臺灣博碩士論文加值系統

本論文主要氧化石墨烯(GO)為基礎，作為電洞傳輸材料，以三明治結構，依序沉積電洞傳輸層、鈣鈦礦吸光層、電子傳輸層於ITO導電玻璃上，最後蒸鍍銀電極，製備正型平板鈣鈦礦太陽能電池，其光轉換效率為13.8%。但由於含氧官能團的引入，破壞了石墨烯的大π共軛結構，氧化石墨烯具有絕緣的特質，使其導電性和其他性能顯著降低，因此我們利用三種不同還原劑，分別為聯胺、硼氫化鈉以及4-肼基苯磺酸，製備還原氧化石墨烯(rGO)，試圖恢復其材料的導電性，成功提升其光電流，光轉換效率分別為16.0%、15.3%以及16.4%。此外，我們用的材料皆是低溫製程，因此還可以製作在可撓式基板，其rGO的效率可高可達13.8%，而GO光轉換效率也將近9%。
另外以PEEDOT:PSS為電洞傳輸與rGO比對，做元件穩定性測試，PEEDOT:PSS在650小時左右，元件已失去效率，而rGO在1000小時候尚有50%以上的效率。rGO材料不僅穩定性提升，在製備上較簡單、成本低，也具有好的載子傳輸特性，但隨著使用不同的還原劑，其還原劑的強弱不同之外，還原劑添加的劑量，皆會影響rGO在導電玻璃ITO上的覆蓋率，故其成膜性將是一個非常重要的議題。

Graphene oxide (GO) and its derivatives as the promising hole-extracting layer (HEL) are used for inverted planar heterojunction (PHJ) perovskite solar cells(PSC). The effect of GO reduction conditions on hole extraction properties is studied. We synthesized reduced graphene oxides (rGO) of three types – rGO-NH, rGO-BH, rGO-HBS – via reduction of GO with reducing agents – hydrazine, sodium borohydride and 4-hydrazino- benzene sulfonic acid – as HEL. The devices fabricated by reduced graphene oxides show the higher photovoltaic performance attaining power conversion efficiency (PCE) 16.0 %, 16.4 % and 15.3 under AM 1.5 G one-sun irradiation , which is superior than GO with PCE 13.8%. Moreover, the flexible solar cell based on rGO shows high PCE of 13.8% and this device is robust against bending and can maintain its efficiency under bending situation. Based on the controlled experiment, it was found that the trap states on GO and rGOs play a significant role. The lower performance of GO is related to its insulating properties of nanosheets. Film formation and coverage of the substrate by graphene nanosheets as the determinant factor was realized.

摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vii
表目錄 xiii
第一章 緒論 1
第二章 文獻回顧 3
2-1鈣鈦礦太陽能電池 (Perovskite Solar Cell) 3
2-1-1 以敏化染料電池為基礎的新技術 5
2-1-2鈣鈦礦材料的導入與發展 7
2-1-3 鈣鈦礦太陽能電池元件結構及工作原理 23
2-2 鈣鈦礦成膜方法 30
2-2-1 一步旋塗法 (OSPD) 31
2-2-2 兩步沉積法 (SDM) 32
2-2-3 蒸氣沉積法 (DSVD) 33
2-2-4 蒸氣輔助溶液製程 (VASD) 34
2-2-5 快速沉積結晶法 (FDC/anti solvent) 34
2-2-6 加合物法 (Adduct method) 36
2-3 電洞傳輸材料的介紹 38
2-3-1 PEDOT:PSS 39
2-3-2 PTAA 41
2-3-3 NiOx 41
2-3-4 MoOx 45
2-3-5 VOx 46
2-4石墨烯的發展 48
2-4-1 前言 48
2-4-2 製備氧化石墨烯及其應用 50
2-4-3 還原氧化石墨烯及其應用 54
2-5 研究動機 57
第三章 實驗步驟與量測方法 58
3-1實驗藥品及儀器 58
3-2 實驗步驟 62
3-2-1 導電玻璃ITO的蝕刻與清洗 62
3-2-2 製備氧化石墨烯(GO) by Hummers Method 62
3-2-3 沉積電洞傳輸層 63
3-2-4 沉積鈣鈦礦薄膜 65
3-2-5 沉積電子傳輸層PCBM 66
3-2-6 沉積電洞阻擋層 Bathocuproine, BCP 66
3-2-7 沉積銀電極 Ag 67
3-3元件量測 68
3-3-1 鈣鈦礦太陽能電池之光電轉換效率量測 68
3-3-2鈣鈦礦太陽能電池之外部量子效率量測 72
第四章 以氧化石墨烯及還原氧化石墨烯衍生物為電極之反式平面鈣鈦礦太陽能電池 73
4-1 氧化石墨烯(GO)的初步測試 73
4-2 製備還原氧化石墨烯(rGO)與其成膜性探討 74
4-3 探討添加不同還原劑量的影響 78
4-4 探討不同溫度下對還原氧化石墨烯的影響 79
4-5 探討其元件光轉換效率 81
4-6 遲滯效應與元件穩定性性測試 86
4-7 螢光光譜及其放光生命週期 89
4-8 VOC ＆ JSC decay 92
4-9 可撓性基板與彎曲測試 94
4-10 將鈣鈦礦製程由手套箱移至手套箱外 97
4-11 結論 100
第五章 探討不同尺寸的氧化石墨烯對反式平面鈣鈦礦太陽能電池之影響 101
5-1 製備不同尺寸的氧化石墨烯 101
5-2 探討不同尺寸的氧化石墨烯 103
5-3 沉積電洞阻擋層 Bathocuproine, BCP 105
5-4 不同尺寸氧化石墨烯之元件光轉換效率 108
5-4-1 手套箱製程 108
5-4-2 小房間製程 (手套箱外) 110
5-5 不同尺寸氧化石墨烯之元件的比較 112
5-6 結論 116
第六章 總結 117
參考文獻 118

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