臺灣博碩士論文加值系統

本論文旨在探討以醋酸鉍及硫粉為反應物以油胺為溶劑及界面保護分子在170℃下以熱裂解方法合成出粒徑均勻之硫化鉍(Bi2S3)奈米棒，其棒的長度為125 nm直徑為20 nm。若上述反應添加油酸鈉時則會形成較為細長奈米棒，其棒的長度為372 nm直徑約為10 nm。另外，由實驗結果發現熱裂解反應中添加不同量的硫粉，可以控制Bi2S3奈米棒產物之尺寸，一系列不同尺寸之奈米棒經由此法獲得，其棒的長度由52 nm至125 nm直徑12.5 nm至20 nm。經由吸收光譜之吸收邊量測顯示這一系列的奈米棒具有可調變的能隙寬度由1.42 eV到1.63 eV ，相對於Bi2S3塊材之能隙為1.3 eV，顯示這一系列的奈米棒具有能隙藍移的效果。此外，使用油醇或Oleyl Amide取代油胺，產物會轉變成奈米花。其花尺寸為0.5μm。
利用上述合成粒徑均Bi2S3奈米棒為板模，將其與不同濃度的硒/ODE(1-Octadecene)溶液於200℃下反應，發現可生成Bi2(S1-XSeX)3 （X = 0.08~0.92）奈米棒，經由吸收光譜之吸收邊量測顯示這一系列的奈米棒具有可調變的能隙寬度由1.37 eV到1.02 eV 。 (Bi2Se3塊材之能隙為0.35 eV )。
此外，以TEM之EDS以Line scanning之方式得知奈米棒知兩端有較高之硒濃度，顯示硒可能經由奈米棒之兩端逐步擴散奈米棒之全體。

Size-uiformed Bi2S3 nanorods (125 nm x 20 nm) have been synthesized via the reaction of bismuth acetate and elemental sulfur in oleylamine at 170 oC. Addition of sodium oleate in the above reaction can lead to more slender nanorods (372 nm x 10 nm). The relative ratio of sulfur to bismuth in the same amount of oleylamine has an effect on the sizes of the products. Higher ratio gives larger nanorods. A series of nanorods ranged from 52 nm to 125 nm in length and 12.5 nm to 20 nm in diameter can be obtained. The absorption spectra of them indicate a blue-shifted and tunable band-gap width from 1.42 to 1.63 eV with respect to the bulk value of 1.3 eV. Replace ing the solvent of oleyamine with oleylalcohol or oleylamide, star-shaped nanoflowers are obtained.
The obtained nanorods in the above-described reactions can be further treated with Se/1-ODE solutions of different concentration to produce Bi2(S1-xSex)3 (guanajuatite) nanorods. The series of guanajuatite nanorods obtained also show tunable band-gap widths (1.37 eV to 1.02 eV, 0.35 eV for the bulk Bi2Se3) with the variation in compositions in the absorption spectra. From the EDS study of the intermediates of the above reactions, the Se concentration is higher at the two ends of the nanorods indicates the diffusion may be preferentially along the b-axis, which is consistent with its chain structures.

誌謝 I
摘要 III
Abstrant IV
目錄 V
表目錄 IX
圖目錄 X
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 2
第二章 理論基礎與文獻回顧 3
2-1 半導體奈米粒子之定義與特性 3
2-1-1 半導體材料分類 4
2-1-2 非侷限型(Unlocalized Type)發光材料 6
2-1-3 侷限型(Localized Type)發光材料 6
2-1-4 化合物半導體奈米粒子之光物理(Photophysics)特性 7
2-2 奈米粒子之物理性質 8
2-2-1 小尺寸效應 8
2-2-2 表面效應 8
2-2-3 量子穿遂效應 10
2-2-4 量子尺寸效應 10
2-3 奈米粒子之合成與穩定性 12
2-3-1 奈米粒子之合成 12
2-3-2 膠體奈米粒子之穩定性 17
2-4 奈米粒子之成核與成長 18
2-4-1 La Mer 高均勻度膠體粒子成長模型 19
2-4-2 成核與成長理論 19
2-4-3 成核與成長機制 20
2-4-4 異向成長機制 21
2-4-5 自組裝 ( Self-Assembly ) 26
2-5 硫化鉍之結構 27
2-6 文獻回顧 30
第三章 實驗方法與步驟 34
3-1 實驗流程 34
3-1-1 實驗流程圖 35
3-1-2 實驗裝置與設備圖 36
3-2 實驗藥品 37
3-2-1 藥品化學結構圖 38
3-3 實驗步驟 40
3-3-1 硫化鉍奈米棒之合成 40
3-3-2 硫化鉍奈米細棒之合成 40
3-3-3 硫化鉍奈米花之合成 41
3-3-4 硫化鉍摻雜硒化物之合成 42
3-4 儀器鑑定之材料特性分析 43
第四章 結果與討論 52
4-1 硫化鉍之合成條件 52
4-1-1 硫化鉍（Bi2S3）奈米棒之合成 53
4-1-2 硫化鉍（Bi2S3）奈米棒之合成參數變化 58
4-1-3 Sodium Oleate對硫化鉍（Bi2S3）之影響 62
4-1-4 界面活性劑對硫化鉍（Bi2S3）奈米棒之影響 66
4-2 硫化鉍摻雜硒化物之合成 74
4-2-1 硫化鉍(Bi2S3)摻雜硒化物之合成參數變化 74
4-2-2 硫化鉍(Bi2S3)摻雜硒化物之EDS分析 79
4-3 硫化鉍之光學特性 86
4-3-1 硫化鉍(Bi2S3)光學性質研究 86
4-3-2 硫化鉍(Bi2S3)奈米棒合成之參數變化光學性質研究 88
4-3-3 Sodium Oleate對硫化鉍(Bi2S3)之光學性質研究 90
4-3-4 界面活性劑對硫化鉍(Bi2S3)之光學性質研究 91
4-3-5 硫化鉍(Bi2S3)摻雜硒化物光學性質研究 93
第五章 結論 96
参考文獻 97
自述 102

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