鈣鈦礦太陽能電池(Perovskite solar cells，簡稱PSC)中的鈣鈦礦(Perovskite，簡稱Psk)容易受水氣的影響而分解，大部分研究者都是在手套箱中製備Psk膜，為了降低成本則開始研究如何在大氣下克服水氣的影響來製備高品質Psk膜，而在大氣下製備Psk膜所沉積之載體常用具疏水性的無機材料，因無機材料具有長時間及熱穩定性且材料便宜，但無機材料常需以高溫(300oC以上)製備成膜，製備成本高且用途受限制，因此如何在低溫下製備無機電洞傳遞層(hole transport layer，簡稱HTL)也是重要的研究。本研究利用一步驟無反溶劑法在大氣下(RT：25~30oC；RH:30~40%)製備Psk膜，且以低溫(200oC)經由Sol-Gel製備ZnCo2O4尖晶石膜作為電洞傳遞層，並將Cu摻雜至ZnCo2O4膜來增加其電洞萃取能力及導電度，其中以2 mol%Cu摻雜之ZnCo2O4膜作為電洞傳遞層且使用無反溶劑法在大氣下所製之Psk膜作為吸收層之元件的最高光電轉換效率可達17.22%且幾乎沒有電流遲滯現象。分別以2 mol%(相對於Zn)Cu摻雜之ZnCo2O4膜及PEDOT:PSS膜作為HTL之元件未封裝放置大氣下(RT：25~30oC；RH：30~40%) 1744 hours，光電轉換效率剩下原效率的90%及12%。若元件未封裝在手套箱中以85oC連續加熱125 hours，光電轉換效率則降為原效率的77%及42%。經2 mol%Cu摻雜之ZnCo2O4膜導電度由(0.94×10-3 S/cm)增加至(1.44×10-3 S/cm)，由TRPL測得之沉積於HTL的Psk載子生命期分別為(7.12 ns)及(4.58 ns)，表示Cu摻雜能加速HTL將Psk受光產生的電洞萃取並傳遞至ITO導電玻璃上，因此所組裝之元件有較高的電流值。ZnCo2O4膜VB能階為-4.63 eV，2 mol%Cu摻雜ZnCo2O4膜的VB能階為-4.82 eV，後者與鈣鈦礦膜的VB能階(-5.44 eV)匹配性較高，因此以後者之HTL所組裝之元件有較高的Voc值。;Perovskite (Psk) used in perovskite solar cells (PSC) is generally prepared in a glove box with one-step anti-solvent dripping method due to the moisture sensitive of perovskite material. To reduce the fabrication costs, preparation of high-quality Psk films in an ambient atmosphere without using an anti-solvent is an important research. Furthermore, inorganic materials with good stability and low-cost are suitable to be used as HTLs in PSC. Nevertheless, inorganic materials need to be prepared at high temperatures (above 300°C) to form dense film with good conductivity, which are costly and have many application limitations. In this study, Psk film is prepared by one-step spin coating without anti-solvent under the ambient atmosphere (RT:25~30oC ; RH: 30~40%) and using ZnCo2O4 spinel HTL prepared via Sol–Gel process at low temperature (200oC). Moreover, Cu2+ was used as an dopant to enhance the hole extraction and transport ability of the ZnCo2O4 base HTLs. The results show PSC based on 2 mol% (vs Zn ) Cu2+ doped ZnCo2O4 HTL exhibit the maximum power conversion efficiency (PCE) of 17.22% and almost no current hysteresis. PSCs based on 2 mol% Cu2+ doped ZnCo2O4 and PEDOT:PSS HTL maintain 90% and 12%, respectively of the original efficiency by standing in air (RT:25~30oC ; RH: 30-40%) for 1744 hours without encapsulation, The cells are maintain 77% and 42%, respectively of their original efficiency by heated at 85oC for 125 hours. The conductivity of the ZnCo2O4 film increased from (0.94×10-3 S/cm) to (1.44×10-3 S/cm) when doped with 2 mol% Cu2+. The excitons lifetimes estimated from TRPL data are (7.12 ns) and (4.58 ns), respectively for Psk deposited on ZnCo2O4 and 2 mol% Cu2+ doped ZnCo2O4 HTLs. The results indicated that Cu2+ doping can enhance the hole extraction and transport ability ofZnCo2O4 based HTL to increase the Jsc of the corresponding cell. The VB energy level of the ZnCo2O4 film is -4.63 eV, and the VB energy level of the 2 mol% Cu2+ doped ZnCo2O4 film is -4.82 eV. The latter shows better energy match with the VB energy level (-5.44 eV) of the perovskite film, reduces the potential loss, therefore PSC based on Cu2+ doped ZnCo2O4 has higher Voc value compared to that based on ZnCo2O4 HTL.
