本研究針對穿透式電子顯微鏡臨場觀測的需求，開發以熱為刺激源的TEM樣品桿。相較於傳統熱爐式加熱樣品桿，升溫速率（100°C/sec）、降溫速率（0.1°C/sec）及熱飄移速率（82nm/sec），為了解決性能上的不足，利用MEMS技術製作加熱晶片，其微區加熱表現出的高性能，能夠快速升溫（15000°C/sec）及降溫（15000°C/sec），於短時間內達熱穩定，且大幅減少樣品因高溫而造成的熱飄移（0.5nm/sec），並利用四點探針即時回饋得到精準的控溫。加熱晶片製程需用到 a.光罩設計 b.黃光微影 c.反應離子蝕刻 d.電子束蒸鍍 e.濕蝕刻 f.化學氣相沈積 g.水平爐管 h.退火爐管。 且利用 i.原子力顯微鏡 及 j.N.K光學分析儀檢測膜厚。 接著用FIB製備TEM樣品，並利用油壓式機械手臂將樣品轉移至加熱晶片上。於穿透式電子顯微鏡內做快速熱退火硒化製程單一相CZTSe（Cu2ZnSnSe4）薄膜，因其在快速升溫過程中，可避開三元硒化物之二次相（Cu2SnSe3）的產生，並解析穿透式電子顯微鏡動態影像，再利用加熱晶片之快速降溫性能，將高溫介穩相淬火至常溫以便用能量色散Ｘ射線光譜-元素分佈分析動態元素分佈，以及解析高解析影像及快速傅立葉轉換轉換繞射圖解析結晶相。

The research is “Development of In-Situ MEMS-Based Heating System for Dynamic Analysis of the Quaternary Compound Semiconductor in Transmission Electron Microscope”. For this research of TEM in-situ observation, we develop the heating process perform in TEM by TEM heating holder. Instead of the heating by traditional resistance wires, the heating resource has implemented by MEMS technology to fabricate the micro heater.
The MEMS-Based micro heater has high performance in heating rapidly & cooling, settling time shortly and reducing significantly the thermal drift caused by heating & cooling. Then the four point resistance feedback is used to precisely control the temperature. The fabrication processes of MEMS-Based micro heater include photo lithography, LPCVD, PECVD, RIE(reactive ion etching), wet etching and E-Beam evaporation. After the MEMS process, N&K analyzer. AFM, SEM and Four-Point Probe were used to detect the MEMS-Based micro heater.
The analysis of solar cell absorption layers (Se/Cu/Sn/Zn/SLG) are prepared by sputter and E-Beam evaporation. After that, the FIB(focused ion beam) is used to prepare the TEM sample. In order to avoid the second phase deposition, RTA(rapid thermal annealing) process were performed in TEM, moreover it observes the high resolution video related to timeline and analysis by EDS(energy dispersive spectrometer) and DP(diffraction pattern).
Key words：In-situ TEM（Transmission electron Microscope）、TEM（Transmission electron Microscope）、MEMS（Microelectromechanical Systems）、Dynamic Analysis、Rapid thermal annealing（RTA）

摘要 i
Abstract ii
致謝 iii
目錄 v
圖目錄 viii
表目錄 xii
第一章 緒論 1
1.1 顯微鏡的發展 1
1.1.1 光學顯微鏡的發展 1
1.1.2 電子顯微鏡的發展 3
1.1.3 掃描式電子顯微鏡 5
1.1.4 穿透式電子顯微鏡 7
1.2 研究動機與目的 8
第二章 文獻回顧 9
2.1 電子顯微鏡加熱載具 9
2.1.1 穿透式電子顯微鏡之加熱載具 10
2.1.2 微機電製程之微型加熱器 14
2.2 臨場加熱電子顯微鏡之分析 17
2.2.1 高溫臨場相變化之分析 17
2.2.2 臨場觀測奈米結構成核與成長 19
2.2.3 臨場觀測原子擴散與電遷移現象 25
2.3 CZTSe(Cu2ZnSnSe4)太陽能電池 28
2.3.1太陽能電池的發展 28
2.3.2 晶體結構 30
2.3.3 缺陷與參雜效果 31
2.3.4 Cu2ZnSnSe4硒化反應機制 33
第三章 載具開發與實驗方法 34
3.1 實驗大綱 34
3.2 製程設備 35
3.3 分析儀器 37
3.4 微型加熱晶片設計與製作 39
3.4.1 微型加熱晶片結構設計 39
3.4.2 光罩繪製與製作 40
3.4.3 黃光微影 41
3.4.4 微型加熱晶片製程流程 44
3.5 穿透式電子顯微鏡臨場觀測之加熱系統架設 47
3.5.1 設備與裝置組件 48
3.5.2 實驗步驟 48
第四章 結果與討論 50
4.1 加熱晶片 50
4.1.1 觀測視窗之膜厚控制 50
4.1.2 四點量測電阻即時控溫 55
4.1.3 熱飄移之量測 59
4.2 快速熱退火形成CZTSe於TEM下臨場觀測 61
4.2.1 Se/Cu/Zn/Sn/Si金屬疊層於TEM中快速熱退火 62
圖4.2-1 TEM中進行快速熱退火於不同溫度下之影像 62
4.2-2 於TEM熱退火過程中之成分分析 63
第五章 結論 64
第六章 參考文獻 65

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