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.

Last year’s mixed Sn–Pb perovskites have been applied as low-bandgap absorbers in efficient solar cells. However, the performance is still limited by tin oxidation, resulting in doping and defects. Here we perform a quantitative analysis on how tin oxidation affects the optoelectronic properties of spin-coated Cs_0.25FA_0.75Sn_0.5Pb_0.5I₃with varying SnF₂additions ranging from 0 to 20 mol %. First, optical spectroscopy is used to determine the fraction of Sn⁴⁺in the spin-coating solution, which varies depending on the purity of the starting SnI₂precursor. By applying steady-state microwave conductance, a large decrease in the dark conductivity from ∼100 to <∼1 S m^–1in the spin-coated films on going from 0 to 2 mol % SnF₂is observed. We conclude that, without SnF₂, ∼12% of the Sn⁴⁺in solution leads to mobile carriers in the form of free holes, p₀, in the perovskite layer. Upon SnF₂addition, p₀decreases to <1 × 10¹⁶cm^–3. We infer that a ∼70 times excess of SnF₂over the initial concentration of Sn⁴⁺in solution is required to scavenge the Sn⁴⁺and obtain layers with reduced doping. Although the reduction of p₀and defects results in increased carrier lifetimes, higher SnF₂additions are also required to decrease the surface defects, leading to even longer lifetimes close to 200 ns. The reduced doping of these perovskite films with SnF₂makes them ideal candidates for efficient solar cells; however, SnF₂also induces compositional heterogeneity and accumulation of SnO_xat the surface.

The potential of the vapor-phase deposition of metal halide perovskites (MHPs) for solar cells remains largely untapped, particularly in achieving rapid deposition rates. In this study, we employ in situ photoluminescence (PL) to monitor the growth dynamics of MHPs deposited via pulsed laser deposition (PLD), with rates ranging from 6 to 80 nm/min. Remarkably, the PL intensity evolution remains consistent across both low- and high-deposition rates, indicating that increased deposition rates do not significantly alter the fundamental mechanisms driving MHP formation via PLD. However, microstructural analysis and time-resolved microwave conductivity (TRMC) measurements reveal that increasing deposition rates lead to randomly oriented films on contact layers and reduced charge mobility compared with films grown at lower deposition rates. These findings emphasize the critical role of controlling initial nucleation and the value of in situ PL monitoring in optimizing the vapor-phase deposition of MHPs for enhanced photovoltaic performance at high deposition rates.

Mixed Sn-Pb halide perovskites are promising absorber materials for solar cells due to the possibility of tuning the bandgap energy down to 1.2-1.3 eV. However, tin-containing perovskites are susceptible to oxidation affecting the optoelectronic properties. In this work, we investigated qualitatively and quantitatively metastable oxygen-induced doping in isolated ASn_xPb_1-xI₃ (where A is methylammonium or a mixture of formamidinium and cesium) perovskite thin films by means of microwave conductivity, structural and optical characterization techniques. We observe that longer oxygen exposure times lead to progressively higher dark conductivities, which slowly decay back to their original levels over days. Here oxygen acts as an electron acceptor, leading to tin oxidation from Sn²⁺ to Sn⁴⁺ and creation of free holes. The metastable oxygen-induced doping is enhanced by exposing the perovskite simultaneously to oxygen and light. Next, we show that doping not only leads to the reduction in the photoconductivity signal but also induces long-term effects even after loss of doping, which is thought to derive from consecutive oxidation reactions leading to the formation of defect states. On prolonged exposure to oxygen and light, optical and structural changes can be observed and related to the formation of SnO_x and loss of iodide near the surface. Our work highlights that even a short-term exposure to oxygen immediately impairs the charge carrier dynamics of the perovskite, while structural perovskite degradation is only noticeable upon long-term exposure and accumulation of oxidation products. Hence, for efficient solar cells, exposure of mixed Sn-Pb perovskites to oxygen during production and operation should be rigorously blocked.

Metal-halide perovskites deposited by wet-chemical deposition have demonstrated great potential for various electronic applications, including solar cells. A remaining question is how light-induced excess charges become distributed over such polycrystalline material. Here, we examine the local conductive properties of MAPbI₃ and CsFAPbI₃ by using scanning microwave microscopy (sMIM) in the dark and light. sMIM is an atomic force microscopy (AFM)-based technique measuring variations of the in-phase and out-of-phase signals due to changes in the tip-sample interaction, yielding MIM-Re and MIM-Im images, respectively. Combining this information leads to a picture for CsFAPbI₃ in which excess charges are distributed evenly over the grains, but due to local defect-rich areas, possibly related to different crystal facets, local perturbations in carrier concentration exist. For solar cells, this distribution in carrier concentration under illumination leads to variation in the local Fermi level splitting, which should be suppressed to reduce the voltage deficit.