臺灣博碩士論文加值系統

目前鈣鈦礦太陽能電池(perovskite-based solar cell)最高光電轉化效率已經超過20%，在實驗上，受惠於生產成本低以及製程簡單，讓這類型電池的商業化前景看漲。除了能源工程外，經由材料工程來降低缺陷密度並優化晶粒尺寸，這些可發出不同顏色的鈣鈦礦薄膜材料也具有應用於光電元件的潛力。
本實驗所使用的鈣鈦礦光電元件為p-i-n結構(ITO / PEDOT:PSS / Perovskite / PC61BM / Ag )，透過優化鈣鈦礦薄膜的結晶性質、降低材料缺陷密度與改善電子注入層與鈣鈦礦薄膜間的介面特性，進而提升鈣鈦礦發光二極體(perovskite-based LED)的電激發螢光效率(current efficiency)；另一方面，我們將利用電子顯微鏡、X光繞射儀與光激發電子放射譜等等研究不同溶液製備之電子傳輸層PC61BM其光學、電性、結構與激發態的特性。
當電子傳輸層PC61BM前驅物溶液中含有10%雙氯苯時，具有最佳薄膜、光電特性及最好的結晶品質，有最大的電流密度為5.16 mA/cm2。擁有最小的理想因子與串聯電阻分別為10.5670Ω與41.611Ω、具有最大的發光亮度為9.3x10-4cd/m2。

Nowadays, the photovoltaic efficiency of perovskite-based solar cells has been boost up to the value of more than 20%; experimentally, owing to low manufacturing cost and simple process, the feasibility of mass production of such cells becomes anticipated. In addition to being used in renewable energy fields, they can also be used for optoelectronic devices as material engineering is conducted to optimize the grain size of perovskite-based thin films with reduced defect density.
The structure of perovskite device in research is ITO / PEDOT:PSS / Perovskite / PC61BM / Ag. We shall devote to improve the luminous efficiency of perovskite-based LEDs through optimizing the structural properties of perovskite thin films with reduced defect density. In addition, the interfacial behavior between the electron injection layer and the perovskite thin film can be reinforced through solvent annealing processes. In the experiment, several facilities such as scanning electron microscope, X-ray diffractometer, and electroluminescence spectrum will be used to investigate the optical, electrical, structural and excitonic properties of perovskite-based thin films synthesized with different electron transport layer PC61BM precursor solution processes.
When the electron transport layer PC61BM precursor solution contains 10% dichlorobenzene, showing the best film, photoelectric properties and the best crystal quality; the maximum current density of 5.16 mA / cm2, with the smallest ideal factor and series resistance were 10.5670Ω and 41.611Ω, and the maximum luminous brightness of 9.3x10-4cd / m2.

指導教授推薦書
口試委員審定書
致謝 iii
摘要 iv
Abstract v
目錄 vii
圖目錄 xii
表目錄 xv
第一章 導論 1
1.1 前言 1
1.2 研究背景 3
1.3 研究動機 6
第二章 研究文獻及實驗原理 8
2.1 鈣鈦礦光電元件之發展簡介 8
2.2 鈣鈦礦光電元件製程方法 14
2.2.1 一階前驅物溶液沉積法(One-Step Precursor Deposition) 14
2.2.2 二階前驅物溶液沉積法(Two-Step Precursor Deposition) 17
2.2.3 雙蒸鍍沉積法(Dual-Source Vapor) 18
2.2.4 真空輔助溶液製程法(Vapor-assisted Solution Process) 19
2.3 鈣鈦礦光電元件的工作原理 20
2.3.1 透明導電層(Transparent Conductive Layer) 21
2.3.2 電洞傳輸層(Hole Transporting Layer, HTL) 21
2.3.3 電子傳輸層(Electron Transporting Layer, ETL) 22
2.3.4 鈣鈦礦層(Perovskite Layer) 25
2.3.5 金屬電極(Metal Electrode) 26
2.4 鈣鈦礦光電元件結構之分類及其發展 26
2.4.1 正式 (n-i-p)介孔結構鈣鈦礦光電元件 27
2.4.2 正式(n-i-p) 平面結構鈣鈦礦光電元件 29
2.4.3 反式(p-i-n) 平面結構鈣鈦礦光電元件 29
2.4.4 液態電解質染敏結構(Liquid Electrolyte Dye sensitive Structure) 32
2.4.5 HTL-Free Structure 32
2.4.6 ETL-Free Structure 33
2.5 鈣鈦礦光電元件輸出特性 33
2.5.1 開路電壓(Open Circuit Voltage, VOC) 34
2.5.2 短路電流(Short circuit current, ISC) 36
2.5.3 填充因子(Fill factor, FF) 36
2.5.4 光電轉換效率(Power conversion efficiency,PCE,η)。 37
2.5.5 光度學 38
2.5.6 光通量 39
2.5.7 發光強度 40
2.5.8 亮度 40
第三章 實驗步驟及方法 41
3.1 鈣鈦礦光電元件結構 41
3.2 實驗藥品 43
3.3 實驗步驟 47
3.3.1 導電玻璃基板清洗 47
3.3.2 前驅物溶液配置 49
3.3.3 光電元件製備製程 50
3.4 製程實驗儀器介紹 52
3.5 量測儀器介紹 54
第四章 結果分析 57
4.1 鈣鈦礦主動層薄膜分析 57
4.1.1 重量莫爾濃度 57
4.1.2 非極性反溶劑滴量 59
4.1.3 非極性反溶劑之沸點 61
4.1.4 總結 64
4.2 鈣鈦礦光電元件薄膜分析 64
4.3 鈣鈦礦電子傳輸層薄膜分析 65
4.3.1 Photoluminescence Spectra 65
4.3.2 IV Curve 67
4.3.3 X-射線繞射分析(X-ray diffraction，XRD) 69
4.3.4 接觸角(Contact angle)量測分析 73
4.3.5 Dark IV特性曲線 75
4.3.6 Electroluminescence (EL) Spectrum 80
4.3.7 Voltage (V)-Luminance (L) Curve 82
第五章 總結 85
參考文獻 86


圖目錄
圖1-1 多層膜發光二極體的能階圖與載子注入示意圖……….………3
圖2-1 被有機材料包覆的量子點（quantum dot, QD）之能階與載子侷限的示圖………………………………………………………………...12
圖2-2 一階前驅物溶液沉積法製程示意圖………………….………..16
圖2-3 滴極性溶劑的沖洗過程長晶示意圖…………………….……..16
圖2-4 電子顯微鏡影像。(a)無甲苯沖洗之鈣鈦礦薄膜；(b)有甲苯沖洗之鈣鈦礦薄膜…………………………………………………………...17
圖2-5 鈣鈦礦薄膜的原子力顯微鏡影像………………………….…..17
圖2-6 二階前驅物溶液沉積法製程示意圖……………………….…..18
圖2-7 雙蒸鍍沉積法製程示意圖……………………………….……..19
圖2-8 真空輔助溶液製程示意圖………………………………...........20
圖2-9 鈣鈦礦光電元件結構示意圖……………………………...........20
圖2-10 有機電洞傳輸材料結構示意圖………………………….……22
圖2-11 鈣鈦礦材料、電子傳輸層以及電洞傳輸之HOMO / LOMO圖………………………………………………………………………...24
圖2-12 鈣鈦礦光電元件中電子電洞傳輸路徑示意圖………….……24
圖2-13 鈣鈦礦結構式示意圖…………………………………….……25
圖2-14 各種鈣鈦礦光電元件結構…………………………….………27
圖2-15 太陽能電池元件材料能階圖……………………………….…35
圖2-16 太陽能電池元件電流對電壓示意圖…………………….……38
圖2-17 人視覺系統對波長之相對光亮敏感度………………….……39
圖3-1 鈣鈦礦光電元件結構示意圖……………………………….......42
圖3-2 導電玻璃基板清洗流程…………………………………….…..49
圖3-3 前驅物溶液配置示意圖…………………………………….…..50
圖3-4 鈣鈦礦光電元件製備製程………………………………….…..52
圖3-5 蒸鍍機系統………………………………………………….…..54
圖4-1 使用AFM量測(a) 濃度為1.25M，(b) 濃度為1.45M，(c)濃度為1.65M，CH3NH3PBI3薄膜的表面型態………………………….....59
圖4-2 使用PL量測濃度分別為1.25M、1.45M以及1.65M，CH3NH3PbBr3薄膜的激子淬滅…………………………………….…..59
圖4-3 使用PL量測滴落甲苯低量分別為250μl、450μl以及650μl之CH3NH3PbBr3薄膜的激子淬滅……………………………….………..61
圖4-4 使用不同非極性反溶劑之CH3NH3PbBr3元件的J-V曲線...….62
圖4-5 使用不同非極性反溶劑之CH3NH3PbBr3元件的PL光譜….....63
圖4-6 PC61BM/CH3NH3PbBr3/PEDOT:PSS/ITO/glass之掃描電子顯微鏡剖面圖………………………………………………………………...65
圖4-7 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的PL光譜………………………………………………66
圖4-8 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的光I-V特性曲線……………………………………...68
圖4-9 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的XRD分析圖…………………………………………71
圖4-10 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之(101)面CH3NH3PbBr3 XRD………………………………..………..….…….72
圖4-11 PC61BM電子傳輸層前驅物溶液在不同DCB/CB比例下對應的接觸角………………………………………………………………...73
圖4-12 PC61BM電子傳輸層前驅物溶液在不同DCB/CB比例下對應的ln(I)-V特性曲線…………………………………………………….78
圖4-13 PC61BM電子傳輸層前驅物溶液在不同DCB/CB比例下對應的暗I-V特性曲線……………………………………………………...79
圖4-14 PC61BM電子傳輸層前驅物溶液在不同DCB/CB比例下對應的的電致發光光譜……………………………………………………...81
圖4-15鈣鈦礦發光二極體，發光面積為0.1cm2……….………………81
圖4-16 PC61BM電子傳輸層前驅物溶液在不同DCB/CB比例下對應的發光特性曲線………………………………………………………...83

表目錄
表2-1 不同鈣鈦礦材料之擴散速率與擴散長度………….………......26
表4-1 非極性反溶劑各種滴量之填充因子大小…………….………..61
表4-2 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的光電特性………………………………….……..........68
表4-3 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的XRD特性………………………….………………....72
表4-4 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之接觸角………………………………………………………………………...74
表4-5 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的暗I-V特性數據整理…………………….…………...79
表4-6 PC61BM電子傳輸層前驅物溶液使用不同比例DCB/CB之CH3NH3PbBr3的V-L特性數據整理……………………..……………..83

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