臺灣博碩士論文加值系統

近幾年來，鈣鈦礦量子點因其在光電材料中的應用價值而受到了廣泛運用，而相比於傳統II-VI族化合物鈣鈦礦的高成本、製作繁瑣及含有劇毒物質，相比下全無機鈣鈦礦量子點因其有更高的光電轉換效率、波長可涵蓋至整個可見光的範圍，且更重要的是製程容易成本也相對低廉許多，因此受到各界學者廣泛的關注及研究。
本研究是利用熱注入法進行不同濃度鎂的摻雜並製備鈣鈦礦量子點樣品CsPbI3、CsPbI3:Mg(3%)、CsPbI3:Mg(5%)及CsPbI3:Mg(7.5%)，並使用變溫光激發光量測系統做分析及探討這四種鈣鈦礦樣品的光學特性。當中發現當溫度逐漸上升時，因受到電子-聲子(Electron-phonon interaction)及熱膨脹(Thermal expansion)相互拉扯的影響，四種不同濃度鈣鈦礦量子點樣品的發光能量皆有產生明顯的藍移現象，且當摻雜鎂的濃度越高時，藍移的變化量也越多。其中也有發現在低溫時，因雜質跟缺陷影響甚小，使半高寬相對來的窄，而當溫度持續升高至300K時，因激子受到電子-聲子散射效應影響，導致半高寬隨著溫度的升高而增加。

In recent years, perovskite quantum dots have been widely used for their application value in optoelectronic materials. Compared to traditional II-VI compound perovskites, which are high in cost, complicated to produce, and contain highly toxic substances, all-inorganic perovskite quantum dots have garnered significant attention and research from scholars due to their higher photoelectric conversion efficiency, ability to cover the entire visible light spectrum, and, most importantly, their simpler manufacturing process and relatively lower cost.
This study employs the hot injection method to dope different concentrations of magnesium and prepare perovskite quantum dot samples CsPbI3, CsPbI3(3%), CsPbI3(5%), and CsPbI3(7.5%). A temperature-dependent photoluminescence measurement system is used to analyze and investigate the optical properties of these four perovskite samples. It was found that as the temperature gradually increases, due to the interplay of electron-phonon interactions and thermal expansion, all four perovskite quantum dot samples with different concentrations exhibit a noticeable blue shift in their emission energy. The higher the magnesium doping concentration, the greater the blue shift. Additionally, it was observed that at low temperatures, the influence of impurities and defects is minimal, resulting in relatively narrow full width at half maximum (FWHM). However, as the temperature continues to heat up to 300K, the excitons are affected by electron-phonon scattering effects, leading to an increase in FWHM with rising temperature.

指導教授推薦書 i
口試委員會審定書 ii
致謝 iii
摘要 iv
Abstract v
目 錄 vi
圖目錄 ix
表目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 鈣鈦礦介紹 1
第二章 理論與實驗 4
2.1金屬離子摻雜CsPbI3量子點 4
2.2 量子侷限效應 4
2.3 量子點合成方式 5
2.4實驗設備 5
2.3.1 電子天平 (Electronic Balance) 5
2.4.2 電磁加熱攪拌器 (Magnetic Stirrer) 6
2.4.3 定溫控制器 (Temperature Controller) 7
2.4.4 離心機 (Centrifuge) 8
2.4.5 超音波震盪清洗器 (Ultrasonic Cleaner) 9
2.4.6 電漿機 (Plasma Cleaner) 10
2.4.7 旋轉塗佈機 (Spin Coaters) 11
2.4.8 定量分注器 (Pipette) 12
2.4.9 手套箱 (Glove Box) 13
2.4.10 UV紫外線固化系統 (UV Curing) 14
2.4.11 光激發光系統 (Photoluminescence，PL) 15
2.5 實驗材料 24
2.6 實驗步驟 25
2.6.1 合成鈣鈦礦量子點CsPbI3:Mg 25
2.6.2 ITO玻璃基板裁切與清潔 26
2.6.3 製備鈣鈦礦量子點薄膜 27
2.6.4 CsPbI3:Mg鈣鈦礦量子點封裝 27
2.6.5 變溫光激發光系統量測 27
第三章 實驗結果與討論 29
3.1 鎂摻雜之無機鈣鈦礦量子點低溫光激發光PL分析 29
3.2 鎂摻雜之無機鈣鈦礦量子點變溫光激發光譜分析 32
3.3 鎂摻雜之無機鈣鈦礦量子點變溫光激發光特性分析 35
3.3.1 變溫光激發光能量變化曲線圖 36
3.3.2 變溫光激發光強度變化曲線圖 39
3.3.3 變溫光激發光之半高寬變化曲線圖 42
3.3.4 CsPbI3 摻雜不同濃度鎂之PL積分 47
第四章 結論 49
參考資料 51

圖目錄

圖 1 鈣鈦礦八面體結構[6] 2
圖 2 鈣鈦礦容忍因子對晶體型態結構圖 3
圖 3 電子天平 6
圖 4 電磁加熱攪拌器 7
圖 5 定溫控制器 8
圖 6 離心機外部 9
圖 7 離心機內部 9
圖 8 超音波震盪清洗器 10
圖 9 電漿機 11
圖 10 旋轉塗佈機 12
圖 11 定量分注器 13
圖 12 手套箱 14
圖 13 UV 紫外線固化系統 15
圖 14 光激發光系統結構圖 16
圖 15 He-Cd 雷射 17
圖 16 衰減片 17
圖 17 光學透鏡 18
圖 18 高通濾光片 19
圖 19 近紅外光譜檢測儀 20
圖 20 光譜儀接收端 20
圖 21 冷卻腔體 21
圖 22 真空幫浦 22
圖 23 冷卻水循環系統 23
圖 24 低溫幫浦壓縮機 23
圖 25 溫度控制器 24
圖 26 實驗流程圖 25
圖 27 鈣鈦礦量子點溶液 26
圖 28 無機鈣鈦礦CsPbI3 20K 光激發光譜 29
圖 29 無機鈣鈦礦CsPbI3:Mg(3%) 20K 光激發光譜 30
圖 30 無機鈣鈦礦CsPbI3:Mg(5%) 20K 光激發光譜 31
圖 31 無機鈣鈦礦CsPbI3:Mg(7.5%) 20K 光激發光譜 31
圖 32 無機鈣鈦礦CsPbI3:Mg 20K Normalized PL 光譜 32
圖 33 無機鈣鈦礦CsPbI3 變溫光激發光光譜 33
圖 34 無機鈣鈦礦CsPbI3:Mg(3%)變溫光激發光光譜 33
圖 35 無機鈣鈦礦CsPbI3:Mg(5%)變溫光激發光光譜 34
圖 36 無機鈣鈦礦CsPbI3:Mg(7.5%)變溫光激發光光譜 35
圖 37 高斯分布曲線示意圖 36
圖 38 無機鈣鈦礦CsPbI3 發光能量變化曲線圖 37
圖 39 無機鈣鈦礦CsPbI3:Mg(3%)發光能量變化曲線圖 37
圖 40 無機鈣鈦礦CsPbI3:Mg(5%)發光能量變化曲線圖 38
圖 41 無機鈣鈦礦CsPbI3:Mg(7.5%)發光能量變化曲線圖 38
圖 42 CsPbI3:Mg 變溫光激發光之發光能量變化比較圖 39
圖 43 無機鈣鈦礦CsPbI3 發光強度變化曲線圖 40
圖 44 無機鈣鈦礦CsPbI3:Mg(3%)發光強度變化曲線圖 40
圖 45 無機鈣鈦礦CsPbI3:Mg(5%)發光強度變化曲線圖 41
圖 46 無機鈣鈦礦CsPbI3:Mg(7.5%)發光強度變化曲線圖 41
圖 47 CsPbI3:Mg 變溫光激發光之發光強度變化比較圖 42
圖 48 半高寬示意圖 43
圖 49 無機鈣鈦礦CsPbI3 半高寬變化曲線圖 44
圖 50 無機鈣鈦礦CsPbI3:Mg(3%)半高寬變化曲線圖 44
圖 51 無機鈣鈦礦CsPbI3:Mg(5%)半高寬變化曲線圖 45
圖 52 無機鈣鈦礦CsPbI3:Mg(7.5%)半高寬變化曲線圖 45
圖 53 CsPbI3:Mg 變溫光激發光之半高寬變化比較圖 46
圖 54 熱膨脹與電子-聲子相互作用關係圖 47
圖 55 CsPbI3:Mg 變溫光激發光之 PL 積分圖 48

表目錄
表 1 實驗材料 24

[1]Lin Zhong-guan, Lai Min-liang, and Li Jun-ting, “新世代鈣鈦礦材料：合成、光電特性及應用” Physics Bimonthly. 2018.
[2]Kai-Hung Wang, “Structural and Photo-physical properties of CH3NH3PbBr3 Perovskite single crystals,” Department of Applied Chemistry National Chiao Tung University, 2016.
[3]陳秋洪，”金屬離子修飾的CsPbI3奈米晶及其發光性質研究，”廣西大學，2022年。
[4]Q. V. Le, H. W. Jang, and S. Y. Kim, ＂Recent advances toward high-efficiency halide perovskite light-emitting diodes: review and perspective＂, Small Methods, 1700419, 2018.
[5]Z. K. Tan, R. S. Moghaddam, M. L. Lai, P. Docampo, R. Higler, F. Deschler, M. Price, A. Sadhanala, L. M. Pazos, D. Credgington, F. Hanusch, T. Bein, H. J. Snaith, and R. H. Friend,＂Bright light-emitting diodes based on organometal halide perovskite＂, Nature Nanotechnology, 9, 687-692, 2014.
[6]Chen, Chia-Chun,” Improving Stability of Two-Dimensional Tin Halide Perovskite Crystals through Mixed Cation Method “ Department of Chemistry, National Taiwan normal University, 2020.
[7]P. Balaz, ＂Mechanochemistry in nanoscience and minerals engineering＂, Springer-Verlag Berlin Heidelberg, 2008
[8]R.J. Sutton, G.E. Eperon, L. Miranda, E.S. Parrott, B.A. Kamino, J.B. Patel, M.T. Horantner, M.B. Johnston, A.A. Haghighirad, D.T. Moore, H.J. Snaith, “Bandgap-tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells,” Advanced Energy Materials, 8, 1502458, 2016.
[9]Yah, Yu-Chun, “Preparation and Application of CsPbI3 Perovskite Quantum Structure” Taipei Tech, 2019.
[10]Si Jia Miao, Yul Jae Cho, “Toward Green Optoelectronics: Environmental-Friendly Colloidal Quantum Dots Photodetectors,” Frontiers in Energy Research, 9, 666534,2021.
[11]Chang-Han Tsai, “Investigating the relation between non-radiative decay process and surface trap states in the CdSe quantum dots” Department of Materials and Optoelectronic Science National Sun Yat-sen University, 2011.
[12]Yuan Zhi-Chang, “Synthesis and ion-exchange characteristics of lead halide perovskite nanocrystals,” Department of Materials Science National University of Tainan, 2017
[13]Jin-Hang Li, Jiawei Chen, Lei-Meng Xu, Sinan Liu, Si Lan, Xian-Sheng Li, Jizhong Song “A zinc non-halide dopant strategy enables efficient perovskite CsPbl3 quantum dot-based light-emitting diodes” Mater Chem Front, 4, 1444, 2020.
[14]Dengji Li, Pengshan Xie, Yuxuan Zhang, You Meng, Yancong Chen, Yini Zheng,Wejjun Wang, Di Yin, Bowen Li, Zenghui Wu, Changyong Lan, SenPo Yip, Dangyuan Lei,Fu-Rong Chen, and Johnny C. Ho, “Phase Engineering for Stability of CsPbls Nanowire Optoelectronics” Advanced Functional Materials, 10, 2314309, 2024.
[15]Fu Yang, Muhammad Akmal Kamarudin, Gaurav Kapil, Daisuke Hirotani, Putao Zhang, Chi Huey Ng, Tingli Ma, Shuzi Hayase, “Magnesium-doped MAPbI3 Perovskite Layer for Enhanced Photovoltaic Performance in Humid Air Atmosphere” Kyushu Institute of Technology, 204, 8080196, 2018.
[16]Chen, Yen-Ting, “Analysis of All Inorganic Csi-xRbxPbBr3 Perovskite Thin Films and Study of Perovskite Light Emitting Diodes Using PEO Buffer Layer” Taipei Tech, 2022.
[17]Hsu Kai-Hsiang, “Fabrication of Large-Area Perovskite Scintillator for Indirect X-ray Detector via Ultrasonic Spray Coating of Inorganic Perovskite Nanocrystal Colloid” Department of Applied Materials and Optoelectronic Engineering of National Chi-Nan University, 2013.
[18]Wang Pan, Wu Zhihai, Wu Manyu, Wei Jiao Sun, Yanni Zhao,Zhen fu, “All-Solution-Processed, Highly Efficient and Stable Green Light-Emitting Devices Based on Zn-Doped CsPbBr3/ZnS Heterojunction Quantum Dots, ” Journal of Materials Science, 56, 4161-4171, 2021.
[19]Bing Ai, Chao Liu, Zhao Deng, Jing Wang, Jian Jun Han, Xiujian Zhao “Low temperature photoluminescence properties of CsPbBr3 quantum dots embedded in glasses,” Physical Chemistry Chemical Physics, 26, 17349-17355, 2017.
[20]Dutta, P. et al. “High mobility single-crystalline-like GaAs thin films on inexpensive flexible metal substrates by metal-organic chemical vapor deposition.” Applied Physics Letters, 105, 092104, 2014.
[21]Tilchin, J. et al. “Hydrogen-like Wannier-Mott Excitons in Single Crystal of Methylammonium Lead Bromide Perovskite.” ACS Nano 10, 6363-6371, 2016.
[22]Mante, P.-A., Stoumpos, C. C., Kanatzidis, M. G. & Yartsev, A. “Electron-acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons.” Nature Communications, 8, 14398, 2017.
[23]G. Rainò, G. Nedelcu, L. Protesescu, M. I. Bodnarchuk, M. V. Kovalenko, R. F. Mahrt, and T. Stöferle, ＂Single cesium lead halide perovskite nanocrystals at low temperature: fast single-photon emission, reduced blinking, and exciton sine structure＂, ACS Nano, 10, 2485-2490, 2016.
[24]S. Ananthakumar, J. R. Kumar, and S. M. Babu, ＂Cesium lead halide (CsPbX3, X = Cl , Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status＂, Journal of Photonics for Energy, 6, 042001, 2016