Mixed-cation metal halide perovskites have shown remarkable progress in photovoltaic applications with high power conversion efficiencies. However, to achieve large-scale deployment of this technology, efficiencies must be complemented by long-term durability. The latter is limited by external factors, such as exposure to humidity and air, which lead to the rapid degradation of the perovskite materials and devices. In this work, we study the mechanisms causing Cs and formamidinium (FA)-based halide perovskite phase transformations and stabilization during moisture and air exposure. We use in situ X-ray scattering, X-ray photoelectron spectroscopy, and first-principles calculations to study these chemical interactions and their effects on structure. We unravel a surface reaction pathway involving the dissolution of FAI by water and iodide oxidation by oxygen, driving the Cs/FA ratio into thermodynamically unstable regions, leading to undesirable phase transformations. This work demonstrates the interplay of bulk phase transformations with surface chemical reactions, providing a detailed understanding of the degradation mechanism and strategies for designing durable and efficient perovskite materials.

Chemical environment and precursor-coordinating molecular interactions within a perovskite precursor solution can lead to important implications in structural defects and crystallization kinetics of a perovskite film. Thus, the opto-electronic quality of such films can be boosted by carefully fine-tuning the coordination chemistry of perovskite precursors via controllable introduction of additives, capable of forming intermediate complexes. In this work, we employed a new type of ligand, namely 1-phenylguanidine (PGua), which coordinates strongly with the PbI₂ complexes in the perovskite precursor, forming new intermediate species. These strong interactions effectively retard the perovskite crystallization process and form homogeneous films with enlarged grain sizes and reduced density of defects. In combination with an interfacial treatment, the resulted champion devices exhibit a 24.6% efficiency with outstanding operational stability. Unprecedently, PGua can be applied in various PSCs with different perovskite compositions and even in both configurations: n–i–p and p–i–n, highlighting the universality of this ligand.

Tin-halide perovskites (THPs) have emerged as promising lead-free perovskites for photovoltaics and photocatalysis applications but still fall short in terms of stability and efficiency with respect to their lead-based counterpart. A detailed understanding of the degradation mechanism of THPs in a water environment is missing. This Letter presents ab initio molecular dynamics (AIMD) simulations to unravel atomistic details of THP/water interfaces comparing methylammonium tin iodide, MASnI₃, with the lead-based MAPbI₃. Our results reveal facile solvation of surface tin–iodine bonds in MASnI₃, while MAPbI₃ remains more robust to degradation despite a larger amount of adsorbed water molecules. Additional AIMD simulations on dimethylammonium tin bromide, DMASnBr₃, investigate the origins of their unprecedented water stability. Our results indicate the presence of amorphous surface layers of hydrated zero-dimensional SnBr₃ complexes which may protect the inner structure from degradation and explain their success as photocatalysts. We believe that the atomistic details of the mechanisms affecting THP (in-)stability may inspire new strategies to stabilize THPs.

The novel Zr^IV-based perfluorinated metal-organic framework (PF-MOF) [Zr₆O₄(OH)₄(TFS)₆] (ZrTFS) was prepared under solvent-free conditions using the commercially available tetrafluorosuccinic acid (H₂TFS) as a bridging ditopic linker. Since H₂TFS can be seen as the fully aliphatic and perfluorinated C₄ analogue of fumaric acid, ZrTFS was found to be isoreticular to zirconium fumarate (MOF-801). The structure of ZrTFS was solved and refined from X-ray powder diffraction data. Despite this analogy, the gas adsorption capacity of ZrTFS is much lower than that of MOF-801; in the former, the presence of bulky fluorine atoms causes a considerable window size reduction. To have PF-MOFs with more accessible porosity, postsynthetic exchange (PSE) reactions on (defective) MOF-801 suspended in H₂TFS aqueous solutions were carried out. Despite the different H₂TFS concentrations used in the PSE process, the exchanges yielded two mixed-linker materials of similar minimal formulae [Zr₆O₄(μ₃-OH)₄(μ₁-OH)_2.08(H₂O)_2.08(FUM)_4.04(HTFS)_1.84] (PF-MOF1) and [Zr₆O₄(μ₃-OH)₄(μ₁-OH)_1.83(H₂O)_1.83(FUM)_4.04(HTFS)_2.09] (PF-MOF2) (FUM^2- = fumarate), where the perfluorinated linker was found to fully replace the capping acetate in the defective sites of pristine MOF-801. CO₂ and N₂ adsorption isotherms collected on all samples reveal that both CO₂ thermodynamic affinity (isosteric heat of adsorption at zero coverage, Q_st) and CO₂/N₂ adsorption selectivity increase with the amount of incorporated TFS^2-, reaching the maximum values of 30 kJ mol^-1 and 41 (IAST), respectively, in PF-MOF2. This confirms the beneficial effect coming from the introduction of fluorinated linkers in MOFs on their CO₂ adsorption ability. Finally, solid-state density functional theory calculations were carried out to cast light on the structural features and on the thermodynamics of CO₂ adsorption in MOF-801 and ZrTFS. Due to the difficulties in modeling a defective MOF, an intermediate structure containing both linkers in the framework was also designed. In this structure, the preferential CO₂ adsorption site is the tetrahedral pore in the "UiO-66-like" structure. The extra energy stabilization stems from a hydrogen bond interaction between CO₂ and a hydroxyl group on the inorganic cluster.

First-principles simulations reveal the competition of defect formation and healing at grain boundaries in lead-halide perovskites. Fast halide migration at GBs mediates structural healing, but also gives rise to enhanced Frenkel defect formation.

Insight into the relation between morphology and transport properties of organic semiconductors can be gained using multiscale simulations. Since computing electronic properties, such as the intermolecular transfer integral, using quantum chemical (QC) methods requires a high computational cost, existing models assume several approximations. A machine learning (ML)–based multiscale approach is presented that allows to simulate charge transport in organic semiconductors considering the static disorder within disordered crystals. By mapping fingerprints of dimers to their respective transfer integral, a kernel ridge regression ML algorithm for the prediction of charge transfer integrals is trained and evaluated. Since QC calculations of the electronic structure must be performed only once, the use of ML reduces the computation time radically, while maintaining the prediction error small. Transfer integrals predicted by ML are utilized for the computation of charge carrier mobilities using off‐lattice kinetic Monte Carlo (kMC) simulations. Benefiting from the rapid performance of ML, microscopic processes can be described accurately without the need for phenomenological approximations. The multiscale system is tested with the well‐known molecular semiconductor pentacene. The presented methodology allows reproducing the experimentally observed anisotropy of the mobility and enables a fast estimation of the impact of disorder.