近年來研究學者開發無機電洞傳輸層應用於錫鈣鈦礦太陽能電池(Tin Perovskite Solar Cells, TPSCs)，因無機材料具有可調控的前置軌域能階、高的光穿透度與好的長時間穩定性等優點。本研究經由Sol-Gel法製備Cu2+摻雜的SnCo2O4(Cu-SCO)膜作為反式錫鈣鈦礦太陽能電池的電洞傳輸層。Cu-SCO膜在300-1000 nm的平均光穿透度(73%)與PEDOT:PSS膜(76%)的數值相近，且Cu-SCO的價帶(-5.47 eV)比PEDOT:PSS的價帶(-5.16 eV)更接近錫鈣鈦礦的價帶(-5.74 eV)，減少電洞在元件中傳遞的能量損失，但Cu-SCO膜和錫鈣鈦礦層存在介面相容性不好的問題，導致組裝成元件的光電轉換效率僅有7.87%。因此在Cu-SCO膜和錫鈣鈦礦層間沉積一層兩性的高分子PTSN作為介面層，FTIR光譜顯示Cu-SCO+PTSN與SnI2+PTSN的thiophene C-S stretching 和amine C-N stretching，兩者皆往高波數位移，顯示PTSN疏水端thiophene硫上的孤對電子及親水鏈上胺基中之氮的孤對電子，都能與Cu-SCO膜和錫鈣鈦礦中配位未飽和的Sn2+作用。TRPL數據顯示，將錫鈣鈦礦沉積於Cu-SCO/PTSN膜上的載子生命週期(0.43 ns)比沉積在Cu-SCO膜上(0.63 ns)短，代表Cu-SCO/PTSN能較有效的萃取錫鈣鈦礦層的電洞。以Cu-SCO/PTSN及PEDOT:PSS作為電洞傳輸層所組裝之元件的最高效率分別為9.30%和8.74%。以Cu-SCO/PTSN作為電洞傳輸層所組裝之元件在未封裝且放置在氮氣手套箱中並在室內光照下3576小時，仍維持原效率的58%；在相同測試條件下，以PEDOT:PSS作為電洞傳輸層所組裝之元件放置2112小時後效率即掉為原效率的32%。;Inorganic hole transporting layers (HTL) for using in Tin Perovskite Solar Cells (TPSCs) have been widely studied in recent year because of inorganic materials have the advantages of controllable orbital energy levels, high light transmittance and good long-term stability amongst others. In this study, Cu2+ doped SnCo2O4 (Cu-SCO) film prepared by Sol-Gel method was used as the hole transporting layer of tin perovskite solar cells. The average light transmittance (73%) of the Cu-SCO film at 300-1000 nm is similar to that (76%) of the commonly used PEDOT:PSS HTL. The valence band edge (-5.47 eV) of Cu-SCO is closer to the valence band of tin perovskite (-5.74 eV) than that (-5.16 eV) of PEDOT:PSS film, which reduces the energy loss when the holes transport in cell. However, there is interfacial compatibility problem between the Cu-SCO film and the tin perovskite layer, results in the power conversion efficiency only 7.87% for the corresponding cell. Therefore, a layer of amphiphilic polymer PTSN was deposited between Cu-SCO film and tin perovskite layer as the interface layer. FTIR spectra showed that the thiophene C-S stretching and amine C-N stretching of Cu-SCO+PTSN and SnI2+PTSN both shifted to high wavenumber indicating that the lone pair electrons on the sulfur of thiophene and on the nitrogen in the amine group can interact with the unsaturated Sn2+ in the Cu-SCO film and tin perovskite. TRPL data shows that the carrier lifetime (0.43 ns) of tin perovskite deposited on the Cu-SCO/PTSN film is shorter than that (0.63 ns) of TPSK film coated on the Cu-SCO film, suggesting that Cu-SCO/PTSN can extract holes from the tin perovskite layer more efficient. The highest efficiency of devices base on Cu-SCO/PTSN and PEDOT:PSS HTLs were 9.30% and 8.74%, respectively. The device used Cu-SCO/PTSN HTL maintained 58% of the original efficiency when it was placed in the nitrogen filled glove box without encapsulating and under room light illumination for 3576 hours. Under the same test conditions, the cell based on PEDOT:PSS HTL drops to 32% of the original efficiency after being stored for 2112 hours.
