本研究以物理氣相傳輸法藉由VS (vapor-solid)成長機制，於高真空密封的石英管內以鈦片作為基板合成鈦硫化合物，並藉由控制成長溫度以及硫供給量探討不同合成條件下樣品之間的差異性。透過多樣材料分析儀器：FE-SEM、XRD、TEM、AFM、Raman光譜，分別對樣品進行表面形貌、晶體結構成分鑑定、表面氧化態、厚度量測與光學性質分析。從實驗分析結果得知所合成的鈦硫化合物為過渡金屬二二硫化鈦TiS2，而鈦基板表面僅合成出單一相的六方單晶片狀結構，此片狀結構的尺寸與厚度隨硫供給量與成長溫度的增加而增加。透過XRD分析，在成長溫度550 ˚C時，當硫供給量越豐富TiS2傾向於以(001)面做為為堆疊的優選取向，而在成長溫度600˚C時，過量的硫供給則是更傾向於以(101)出平面方向堆疊。而經由XPS分析可得知TiS2的Ti 2p主要存在兩種不同組成形式的鍵結，一為Ti-S鍵結所產生的峰，另一則是因TiS2樣品與大氣中的氧接觸所生的Ti-O峰，而在S 2p核層能譜中有發現代表硫缺陷(sulfur vacancies)的分峰，而TiS2樣品硫缺陷所佔比例會受到成長條件的不同而產生變化。最後在Raman光譜中確認以不同合成條件下所合成的二維結構皆為1T相的TiS2，並透過分析Raman震動模式觀察到TiS2樣品的層數相依性以及樣品之間硫缺陷的差異性，結果顯示隨TiS2的層數與A1g峰強度和A1g與Eg峰位置之間的差異呈負相關；TiS2奈米片的硫缺陷程度則是隨硫供給量增加而下降，與XPS分析結果相符。

In this study, the physical vapor transport method and the VS (vapor-solid) growth mechanism were used to synthesize titanium-sulfur compounds in a high-vacuum-sealed quartz tube using a titanium sheet as a substrate. The samples were obtained under different synthesis conditions by adjusting the growth temperature and the amount of sulfur supplied during growth. The surface morphology, structural properties, composition, surface oxidation state, thickness and optical property of the samples were characterized through a variety of characterization method such as: FE-SEM, EDS, XRD, TEM, AFM and Raman spectroscopy. According to the experimental results, the as-synthesized samples consisted of titanium disulfide (TiS2) nanoplates. Furthermore, only single crystal hexagonal TiS2 nanoplates were obtained. Moreover it was found that the size and the thickness of TiS2 nanoplates increases with the increasing supplements of sulfur vapor and growth temperature. The samples with excess supplements of sulfur grew under 550 ˚C, exhibit a (001) preferred stacking orientation. On the country, for the samples grew with excess supplements of sulfur at a higher growth temperature of 600 ˚C, shows a (101) stacking orientation. The XPS results show that sample is present in the form of two different components, one is the Ti-S bond, and another is Ti-O bond which due to TiS2 sample contact with an oxygen environment. The sulfur vacancy peak was also observed in the S 2p core-level spectrum. The quantity of sulfur vacancies in TiS2 samples will vary depending on the growth conditions. The Raman spectroscopy was utilized to verify the vibrational properties of TiS2 samples, the results confirmed that all the as-synthesized samples are 1T TiS2 structure. We also observe the thickness dependence of TiS2 samples and the different amount of sulfur vacancies between samples through the analysis of Raman vibration modes. The results confirm that the thickness dependence of TiS2 is negatively correlated with the intensity of the A1g peak and the difference between the peak position of A1g and Eg. The amount of sulfur vacancies of TiS2 nanoplates decreases as the amount of supplements of sulfur increases. The results are in consist with the XPS analysis results.

致謝 I
摘要 III
Abstract V
目錄 VII
圖目錄 XI
表目錄 XVII
第1章 緒論 1
1.1 前言 1
1.2 研究目標 2
第2章 文獻回顧 5
2.1 二維材料的特性與發展 5
2.2 二硫化鈦TiS2 5
2.3 TiS2合成 6
2.3.1 化學氣相傳輸法合成TiS2 6
2.3.2 氣相傳輸法合成鈦硫化物 7
2.3.3 熱溶劑法 8
2.3.4 球磨法 8
2.4 成長機制 9
2.5 二硫化鈦TiS2特性與應用 10
2.5.1 層數相依姓 10
2.5.2 電學特性 11
第3章 實驗步驟與分析儀器 23
3.1 實驗設計 23
3.2 實驗材料 23
3.2.1 使用儀器 23
3.2.2 材料 23
3.2.3 清潔溶液 24
3.3 實驗步驟 24
3.3.1 基板清洗及表面處理 24
3.3.2 以傳統氣相傳輸法合成Ti-S材料 24
3.3.3 石英管前處理及封管 25
3.3.4 以封管方式合成Ti-S材料 26
3.4 實驗分析儀器 26
3.4.1 場發射掃描式電子顯微鏡 (FE-SEM) 26
3.4.2 X光繞射分析儀 (XRD) 27
3.4.3 X射線光電子能譜儀 (XPS) 27
3.4.4 穿透式電子顯微鏡 (TEM) 28
3.4.5 拉曼光譜儀(Raman Spectroscopy) 28
3.4.6 原子力顯微鏡(AFM) 29
第4章 結果與討論 33
4.1 嘗試以氣相傳輸法成長TiS2 33
4.1.1 EDS定性分析 33
4.1.2 XRD鑑定分析與表面形貌分析 33
4.2 於高真空封管條件下合成Ti-S化合物 35
4.2.1 EDS定性分析 35
4.2.2 表面形貌分析 36
4.3 晶體結構與相鑑定 37
4.3.1 XRD分析 37
4.3.2 TEM分析與鑑定 40
4.4 XPS分析 42
4.4.1 XPS定性分析 42
4.4.2 定量分析 43
4.4.3 成長溫度與硫供給量變化對電子能譜的影響 44
4.4.4 XPS分析小結論 46
4.5 AFM厚度量測 46
4.6 Raman光譜 47
第5章 結論 73
第6章 參考文獻 77

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