RESUMO
Developing high-performance and stable Sn-based perovskite solar cells (PSCs) is difficult due to the inherent tendency of Sn2+ oxidation and, the huge energy mismatch between perovskite and Phenyl-C61-butyric acid methyl ester (PCBM), a frequently employed electron transport layer (ETL). This study demonstrates that perovskite surface defects can be passivated and PCBM's electrical properties improved by doping n-type polymer N2200 into PCBM. The doping of PCBM with N2200 results in enhanced band alignment and improved electrical properties of PCBM. The presence of electron-donating atoms such as S, and O in N2200, effectively coordinates with free Sn2+ to prevent further oxidation. The doping of PCBM with N2200 offers a reduced conduction band offset (from 0.38 to 0.21 eV) at the interface between the ETL and perovskite. As a result, the N2200 doped PCBM-based PSCs show an enhanced open circuit voltage of 0.79 V with impressive power conversion efficiency (PCE) of 12.98% (certified PCE 11.95%). Significantly, the N2200 doped PCBM-based PSCs exhibited exceptional stability and retained above 90% of their initial PCE when subjected to continuous illumination at maximum power point tracking for 1000 h under one sun.
RESUMO
In the planar heterostructure of perovskite-based solar cells (PSCs), tin oxide (SnO2) is a material that is often used as the electron transport layer (ETL). SnO2 ETL exhibits favorable optical and electrical properties in the PSC structures. Nevertheless, the open circuit voltage (VOC) depletion occurs in PSCs due to the defects arising from the high oxygen vacancy on the SnO2 surface and the deeper conduction band (CB) energy level of SnO2. In this research, a cerium (Ce) dopant was introduced in SnO2 (Ce-SnO2) to suppress the VOC loss of the PSCs. The CB minimum of SnO2 was shifted closer to that of the perovskite after the Ce doping. Besides, the Ce doping effectively passivated the surface defects on SnO2 as well as improved the electron transport velocity by the Ce-SnO2. These results enabled the power conversion efficiency (PCE) to increase from 21.1% (SnO2) to 23.0% (Ce-SnO2) of the PSCs (0.09 cm2 active area) with around 100 mV of improved VOC and reduced hysteresis. Also, the Ce-SnO2 ETL-based large area (1.0 cm2) PSCs delivered the highest PCE of 22.9%. Furthermore, a VOC of 1.19 V with a PCE of 23.3% was demonstrated by Ce-SnO2 ETL-based PSCs (0.09 cm2 active area) that were treated with 2-phenethylamine hydroiodide on the perovskite top surface. Notably, the unencapsulated Ce-SnO2 ETL-based PSC was able to maintain above 90% of its initial PCE for around 2000 h which was stored under room temperature condition (23-25 °C) with a relative humidity of 40-50%.
RESUMO
Tin-based halide perovskite solar cells (Sn-PSCs) have attracted a progressive amount of attention as a potential alternative to lead-based PSCs (Pb-PSCs). Sn-perovskite films are fabricated by a solution process spin-coating technique. However, the efficiency of these devices varies significantly with the different batches of precursor solution due to the poor chemical stability of SnI2-DMSO and the oxidation of Sn2+ to Sn4+. This study investigated the origin of Sn2+ oxidation before film formation, and it was identified that the ionization of SnI2 in dimethyl sulfoxide (DMSO) causes the oxidation of free Sn2+ and I- ions. To address these issues, this study introduces the reductive additive 4-fluorophenylhydrazine hydrochloride (4F-PHCl) in the FASnI3 perovskite precursor solution. The hydrazine functional (-NH-NH2) group converted detrimental Sn4+ and I2 defects back to Sn2+ and I- in precursor solution while retaining the properties of the perovskite solution. Furthermore, the addition of 4F-PHCl in the precursor solution effectively slows the crystallization process, enhancing the crystallinity of FASnI3 perovskite films and guaranteeing the Sn2+/I- stoichiometric ratio, ultimately leading to a power conversion efficiency (PCE) of 10.86%. The hydrophobic fluorinated benzene ring in 4F-PHCl ensures moisture stability in perovskite films, allowing unencapsulated PSCs to retain over 92% of their initial PCE in an N2-filled glovebox for 130 days. Moreover, the 4F-PHCl-modified encapsulated PSCs showed superior operational stability for 420 h and maintained 95% of their initial PCE for 300 h under maximum power point tracking at 1 sun continuous illumination. This study's findings provide a promising pathway to create a controlled Sn-based perovskite precursor solution for highly reproducible and stable Pb-free Sn-PSCs.