本實驗以Se/Cu/Sn/Zn/SLG疊層利用RTP (rapid thermal process) 硒化製程鍍製單一相CZTSe (Cu2ZnSnSe4)薄膜，因其在快速升溫過程中，避開三元硒化物(Cu2SnSe3)的產生，可使反應在短時間內完成，並探討N2和Se量對薄膜品質及附著性的影響，以及確認以RTP硒化製程單一相CZTSe的組成範圍，和利用退火及改變疊層(Se/Cu/Zn/Sn/SLG)方式改善薄膜均勻性，並將其疊至Mo/SLG上，調變升溫速度改善附著性的問題。其結果顯示N2太少時，提供外在壓力太小，使得Se容易跑掉，和N2太大會使多餘的高蒸氣壓氣體快速逃離試片，造成試片隆起，與基板附著性不佳，此外在CZTSe單一相的判斷上，除了XRD和Raman分析，需再由光性分析其能隙值( Eg )大小，進一步判斷是否為單一相結果，本實驗EPMA結果顯示組成落在Cu-poor和Zn-poor範圍內，能隙值在0.88~1.04 eV，電阻率1~10-2 Ω-cm。利用RTP硒化製程，因快速升降溫，使得前驅物之間互相擴散不均，造成薄膜均勻性不佳，利用再退火和改變疊層方式皆有效改善薄膜均勻性，但因Se/Cu/Zn/Sn疊層液相Sn在鈉玻璃基板上產生非濕潤效應，使得薄膜表面成島狀隆起，故以本實驗以Se/Cu/Sn/Zn/Mo/SLG疊層為主，並以15℃/sec的升溫速度，在250℃下退火一分鐘，提升CZTSe與Mo的附著性。

This experiment was growing CZTSe (Cu2ZnSnSe4) single phase thin film by using rapid thermal selenization process on Se/Cu/Sn/Zn/SLG thin film. It can complete the reaction to avoid Cu2SnSe3 appearing during the RTP. To discuss the effect of nitrogen and selenium flow rates on the thin film quality and adhesion, and to confirm the composition of the CZTSe single phase thin film. And I also annealed and changed the Se/Cu/Zn/Sn/SLG stacked layer to improve the thin film uniformity. Finally, it was stacked on the Mo/SLG and annealed by varying raising rate of temperature in order to enhance the adhesion. The results indicated that the various flow of nitrogen could cause different conditions. The element selenium easily escaped due to lower nitrogen flow could not provide enough outer pressure; larger nitrogen flow carried the extra high vapor pressure gas go through the surface of substrate and lead to the worse adhesion with the substrate. Unfortunately, using the analysis of X-ray diffraction and Raman spectrum couldn’t determine the single phase of CZTSe. However, it has been confirmed by optical bandgap. In this experiment, the compositions of CZTSe single phase are found to be Cu-poor and Zn-poor, the optical bandgap (Eg) is 0.88~1.04 eV, and the resistivity (ρ) is 1~10-2 Ω-cm. By the rapid thermal selenization process, because of the rapid gradient of temperature, it brought out the diffused non-uniformly among the precursors. Therefore, the uniformity of thin films would not be perfect. As the result, re-annealing and change are the efficient methods to improve the uniformity of the thin film. The problems are un-wetting effect exists in the stacked liquid phase Se/Cu/Zn/Sn and the sodium glass substrates. The morphologies of the thin films are island connection. Finally, increasing the temperature in 15 oC per second and annealing the thin film for one minute at 250 oC with the stacked layer of Se/Cu/Sn/Zn/Mo/SLG are successful to promote the adhesion between the CZTSe and Mo.

目錄
致謝 ii
摘要 iii
Abstract iv
目錄 iv
圖目錄 viii
表目錄 x
一、簡介 1
1.1前言 1
1.2太陽電池原理 2
二、文獻回顧 4
2.1 Cu2ZnSnSe4 (CZTSe)主吸收層 4
2.1.1 CZTSe薄膜特性 4
2.1.2 CZTSe薄膜製程 11
2.2實驗動機與目的 12
三、實驗流程與分析儀器 14
3.1鍍製CZTSe薄膜流程 14
3.1.1 鈉玻璃基板(SLG)清洗 14
3.1.2 Cu、Sn和Zn薄膜鍍製 15
3.1.2Se薄膜鍍製 16
3.1.2快速熱退火RTA 17
3.2薄膜分析儀器 18
3.2.1四點探針(4-point) 18
3.2.2 熱探針 19
3.2.3 X光繞射分析(XRD) 19
3.2.4 掃描式電子顯微鏡(SEM) 19
3.2.5吸收光譜儀 20
3.2.6 能量解析光譜儀(EDS) 20
3.2.7 電子探針微區分析儀(EPMA) 20
3.2.8拉曼光譜(Raman) 21
3.2.9霍爾效應量測儀(Hall effect measurement) 21
3.3 實驗流程圖 22
3.4 實驗參數 23
3.4.1 反應途徑 23
3.4.2 N2、Se量調變 23
3.4.3 組成調變 24
3.4.4 薄膜均勻性改善 25
3.5 CZTSe/Mo/SLG 26
四、實驗結果與討論 27
4.1 膜厚估計與誤差 27
4.2 CZTSe RTA製程反應途徑 28
4.3 N2、Se量和升溫速度調變 30
4.4組成調變 35
4.5薄膜均勻性改善 42
4.6 CZTSe/Mo/SLG 47
五、結論 51
六、參考文獻 53

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