In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO(2) on Formamidinium-Based Lead Halide Perovskite

[Image: see text] Perovskite photovoltaics has achieved conversion efficiencies of 26.0% by optimizing the optoelectronic properties of the absorber and its interfaces with charge transport layers (CTLs). However, commonly adopted organic CTLs can lead to parasitic absorption and device instability. Therefore, metal oxides like atomic layer-deposited (ALD) SnO(2) in combination with fullerene-based electron transport layers have been introduced to enhance mechanical and thermal stability. Instead, when ALD SnO(2) is directly processed on the absorber, i.e., without the fullerene layer, chemical modifications of the inorganic fraction of the perovskite occur, compromising the device performance. This study focuses on the organic fraction, particularly the formamidinium cation (FA(+)), in a CsFAPb(I,Br)(3) perovskite. By employing in situ infrared spectroscopy, we investigate the impact of ALD processing on the perovskite, such as vacuum level, temperature, and exposure to half and full ALD cycles using tetrakis(dimethylamido)-Sn(IV) (TDMA-Sn) and H(2)O. We observe that exposing the absorber to vacuum conditions or water half-cycles has a negligible effect on the chemistry of the perovskite. However, prolonged exposure at 100 °C for 90 min results in a loss of 0.7% of the total formamidinium-related vibrational features compared to the pristine perovskite. Supported by density functional theory calculations, we speculate that FA(+) deprotonates and that formamidine desorbs from the perovskite surface. Furthermore, the interaction between TDMA-Sn and FA(+) induces more decomposition of the perovskite surface compared to vacuum, temperature, or H(2)O exposure. During the exposure to 10 ALD half-cycles of TDMA-Sn, 4% of the total FA(+)-related infrared features are lost compared to the pristine perovskite. Additionally, IR spectroscopy suggests the formation and trapping of sym-triazine, i.e., a decomposition product of FA(+). These studies enable to decouple the effects occurring during direct ALD processing on the perovskite and highlight the crucial role of the Sn precursor in affecting the perovskite surface chemistry and compromising the device performance.