臺灣博碩士論文加值系統

過去10年來，金屬鹵化物鈣鈦礦太陽能電池的效率迅速提升，成為太陽能電池技術領域中最受關注的技術。在鈣鈦礦太陽能電池的製造過程中，旋轉塗佈法因操作簡便和成膜均勻的特點，在小面積元件上取得了高效率的成果。但這種技術在電池面積擴大時，效率會顯著降低。

刮刀塗佈法被認為是製作大面積且均勻鈣鈦礦薄膜的有潛力的塗佈技術，然而，其目前所面臨的最大問題為利用刮刀塗佈法所製作的鈣鈦礦薄膜表面具有較多缺陷，並且目前文獻中刮刀塗佈鈣鈦礦太陽電池主要為穩定性較差的單元鈣鈦礦材料。為解決目前刮刀塗佈缺陷及穩定性不佳的問題，我們開發了刮刀塗佈法製作三元鈣鈦礦太陽電池技術，並利用鈍化層結構來修飾鈣鈦礦薄膜表面的缺陷，以提高刮刀塗佈鈣鈦礦太陽電池的效率和穩定性。

在本論文中，我們使用三元鈣鈦礦材料並結合不同濃度的冠醚（Dibenzo-24-Crown-8）作為鈣鈦礦/電洞傳輸層之間的鈍化層。實驗結果顯示，冠醚能改善刮刀塗佈鈣鈦礦薄膜表面的平整性，有效填補鈣鈦礦薄膜的缺陷，抑制薄膜中載子的非輻射複合，使得所製作的鈣鈦礦元件漏電流大幅下降，進而提高光電轉換效率。經過冠醚鈍化層結構處理（20 mM）後，開路電壓從0.98 V提升至1.03 V，短路電流密度從21.64 mA/cm²提升至22.61 mA/cm²，填充因子從64%提升至70%。光電轉換效率從傳統結構的13.83%提升至16.55%。此外，由於冠醚具有疏水性，可以有效地防止水氣進入鈣鈦礦薄膜所造成的降解問題，從而大幅延長刮刀塗佈鈣鈦礦太陽能電池元件在高濕度環境(RH 50%-60%)下的穩定性。

總之，在本研究中，我們成功地應用鈍化保護層結構來降低刮刀塗佈鈣鈦礦薄膜表面缺陷並提高其穩定性，進一步提高太陽電池元件的轉換效率和穩定性。這項研究解決了目前刮刀塗佈鈣鈦礦太陽能電池表面缺陷過多及穩定性不佳的問題，並提供了一個新結構和可行性方法，為鈣鈦礦太陽能電池未來大面積製作開創了新的可能性。

Over the past 10 years, the efficiency of metal halide perovskite solar cells has rapidly increased, making it the most attention-grabbing technology in the field of solar cell technology. In the manufacturing process of perovskite solar cells, spin-coating has been favored for its simplicity and uniform film formation, achieving high efficiency in small-area devices. However, this technique's efficiency significantly decreases when applied to larger areas.

Doctor blade coating is considered a promising technique for fabricating large-area and uniform perovskite thin films. However, the biggest issue it currently faces is the presence of numerous defects on the surface of the perovskite thin films produced using this method. Moreover, the existing literature on doctor blade-coated perovskite solar cells primarily focuses on less stable single-unit perovskite materials. To address these issues, we have developed a technique for fabricating ternary perovskite solar cells using doctor blade coating and employed a passivation layer structure to modify the defects on the surface of the perovskite thin films, enhancing the efficiency and stability of the cells.

In this study, we used ternary perovskite materials and combined different concentrations of dibenzo-24-crown-8 ether as the passivation layer between the perovskite and hole transport layers. The experimental results showed that the crown ether improved the surface smoothness of the doctor blade-coated perovskite thin films, effectively filling the defects, suppressing non-radiative recombination of carriers in the film, significantly reducing the leakage current of the fabricated perovskite devices, and consequently increasing the photoelectric conversion efficiency. After treatment with the 20 mM crown ether passivation layer structure, the open-circuit voltage increased from 0.98 V to 1.03 V, the short-circuit current density from 21.64 mA/cm² to 22.61 mA/cm², and the fill factor from 64% to 70%. The photoelectric conversion efficiency increased from the traditional structure's 13.83% to 16.55%. Additionally, the hydrophobic nature of the crown ether effectively prevents water vapor ingress, mitigating the degradation of the perovskite thin films and significantly extending the stability of doctor blade-coated perovskite solar cell devices under high humidity conditions (RH 50%-60%).

In conclusion, this study successfully applied a passivation layer structure to reduce the surface defects and enhance the stability of doctor blade-coated perovskite thin films, further improving the conversion efficiency and stability of solar cell devices. This research addresses the issues of excessive surface defects and poor stability in current doctor blade-coated perovskite solar cells and provides a new structure and feasible approach for large-area fabrication of perovskite solar cells in the future.

中文摘要 I
Abstract III
誌謝 V
目錄 VI
圖目錄 IX
表目錄 XI
符號說明 XII
第一章 緒論 1
1-1前言 1
1-2太陽能電池發展種類 4
1-3研究動機 6
第二章 基礎理論與文獻回顧 8
2-1 太陽能電池之工作原理(光伏效應) 8
2-1-1 太陽能電池之等效電路模型 8
2-2 太陽能電池之量測特性參數 9
2-2-1 短路電流密度(Jsc) 9
2-2-2 開路電壓(Open-Circuit Voltage , Voc) 9
2-2-3 填充因子(Fill Factor, F.F) 10
2-2-4 能量轉換效率(PCE) 10
2-3鈣鈦礦太陽能電池元件之材料與結構 11
2-3-1 陰極-氧化錫摻氟透明導電層(Fluorine-doped tin oxide,FTO) 11
2-3-2 電子傳輸層-二氧化錫(SnO2) 11
2-3-3 三元有機-無機鈣鈦礦光吸收層 12
2-3-4 電洞傳輸層-Spiro-OmeTAD 12
2-3-5 陽極-金屬電極 12
2-4文獻回顧與實驗設計 13
2-4-1 文獻回顧 13
2-4-2 實驗設計 15
第三章 實驗製程與分析設備 29
3-1 製程材料 29
3-2 鈣鈦礦太陽能電池元件之製程 30
3-2-1 鈣鈦礦前驅溶液的配置 30
3-2-2 蝕刻與清洗基板 30
3-2-3 緻密層(TiO2) 30
3-2-4 電子傳輸層(SnO2) 30
3-2-5 主動層(鈣鈦礦) 31
3-2-6 鈍化層(Dibenzo-24-Crown-8 (DB24C8)) 31
3-2-7 電洞傳輸層(Spiro-OMeTAD)&電極(Au) 31
3-3 實驗分析設備 32
3-3-1掃描式電子顯微鏡(Scanning Electron Microscope,SEM) 32
3-3-2導電原子力顯微鏡(Conductive Atomic Force Microscope,C-AFM) 33
3-3-3光致發光(Photoluminescence,PL) 33
3-3-4時間解析光激螢光分析儀(Time-Resolved Photoluminescence,TRPL) 33
3-3-5太陽光模擬器系統 33
3-3-6外部量子效率(External Quantum Efficiency,EQE) 34
3-3-7 X光繞射儀(X-Ray Diffration,XRD) 34
3-3-8 X光電子能譜儀(X-ray Photoelectron Spectrometer,XPS) 35
第四章 實驗結果與討論 45
4-1掃描式電子顯微鏡(Scanning Electron Microscopy,SEM) 45
4-1-1 上視圖(Top View) 45
4-1-2 橫截面(Cross Section) 45
4-2 X光繞射儀(X-Ray Diffraction, XRD) 46
4-3 X光電子能譜儀(X-ray Photoelectron Spectrometer,XPS) 46
4-4導電原子力顯微鏡(Conductive Atomic Force Microscope,C-AFM) 48
4-5光致發光(Photoluminescence,PL) 48
4-6時間分辨光致發光(Time-Resolved Photoluminescence,TRPL)49
4-7暗電流(Dark current) 49
4-8空間電荷限制電流(The space-charge-limited-current,SCLC) 50
4-9電池元件量測(I-V電性分析) 51
4-10外部量子效率(External Quantum Efficiency,EQE) 52
4-11水滴角(Contact angle)測試 52
4-12電池元件老化測試 53
第五章 結論與未來展望 73
5-1 結論 73
5-2 未來展望 75
參考文獻 76

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