Separate and combined effects of Gua⁺ and SCN⁻ions on charge carrier dynamics in mixed Sn–Pb perovskites

Here, we investigated the separate and combined effects of guanidinium (Gua⁺) and/or thiocyanate (SCN⁻) ions on the opto-electronic properties of mixed Sn–Pb perovskites, which are used as absorber layers in photovoltaics. Therefore, we spin-coated Cs_0.25FA_0.75Sn_0.5Pb_0.5I₃ thin films with GuaI, Pb(SCN)₂ or GuaSCN, in the absence or presence of SnF₂. By comparing the (micro)structural and opto-electronic properties of the perovskite films, we elucidated the functions of both ions. We found that SCN⁻ suppresses tin oxidation and doping, reduces crystal defects and improves the carrier transport properties, regardless of SnF₂ addition. We demonstrate that this is due to coordination with Sn²⁺ and scavenging of Sn⁴⁺ in the spin-coating solution, resulting in a pile-up of SnO_x at the film surface. Gua⁺ is incorporated to a limited extent into the 3D cubic perovskite structure. Gua⁺ cannot suppress tin oxidation and doping, making this additive useless without SnF₂. Conversely, when combined with SnF₂, Gua⁺ enhances the carrier transport properties. Combining Gua⁺ and SCN⁻ until a maximum addition of 4 mol% and SnF₂ results in large grains and pinhole-free films with superior charge carrier transport properties, leading to a substantial increase in the pseudo-open circuit voltage of 50 mV. Addition of >4 mol% GuaSCN leads to the formation of Gua-based 2D perovskites, including Gua_xFA_2−xSn_yPb_1−yI₄ and Gua_xFA_3−xSn_yPb_2−yI₇, which do not improve the carrier dynamics. In short, we observe a synergistic effect on addition of Gua⁺ and SCN⁻ ions, which leads to improved structural and opto-electronic properties, which is promising for implementation in solar cells.