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研究生: 蔡慧穎
Tsai, Hui-Ying
論文名稱: 全無機二維層狀錫鹵素鈣鈦礦奈米晶體
All-Inorganic Tin Halide Ruddlesden-Popper phase Perovskite Nanocrystals
指導教授: 陳家俊
Chen, Chia-Chun
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 60
中文關鍵詞: 無鉛錫鈣鈦礦全無機Ruddlesden-Popper奈米材料
英文關鍵詞: Lead-free, Tin-based perovskite, all-inorganic, Ruddlesden-Popper, nanocrystal
DOI URL: http://doi.org/10.6345/NTNU202000675
論文種類: 學術論文
相關次數: 點閱:140下載:0
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  • 近幾年來,由於鉛具有劇毒且環境危害,使無鉛的新型全無機鈣鈦礦材料變成研究的熱點,其中,以全無機錫鹵素鈣鈦礦為較具有前瞻性的替代品,因為具有較窄的能隙以及與鉛類似的光電特性。然而,三維錫鹵素鈣鈦礦在空氣中的穩定性極差,阻礙了三維錫鹵素鈣鈦礦在光伏領域上的發展,為了得到穩定性較佳且導電度較好的錫鹵素鈣鈦礦奈米材料,本篇研究使用熱注射法將十八烷二酸(Octadecanedioic acid)引入形成強的表面配體,成功合成出層數為三且相穩定的全無機二維層狀Ruddlesden-Popper (RP)相鈣鈦礦Cs4Sn3Br10奈米晶體。由電子顯微鏡觀察到材料大小約為150 nm的長方體,且選區繞射圖譜可對應X-光粉末繞射圖的繞射峰。由X-光粉末繞射圖中的重複單元確認該材料為層狀結構,其結果符屬於n = 3的計算圖。而其最大放光波長在450 nm,且螢光量子產率為12%。此外,由於量子井效應影響,使其放光波長產生藍移,並使螢光量子產率提升。另外,在室溫和相對濕度為60%的情況下通過固態螢光光譜儀和X-光繞射測量,發現二維材料的穩定性比三維材料更好。

    Recently, many literatures demonstrated three-dimensional (3D) lead–free perovskite materials such as Tin-based all-inorganic perovskite CsSnX3 (X =Cl, Br, I) to replace toxic Pb-based all-inorganic perovskite. This class of materials have a narrow energy bandgap and the optical and electrical characteristics are similar to lead-based perovskite. However, the key issue for commercialization is poor environmental stability. In order to obtain perovskite nanomaterials with better stability, we present a strong binding energy surface ligand octadecanedioic acid (ODA) to synthesis all-inorganic Ruddlesden-Popper phase tin-based perovskite nanocrystals with a quantum well structure by hot injection method. The TEM images show a 150 nm rectangle and the SAED match with XRD patterns. The repeating unit of the XRD pattern confirms that the material is a layered structure, and the results are fitted the calculation pattern which belong to n=3. The PL emission of 3D CsSnBr3 is about 680nm, and the PLQY is below 1%. In contrast, the PL emission of 2D NCs is about 450 nm, and the PLQY is about 12%. As a result of strong quantum well effect, the PL emission blue shifted and the PLQY increased. Compared to 3D CsSnBr3 NCs (several hours), the 2D NCs performed better stability (one month) than 3D at room temperature under 60% relative humidity by solid-state PL and XRD measurement.

    摘要 I Abstract II 目錄 III 圖目錄 VII 第一章 緒論 1 1-1 奈米材料 1 1-1-1 奈米材料之物理效應 2 1-1-2 奈米材料之特性 4 1-1-3 奈米材料之發展及應用 5 1-2 鈣鈦礦 6 1-2-1 鈣鈦礦的發展 9 1-2-2 鈣鈦礦結構的多樣性 12 1-2-3 鈣鈦礦的製作 13 第二章 文獻回顧與研究動機 14 2-1 錫鹵素鈣鈦礦介紹 14 2-2 二維Ruddlesden-Popper Phase層狀鈣鈦礦介紹 16 2-2-1 不同空間劑的二維鈣鈦礦 19 2-2-2 不同維度二維鈣鈦礦 23 2-3 二維層狀鈣鈦礦的應用 24 2-3-1 太陽能電池 (Solar Cell) 24 2-3-2 發光二極體 (Light Emitting Diode, LED) 26 2-3-3 光感測器 (Photodetector) 27 2-4 研究動機 28 第三章 儀器設備 29 3-1 紫外光/可見光/近紅外光光譜儀(UV-Vis) 29 3-2 螢光光譜儀(PL) 30 3-3 時間解析螢光光譜儀(TRPL) 31 3-4 絕對量子產率(PLQY) 32 3-5 原子力顯微鏡(AFM) 33 3-6 穿透式電子顯微鏡(TEM) 34 3-7 X-ray粉末繞射儀(XRD) 35 3-8 旋轉塗佈機(Spin-coater) 37 第四章 實驗藥品及步驟 38 4-1 實驗藥品 38 4-2 實驗步驟 39 4-2-1 三維鈣鈦礦CsSnBr3之合成步驟 39 4-2-2 二維層狀鈣鈦礦Csn+1SnnBr3n+1之合成步驟 40 第五章 結果與討論 42 5-1 全無機三維與二維錫鹵素鈣鈦礦之結構分析 42 5-1-1 全無機三維與二維錫鹵素鈣鈦礦TEM及HR-TEM圖 42 5-1-2 二維錫鹵素鈣鈦礦之表面型態影像 44 5-1-3 全無機三維與二維錫鹵素鈣鈦礦X-光粉末繞射圖 45 5-1-4 二維錫鹵素鈣鈦礦之層數推算 46 5-2 全無機三維與二維錫鹵素鈣鈦礦之光學性質分析 48 5-3-1 全無機三維與二維層狀鈣鈦礦吸收與螢光光譜分析 48 5-3-2 全無機三維與二維層狀鈣鈦礦時間解析螢光光譜圖 49 5-3 全無機三維與二維錫鹵素鈣鈦礦穩定度比較 50 5-3-1 三維與二維層狀鈣鈦礦之結構穩定性比較 50 5-3-2 三維與二維層狀鈣鈦礦之光學穩定性比較 52 第六章 結論與未來展望 54 第七章 參考文獻 55

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