錫鈣鈦礦(TPsk)太陽能電池是將鉛鈣鈦礦太陽能電池吸光層的中心金屬以錫取代，TPsk有較鉛鈣鈦礦更接近Shockley–Queisser limit (S–Q limit)中最佳光電轉換效率所需具備的吸光層能隙(1.3-1.4 eV)且在環境中形成毒性較低的SnO2，具未來性。大多數錫鈣鈦礦太陽能電池(TPSC)的研究都著重在減少TPsk膜中Sn4+的量或調整吸光層能階來匹配電洞傳遞層(HTL)的能階進而提高TPSC的光電轉換效率及穩定性，本研究是以調整HTL能階的方式來提高HTL與吸光層之能階的匹配並同時改善沉積在HTL上之錫鈣鈦礦膜的品質來增加元件的效率。實驗將Sulfamic acid (SA)添加到PEDOT:PSS(aq) (PS)調整HTL的導電度及能階並沉積在PS膜上製備PS/SA@PS雙層HTL，以PS/SA@PS雙層膜作為HTL所組裝之元件的光電轉換效率可達10.49%且放置在手套箱中2016小時後光電轉換效率可維持原來的95%，比用PS單層膜作為HTL之元件的光電轉換效率(8.17%)高28%，PS單層膜作為HTL之元件的穩定性在相同測試條件下光電轉換效率也僅維持原來的63%。摻雜SA之PS膜的導電度約為PS膜的1.5倍、光穿透度在波長範圍380-700 nm比PS膜高且其work function(WF, -5.38 V)與TPsk膜之Valence band (-5.40)匹配性高。此外，沉積在含SA之HTL的TPsk膜中Sn2+/Sn4+比例(72/28)比沉積在PS膜上之TPsk膜的Sn2+/Sn4+比例(60/40)高，因SA中磺酸基團氧上的孤對電子會與SnI2及SnF2中之Sn2+產生交互作用製備出高品質的TPsk膜，使Sn2+不易氧化成Sn4+且減少SnF2在TPsk膜表面形成聚集，沉積在摻雜SA之PS膜上的錫鈣鈦礦膜比沉積在PS單層膜上的錫鈣鈦礦膜平坦且緻密且結晶度高。;Tin perovskite (TPsk) is a material used tin to replace lead in lead perovskite sola cell (PSC). TPsk with a band gap close to the ideal energy gap (~1.34 eV) in Shockley–Queisser limit (S–Q limit) and low toxic catches a great attention in solar cell community. Most research on tin perovskite solar cells (TPSC) focuses on reducing the amount of Sn4+ in the TPsk film or adjusting the energy level of the light-absorbing layer to match the energy level of the hole transporting layer (HTL) to improve the power conversion efficiency (PCE) and stability of TPSC In this study, the energy level of the PEDOT:PSS based HTL is adjusted to improve match of the energy level of light-absorbing layer, and improve the quality of the tin perovskite film deposited on the HTL to enhance the photovoltacic performance of the device. Sulfamic acid (SA) was added to PEDOT:PSS(aq) (PS) HTL to adjust the conductivity and energy level of SA@PS HTL. A layer of PS film was insert in-between ITO and SA@PS to prepare PS/SA@PS double-layer HTL. The PCE of the device based on PS/SA@PS HTL achieved the highest PCE of 10.49% and the PCE maintains 95% of the initial value when the cells was placed in the glove box for 2016 hours. On the other hand, the PCE of the device based on PS HTL (8.17 %) is 28% lower and its stability under the same test conditions maintains only 63% of the initial PCE. The conductivity of the PS film doped with SA is about 1.5 of that for the PS film and the light transmittance is slightly higher than the PS film in the wavelength range of 380-700 nm. The work function (WF, -5.38 V) of SA@PS has good match with the valence band (-5.40) of the TPsk film. In addition, the Sn2+/Sn4+ ratio (72/28) of the TPsk film deposited on SA@PS HTL is higher than that (60/40) of the TPsk film deposited on PS film, because of the lone pair of the oxygen in the sulfonic acid group will interact with Sn2+ in SnI2 and SnF2 to passivate TPsk film, making Sn2+ difficult to oxidize to Sn4+ and at the same time reducing the aggregation of SnF2 in the TPsk film. The tin perovskite film deposited on the PS/SA@PS film is flatter, denser and more crystalline than that deposited on PS HTL.
