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研究生: 黃智盈
Huang, Chih-Ying
論文名稱: 利用混合陽離子方法提升二維錫鈣鈦礦穩定性
Improving Stability of Two-Dimensional Tin Halide Perovskite Crystals through Mixed Cation Method
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: 46
中文關鍵詞: 混合陽離子鈣鈦礦無鉛鈣鈦礦二維Ruddlesden-Popper鈣鈦礦
英文關鍵詞: mixed cation, lead-free, two-dimensional Ruddlesden-Popper perovskite
DOI URL: http://doi.org/10.6345/NTNU202000877
論文種類: 學術論文
相關次數: 點閱:88下載:25
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  • 有機-無機鈣鈦礦憑著其優異的光電性質在近十年受到各界大量的關注,但是常見的鈣鈦礦材料中含有鉛,存在環境汙染與毒性之風險,尋找替代元素即成為重要的研究議題。然而,錫鈣鈦礦具有高吸收係數與低能隙的優點而成為相當好的替代元素,不幸的是錫鈣鈦礦穩定性極差容易受環境影響而氧化,因此本研究專注於錫鈣鈦礦的穩定性提升。
    本篇成功將合成二維錫鈣鈦礦晶體BA2FASn2I7 (n = 2),再利用混合陽離子方法將甲脒與銫共同摻入鈣鈦礦製成BA2FA0.5Cs0.5Sn2I7 (n = 2),藉由粉末X光繞射鑑定結構得知銫確實有進入錫鈣鈦礦晶格且具有清楚的等間距繞射峰,測量吸收光譜得知能隙僅有略微變化依序為1.74 eV和1.72 eV,又發現BA2FASn2I7經過雷射激發後會出現錫鈣鈦礦主體以外的放射光,而在BA2FA0.5Cs0.5Sn2I7沒有發現此現象,僅有螢光強度的衰退,證明混合陽離子確實能夠抑制其他晶相的產生提升錫鈣鈦礦穩定性。最後將二維錫鈣鈦礦晶體置於大氣中觀察其結構變化,發現BA2FA0.5Cs0.5Sn2I7經過12小時候仍維持其二維層狀結構,表示混合陽離子的二維錫鈣鈦礦結構比BA2FASn2I7穩定。
    未來可嘗試合成更高層數的混合陽離子二維錫鈣鈦礦,應用於光伏元件,將有機會提升效率以及穩定性。

    Organic-inorganic perovskites have received a lot of attention from different field in the past decade due to their excellent photoelectric properties. However, perovskite materials usually contain lead element, which has the risk of environmental pollution and toxicity. Finding alternative elements has become an important research issue. Tin halide perovskites have the advantages of high absorption coefficient and low energy gap and become a good substitute candidate. Unfortunately, the stability of tin halide perovskite is very limited and it is easily oxidized by ambient.
    In this article, we successfully synthesized two-dimensional tin halide perovskite crystals BA2FASn2I7 (n = 2), and then mixed formamidine and cesium into perovskite to form BA2FA0.5Cs0.5Sn2I7 (n = 2) by mixed cation method. The powder X-ray diffraction revealed that cesium did induce to the tin halide perovskite lattice and had clear repeating unit diffraction pattern. The band gap is 1.74 eV and 1.72 eV, respectively. After laser excitation, BA2FASn2I7 will emit the unknown photoluminescence, which is not same as tin perovskites’ original emission. This phenomenon has not been found in BA2FA0.5Cs0.5Sn2I7 crystals, also proves that mixed cations indeed suppress the production of other crystal phases. The two-dimensional tin halide perovskite crystals were placed in the ambient to observe the structural changes. It was found that BA2FA0.5Cs0.5Sn2I7 still maintained its layered structure after 12 hours, indicating that the mixed cation method can stabilize the structure.
    In the future, a higher layered of mixed cation two-dimensional tin halide perovskite have the potential to improve photovoltaic devices efficiency and stability.

    謝辭 I 摘要 II Abstract III 圖次 VI 第1章 緒論 1 1-1 前言 1 1-2 鈣鈦礦材料多樣性 2 1-2-1 鈣鈦礦晶體結構與基本性質 2 1-2-2 維度多樣性 4 1-2-3 組成多樣性 8 1-3 無毒鈣鈦礦 10 1-3-1 非等價金屬鈣鈦礦 10 1-3-2 等價金屬鈣鈦礦 12 1-4 研究動機與目的 13 第2章 文獻回顧 14 2-1 三維錫鈣鈦礦 14 2-1-1 基本結構與光物理性質 14 2-1-2 不同A位陽離子的錫鈣鈦礦 15 2-2 混合陽離子錫鈣鈦礦 16 2-3 二維Ruddlesden-Popper錫鈣鈦礦 19 2-4 二維錫鈣鈦礦材料應用 22 第3章 儀器設備 23 3-1 粉末X光繞射儀(Powder X-ray Diffraction) 23 3-2 光致發光光譜儀(Photoluminescence Spectroscopy) 24 3-3 時間解析光譜(Time-Resolved Photoluminescence) 24 3-4 旋轉塗佈機(Spin Coater) 25 3-5 恆溫水槽(Constant Temperature Water Bath) 25 3-6 紫外光臭氧處理機(UV Ozone Cleaner) 25 第4章 實驗藥品與步驟 26 4-1 實驗藥品 26 4-2 實驗步驟 27 4-2-1 合成BA2FASnI7晶體 27 4-2-2 合成BA2FA0.9Cs0.1Sn2I7晶體 28 4-2-3 BA2FA1-xCsxSn2I7反應物比例 29 4-2-4 二維錫鈣鈦礦薄膜製作 30 第5章 結果與討論 31 5-1 二維有機-無機錫鈣鈦礦晶體 31 5-1-1 不同A位陽離子之結構分析 31 5-1-2 不同A位陽離子之光學性質 32 5-2 二維混合陽離子錫鈣鈦礦 33 5-2-1 混合比例變化對晶體結構之影響 33 5-2-2 混合比例變化對光學性質之影響 34 5-2-3 光穩定性探討 36 5-2-4 結構穩定性探討 38 第6章 結論與未來展望 40 第7章 參考文獻 41

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