臺灣博碩士論文加值系統

在本論文中，利用固態燒結法合成出兩種鹼土硫族化合物，Ba12Sn4Se23和SrCu2SiSe4。由X光單晶繞射解析結構，並且利用理論計算驗證其鍵結與能隙。
第一部份中，在750°C 下進行燒結得到Ba12Sn4Se23，為新結構化合物，晶體晶胞為 a = 27.8351 (3) Å、b = 12.8469 (2) Å、c = 32.28653 (5) Å、β = 25.437 (12)°、V = 4959.09(17) Å3 以及Z = 4，晶系為單斜晶系 (Monoclinic)，空間群為P21/c且R1/wR2值為R1/wR2= 0.0539/0.1055。結構中包含獨立形成層狀的SnSe4四面體、填佔於層間隙地Se22-單鍵、孤立Se2-離子與鋇形成扭曲八面體結構以及+2價鋇離子組成，為Ba12(SnSe44-)4(Se22-)3(Se2-)，其他具有相似結構的結構於此討論。理論計算則顯示其具有半導體的特性，能隙為0.44 eV。
第二部份中，經由750°C 燒結流程得到SrCu2SiSe4，晶胞為a = 6.3649(17) Å、b = 6.3649(17) Å、c = 15.910(6) Å、β = 120°、V = 558.2(3) Å3以及Z = 2，晶系為三方晶系 (Trigonal)，空間群為P32，且R1/wR2 = 0.0573/0.0971。結構中包含彼此共角的CuSe4、SiSe4四面體以及+2價鍶離子，與此結構具有相同化學式之化合物亦於此進行討論，理論計算顯示其具有半導體性質，能隙為0.9 eV，能帶計算揭露其直接半導體性質，並利用COHP結果證實結構中共價鍵的存在。

Ba12Sn4Se23 and SrCu2SiSe4 were synthesized by solid-state reaction. Both of them were characterized by X-ray diffraction to define their structures. Theoretical calculations determined their density of state, band structure and crystal orbital hamilton population (COHP).
Ba12Sn4Se23 crystallizes in monoclinic space group P21/c (No. 14). With a = 27.8351 (3) Å, b = 12.8469 (2) Å, c = 32.28653 (5) Å, β = 25.437 (12)°, V = 4959.09(17) Å3 and Z = 4. The final R values are R1=0.0539, wR2=0.1055. The structure contains SnSe4 tetrahedral, diselenide Se22-, isolated Se2- anion and Ba2+. Can be written in Ba12 (SnSe44-)4(Se22-)3(Se2-). Calculation of electronic structure shows semiconductor behavior with band gap 0.44 eV.
SrCu2SiSe4 crystallizes in trigonal space group P3¬2 (No. 145). With a = 6.3649(17) Å、b = 6.3649(17) Å、c = 15.910(6) Å、β = 120°,V = 558.2(3) Å3 and Z = 2. The final R values are R1=0.0573, wR2=0.0971. SrCu2SiSe4 is build up by corner-sharing CuSe4 and SiSe4 tetrahedral form a three-dimensional network. With the oxidation state of Sr is 2+. Theoretical calculation indicates the semiconductor behavior with band gap 0.9 eV.

摘要 I
Abstract II
誌謝 III
表目錄 VI
圖目錄 VI
第一章 緒論 1
1.1 介紹 1
1.2 潛在應用 1
1.2.1 熱電材料 1
1.2.4 非線性光學 3
1.2.5 輻射偵測 4
1.3 文獻回顧 4
1.3.2 鹼金族硫族化合物 4
1.3.3 鹼土族硫族化合物 5
1.3.4 鑭系硫族化合物 10
1.3.5 多硫化合物 11
1.4 研究動機 13
第二章 實驗流程 14
2.1 合成方法 14
2.2 空氣敏感物質 15
2.3 藥品 17
2.4 儀器 18
2.5 X光概略 19
2.6 X光粉末繞射 20
2.7 X光單晶繞射 22
2.7.1 晶體的選擇與安置 22
2.7.2 晶格常數測定 24
2.7.3 繞射數據校正 25
2.7.4 結構解析 27
2.7.5 結構模型精修 27
2.8 特性測量 28
2.9 物理性質測量 28
2.10 理論計算 29
第三章 結果與討論 30
3.1 Ba12Sn4Se23 30
3.1.1 晶體結構 30
3.1.2 純化 44
3.1.3 電子結構 47
3.2 SrCu2SiSe4 48
3.2.1 晶體結構 48
3.2.2 純化 58
3.2.3 電子結構與鍵結狀態 60
第四章 結論 63
參考文獻 64

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