臺灣博碩士論文加值系統

本論文主要探討Ag金屬摻雜與Ag金屬薄層沉積位置對吸收層薄膜品質與特性之影響。實驗部份，選擇二氧化錫摻氟(SnO2:F，FTO)透明導電玻璃作為本實驗沉積薄膜之基板，並使用熱蒸鍍法沉積金屬前驅物疊層後，搭配硒化製程完成Cu2ZnSnSe4 (CZTSe)和摻雜銀的(Ag,Cu)2ZnSnSe4 (ACZTSe)吸收層之製備。實驗發現Ag摻雜能作為助熔劑，在硒化過程中形成Cu-Ag-Sn液態合金，有效提升薄膜晶粒尺寸以及協助元素擴散。但是，改變銀層於金屬前驅物疊層中的沉積位置會對金屬前驅物薄膜於硒化過程中的生長機制產生變化，尤其是Ag3Sn合金形成時間會影響Zn元素擴散均勻性的問題，進而影響到最終ACZTSe薄膜品質。最後，本實驗發現FTO/Sn/Zn/Ag/Cu之金屬疊層順序之薄膜有最佳的元素擴散均勻性，有效改善薄膜雙層結構及缺陷數量，並且與CdS緩衝層之間具有最小CBO值，利於電荷傳輸。

This study mainly discusses the influence of Ag metal doping and Ag metal thin layer deposition position on the quality and characteristics of the absorber layer film. In the experimental section, SnO2:F (FTO) transparent conductive glass was chosen as the substrate for depositing thin films. A thermal evaporation method was employed to deposit metal precursor layers, followed by a selenization process to complete the preparation of Cu2ZnSnSe4 (CZTSe) and (Ag,Cu)2ZnSnSe4 (ACZTSe) absorber layers with silver doping. The experiments revealed that Ag doping acts as a flux agent, forming a Cu-Ag-Sn liquid alloy during selenization, effectively enhancing grain size and aiding in element diffusion. However, altering the deposition position of the silver layer in the metal precursor stack influences the growth mechanism of the metal precursor films during selenization, especially the formation time of Ag3Sn alloy, which impacted the uniformity of Zn element diffusion. Consequently, this affected the final quality of the ACZTSe film. Ultimately, it was found that the metal stacking order of FTO/Sn/Zn/Ag/Cu resulted in the optimal uniformity of element diffusion in the film, effectively improving the film's bilayer structure and reducing the number of defects. Additionally, this stacking order exhibited the minimum conduction band offset (CBO) with the CdS buffer layer, facilitating charge transfer.

書 名 頁 I
論文口試委員審定書 II
中文摘要 III
英文摘要 IV
誌 謝 VI
目 錄 VII
表 目 錄 IX
圖 目 錄 X
第一章、緒論 1
1.1 前言 1
1.2 太陽能電池基本原理 2
1.3 CZTSe薄膜太陽能電池發展背景 7
第二章、文獻回顧 9
2.1 CZTSe材料介紹 9
2.2 CZTSe薄膜太陽能電池的基本結構 14
2.3 CZTSe薄膜的製備介紹 17
2.3.1 蒸鍍法 (Evaporation) 17
2.3.2 濺鍍法(Sputtering) 22
2.3.3 電鍍法(Electrodeposition) 25
2.3.4 噴霧熱解法(Spary-Pyrolysis) 29
2.3.5 旋轉塗佈法(Spin coating) 32
2.4 Ag摻雜對CZTSe的影響 37
2.5 金屬前驅物疊層順序對CZTSe的影響 42
2.6 FTO透明背電極製備CZTSe太陽能電池 46
2.7 研究動機與目的 50
第三章、實驗步驟及分析儀器 51
3.1 實驗設備 51
3.1.1 熱蒸鍍機 51
3.1.2 高溫硒化爐管 52
3.2 實驗流程 52
3.2.1 基板清洗 52
3.2.2 蒸鍍金屬前驅物薄膜 53
3.2.3 硒化退火 53
3.3 分析儀器介紹 54
3.3.1 場發射型掃描電子顯微鏡(FE-SEM)與能量解析光譜儀(EDS) 54
3.3.2 X光繞射儀(XRD) 55
3.3.3 拉曼光譜儀(Raman spectrometer) 56
3.3.4 紫外-可見光-近紅外光譜儀(UV-Vis-NIR Spectrophotometer) 57
3.3.5 二次離子質譜分析儀(SIMS) 58
3.3.6 接觸式原子力顯微鏡(AFM)與導電式原子力顯微鏡(CAFM) 59
3.3.7 紫外光電子能譜(UPS) 59
第四章、結果與討論 62
第五章、結論 83
參考文獻 84

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