Passivation of organometal halide perovskites with polar molecules has been recently demonstrated to improve the photovoltaic device efficiency and stability. However, the mechanism is still elusive. Here, it is found that both polymers with large and small dipole moment of 3.7 D and 0.6 D have negligible defect passivation effect on the MAPbI 3 perovskite films as evidenced by photo thermal deflection spectroscopy. The photovoltaic devices with and without the polymer additives also have comparable power conversion efficiencies around 19%. However, devices with the additives have noticeable improvement in stability under continuous light irradiation. It is found that although the initial mobile ion concentrations are comparable in both devices with and without the additives, the additives can strongly suppress the ion migration during the device operation. This contributes to the significantly enhanced electrical-field stress tolerance of the perovskite solar cells (PVSCs). The PVSCs with polymer additives can operate up to −2 V reverse voltage bias which is much larger than the breakdown voltage of −0.5 V that has been commonly observed. This study provides insight into the role of additives in perovskites and the corresponding device degradation mechanism.

Functional additives that can interact with the perovskite precursors to form the intermediate phase have been proven essential in obtaining uniform and stable α-FAPbI 3 films. Among them, Cl-based volatile additives are the most prevalent in the literature. However, their exact role is still unclear, especially in inverted perovskite solar cells (PSCs). In this work, we have systematically studied the functions of Cl-based volatile additives and MA-based additives in formamidinium lead iodide (FAPbI 3 )based inverted PSCs. Using in situ photoluminescence, we provide clear evidence to unravel the different roles of volatile additives (NH 4 Cl, FACl, and MACl) and MA-based additives (MACl, MABr, and MAI) in the nucleation, crystallization, and phase transition of FAPbI 3 . Three different kinds of crystallization routes are proposed based on the above additives. The non-MA volatile additives (NH 4 Cl and FACl) were found to promote crystallization and lower the phase-transition temperatures. The MA-based additives could quickly induce MA-rich nuclei to form pure α-phase FAPbI 3 and dramatically reduce phase-transition temperatures. Furthermore, volatile MACl provides a unique effect on promoting the growth of secondary crystallization during annealing. The optimized solar cells with MACl can achieve an efficiency of 23.1%, which is the highest in inverted FAPbI 3 -based PSCs.

Mixed‐halide wide‐bandgap perovskites are key components for the development of high‐efficiency tandem structured devices. However, mixed‐halide perovskites usually suffer from phase‐impurity and high defect density issues, where the causes are still unclear. By using in situ photoluminescence (PL) spectroscopy, it is found that in methylammonium (MA+)‐based mixed‐halide perovskites, MAPb(I0.6Br0.4)3, the halide composition of the spin‐coated perovskite films is preferentially dominated by the bromide ions (Br−). Additional thermal energy is required to initiate the insertion of iodide ions (I−) to achieve the stoichiometric balance. Notably, by incorporating a small amount of formamidinium ions (FA+) in the precursor solution, it can effectively facilitate the I− coordination in the perovskite framework during the spin‐coating and improve the composition homogeneity of the initial small particles. The aggregation of these homogenous small particles is found to be essential to achieve uniform and high‐crystallinity perovskite film with high Br− content. As a result, high‐quality MA0.9FA0.1Pb(I0.6Br0.4)3 perovskite film with a bandgap (Eg) of 1.81 eV is achieved, along with an encouraging power‐conversion‐efficiency of 17.1% and open‐circuit voltage (Voc) of 1.21 V. This work also demonstrates the in situ PL can provide a direct observation of the dynamic of ion coordination during the perovskite crystallization.

Ion dissociation has been identified to determine the intrinsic stability of perovskite solar cells (PVSCs), but the underlying degradation mechanism is still elusive. Herein, by combining highly sensitive sub‐bandgap external quantum efficiency (s‐EQE) spectroscopy, impedance analysis, and theoretical calculations, the evolution of defect states in PVSCs during the degradation can be monitored. It is found that the degradation of PVSCs can be divided into three steps: 1) dissociation of ions from perovskite lattices, 2) migration of dissociated ions, and 3) consumption of I− by reacting with metal electrode. Importantly, step (3) is found to be crucial as it will accelerate the first two steps and lead to continuous degradation. By replacing the metal with more chemically robust indium tin oxide (ITO), it is found that the dissociated ions under light soaking will only saturate at the perovskite/ITO interface. Importantly, the dissociated ions will subsequently restore to the corresponding vacancies under dark condition to heal the perovskite and photovoltaic performance. Such shuttling of mobile ions without consumption in the ITO‐contact PVSCs results in harvesting–rest–recovery cycles in natural day/night operation. It is envisioned that the mechanism of the intrinsic perovskite material degradation reported here will lead to clearer research directions toward highly stable PVSCs.