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研究生: 陳冠庭
Chen, Guan-Ting
論文名稱: 利用摻雜錳於二維層狀鈣鈦礦提升激子磁光效應
Enhanced the Excitonic Magneto-Optical Effect by Doping Mn2+ in Two Dimensional Ruddlesden-Popper Hybrid Perovskite
指導教授: 陳家俊
Chen, Chia-Chun
口試委員: 陳家俊
Chen, Chia-Chun
陳俊維
Chen, Chun-Wei
王迪彥
Wang, Di-Yan
郭聰榮
Kau, Tsung-Rong
李紹先
Li, Shao-Sian
口試日期: 2021/07/30
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 57
中文關鍵詞: 錳摻雜鈣鈦礦二維Ruddlesden-Popper鈣鈦礦磁光效應電場控制
英文關鍵詞: manganese ion-doped perovskite, two-dimensional Ruddlesden-Popper perovskite, magneto-optical effect, electric field control
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202101094
論文種類: 學術論文
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  • 有機-無機鈣鈦礦因為其良好的光電特性,使得鈣鈦礦材料在各個光電領域上均有突出的表現,除了最受矚目的太陽能電池的能源轉換效率從3.8%提升至25.2%,以及常見的發光二極體、光感應器、雷射等應用外,近年來,鈣鈦礦也逐漸踏入了磁光領域中,利用其良好的吸收係數與較大的原子序和半徑的鉛離子所引起的自旋軌道耦合產生的能階分裂,使鈣鈦礦在磁場下,對於左右旋偏振光有不同的吸收度與折射率,進而產生磁光效應。
    本篇將摻雜錳離子於材料內以增強磁光效應。成功將合成出二維鈣鈦礦晶體BA2PbI4 (n=1)與BA2MAPb2I7 (n=2¬),以摻雜錳離子的方式製作成Mn-doped BA2PbI4 (n=1)與Mn-doped BA2MAPb2I7 (n=2¬),利用粉末X光繞射鑑定結構與測量吸收光譜確定能隙發現結構與能隙皆與無摻雜晶體相同,特別的是在放射光譜中,因為磁場的影響,增強了雷射激發後所產生的放射光,而無摻雜錳離子之晶體則沒有這個現象發生。最後透過測量磁性圓二色性,確實在Mn-doped BA2PbI4製作成的元件中,訊號會受到錳離子產生的內部磁場影響,有部分增強,也有部分減弱,但在零磁場的情況下,可以明顯看出訊號增強將近六倍,最後也利用外加電場達到控制磁性圓二色性訊號,進而增加材料的應用性。
    未來將有機會合成出更高層數的鈣鈦礦,實現涵蓋可見光區域之錳摻雜二維鈣鈦礦,使材料在光學應用上更加廣泛。

    Organic-inorganic perovskites have outstanding performance in various optoelectronic fields due to their good photoelectric properties, except for the most eye-catching solar cell energy conversion efficiency increased from 3.8% to 25.2%, and light-emitting diodes, light sensors, lasers, etc. In recent years, perovskites have gradually entered the field of magneto-optics, their good absorption coefficient, large atomic order and large radius of lead ions cause the spin-orbit coupling. This coupling makes the perovskite energy-level splitting. And under a magnetic field, the perovskite has different absorption and refractive index for left and right polarized light, which in turn produces a magneto-optical effect.
    In this article, manganese ions will be incorporated into the material to enhance the magneto-optical effect. We successfully synthesized two-dimensional perovskite crystals BA2PbI4 (n=1) and BA2MAPb2I7 (n=2), and produced Mn-doped BA2PbI4 (n=1) and Mn-doped BA2MAPb2I7 (n=2) by doping with manganese ions, using powder X-ray diffraction to identify the structure and measuring the absorption spectrum to identify the energy gap, it is found that the structure and energy gap are the same as those of undoped crystals. Especially in the emission spectrum, because of the influence of the magnetic field, the laser excitation is enhanced. And there is no enhancement in undoped crystals Finally, by measuring the magnetic circular dichroism, it is true that in the components made of Mn-doped BA2PbI4, the signal will be affected by the internal magnetic field generated by manganese ions, some of which are strengthened and some are weakened. In the case of zero magnetic field, it can be clearly seen the output signal is nearly six times stronger. The external electric field is also used to control the magnetic circular dichroism signal and increase the applicability of the material.
    In the future, there will be opportunities to synthesize higher layers of perovskite, realize manganese-doped two-dimensional perovskite covering the visible light region, and make the material more widely used in optical applications.

    謝辭 I 摘要 II Abstract III 目錄 IV 圖表目錄 VII 第一章 緒論 1 1-1 前言 1 1-2 鈣鈦礦材料簡介 2 1-2-1 晶體結構 2 1-2-2 基本性質 3 1-2-3 鈣鈦礦之應用 5 1-3 二維層狀鈣鈦礦 7 1-3-1 二維鈣鈦礦結構 7 1-3-2 二維鈣鈦礦性質 8 第二章 文獻回顧與研究動機 10 2-1 磁光效應簡介 10 2-1-1 磁光效應 10 2-1-2 磁光效應之應用 13 2-2 鈣鈦礦之磁光效應 16 2-2-1 三維鈣鈦礦之磁光效應 16 2-2-2 自旋-軌道耦合 17 2-2-3 二維鈣鈦礦之磁光效應 19 2-3 錳摻雜材料之磁光效應 23 2-4 電場控制 26 2-5 研究動機 27 第三章 儀器設備 28 3-1 粉末X光繞射儀 (Powder X-ray Diffraction) 28 3-2 紫外光-可見光-近紅外光分光光譜儀(UV-Vis-Near IR Spectrophotometer) 29 3-3 移動式顯微拉曼光譜儀(Mobile Raman Microscope) 30 3-4 電子順磁共振光譜儀 (electron paramagnetic resonance) 31 3-5 電感耦合電漿體質譜儀(Inductively coupled plasma mass spectrometry) 32 3-6 磁性圓二色性光譜儀(Magnetic Circular Dichroism) 33 3-7 旋轉塗佈機 (Spin coater) 34 3-8 紫外光臭氧處理機(UV Ozone Cleaner) 34 第四章 實驗藥品及步驟 35 4-1 實驗流程圖 35 4-2 實驗藥品 36 4-3 實驗步驟 37 4-3-1 合成BA2PbBr4 晶體 與 錳摻雜 BA2PbBr4 晶體 37 4-3-2 合成 錳摻雜 BA2PbBr4 微米晶體 38 4-3-3 合成 錳摻雜 BA2MAPb2Br7 微米晶體 39 4-3-4 錳摻雜二維鈣鈦礦薄膜製作 40 第五章 結果與討論 41 5-1 二維鈣鈦礦與錳摻雜二維鈣鈦礦 41 5-1-1 結構分析 41 5-1-2 組成元素分析 42 5-1-3 光學性質分析 43 5-1-4 磁性圓二色性與圓二色性比較 44 5-2 磁性圓二色性之電場控制 46 5-3 不同層數錳摻雜二維鈣鈦礦 48 5-3-1 結構分析 48 5-3-2 組成元素分析 49 5-3-3 光學性質分析 50 5-4 磁場下之光學性質 51 第六章 結論與未來展望 53 參考資料 54

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