tellurium elements. The phases of the equilibrated samples were analyzed by SEM (Scanning Electron Microscopy), EPMA (Electron Probe Microanalysis) and XRD (X-ray Diffraction). The experimental results were used together with the phase diagrams of the constituent binary systems to construct the phase diagrams of ternary systems.
In the ternary In-Se-Te ternary system at 250oC, there are terminal phases, liquid (In) phase, liquid (Se) phase, and (Se,Te) solid phase, binary phases, In4Se3, In6Se7, In2Se3, InSe, In4Te3, InTe, In3Te4, In2Te3 and In2Te5 phases, and two ternary phases, In4Se7Te9 and In4SeTe2 phases. The phase boundaries and compositions of these two ternary compounds need further examinations. There are 15 three-phase regions in the In-Se-Te 250oC isothermal section, and they are In2Se3+(Se,Te)+Liquid(Se), Te+In2Se3+In6Se7, Te+InSe+In6Se7, Te+InSe+ In7Se4Te9, Te+In2Te5+In7Se4Te9, In2Te3+In2Te5+In7Se4Te9, In2Te3+In2Te5+ In7Se4Te9, In3Te4+In2Te3+ In7Se4Te9, InTe+ n3Te4+ In7Se4Te9, InTe+InSe+ In7Se4Te9, InTe+InSe+In4Te3, In4SeTe2+InSe+In4Te3, In4SeTe2+In+In4Te3, In4SeTe2+In+In4Se3 and In4SeTe2+ InSe+ In4Se3.
There is no ternary compound in the Bi-Se-Te ternary system at 250oC. The complicated binary phases in the Bi-Se and Bi-Te binary systems are grouped as Bi2Se3 and (Bi2)n(Bi2Se3)m and Bi2Te3 and (Bi2)n(Bi2Te3)m phases. The (Bi2)n(Bi2Se3)m and (Bi2)n(Bi2Te3)m form a continuous solid solution phase, (Bi2)n(Bi2(Se,Te)3)m. Both Bi2Te3 and Bi2Te3 phases have significant ternary solubilities, but they do not form a continuous solid solution. In the 250oC Bi-Se-Te isothermal section, there are 3 ternary-phase region, and are (Bi2)n(Bi2(Se,Te)3)m+ Bi2Te3+ Bi2Se3, Bi2Te3+ Bi2Se3+ (Se,Te) and Bi2Se3+ (Se,Te)+ Liquid.

摘要..........................................I
Abstract.....................................III
目錄..........................................VII
圖目錄........................................X
表目錄........................................XIV
一、前言......................................1
二、文獻回顧..................................3
2-1 相圖....................................3
2-2 二元系統文獻回顧.........................5
2-2-1 In-Se二元系統........................5
2-2-2 In-Te二元系統........................5
2-2-3 Se-Te二元系統........................5
2-2-4 Bi-Se二元系統........................6
2-2-5 Bi-In二元系統........................6
2-2-6 Bi-Te二元系統........................7
2-3 三元系統文獻回顧..........................7
2-3-1 Bi-In-Se三元系統.....................7
2-3-2 Bi-In-Te三元系統.....................8
2-3-3 Bi-Se-Te三元系統.....................8
2-3-4 In-Se-Te三元系統.....................8
2-4 Bi-In-Se-Te四元系統相圖...................9
三、研究方法...................................19
3-1 In-Se-Te、Bi-Se-Te三元熱電材料系統之相平衡.19
3-1-1 合金製備.............................19
3-1-2 相平衡之熱處理........................19
3-1-3 金相結構分析..........................19
3-1-4 X光粉末繞射分析........................20
四、結果與討論...................................21
4-1 In-Se-Te三元系統於250oC下的等溫橫截面圖.....21
4-1-1 In2Se3-(Se,Te)兩相區..................25
4-1-2 In2Se3-(Se,Te)-Liquid三相區...........27
4-1-3 In2Se3-Liquid兩相區...................27
4-1-4 In4Se7Te9-InSe-Te三相區...............28
4-1-5 In2Se3-Te兩相區.......................30
4-1-6 In4Se7Te9-In2Se5-Te三相區.............32
4-1-7 In4SeTe2-InSe-In4Se3三相區............34
4-1-8 In4SeTe2-In-In4Se3三相區..............36
4-1-9 In4SeTe2-In-In4Te3三相區..............38
4-1-10 In4SeTe2 -In4Te3二相區...............40
4-1-11 In3Te4 -InTe二相區...................42
4-1-12 不確定相區...........................44
4-1-13 In-Se-Te三元系統250oC等溫橫截面圖實驗結果.44
4-2 Bi-Se-Te三元系統於250oC下的等溫橫截面圖......46
4-2-1 Bi-[(Bi2)n(Bi2Te3)m+(Bi2)n(Bi2Se3)m]兩相區.50
4-2-2 Te-Bi2Te3兩相區.........................55
4-2-3 (Se,Te)-Bi2Se3兩相區....................59
4-2-4 (Se,Te)-Liquid-Bi2Se3三相區.............63
4-2-5 Liquid-Bi2Se3兩相區.....................63
4-2-6 Bi2Se3- Bi2Te3兩相區....................64
4-2-7 Bi2(Se,Te)3-(Bi2)n(Bi2(Se,Te)3)m相區....66
4-2-8 Bi-Se-Te三元系統250oC等溫橫截面圖實驗結果.72
4-3 Bi-In-Se-Te四元系統於250oC下的等溫橫截面圖....74
五、結論..........................................76
六、參考文獻.......................................78


                                

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