單層二維半導體材料，如過渡金屬硫族化合物，具有優異的特性
及特殊的電子結構，豐富且新穎的物理現象受到國際高度關注，然而，
關於單層二維半導體摻雜物的調控，為必要而長期充滿挑戰的議題，
本論文透過常壓化學氣相沉積系統，達成單層二維半導體的摻雜物調
控，期望將磁性摻雜物於引入材料合成反應中，實現具有磁性或獨特
晶體結構的單層二硫化鎢晶格，透過摻雜效應研究材料相變化及物理
性質的改變，此外，發現促進劑於成長行為及合成材料的摻雜，具有
關鍵的影響並能夠促進摻雜物加入二維晶格，進而產生相轉變及相關
物性的響應，本研究深入討論二維材料之摻雜行為及相關成長機制。
此外，本實驗針對所合成材料及元素摻雜，設計並研發相關分析
與量測技術，透過各種材料分析及奈米檢測技術，釐清材料成長機制
及參雜物的組成與分布，同時，結合光學分析深入探討相變化及結構
相關的效應，透過電性量測，驗證半導性二維晶體因相變化引發金屬
性傳輸特性。期望透過對二維材料摻雜及衍生的相變化及物性之研究，
對於未來二維材料及新穎電子元件應用，提出貢獻。

Monolayer of two dimensional (2D) semiconductors, such as
transition metal dichalcogenides (TMD), exhibits excellent properties and unique electronic structure. It enables fascinating physical phenomena and novel properties, which attracts considerable attentions. However, doping of monolayer 2D lattices remains a long lasting challenge but essential manipulation of materials for semiconductor industry.
In this thesis, tunable doping of monolayer TMD semiconductors is realized by promoter-assisted ambient -pressure chemical vapor deposition
(APCVD). Magnetic dopants are successfully incorporated into the 2D lattice to include significant change on crystal and electronic structures for novel properties, such as ferromagnetism or phase transition in the grown monolayer of tungsten disulfide (WS2). It has been verified that existence of the salt promoter in the CVD reactions clearly enhance the involve of the dopants in the monolayer growth process. With the dopants involved, a significant phase transition and novel performances are found for the first
time. Doping and growth mechanism of the monolayer TMD are studied. Techniques for analysis and measurements are developed for the synthesized monolayers with designed dopants, which is essential for better understanding on growth mechanism and doping process. We carried out electrical measurements combined with various analysis on optical, compositional, crystal and electronic structures for the study of highlight issues. We wish that the perspectives of tunable doping of the monolayer 2D lattice would initiate significance in following research or applications.

摘要................................................................................................................................ 1
Abstract .......................................................................................................................... 2
目錄................................................................................................................................ 3
第一章 緒論............................................................................................................ 5
第二章 文獻回顧.................................................................................................... 6
2-1 過渡金屬硫族化合物 ............................................................................................ 6
2-1-1 二維材料 ............................................................................................................ 6
2-1-2 晶體結構 .................................................................................................. 7
2-1-3 電子能帶結構 .......................................................................................... 9
2-1-4 光學性質 ................................................................................................ 10
2-1-5 磁學特性 ................................................................................................ 11
2-2 摻雜型二維材料之製程 ...................................................................................... 12
2-2-1 摻雜 ........................................................................................................ 12
2-2-2 溶液法 .................................................................................................... 13
2-2-3 物理法 .................................................................................................... 14
2-2-4 化學法 .................................................................................................... 15
2-3 化學氣相沉積調控二維材料生長 ........................................................................ 16
2-3-1 反應溫度 .......................................................................................................... 16
2-3-2 還原氣氛 .......................................................................................................... 17
2-3-3 促進劑的使用與類型 ...................................................................................... 17
第三章 實驗方法.................................................................................................. 31
3-1 材料合成系統 ...................................................................................................... 32
3-1-1 試片清理流程 ........................................................................................ 32
3-1-2 實驗步驟 ................................................................................................ 32
3-2 材料分析與量測 .................................................................................................. 33
3-2-1 光學顯微鏡 ............................................................................................ 33
3-2-2 光學檢測分析 ........................................................................................ 33
3-2-3 表面形貌與特性 ...................................................................................... 36
4
3-2-4 掃描式電子顯微鏡與能量色散X 射線 ................................................. 36
3-2-5 X 光繞射分析 (X-ray Diffraction, XRD) ............................................. 37
3-2-6 化學組態及成分分析 .............................................................................. 37
3-3-7 原子結構分析 .......................................................................................... 37
3-3-8 半導體元件參數分析儀 ........................................................................ 38
第四章 二硫化鎢的合成與分析.......................................................................... 41
4-1 促進劑之加入 ...................................................................................................... 42
4-1-1 二階段製程 .......................................................................................... 43
4-1-2 促進劑之更換(硝酸鉀) ....................................................................... 44
4-1-3 促進劑之比較與機制 ............................................................................ 47
4-2 製程參數變化 ...................................................................................................... 53
4-2-1 促進劑擺放位置之影響 ........................................................................ 53
4-2-2 摻雜物、促進劑之質量與比例影響 .................................................... 54
4-2-3 製程溫度 ................................................................................................ 56
4-2-4 還原氣氛（氫氣）之影響 .................................................................... 57
4-3 摻雜型二維材料之分析與量測技術 .................................................................. 63
4-3-1 光學量測 ................................................................................................ 63
4-3-2 成分與結構分析 .................................................................................... 66
4-3-3 電性量測 ................................................................................................ 68
4-3-4 磁性(MFM) ............................................................................................ 69
第五章 結論.......................................................................................................... 81
參考文獻...................................................................................................................... 82
附錄.............................................................................................................................. 87

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