二氧化鈦奈米粒徑尺寸對介觀結構鈣鈦礦太陽能電池光伏特性之影響

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林威志(Wei-Jhih Lin) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

二氧化鈦奈米粒徑尺寸對介觀結構鈣鈦礦太陽能電池光伏特性之影響
(Influence of the Titanium Dioxide Nano-particles Size on the Performance of Mesoscopic Perovskite Solar Cell)

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摘要(中)

近年鈣鈦礦太陽能電池蓬勃發展，憑藉其低製作成本、高效率等顯著優點，迅速成為太陽能電池領域的研究重點。其中又以正結構鈣鈦礦太陽能電池具備較傑出的光電轉換效率，但元件量測上普遍存在J-V遲滯現象，造成太陽能電池在量測時因正逆掃曲線不吻合，嚴重降低電池效率量測的不準確性。
本論文利用水熱法合成高純度銳鈦礦(anatase)二氧化鈦奈米顆粒，並透過調控高壓釜之反應操作條件，合成出不同的粒徑之二氧化鈦奈米粒子，以此探討二氧化鈦介孔層對正結構鈣鈦礦太陽電池的影響，並搭配二流體化噴塗高溫裂解方式製備二氧化鈦緻密層與透過鋰鹽(LiTFSI)摻雜優化二氧化鈦介孔層，提高電子傳遞效率，有效降低正結構鈣鈦礦太陽能電池於量測中的遲滯現象。本研究最佳條件是以粒徑22 nm的二氧化鈦粒子所製備之光電元件，其光電轉換效率達逆掃值18.46%、正掃值16.37%，且遲滯因子僅0.092。
另外再以正結構全網印介觀鈣鈦礦太陽能電池系統搭配不同粒徑二氧化鈦作驗證，其結果與標準正結構趨勢相符，證明電子傳輸層中二氧化鈦粒徑是影響正結構鈣鈦礦太陽能電池光電轉換特性之關鍵。透過提高二氧化鈦介孔層比表面積能有效提高鈣鈦礦層與二氧化鈦介孔層的接觸面積，使光生電子傳遞更快速。此系統以粒徑22 nm二氧化鈦奈米粒子所製備的元件有最佳效率表現，其電池優化後效率達10.86%，並於室溫環境下經過450小時仍穩定維持在10.16%，仍保有原始效率96%。

摘要(英)

In recent years, organic–inorganic perovskite based solar cells have got sub-stantial attention due to their low fabrication cost and excellent photovoltaic properties. Although the power conversion efficiency of the perovskite solar cells have achieved over than 20%, anomalous hysteresis in current–voltage curves remain as major challenge, which cause inaccuracy of the PCE measurements.
In this work, we use hydrothermal method to synthesize high purity anatase titanium dioxide nanoparticles by controlling the reaction conditions of the auto-clave. We investigate the particle size effect of titanium dioxide mesoporous layer on conventional mesoscopic perovskite solar cells, and with spray pyroly-sis deposition method to prepare titanium dioxide dense layer and through the lithium (LiTFSI) doping to optimize titanium dioxide mesoporous layer, im-prove the efficiency of electronic transmission and reduce the hysteresis of the conventional mesoscopic perovskite solar cells in the measurement effectively. The best performance of the cells is 22 nm particle size, its power conversion ef-ficiency of reverse scan is up to 18.46%, forward scan is 16.37%, and the hyste-resis index is decrease to 0.092.
In addition, we verify the particle size effect of titanium dioxide mesoporous by the system of fully printable mesoscopic perovskite solar cells, the results are match to the conventional structural tendency. It is proved that the particle size of titanium dioxide in the electron transport layer is the key to the photoelectric conversion characteristics of the conventional structure perovskite solar cells. In-creasing the specific surface area of titanium dioxide mesoporous layer improves the contact area between the perovskite layer and the titanium dioxide mesopo-rous layer effectively. The rate of the electron injection from perovskite into tita-nium dioxide becomes faster, resulting in higher injection quantum efficiency after the electron-hole separation. This system has the best performance of the components prepared with 22 nm particle size of titanium dioxide, the efficiency of cells up to 10.86% after optimization. It is stable for 450 hours in ambient air and still retain 96% of original efficiency.

關鍵字(中)

★ 鈣鈦礦太陽能電池
★ 二氧化鈦奈米顆粒
★ 全網印鈣鈦礦太陽能電池

關鍵字(英)

論文目次

第一章緒論 1
1.1 前言 1
1.2 太陽能電池發展歷史與種類簡介 3
1.2.1 無機太陽能電池 5
1.2.2 有機太陽能電池 6
1.2.2.1 小分子有機太陽能電池（Molecular solar cells） 6
1.2.2.2 高分子有機太陽能電池（Polymer solar cells） 7
1.2.2.3 染料敏化太陽能電池 (Dye-sensitized solar cells) 8
1.3 文獻回顧 10
1.3.1 鈣鈦礦結構源起 10
1.3.2 鈣鈦礦太陽能電池發展史 12
1.3.3 介觀結構鈣鈦礦太陽能電池元件結構演進 15
1.3.3.1 正結構介觀鈣鈦礦太陽能電池 (Conventional mesoscopic perovskite solar cells) 15
1.3.3.2 反結構介觀鈣鈦礦太陽能電池 (Inverted-type mesoscopic perovskite solar cells) 18
1.3.3.3 無電洞傳輸材料介觀結構鈣鈦礦太陽能電池(HTM-free MPSCs) 19
1.4 電流-電壓遲滯現象(J-V HYSTERESIS) 24
1.4.1 缺陷位捕獲與釋出載子(Trapping/Detrapping) 25
1.4.2離子遷移(Ion migration) 27
1.4.3 鐵電現象(Ferroelectricity) 30
1.4.4 元件結構與材料(Device architecture and materials) 31
1.5電子傳導層對正結構鈣鈦礦電池的影響 33
1.5.1緻密層-電子傳導層(Compact electron transport layer ) 34
1.5.2介孔層-電子傳導層(Mesoporous electron transport layer) 36
1.5.3 元素摻雜-電子傳導層(Elemental doping electron transport layer) 40
1.6 研究動機 41
第二章實驗方法 43
2.1實驗藥品及儀器 43
2.2 材料合成 46
2.2.1甲基胺碘(CH3NH3I)合成 46
2.2.2二氧化鈦漿料(TiO2 paste)合成 47
2.3 正結構介觀鈣鈦礦太陽能電池製備 49
2.3.1鈣鈦礦前驅液配置 50
2.3.2配置二氧化鈦緻密層溶液方法 50
2.3.3配置二氧化鈦介孔層溶液方法 50
2.3.4配置電洞傳輸層(Spiro-OMeTAD)溶液方法 51
2.3.5正結構介觀鈣鈦礦太陽能電池元件製作 51
2.3.6全網印介觀鈣鈦礦太陽能電池製作 56
2.4儀器分析原理 59
2.4.1掃描式電子顯微鏡 (Scanning Electron Microscope , Hittachi S-800) 59
2.4.2太陽光模擬器 (Solar Simulator , YSS-50A) 60
2.4.3太陽能電池外部量測效率量測系統 (Incident Photon to Current Conversion Efficiency, IPCE) 61
2.4.4 X光繞射儀 (X-Ray Diffractometer , BRUKER ) 62
2.4.5 紫外光/可見光光譜儀 (UV/VIS/NIR Spectrophotometer , Hitachi U-4100) 63
2.4.6光激發螢光光譜儀、時間解析之螢光光譜儀 (Photoluminescence, PL, UniRAM)、( Time-resolved photoluminescence spectrometer) 64
第三章結果與討論 66
3.1正結構介觀鈣鈦礦太陽能電池 66
3.1.1 二氧化鈦緻密層對鈣鈦礦電池之影響 66
3.1.2 二氧化鈦介孔層其厚度對鈣鈦礦元件之影響 71
3.1.3鋰離子摻雜濃度對鈣鈦礦元件之影響 76
3.1.4不同粒徑二氧化鈦奈米顆粒對正結構介觀鈣鈦礦元件之影響 79
3.2全網印介觀鈣鈦礦太陽能電池 91
3.2.1全網印系統鈣鈦礦太陽能電池二氧化鋯介孔層最適化 92
3.2.2不同鈣鈦礦前驅液溶劑對元件之影響 95
3.2.3不同鈣鈦礦前驅液濃度對元件之影響 97
3.2.4五胺戊酸混合陽離子鈣鈦礦材料 99
3.2.5不同濃度之混合陽離子鈣鈦礦前驅液對元件之影響 101
3.2.6二氧化鈦緻密層後處理對元件之影響 102
3.2.7二氧化鈦奈米顆粒粒徑對全網印介觀鈣鈦礦元件之影響 104
3.2.8全網印介觀鈣鈦礦元件之穩定性測試 106
第四章結論 107
第五章參考文獻 109

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指導教授

張博凱、李坤穆

審核日期

2017-7-18

推文